ORCID Profile
0000-0003-1072-7863
Current Organisation
University of South Australia
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Publisher: Elsevier BV
Date: 06-2015
DOI: 10.1016/J.COLSURFB.2015.04.021
Abstract: Here, we report on the development of advanced biopolymer-coated drug-releasing implants based on titanium (Ti) featuring titania nanotubes (TNTs) on its surface. These TNT arrays were fabricated on the Ti surface by electrochemical anodization, followed by the loading and release of a model antibiotic drug, gentamicin. The osteoblastic adhesion and antibacterial properties of these TNT-Ti s les are significantly improved by loading antibacterial payloads inside the nanotubes and modifying their surface with two biopolymer coatings (PLGA and chitosan). The improved osteoblast adhesion and antibacterial properties of these drug-releasing TNT-Ti s les are confirmed by the adhesion and proliferation studies of osteoblasts and model Gram-positive bacteria (Staphylococcus epidermidis). The adhesion of these cells on TNT-Ti s les is monitored by fluorescence and scanning electron microscopies. Results reveal the ability of these biopolymer-coated drug-releasing TNT-Ti substrates to promote osteoblast adhesion and proliferation, while effectively preventing bacterial colonization by impeding their proliferation and biofilm formation. The proposed approach could overcome inherent problems associated with bacterial infections on Ti-based implants, simultaneously enabling the development of orthopedic implants with enhanced and synergistic antibacterial functionalities and bone cell promotion.
Publisher: Elsevier BV
Date: 2019
DOI: 10.1016/J.COLSURFB.2018.10.015
Abstract: As some proteins are known to interact with sulfated and phosphated biomolecules such as specific glycosaminoglycans, this study derives from the hypothesis that sulfonate and phosphonate groups on solid polymer surfaces might cause specific interfacial interactions. Such surfaces were prepared by plasma polymerization of heptylamine (HA) and subsequent grafting of sulfonate or phosphonate groups via Michael-type addition of vinylic compounds. Adsorption of the proteins fibrinogen, albumin (HSA) and lysozyme on these functionalised plasma polymer surfaces was studied by XPS and quartz crystal microbalance with dissipation (QCM-D). It was also studied whether pre-adsorption with HSA would lead to a passivated surface against further adsorption of other proteins. XPS confirmed grafting of vinyl sulfonate and vinyl phosphonate onto the amine surface and showed that the proteins adsorbed to saturation at between 1 and 2 h. QCM-D showed rapid and irreversible adsorption of albumin on all three surfaces, while lysozyme could be desorbed with PBS to substantial extents from the sulfonated and phosphonated surfaces but not from the amine surface. Fibrinogen showed rapid initial adsorption followed by slower additional mass gain over hours. Passivation with albumin led to small and largely reversible subsequent adsorption of lysozyme, whereas with fibrinogen partial displacement yielded a mixed layer, regardless of the surface chemistry. Thus, protein adsorption onto these sulfonated and phosphonated surfaces is complex, and not dominated by electrostatic charge effects.
Publisher: Springer New York
Date: 17-08-2012
Publisher: Wiley
Date: 20-06-1989
Publisher: American Chemical Society (ACS)
Date: 13-10-2021
Abstract: This study demonstrates the ability of
Publisher: American Chemical Society (ACS)
Date: 07-2008
DOI: 10.1021/LA8007206
Abstract: A critical requirement toward the clinical use of nanocarriers in drug delivery applications is the development of optimal biointerfacial engineering procedures designed to resist biologically nonspecific adsorption events. Minimization of opsonization increases blood residence time and improves the ability to target solid tumors. We report the electrostatic self-assembly of polyethyleneimine-polyethylene glycol (PEI-PEG) copolymers onto porous silica nanoparticles. PEI-PEG copolymers were synthesized and their adsorption by self-assembly onto silica surfaces were investigated to achieve a better understanding of structure-activity relationships. Quartz-crystal microbalance (QCM) study confirmed the rapid and stable adsorption of the copolymers onto silica-coated QCM sensors driven by strong electrostatic interactions. XPS and FT-IR spectroscopy were used to analyze the coated surfaces, which indicated the presence of dense PEG layers on the silica nanoparticles. Dynamic light scattering was used to optimize the coating procedure. Monodisperse dispersions of the PEGylated nanoparticles were obtained in high yields and the thin PEG layers provided excellent colloidal stability. In vitro protein adsorption tests using 5% serum demonstrated the ability of the self-assembled copolymer layers to resist biologically nonspecific fouling and to prevent aggregation of the nanoparticles in physiological environments. These results demonstrate that the electrostatic self-assembly of PEG copolymers onto silica nanoparticles used as drug nanocarriers is a robust and efficient procedure, providing excellent control of their biointerfacial properties.
Publisher: American Vacuum Society
Date: 29-08-2017
DOI: 10.1116/1.4986054
Abstract: There is a need for coatings for biomedical devices and implants that can prevent the attachment of fungal pathogens while allowing human cells and tissue to appose without cytotoxicity. Here, the authors study whether a poly(2-hydroxyethylmethacrylate) (PHEMA) coating can suppress attachment and biofilm formation by Candida albicans and whether caspofungin terminally attached to surface-tethered polymeric linkers can provide additional benefits. The multistep coating scheme first involved the plasma polymerization of ethanol, followed by the attachment of α-bromoisobutyryl bromide (BiBB) onto surface hydroxyl groups of the plasma polymer layer. Polymer chains were grafted using surface initiated activators regenerated by electron transfer atom transfer radical polymerization with 2-hydroxyethylmethacrylate, yielding PHEMA layers with a dry thickness of up to 89 nm in 2 h. Hydroxyl groups of PHEMA were oxidized to aldehydes using the Albright–Goldman reaction, and caspofungin was covalently immobilized onto them using reductive amination. While the PHEMA layer by itself reduced the growth of C. albicans biofilms by log 1.4, the addition of caspofungin resulted in a marked further reduction by & log units to below the threshold of the test. The authors have confirmed that the predominant mechanism of action is caused by antifungal drug molecules that are covalently attached to the surface, rather than out-diffusing from the coating. The authors confirm the selectivity of surface-attached caspofungin in eliminating fungal, not mammalian cells by showing no measurable toxicity toward the myeloid leukaemia suspension cell line KG-1a.
Publisher: Elsevier BV
Date: 06-2013
DOI: 10.1016/J.COLSURFB.2013.01.052
Abstract: Addition of ionized terminal groups to PEG graft layers may cause additional interfacial forces to modulate the net interfacial interactions between PEG graft layers and proteins. In this study we investigated the effect of terminal sulfonate groups, characterizing PEG-aldehyde (PEG-CHO) and sulfonated PEG (PEG-SO3) graft layers by XPS and colloid probe AFM interaction force measurements as a function of ionic strength, in order to determine surface forces relevant to protein resistance and models of bio-interfacial interaction of such graft coatings. On the PEG-CHO surface the measured interaction force does not alter with ionic strength, typical of a repulsive steric barrier coating. An analogous repulsive interaction force of steric origin was also observed on the PEG-SO3 graft coating however, the net interaction force changed with ionic strength. Interaction forces were modelled by steric and electrical double layer interaction theories, with fitting to a scaling theory model enabling determination of the spacing and stretching of the grafted chains. Albumin, fibrinogen, and lysozyme did not adsorb on the PEG-CHO coating, whereas the PEG graft with terminal sulfonate groups showed substantial adsorption of albumin but not fibrinogen or lysozyme from 0.15 M salt solutions. Under lower ionic strength conditions albumin adsorption was again minimized as a result of the increased electrical double-layer interaction observed with the PEG-SO3 modified surface. This unique and unexpected adsorption behaviour of albumin provides an alternative explanation to the "negative cilia" model used by others to rationalize observed thromboresistance on PEG-sulfonate coatings.
Publisher: Informa UK Limited
Date: 1994
Publisher: Elsevier BV
Date: 08-1982
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/B926441H
Publisher: American Chemical Society (ACS)
Date: 13-01-2015
DOI: 10.1021/AC5031978
Abstract: Long-range surface plasmon resonance (LRSPR) is a powerful biosensing technology due to a substantially larger probing depth into the medium and sensitivity, compared with conventional SPR. We demonstrate here that LRSPR can provide sensitive noninvasive measurement of the dynamic fluctuation of adherent cells, often referred to as the cellular micromotion. Proof of concept was achieved using confluent layers of 3T3 fibroblast cells and MDA-MB-231 cancer cells. The slope of the power spectral density (PSD) of the optical fluctuations was calculated to determine the micromotion index, and significant differences were measured between live and fixed cell layers. Furthermore, the performances of LRSPR and conventional surface plasmon resonance (cSPR) were compared with respect to micromotion monitoring. Our study showed that the micromotion index of cells measured by LRSPR sensors was higher than when measured with cSPR, suggesting a higher sensitivity of LRSPR to the micromotion of cells. To investigate further this finding, simulations were conducted to establish the relative sensitivities of LRSPR and cSPR to membrane fluctuations. Increased signal intensity was predicted for LRSPR in comparison to cSPR, suggesting that membrane fluctuations play a significant role in the optical micromotion measured in LRSPR. Analogous to cellular micromotion measured using impedance techniques, LRSPR micromotion has the potential to provide important biological information on the metabolic activity and viability of adherent cells.
Publisher: American Chemical Society (ACS)
Date: 12-05-2020
Abstract: Hyperbranched polyglycerol (HPG) was previously investigated as a nonfouling hydrophilic grafted layer on biomaterial surfaces, analogous to the well-known poly(ethylene oxide) (PEO), but the range of adsorbing cells and proteins tested was limited and at times the assays used were not the most sensitive. Thus, the questions arise whether HPG-grafted layers can indeed efficiently resist adsorption of a wider range of adsorbing biological entities, and how would different biological entities interact with such a coating. An HPG coating of 25 nm thickness was grafted onto a spin-coated and plasma-treated polystyrene (PS) layer on a silicon wafer substrate this provided a well-suited system for surface analyses by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM), which verified the presence of a uniform, smooth grafted HPG layer. Adsorption of bovine serum albumin, lysozyme, fibrinogen, and endothelial cell growth medium 2 (EGM2) was reduced by >90%, with the adsorbed amounts close to the detection limit of XPS but still detectable by ToF-SIMS using principal component analysis. With human serum, however, the reduction in adsorption was slightly less pronounced. Smooth muscle cells (SMCs) and fibroblasts were virtually unable to attach onto the grafted HPG layer, with >99% reductions at 6 h compared with plasma-treated PS the few attached cells remaining rounded and unable to spread. Their attachment might have resulted from coating defects. Testing with full blood showed that unlike for the control surface (plasma-treated PS), platelets did not adhere to the HPG surface, but there was attachment of some cells that stained CD11b positive and likely are neutrophils. Cells of the fungal organism
Publisher: Elsevier BV
Date: 03-2009
DOI: 10.1016/J.BIOMATERIALS.2008.12.026
Abstract: Real-time control over and reversibility of biomolecule-surface interactions at interfaces is an increasingly important goal for a range of scientific fields and applications. The field of stimuli-responsive, smart or switchable systems has generated much research interest due to its potential to attain unprecedented levels of control over biomolecule adsorption processes and interactions at engineered interfaces, including the control over reversibility of adsorption. Advances in this field are particularly relevant to applications in the areas of biosensing, chromatography, drug delivery and regenerative medicine. The control over biomolecule adsorption and desorption processes at interfaces is often used to control subsequent events such as cell-surface interactions. Considerable research interest has been directed at systems that can be reversibly switched between interacting and non-interacting states and used thus for switching, on and off, bio-interfacial interactions such as protein adsorption. Such switchable coatings often incorporate features such as temporal resolution, spatial resolution and reversibility. Here we review recent literature on switchable coatings that employ stimuli such as light, temperature, electric potential, pH and ionic strength to control protein adsorption/desorption and cell attachment/detachment en route to the development of next-generation smart bio-interfaces.
Publisher: Elsevier BV
Date: 06-1988
Publisher: Elsevier BV
Date: 03-2014
DOI: 10.1016/J.BIOTECHADV.2013.10.015
Abstract: Microbial attachment onto biomedical devices and implants leads to biofilm formation and infection such biofilms can be bacterial, fungal, or mixed. In the past 15 years, there has been an increasing research effort into antimicrobial surfaces but the great majority of these publications present research on bacteria, with some reports also testing resistance to fungi. Very few studies have focused exclusively on antifungal surfaces. However, with increasing recognition of the importance of fungal infections to human health, particularly related to infections at biomaterials, it would seem that the interest in antifungal surfaces is disproportionately low. In studies of both bacteria and fungi, fungi tend to be the minor focus with hypothesized antibacterial mechanisms of action often generalized to also explain the antifungal effect. Yet bacteria and fungi represent two Distinct biological Domains and possess substantially different cellular physiology and structure. Thus it is questionable whether these generalizations are valid. Here we review the scientific literature focusing on surface coatings prepared with antifungal agents covalently attached to the biomaterial surface. We present a critical analysis of generalizations and their evidence. This review should be of interest to researchers of "antimicrobial" surfaces by addressing specific issues that are key to designing and understanding antifungal biomaterials surfaces and their putative mechanisms of action.
Publisher: Elsevier BV
Date: 10-2013
Publisher: Elsevier BV
Date: 07-1995
Abstract: Of significance in the routine use of BIAcore is the cost of the sensor chips. This is particularly evident during the phase of method development of an assay where it is not unusual to expend several chips in a day in attempts to optimize immobilization conditions for a novel peptide or protein. In addition, it is accepted practice to discard a chip once its ligand binding capacity has diminished to an unacceptable level. While the high cost of sensor chips has been addressed to some degree through the recent introduction of research-grade sensor chips, we were interested in assessing the possibility of regenerating or reconditioning sensor chips in order to allow them to be reused. In particular, we concerned ourselves with regenerating sensor chips onto which peptide or protein had been immobilized. Our aim was to develop a general procedure that would allow reuse of such chips but would not decrease ligand immobilization capacity or increase nonspecific ligand adsorption properties. We present a method which employs a combination of enzymatic (Pronase E) and chemical (bromoacetic acid) treatments of used sensor chips. Regeneration requires an overnight incubation of the sensor chip ex situ so that one can continue to perform BIAcore experiments. The data demonstrate that this simple two-step procedure substantially removes immobilized proteins such as IgG, Protein G, an HIV-1 envelope glycoprotein (gp 120) and a neoglycoprotein based on bovine serum albumin, as determined by reflectance measurements and X-ray photoelectron spectroscopy.(ABSTRACT TRUNCATED AT 250 WORDS)
Publisher: Springer Science and Business Media LLC
Date: 14-01-2015
DOI: 10.1038/SREP07760
Publisher: American Chemical Society (ACS)
Date: 24-10-2018
Publisher: Elsevier BV
Date: 1989
Publisher: Walter de Gruyter GmbH
Date: 20-08-2014
Abstract: Host-defense antimicrobial peptides (AMPs) are a promising lead in the search for novel antibiotics. Many of these peptides exhibit broad-spectrum antibacterial ability, low toxicity toward human cells, and little susceptibility to induction of bacterial resistance. Our research focuses on the development of synthetic polymers that are able to mimic the hiphilic and cation-rich characteristics of AMPs. This derives bioactive polymers that retain the activity profile of AMPs while utilizing a construct that is less expensive and easier to produce and manipulate chemically. This review details structure–activity relationships (SARs) of a new class of arginine-rich, synthetic AMP mimicking polymers (SAMPs), the guanylated polymethacrylates. These are contrasted with those of amine-based polymers that are mimics of lysine-rich AMPs. The ideal composition for candidates for practical applications was identified as those containing guanidines as a cation source, having a low molecular weight and a low level of lipophilicity. This gave polymers with high potency against Gram-positive strains of bacteria (e.g., Staphylococcus epidermidis MIC = 10 μg/mL) and low toxicity towards human red blood cells ( % hemolysis at given MIC). This work emphasizes the need to rationalize observed biological activities based not purely on the global lipophilic and cationic character of polymers but rather to consider the profound effect that specific pendant functional groups may have on the potency, selectivity, and mechanisms behind the action of antimicrobial polymers.
Publisher: Wiley
Date: 04-11-2009
Publisher: Wiley
Date: 1992
Publisher: American Chemical Society (ACS)
Date: 02-09-2010
DOI: 10.1021/LA1010677
Abstract: Successful implantation of any biomaterial depends on its mechanical, architectural, and surface properties. Materials with good bulk properties seldom possess the appropriate surface characteristics required for good biointegration. The present study investigates the results of surface modification of a highly porous, fully fluorinated polymeric substrate, expanded poly(tetrafluoroethylene) (ePTFE), with a view to improving the surface bioactivity and hence ultimately its biointegration. Modification involved gamma irradiation-induced graft copolymerization with the monomers monoacryloxyethyl phosphate (MAEP) and methacryloxyethyl phosphate (MOEP) in various solvent systems (water, methanol, methyl ethyl ketone, and mixtures thereof). In order to determine the penetration depth of the graft copolymer into the pores and/or the bulk of the ePTFE membranes, angle-dependent X-ray photoelectron spectroscopy (XPS) and magnetic resonance imaging (MRI) were used. It was found that the penetration depth was critically affected by the choice of monomer and solvent as well as by the technique used to remove dissolved oxygen from the grafting mixture: nitrogen degassing versus vacuum. Difficulties due to the porous nature of the membranes in establishing the lateral position of the graft copolymers were largely overcome by combining data from microattenuated total reflectance Fourier transfer infrared (μ-ATR-FTIR) mapping and time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging. Results show that the large variation in graft heterogeneity found between different s les is largely an effect of the underlying substrate and choice of monomer. The results from this study provide the necessary knowledge and experimental data to control both the graft copolymer lateral position and depth of penetration in these porous ePTFE membranes.
Publisher: Wiley
Date: 05-03-2012
Publisher: IOP Publishing
Date: 30-04-2010
DOI: 10.1088/0957-4484/21/21/215102
Abstract: This paper presents a novel and facile method for the generation of efficient antibacterial coatings which can be applied to practically any type of substrate. Silver nanoparticles were stabilized with an adsorbed surface layer of polyvinyl sulphonate (PVS). This steric layer provided excellent colloidal stability, preventing aggregation over periods of months. PVS-coated silver nanoparticles were bound onto amine-containing surfaces, here produced by deposition of an allylamine plasma polymer thin film onto various substrates. SEM imaging showed no aggregation upon surface binding of the nanoparticles they were well dispersed on amine surfaces. Such nanoparticle-coated surfaces were found to be effective in preventing attachment of Staphylococcus epidermidis bacteria and also in preventing biofilm formation. Combined with the ability of plasma polymerization to apply the thin polymeric binding layer onto a wide range of materials, this method appears promising for the fabrication of a wide range of infection-resistant biomedical devices.
Publisher: Wiley
Date: 11-01-2016
Publisher: Elsevier BV
Date: 2014
Publisher: Wiley
Date: 27-07-2017
Publisher: Wiley
Date: 03-11-2005
DOI: 10.1002/JBM.A.30514
Abstract: Adherent and optically semitransparent thin calcium phosphate (CaP) films were electrochemically deposited on titanium substrates in a modified simulated body fluid at 37 degrees C. Coatings deposited by using periodic pulsed potentials showed better adhesion and better mechanical properties than coatings deposited with use of a constant potential. Scanning electron microscopy was used to study the morphology of the coatings. The coatings displayed a polydispersed porous structure with pores in the range of a few nanometers to 1 mum. Furthermore, X-ray diffractometry and the O(1s) satellite peaks in X-ray photoelectron spectroscopy indicated that the coatings possessed a similar surface chemistry to that of natural bone minerals. These results were confirmed by inductively coupled plasma optical emission spectrometry, which yielded a Ca:P ratio of 1.65, close to that of hydroxyapatite. Contact mode atomic force microscopy (AFM) showed the average thickness of the coatings was in the order of 200 nm. Root-mean-square (RMS) roughness values, also derived by AFM, were shown to be much higher on the titanium-CaP surfaces in comparison with untreated titanium substrates, with RMS values of about 300 and 110 nm, respectively. Cell culture experiments showed that the CaP surfaces are nontoxic to MG63 osteoblastic cells in vitro and were able to support cell growth for up to 4 days, outperforming the untreated titanium surface in a direct comparison. These easily prepared coatings show promise for hard-tissue biomaterials.
Publisher: American Chemical Society (ACS)
Date: 30-08-2012
DOI: 10.1021/NP300433R
Abstract: In an effort to identify new anti-inflammatory and antibacterial agents with potential application in wound healing, five new dibenzofurans, 1,3,7,9-tetrahydroxy-2,8-dimethyl-4,6-di(2-methylbutanoyl)dibenzofuran (1), 1,3,7,9-tetrahydroxy-2,8-dimethyl-4-(2-methylbutanoyl)-6-(2-methylpropionyl)dibenzofuran (2), 1,3,7,9-tetrahydroxy-2,8-dimethyl-4,6-di(2-methylpropionyl)dibenzofuran (3), 1,3,7,9-tetrahydroxy-4,6-dimethyl-2-(2-methylbutanoyl)-8-(2-methylpropionyl)dibenzofuran (4), and 1,3,7,9-tetrahydroxy-4,6-dimethyl-2,8-di(2-methylpropionyl)dibenzofuran (5), were isolated from the leaves of Pilidiostigma glabrum together with one previously described dibenzofuran. Structure elucidation was achieved by way of spectroscopic measurements including 2D-NMR spectroscopy. Compounds with 2,8-acyl substitutions had potent antibacterial activity against several Gram-positive strains (MIC in the low micromolar range), while compounds with 4,6-acyl substitutions were less active. All compounds except 3 inhibited the synthesis of nitric oxide in RAW264 macrophages with IC(50) values in the low micromolar range. Compounds with 2,8-acyl substitutions also inhibited the synthesis of PGE(2) in 3T3 cells, whereas 4,6-acyl-substituted compounds were inactive. None of the compounds inhibited the synthesis of TNF-α in RAW264 cells. The compounds showed variable but modest antioxidant activity in the oxygen radical absorbance capacity assay. These findings highlight that much of the Australian flora remains unexplored and may yet yield many new compounds of interest. Initial clues are provided on structure/activity relationships for this class of bioactives, which may enable the design and synthesis of compounds with higher activity and/or selectivity.
Publisher: Informa UK Limited
Date: 1998
Abstract: Implant devices for orthopaedic applications may be improved if the surface of the biomaterial provides for osteointegration. To understand the effect of hydrophilicity on colonisation by human bone derived (HBD) cells, we compared untreated polystyrene (PS) and a sulfuric acid-treated PS surface for mechanisms of cell migration. The chemical composition of the acid-treated PS surface was analysed by monochromatic X-ray photoelectron spectroscopy and found to contain various oxidatively produced groups and a minor amount of sulfonate groups. It was found that migration of HBD cells on both PS and acid-treated PS surface was dependent on the presence of vitronectin (Vn) and was higher on the hydrophilic acid-treated surface. Minimal migration of HBD cells occurred on either surface in the absence of Vn, even when fibronectin was present in the culture medium. Using radiolabelled protein, it was shown that Vn adsorption onto the acid-treated surface was two to three fold greater than that on the hydrophobic PS. When HBD cells were seeded onto a patterned surface in a medium containing Vn, the cells preferentially colonised the hydrophilic region and few, if any, cells traversed the haptotactic boundary from the hydrophilic to the hydrophobic side. Thus the enhanced HBD cell migration seen on the acid-treated PS compared with the untreated PS surface and the haptotactic boundary phenomenon, relate to Vn adsorption.
Publisher: Elsevier BV
Date: 1989
Publisher: Elsevier BV
Date: 10-1981
Publisher: Wiley
Date: 17-11-2014
Publisher: American Vacuum Society
Date: 12-2015
DOI: 10.1116/1.4937464
Abstract: In the development of bioactive coatings on biomaterials, it is essential to characterize the successful fabrication and the uniformity of intended coatings by sensitive surface analytical techniques, so as to ensure reliable interpretation of observed biointerfacial responses. This can, however, be challenging when small bioactive molecules are grafted onto biomaterials surfaces at sub- and near-monolayer densities. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) provides the required sensitivity, but ion signals from small grafted molecules may still be dominated by fragment ions from the underlying polymer. In such cases, multivariate analysis provides valuable enhancement of spectral data, as illustrated here by ex les comprising the surface grafting of bioactive serrulatane molecules, the peptide GRGDSP, the oligonucleotide 15-thymidine, and the antifungal compound Amphotericin B. The authors also show how ToF-SIMS plus principal component analysis can distinguish between covalent grafting and physisorption of the antibiotics caspofungin and micafungin.
Publisher: American Chemical Society (ACS)
Date: 24-08-2005
DOI: 10.1021/JP050431+
Abstract: PEGylated Nb2O5 surfaces were obtained by the adsorption of poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) copolymers, allowing control of the PEG surface density, as well as the surface charge. PEG (MW 2 kDa) surface densities between 0 and 0.5 nm(-2) were obtained by changing the PEG to lysine-mer ratio in the PLL-g-PEG polymer, resulting in net positive, negative and neutral surfaces. Colloid probe atomic force microscopy (AFM) was used to characterize the interfacial forces associated with the different surfaces. The AFM force analysis revealed interplay between electrical double layer and steric interactions, thus providing information on the surface charge and on the PEG layer thickness as a function of copolymer architecture. Adsorption of the model proteins lysozyme, alpha-lactalbumin, and myoglobin onto the various PEGylated surfaces was performed to investigate the effect of protein charge. In addition, adsorption experiments were performed over a range of ionic strengths, to study the role of electrostatic forces between surface charges and proteins acting through the PEG layer. The adsorbed mass of protein, measured by optical waveguide lightmode spectroscopy (OWLS), was shown to depend on a combination of surface charge, protein charge, PEG thickness, and grafting density. At high grafting density and high ionic strength, the steric barrier properties of PEG determine the net interfacial force. At low ionic strength, however, the electrical double layer thickness exceeds the thickness of the PEG layer, and surface charges "shining through" the PEG layer contribute to protein interactions with PLL-g-PEG coated surfaces. The combination of AFM surface force measurements and protein adsorption experiments provides insights into the interfacial forces associated with various PEGylated surfaces and the mechanisms of protein resistance.
Publisher: American Chemical Society (ACS)
Date: 19-03-2014
DOI: 10.1021/MZ5001527
Abstract: This study describes a facile and high yielding route to two series of polymethacrylates inspired by the naturally occurring, tryptophan-rich cationic antimicrobial polymers. Appropriate optimization of indole content within each gave rise to polymers with high potency against
Publisher: Wiley
Date: 14-02-2012
Publisher: Elsevier BV
Date: 03-2014
DOI: 10.1016/J.FITOTE.2013.12.008
Abstract: Five anthranilic acid derivatives, a mixture I of three new compounds 11'-hexadecenoylanthranilic acid (1), 9'-hexadecenoylanthranilic acid (2), and 7'-hexadecenoylanthranilic acid (3), as well as a new compound 9,12,15-octadecatrienoylanthranilic acid (4) together with a new natural product, hexadecanoylanthranilic acid (5), were isolated from Geijera parviflora Lindl. (Rutaceae). Their structures were elucidated by extensive spectroscopic measurements, and the positions of the double bonds in compounds 1-3 of the mixture I were determined by tandem mass spectrometry employing ozone-induced dissociation. The mixture I and compound 5 showed good antibacterial activity against several Gram-positive strains.
Publisher: Wiley
Date: 29-12-2014
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH11354
Abstract: Hydrophilically substituted diterpenes of the structural class of serrulatanes have attracted attention as novel antibacterial compounds that are effective even against multidrug-resistant Staphylococcus aureus, a key bacterium involved in human infections. The mechanism of action has, however, not been established yet. Available data on structure–activity relationships suggest that the aromatic hydroxy group is essential for activity, and the strongest activity has been found for naphthyl compounds. In this context, it is reported that two highly active serrulatanes isolated from leaf resin of the Australian plant species Eremophila duttonii showed instability upon separation. Acetylation of hydroxy groups generated stable compounds that could be isolated and identified by NMR spectroscopy. The acetylated compounds showed little antibacterial activity, but such activity, as well as oxidative instability, was restored after hydrolysis of the acetate groups. Thus, phenolic hydroxy groups are essential for the mechanism of action of these compounds. The reaction products were not purifiable in sufficient quantities, but indications point to oxidation to quinones. Such oxidation may be a key aspect of the antibacterial activity of this class of compounds.
Publisher: Elsevier BV
Date: 02-2006
Publisher: MDPI AG
Date: 04-12-2020
DOI: 10.20944/PREPRINTS202012.0116.V1
Abstract: To combat infections on biomedical devices, antimicrobial coatings have attracted considerable attention, including coatings comprising naturally occurring antimicrobial peptides (AMPs). In this study the aim was to explore performance upon extended challenge by bacteria growing in media above s les. The AMPs LL37, Magainin 2, and Parasin 1 were covalently grafted onto a plasma polymer platform, which enables application of this multilayer coating strategy to a wide range of biomaterials. Detailed surface analyses were performed to verify the intended outcomes of the coating sequence. S les were challenged by incubation in bacterial growth media for 5 and 20 hrs. Compared with the control plasma polymer surface, all three grafted AMP coatings showed considerable reductions in bacterial colonization even at the high bacterial challenge of initial seeding at 1x107 CFU, but there were increasing numbers of dead bacteria attached to the surface. All three grafted AMP coatings were found to be non-toxic to primary fibroblasts. These coatings thus could be useful to produce antibacterial surface coatings for biomaterials, though possible consequences arising from the presence of dead bacteria need to be studied further, and compared to non-fouling coatings that avoid attached dead bacteria.
Publisher: Elsevier BV
Date: 07-1999
DOI: 10.1016/S0142-9612(99)00037-X
Abstract: Human serum albumin (HSA) was specifically spin labelled with 4-maleimido-tempo (MSL) at its cysteine 34 residue (HSA-MSL). The irreversible adsorption of HSA-MSL to hydrogel contact lenses (etafilcon A, tefilcon and vifilcon A) was investigated using electron spin resonance (ESR) spectroscopy. Changes in ESR spectral characteristics of adsorbed HSA-MSL as compared to HSA-MSL in solution displayed an additional immobilisation of the spin label due to the adsorption. This immobilisation of MSL corresponds to a large conformational alteration of the HSA-MSL near the modified Cys 34 residue. For both etafilcon A and tefilcon, the rate of irreversible adsorption was relatively slow compared with that of vifilcon A where the maximum state of immobilisation and hence conformational change occurred within the first hour of adsorption. Furthermore, tefilcon produced markedly different ESR spectra where a strong conformational change to a less mobile protein was apparent. This supported a model where the direct irreversible adsorption of HSA from solution dominated on tefilcon as opposed to conversion of the adsorbed protein from the reversible to the irreversible state on both etafilcon A and vifilcon A. HSA-MSL adsorption onto hydrophobic poly(methylmethacrylate) (PMMA) and hydrophilic poly(N-ter-butylacrylamide) (PTBAM) latex beads was also investigated. The spin label MSL was found to be less mobile when HSA was adsorbed onto PMMA compared with PTBAM beads. It was also found that the rate of irreversible adsorption of HSA is far higher onto PMMA surfaces than onto PTBAM surfaces.
Publisher: Elsevier BV
Date: 10-2013
Publisher: SPIE
Date: 21-12-2011
DOI: 10.1117/12.903304
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7CP08166A
Abstract: The multiple roles hydrogen plays in depositing plasmas is investigated by addition of H 2 O and D 2 O to ethyltrimethylacetate plasmas.
Publisher: Elsevier BV
Date: 10-2000
DOI: 10.1016/S0927-7765(99)00149-6
Abstract: Coatings from carboxymethylated dextrans (CMDs) were fabricated, analyzed by XPS, and investigated for their ability to inhibit corneal epithelial tissue outgrowth and bovine corneal epithelial cell attachment and growth. CMDs with differing degrees of carboxymethyl substitution and various molecular weights were synthesized by the solution reaction of dextrans with bromoacetic acid under different reactant ratios. The CMD compounds thus obtained were attached onto aminated surfaces produced in two ways: by the plasma deposition of a coating from n-heptylamine vapour, and by the plasma deposition of an acetaldehyde coating onto whose surface aldehyde groups the polyamine compounds polylysine, polyethyleneimine and polyallylamine were immobilized to provide platforms for CMD immobilization. XPS spectra showed that the latter route produced thicker coatings than the former approach. CMD molecules attached directly onto the plasma-fabricated amine surface supported some tissue migration the extent of carboxymethyl substitution and the molecular weight of the CMDs had little influence. For CMDs immobilized via polyamine spacers, on the other hand, tissue outgrowth was completely inhibited, and again there were no discernible effects from the extent of carboxymethyl substitution and the molecular weight of the CMDs. In assays involving cell attachment and growth, analogous observations were found. Thus, the mode of immobilization of these polysaccharide coatings is the dominant factor in their anti-fouling performance, suggesting that optimization of the architecture of polysaccharide coatings may be an important factor for maximizing their cell-repellent abilities.
Publisher: Elsevier BV
Date: 11-1997
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5TB00961H
Abstract: In this work we have prepared surface coatings formulated with the antifungal drug caspofungin, an approved pharmaceutical lipopeptide compound of the echinocandin drug class.
Publisher: Wiley
Date: 29-08-2012
Publisher: Elsevier BV
Date: 09-1999
Publisher: Wiley
Date: 13-06-2012
Publisher: Informa UK Limited
Date: 1995
Abstract: Optimization of strategies for the covalent attachment of proteins onto polymer surfaces requires the development of analytical methods which can differentiate between proteins that are covalently attached and those that are non-covalently bound (physisorbed). We probed for the surface density of reactive amine, carbonyl, and hydrazide groups using solution phase derivatization reactions to mimic and explore protein immobilization reaction strategies. Labeling compounds investigated were fluorescein derivatives, which were quantified by adsorption spectroscopy, and fluorinated phenyl compounds which were quantified by XPS. Control experiments consisted of performing the same labeling reactions using surfaces without reactive groups, or immersing the polymer surface into the labeling solution after blocking the reactive group of the labeling compound by a covalent reaction in solution. We always found non-negligible contributions arising from physisorption of the derivatization labels. Multiple control surfaces and a novel 'crossover derivatization-XPS' method were studied with the aim of improving compensation for physisorption. Our documentation of surprisingly large physisorption components even for small molecule labels, together with the known propensity of proteins to adsorb onto polymers, suggests caution in quantitative analysis of surface groups by derivatization, and in interpreting covalent protein immobilizations onto polymeric surfaces.
Publisher: American Society for Microbiology
Date: 2013
DOI: 10.1128/AAC.01735-12
Abstract: Treatment options are limited for implant-associated infections (IAI) that are mainly caused by biofilm-forming staphylococci. We report here on the activity of the serrulatane compound 8-hydroxyserrulat-14-en-19-oic acid (EN4), a diterpene isolated from the Australian plant Eremophila neglecta . EN4 elicited antimicrobial activity toward various Gram-positive bacteria but not to Gram-negative bacteria. It showed a similar bactericidal effect against logarithmic-phase, stationary-phase, and adherent Staphylococcus epidermidis , as well as against methicillin-susceptible and methicillin-resistant S. aureus with MICs of 25 to 50 μg/ml and MBCs of 50 to 100 μg/ml. The bactericidal activity of EN4 was similar against S. epidermidis and its Δ ica mutant, which is unable to produce polysaccharide intercellular adhesin-mediated biofilm. In time-kill studies, EN4 exhibited a rapid and concentration-dependent killing of staphylococci, reducing bacterial counts by log 10 CFU/ml within 5 min at concentrations of μg/ml. Investigation of the mode of action of EN4 revealed membranolytic properties and a general inhibition of macromolecular biosynthesis, suggesting a multitarget activity. In vitro -tested cytotoxicity on eukaryotic cells was time and concentration dependent in the range of the MBCs. EN4 was then tested in a mouse tissue cage model, where it showed neither bactericidal nor cytotoxic effects, indicating an inhibition of its activity. Inhibition assays revealed that this was caused by interactions with albumin. Overall, these findings suggest that, upon structural changes, EN4 might be a promising pharmacophore for the development of new antimicrobials to treat IAI.
Publisher: IEEE
Date: 08-2010
Publisher: American Vacuum Society
Date: 11-2020
DOI: 10.1116/6.0000511
Abstract: A drug-eluting coating applied onto biomedical devices and implants is an appropriate way to ensure that an inhibitory concentration of antimicrobial drugs is present at the device surface, thus preventing surface colonization and subsequent biofilm formation. In this study, a thin polymer coating was applied to materials, and it acted as a drug-delivery reservoir capable of surface delivery of the antifungal drug fluconazole to amounts up to 21 μg/cm2. The release kinetics into aqueous solution were quantified by UV spectroscopy and conformed to the Ritger–Peppas and Korsmeyer–Peppas model. Complementary microbiological assays were used to determine effectiveness against Candida albicans attachment and biofilm formation, and against the control heptylamine plasma polymer coating without drug loading, on which substantial fungal growth occurred. Fluconazole release led to marked antifungal activity in all assays, with log 1.6 reduction in CFUs/cm2. Cell viability assays and microscopy revealed that fungal cells attached to the fluconazole-loaded coating remained rounded and did not form hyphae and biofilm. Thus, in vitro screening results for fluconazole-releasing surface coatings showed efficacy in the prevention of the formation of Candida albicans biofilm.
Publisher: Elsevier BV
Date: 12-1997
DOI: 10.1016/S0142-9612(97)80006-3
Abstract: The initial attachment of cultured bovine corneal epithelial cells and stromal fibroblasts to two oxygen-containing synthetic polymers was studied. Cultured epithelial cells and stromal fibroblasts were seeded onto two oxygen-containing surfaces: 'tissue culture' polystyrene (TCPS) and a polymer film deposited by RF plasma deposition using a methylmethacrylate monomer (MMA/FEP). To establish the mechanism of cell attachment, the effect of the selective removal of the vitronectin and fibronectin from the serum used in the culture medium was tested. The attachment of cultured epithelial cells during the first 90 min of culture was reduced by 40% (TCPS)-80% (MMA/FEP) as a result of removing vitronectin from the medium. Attachment of these cells to TCPS was reduced by 85-95% when the serum was depleted of both fibronectin and vitronectin. However, depletion of fibronectin reduced cell attachment to TCPS by 20%, whilst on MMA/FEP cell attachment was equivalent, or higher, than that for intact serum. The attachment of cultured corneal stromal fibroblasts was similarly dependent on vitronectin but less dependent on fibronectin. Therefore, for the attachment of both cultured epithelial cells and fibroblasts to oxygen-containing surfaces in the presence of serum, there is a high requirement for serum vitronectin but a lesser requirement for fibronectin. The effects of the establishment of corneal epithelial cells in culture and the site of origin of the cells, were determined. Primary isolates of epithelial cells isolated from the limbal, central or peripheral regions of the cornea were less dependent on vitronectin for initial attachment to TCPS than were these cells after several passages in culture. Furthermore, the primary isolates were dramatically less responsive to vitronectin than the cultured cells. These results indicate that the mechanism of attachment of corneal epithelial cells to TCPS varies with the culture experience of the cells. Cells that are culture neophytes can employe endogenous mechanisms for the initial attachment to TCPS, whereas cells established in culture are dependent on exogenous vitronectin in order to attach.
Publisher: Elsevier BV
Date: 2018
DOI: 10.1016/J.BIOTECHADV.2017.11.010
Abstract: In recent years, increasing evidence has been collated on the contributions of fungal species, particularly Candida, to medical device infections. Fungal species can form biofilms by themselves or by participating in polymicrobial biofilms with bacteria. Thus, there is a clear need for effective preventative measures, such as thin coatings that can be applied onto medical devices to stop the attachment, proliferation, and formation of device-associated biofilms. However, fungi being eukaryotes, the challenge is greater than for bacterial infections because antifungal agents are often toxic towards eukaryotic host cells. Whilst there is extensive literature on antibacterial coatings, a far lesser body of literature exists on surfaces or coatings that prevent attachment and biofilm formation on medical devices by fungal pathogens. Here we review strategies for the design and fabrication of medical devices with antifungal surfaces. We also survey the microbiology literature on fundamental mechanisms by which fungi attach and spread on natural and synthetic surfaces. Research in this field requires close collaboration between biomaterials scientists, microbiologists and clinicians we consider progress in the molecular understanding of fungal recognition of, and attachment to, suitable surfaces, and of ensuing metabolic changes, to be essential for designing rational approaches towards effective antifungal coatings, rather than empirical trial of coatings.
Publisher: Royal Society of Chemistry (RSC)
Date: 2016
DOI: 10.1039/C6RA12886F
Abstract: Although polyaniline (PAni) has been studied extensively in the past, little work has been done on producing films of this material via plasma deposition.
Publisher: Elsevier BV
Date: 2006
DOI: 10.1016/J.BIOMATERIALS.2005.05.037
Abstract: Control of the precise location and extent of cellular attachment and proliferation, and of tissue outgrowth is important in a number of biomedical applications, including biomaterials and tissue engineered medical devices. Here we describe a method to control and direct the location and define boundaries of tissue growth on surfaces in two dimensions. The method relies on the generation of a spatially defined surface chemistry comprising protein adsorbing and non-adsorbing areas that allow control over the adsorption of cell-adhesive glycoproteins. Surface modification was carried out by deposition of thin acetaldehyde and allylamine plasma polymer coatings on silicon wafer and FEP substrates, followed by grafting of a protein resistant layer of poly(ethylene oxide). Spatially controlled patterning of the surface chemistry was achieved by masking during plasma polymerization. XPS and AFM were used to provide evidence of successful surface modifications. Adsorption of the extracellular matrix protein collagen I followed by tissue outgrowth experiments with bovine corneal epithelial tissue for up to 21 days showed that two-dimensional control over tissue outgrowth is achievable with our patterning method over extended time frames. The method promises to be an effective tool for use in a number of in vitro and in vivo applications.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C4SM02669A
Abstract: A colloid-probe AFM based approach investigates the interaction between protein coatings on colloid probes and surfaces decorated with close-packed colloidal crystal layers.
Publisher: Wiley
Date: 08-09-2009
Publisher: Elsevier BV
Date: 04-2002
DOI: 10.1016/S0168-3659(02)00023-8
Abstract: Liposomes were immobilized onto the surface of perfluorinated polymer tape s les and tissue culture polystyrene well-plates using a multilayer immobilization strategy. In the first step, a thin interfacial bonding layer with surface aldehyde groups was deposited from a glow discharge struck in acetaldehyde vapour. Polyethylenimine was then covalently bound onto the aldehyde groups by reductive amination, followed by covalent binding of NHS-PEG-biotin molecules onto the surface amine groups by carbodiimide chemistry. Next, NeutrAvidin protein molecules were bound onto the PEG-biotin layer. Finally, liposomes containing PEG-biotinylated lipids were docked onto the remaining binding sites of the surface-immobilized NeutrAvidin molecules. AFM was used to image surface-bound liposomes and revealed a density well below close packing. The release characteristics of the surface-bound liposomes were measured by the fluorescence intensity changes of carboxyfluorescein upon release. Liposomes filled with sodium orthovanadate were surface immobilized and used in two in vitro angiogenesis assays. Marked differences compared to various control s les were observed, demonstrating the utility of drug-filled, surface-bound liposomes for evoking localized, controlled biological host responses proximal to an implanted biomedical device.
Publisher: American Vacuum Society
Date: 27-11-2018
DOI: 10.1116/1.5050043
Abstract: Antimicrobial surface coatings that act through a contact-killing mechanism (not diffusive release) could offer many advantages to the design of medical device coatings that prevent microbial colonization and infections. However, as the authors show here, to prevent arriving at an incorrect conclusion about their mechanism of action, it is essential to employ thorough washing protocols validated by surface analytical data. Antimicrobial surface coatings were fabricated by covalently attaching polyene antifungal drugs to surface coatings. Thorough washing (often considered to be sufficient to remove noncovalently attached molecules) was used after immobilization and produced s les that showed a strong antifungal effect, with a log 6 reduction in Candida albicans colony forming units. However, when an additional washing step using surfactants and warmed solutions was used, more firmly adsorbed compounds were eluted from the surface as evidenced by XPS and ToF-SIMS, resulting in reduction and complete elimination of in vitro antifungal activity. Thus, polyene molecules covalently attached to surfaces appear not to have a contact-killing effect, probably because they fail to reach their membrane target. Without additional stringent washing and surface analysis, the initial favorable antimicrobial testing results could have been misinterpreted as evidencing activity of covalently grafted polyenes, while in reality activity arose from desorbing physisorbed molecules. To avoid unintentional confirmation bias, they suggest that binding and washing protocols be analytically verified by qualitative/quantitative instrumental methods, rather than relying on false assumptions of the rigors of washing/soaking protocols.
Publisher: Elsevier BV
Date: 06-1982
Publisher: American Vacuum Society
Date: 12-2015
DOI: 10.1116/1.4936957
Abstract: Materials intended for use as implantable or diagnostic devices are required not only to display the required functional bulk properties but also have surface properties that elicit a desired biological response, and do so with high selectivity. The area of surface functionalization approaches and bioactive coatings for biomaterials and biomedical devices has been the subject of much research over several decades yet, many challenges still remain to be solved. The 5th International Symposium on Surface and Interface of Biomaterials (ISSIB) held in Sydney (Australia) in April 2015 was an ideal forum to discuss the most recent developments in biomaterial surface modification, characterization, and evaluation of biological responses. The conference covered a range of topics including antimicrobial coatings, analysis of biomaterial surfaces and interfaces, biomolecules and cells at surfaces and interfaces, nanoparticles, functional coatings, patterned biomaterials, nanofabrication, bioreactors, and biosensors. In this special conference issue, the authors include papers that detail some of the highlights from the meeting.
Publisher: American Chemical Society (ACS)
Date: 07-12-2009
DOI: 10.1021/NL903274Q
Abstract: Bacterial infections present an enormous problem causing human suffering and cost burdens to healthcare systems worldwide. Here we present novel tunable antibacterial coatings which completely inhibit bacterial colonization by Staphylococcus epidermidis but allow normal adhesion and spreading of osteoblastic cells. The coatings are based on amine plasma polymer films loaded with silver nanoparticles. The method of preparation allows flexible control over the amount of loaded silver nanoparticles and the rate of release of silver ions.
Publisher: Elsevier BV
Date: 12-2001
DOI: 10.1016/S0142-9612(01)00166-1
Abstract: XPS and MALDI-MS were used to analyse initial adsorption events in the fouling of HEMA-based contact lenses. All of the lenses tested accumulated tear film deposits within 10 min of wear. XPS indicated the presence of mainly proteinaceous deposits, with indications of some contributions by mucins or lipids on some lenses and the nature of the deposit being influenced by the lens chemistry. MALDI-MS detected the presence of surface-adsorbed species with molecular weights < 15 kDa. While lysozyme could be identified by comparison of MALDI-MS signals with known protein mass and assignments are suggested for some other signals, several other species, with MWs less than that of lysozyme, could not be identified as no ocular proteins with corresponding MWs had been reported in previous biochemical tear film analyses. These species, and others, were also detected in MALDI-MS analysis of reflex tear film, suggesting that the adsorbed unidentified species were not simply products of surface-induced dissociation of adsorbing higher-MW proteins. This short-term wear study detected rapid interface conversion and demonstrated the utility and surface sensitivity of XPS and MALDI-MS in characterising contact lens deposits at the initial stages when sub-monolayer adsorbed amounts are present on lenses.
Publisher: American Chemical Society (ACS)
Date: 10-1995
DOI: 10.1021/LA00010A078
Publisher: American Chemical Society (ACS)
Date: 23-05-2014
DOI: 10.1021/AM501228Q
Abstract: Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a low TMDSO-to-oxygen ratio had little to no singly substituted moieties, displayed a highly cross-linked structure, and showed less post-plasma reactions. However, these chemically more stable coatings are less compatible mechanically with plastic substrates, because of their high stiffness.
Publisher: American Chemical Society (ACS)
Date: 13-08-2019
DOI: 10.1021/ACS.LANGMUIR.9B02176
Abstract: Manipulating the surface properties of materials via the application of coatings is a widely used strategy to achieve desired interfacial interactions, implicitly assuming that the interfacial forces of coated s les are determined exclusively by the surface properties of the coatings. However, interfacial interactions between materials and their environments operate over finite length scales. Thus, the question addressed in this study is whether interactions associated with bulk substrate materials could act through thin coatings or, conversely, how thick a coating needs to be to completely screen subsurface forces contributed by underlying substrates. Plasma polymer layers were deposited on silicon wafer substrates from ethanol vapor, with identical chemical composition, ultrasmooth surfaces, and varying thicknesses. Using colloid-probe atomic force microscopy, electrical double-layer forces were determined in solutions of various ionic strengths and fitted using the Derjaguin-Landau-Verwey-Overbeek theory. For the thicker ethanol plasma polymers, the fitted surface potentials reflected the presence of surface carboxylate groups and were invariant with thickness. In contrast, for coatings <18 nm thick, the surface potentials increased steadily with decreasing film thickness the measured electrical double-layer forces contained contributions from both the coating and the substrate. Theoretical calculations were in agreement with this model. Thus, our observations indicate that the higher surface potential of the underlying SiO
Publisher: Wiley
Date: 05-07-2018
Publisher: Wiley
Date: 07-2010
Publisher: Elsevier BV
Date: 2000
Publisher: Elsevier BV
Date: 02-2002
Publisher: American Chemical Society (ACS)
Date: 15-08-2019
Abstract: Microbial pathogens use hydrolases as a virulence strategy to spread disease through tissues and colonize medical device surfaces however, visualizing this process is a technically challenging problem. To better understand the role of secreted fungal hydrolases and their role in
Publisher: Informa UK Limited
Date: 1995
Abstract: Fluoropolymers modified by plasma modification were studied for their suitability as surfaces for the adhesion of cells. We compared films made by plasma modification of fluoroethylenepropylene (FEP) using nitrogen-containing gases (ammonia or dimethyl acetamide) with films deposited using oxygen-containing monomers (methanol, methyl methacrylate or sequential treatment with toluene then water). The surfaces were compared for the attachment and spreading of human vein endothelial cells and human dermal fibroblasts. The initial attachment and spreading of cultured fibroblasts and endothelial cells onto films deposited using nitrogen-containing gases were equivalent to that onto films deposited using oxygen-containing monomers, but there were some differences in the mechanism of attachment. With films deposited using oxygen-containing monomers, the initial attachment and spreading of endothelial cells failed when the medium contained 15% (v/v) serum from which both fibronectin (Fn) and vitronectin (Vn) had been removed. Similarly, initial attachment and spreading of endothelial cells onto films deposited using oxygen-containing monomers were reduced by 62-86% when the cells were seeded in medium containing Vn-depleted serum (which contained Fn). Endothelial cells attached and spread onto films made using oxygen-containing monomers, when seeded in medium containing Fn-depleted serum (which contained Vn). On films deposited using nitrogen-containing gases, the adhesion of endothelial cells was only slightly reduced in Vn-depleted medium (as compared to attachment in medium containing unmodified serum). Furthermore, surfaces which had incorporated nitrogen were more effective than were oxygen-containing films in adsorbing sufficient serum Fn as to promote endothelial cell attachment. Similar results were seen for the attachment and spreading of fibroblasts as for the endothelial cells. For fibroblasts, attachment and spreading onto oxygen-containing films and onto nitrogen-containing films were not simply dependent upon either the Vn content or the Fn content of the medium. Maximal attachment and spreading of fibroblasts were, however, dependent upon adsorption of both serum Vn and Fn.
Publisher: Elsevier BV
Date: 07-1993
Publisher: SPIE
Date: 26-05-1997
DOI: 10.1117/12.275104
Publisher: Informa UK Limited
Date: 1998
Abstract: The nature of the proteinaceous film deposited on a biomaterial surface following implantation is a key determinant of the subsequent biological response. To achieve selectivity in the formation of this film, monoclonal antibodies have been coupled to a range of solid substrates using avidin-biotin technology. Antibody clones varied in their antigen-binding activity following insertion of biotin groups into lysine residues. Biotinylated antibodies coupled to solid substrates via an immobilized avidin bridge retained their biological activity. During immobilization of avidin a significant proportion of the protein molecules were passively adsorbed rather than covalently attached to the surface. This loosely bound material could be removed by stringent elution procedures which resulted in a surface density of 5.4 pmol avidin cm(-2). Although these conditions would be harsh enough to denature monoclonal antibodies, they did not destroy the biotin-binding activity of the residual surface-coupled avidin, enabling the subsequent immobilization of biotinylated antibodies. The two-step immobilization technique allowed the use of gentle protein modification procedures, reduced the risk of surface-induced denaturation and removed loosely bound material from the surface. The versatility of the technique encourages its application to a wide range of immobilization systems where retention of biological activity is a key requirement.
Publisher: Elsevier BV
Date: 1980
Publisher: IOP Publishing
Date: 20-09-2002
Publisher: American Chemical Society (ACS)
Date: 17-11-2005
DOI: 10.1021/LA052143A
Abstract: Interaction forces between surfaces designed to be protein resistant and fibrinogen (Fg) were investigated in phosphate-buffered saline with colloid probe atomic force microscopy. The surfaces of the silica probes were coated with a layer of fibrinogen molecules by adsorption from the buffer. The technique of low-power, pulsed AC plasma polymerization was used to make poly(ethylene glycol) (PEG)-like coatings on poly(ethylene teraphthalate) by using diethylene glycol vinyl ether as the monomer gas. The degree of PEG-like nature of the films was controlled by use of a different effective plasma power in the chamber for each coating, ranging from 0.6 to 3.6 W. This produced a series of thin films with a different number of ether carbons, as assessed by X-ray photoelectron spectroscopy. The interaction force measurements are discussed in relation to trends observed in the reduction of fibrinogen adsorption, as determined quantitatively by (125)I radio-labeling. The plasma polymer coatings with the greatest protein-repelling properties were the most PEG-like in nature and showed the strongest repulsion in interaction force measurements with the fibrinogen-coated probe. Once forced into contact, all the surfaces showed increased adhesion with the protein layer on the probe, and the strength and extension length of adhesion was dependent on both the applied load and the plasma polymer surface chemistry. When the medium was changed from buffer to water, the adhesion after contact was eliminated and only appeared at much higher loads. This indicates that the structure of the fibrinogen molecules on the probe is changed from an extended conformation in buffer to a flat conformation in water, with the former state allowing for stronger interaction with the polymer chains on the surface. These experiments underline the utility of aqueous surface force measurements toward understanding protein-surface interactions, and developing nonfouling surfaces that confer a steric barrier against protein adsorption.
Publisher: Wiley
Date: 16-07-2010
Abstract: Ultrathin functional coatings deposited by plasma polymerization have utility in nano‐ and microtechnologies, however, until now very little has been reported to validate the widely held view that these coatings can be deposited onto any type of substrate, without substrate influence. In order to ascertain the role of the substrate in the early stages of plasma growth we address the growth rate and chemistry of plasma polymer coatings from two nitrogen‐ and two oxygen‐containing monomers during the first stages of deposition onto gold and onto thiol MUA‐coated gold surfaces. SPR thickness measurements and XPS analyzes indicate the substrate must be taken into account when ultrathin plasma polymer coatings are used for surface modification and we speculate on why this should be so. magnified image
Publisher: Elsevier BV
Date: 1991
Publisher: American Chemical Society (ACS)
Date: 22-05-0044
DOI: 10.1021/JP807986K
Abstract: The generation of nanosized cavities within thin film layers is of interest for a number of fundamental and applied reasons. One challenge is to make such systems sufficiently robust mechanically. Plasma polymer (pp) films possess excellent mechanical stability if deposition conditions are selected such as to achieve a sufficient density of cross-linking and resistance to extraction of polymeric material by solvents. In this study, gold nanoparticles of 15 and 70 nm diameter were used as sacrificial templates to generate nanocavities in pp films of various thickness values in the tens of nanometers range. A first pp layer was deposited onto substrates using n-heptylamine (HA) to a thickness of 20 nm. Carboxy-thiolated gold nanoparticles were electrostatically bound onto the surface amine groups of the n-heptylamine plasma polymer (HApp) layer. A second HApp layer was then coated to various thicknesses onto the nanoparticle/HApp surface. The template particles embedded thus in-between the two HApp layers were then dissolved using aqueous KCN solution monitoring of the plasmon resonance band of the gold nanoparticles enabled verification of template stripping and measurement of the kinetics of stripping. AFM topography images showed little change on extraction of the template nanoparticles, indicating that the plasma polymer layer maintained structural integrity upon template extraction and subsequent drying, and thereby prevented collapse of the empty nanocavities. The concept of template stripping to generate controlled size free volume in thin plasma polymer layers is thus shown to produce robust structures.
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B820137D
Abstract: Towards a robust and universal functionalization procedure with alkanethiols for gold nanorods and plasmonic nanoparticles, a straightforward two-step approach is described.
Publisher: Ovid Technologies (Wolters Kluwer Health)
Date: 05-2008
Publisher: American Chemical Society (ACS)
Date: 21-06-2013
DOI: 10.1021/LA400721C
Abstract: Poly(ethylene glycol) (PEG) is one of the most extensively studied antifouling coatings due to its ability to reduce protein adsorption and improve biocompatibility. Although the use of PEG for antifouling coatings is well established, the stability and density of PEG layers are often inadequate to provide optimum antifouling properties. To improve on these shortcomings, we employed the stepwise construction of PEG layers onto a silicon surface. Acetylene-terminated alkyl monolayers were attached to nonoxidized crystalline silicon surfaces via a one-step hydrosilylation procedure with 1,8-nonadiyne. The acetylene-terminated surfaces were functionalized via a copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of the surface-bound alkynes with an azide to produce an amine terminated layer. The amine terminated layer was then further conjugated with PEG to produce an antifouling surface. The antifouling surface properties were investigated by testing adsorption of human serum albumin (HSA) and lysozyme (Lys) onto PEG layers from phosphate buffer solutions. Detailed characterization of protein fouling was carried out with X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with principal component analysis (PCA). The results revealed no fouling of albumin onto PEG coatings whereas the smaller protein lysozyme adsorbed to a very low extent.
Publisher: Elsevier BV
Date: 06-2000
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4PY00652F
Abstract: We report the use of RAFT polymerization to obtain eight cationic methacrylate polymers bearing amine or guanidine pendant groups, while varying the R- and Z-RAFT end-groups.
Publisher: American Chemical Society (ACS)
Date: 07-1995
DOI: 10.1021/LA00007A042
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B912324E
Publisher: American Chemical Society (ACS)
Date: 07-1995
DOI: 10.1021/LA00007A043
Publisher: Wiley
Date: 15-08-2006
Abstract: Summary: This review surveys methods for the fabrication, by plasma surface treatments or plasma polymerization, of polymeric surfaces and thin plasma polymer coatings that contain reactive chemical groups useful for the subsequent covalent immobilization, by solution chemical reactions or vapor phase grafting, of molecules or polymers that can exert bio‐specific interfacial responses. Surfaces containing amine, carboxy, hydroxy, and aldehyde groups are the subject of this review. Aminated surfaces have been fabricated using various plasma vapors or mixtures and have found wide use for bio‐interface applications. However, in many cases the amine surfaces have a rather limited shelf life, with post‐plasma oxidation reactions and surface adaptation leading to the disappearance of amine groups from the surface. Aging is a widespread phenomenon that often has not been recognized, particularly in some of the earlier studies on the use of plasma‐fabricated surfaces for bio‐interfacial applications, and can markedly alter the surface chemistry. Plasma‐fabricated surfaces that contain carboxy groups have also been well documented. Fewer reports exist on hydroxy and aldehyde surfaces prepared by plasma methods. Hydroxy surfaces can be prepared by water plasma treatment or the plasma polymerization of alkyl alcohol vapors. Water plasma treatment on many polymer substrates suffers from aging, with surface adaptation leading to the movement of surface modification effects into the polymer. Both hydroxy and aldehyde surfaces have been used for the covalent immobilization of biologically active molecules. Aging effects are less well documented than for amine surfaces. This review also surveys studies using such surfaces for cell colonization assays. Generally, these surface chemistries show good ability to support cell colonization, though the effectiveness seems to depend on the process vapor and the plasma conditions. Carboxylate co‐polymer surfaces have shown excellent ability to support the colonization of some human cell lines of clinical interest. Immobilization of proteins onto plasma‐carboxylated surfaces is also well established. XPS O/C ratios (0 0 emission) as a function of storage time, of plasma‐polymerized methyl methacrylate deposited at power levels of 5 and 40 W. magnified image XPS O/C ratios (0 0 emission) as a function of storage time, of plasma‐polymerized methyl methacrylate deposited at power levels of 5 and 40 W.
Publisher: American Vacuum Society
Date: 14-10-2015
DOI: 10.1116/1.4933108
Abstract: Not only bacteria but also fungal pathogens, particularly Candida species, can lead to biofilm infections on biomedical devices. By covalent grafting of the antifungal drug caspofungin, which targets the fungal cell wall, onto solid biomaterials, a surface layer can be created that might be able to provide long-term protection against fungal biofilm formation. Plasma polymerization of propionaldehyde (propanal) was used to deposit a thin (∼20 nm) interfacial bonding layer bearing aldehyde surface groups that can react with amine groups of caspofungin to form covalent interfacial bonds for immobilization. Surface analyses by x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry confirmed the intended grafting and uniformity of the coatings, and durability upon extended washing. Testing for fungal cell attachment and ensuing biofilm formation showed that caspofungin retained activity when covalently bound onto surfaces, disrupting colonizing Candida cells. Mammalian cytotoxicity studies using human primary fibroblasts indicated that the caspofungin-grafted surfaces were selective in eliminating fungal cells while allowing attachment and spreading of mammalian cells. These in vitro data suggest promise for use as antifungal coatings, for ex le, on catheters, and the use of a plasma polymer interlayer enables facile transfer of the coating method onto a wide variety of biomaterials and biomedical devices.
Publisher: Elsevier BV
Date: 03-2003
DOI: 10.1016/S0021-9797(02)00185-6
Abstract: For a number of potential applications, it is desirable to immobilize avidin class molecules onto solid supports and exploit their ability to bind biotinylated molecules with high affinity. NeutrAvidin molecules were surface immobilized in various ways. In this study, NeutrAvidin was covalently attached by carbodiimide chemistry onto carboxyl groups of polyacrylic acid and carboxymethyl-dextran hydrogel interlayers. A third strategy involved the affinity "docking" of NeutrAvidin onto a biotinylated poly(ethylene glycol) interlayer. These three interlayers were selected for their low nonspecific binding of proteins, which was expected to minimize surface binding of NeutrAvidin by nonspecific interfacial adsorption. X-ray photoelectron spectroscopy (XPS) analyses allowed detailed characterization of the multilayer fabrication steps. An ELISA assay was used to measure NeutrAvidin activity, which varied with the surface immobilization route. Atomic force microcopy (AFM) force measurements showed that the hydrogel interlayer contributed to a repulsive force and verified the specific interaction between biotinylated AFM tips and the NeutrAvidin surfaces. When a solution of free biotin was injected into the AFM liquid cell, the force curve changed substantially and became identical to that recorded between surfaces carrying no NeutrAvidin, indicating that the free solution biotin had displaced NeutrAvidin proteins off the PEG-biotin layer.
Publisher: Penerbit Universiti Kebangsaan Malaysia (UKM Press)
Date: 31-08-2018
Publisher: Elsevier BV
Date: 04-2016
DOI: 10.1016/J.JEP.2016.02.011
Abstract: For traditional medicinal purposes Aboriginal Australians have utilised numerous plant species, Eremophila alternifolia is among the most prominent. Traditionally, fresh leaves, leaf-infusions and handmade leaf-pastes have been used as both external and internal preparations to provide relief from a variety of conditions. Preparations of the species have been used to treat various infections of skin, eyes and throat including the treatment of septic wounds. These usages suggest that the plant contains antibacterial compounds however, to date they have not been isolated and identified. The present study aimed to identify antibacterial compounds from this important traditionally recorded medicinal species. Bioassay-guided fractionation was used to isolate compounds from the crude leaf-extract. Antibacterial activity of pure compounds was assessed through broth microdilution method by determining both minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs). Structure elucidation was performed using spectroscopic techniques such as 1D and 2D nuclear magnetic resonance spectroscopy and high resolution mass spectrometry. Four compounds have been isolated from the leaf-extract they include previously known flavanones [pinobanksin (1), pinobanksin-3-acetate (2) and pinobanksin-3-cinnamate (3)] and a serrulatane diterpene, 8-hydroxyserrulat-14-en-19-oic acid (4). While compound 4 had been found in other Eremophilas, flavanones 2 and 3 are identified for the first time from the genus Eremophila. The flavanone 3 is the most promising antibacterial compound with significant activity (10-20µM) against strains of the Gram-positive bacterium Staphylococcus aureus including methicillin resistant and biofilm forming strains. No activity was observed for any isolated compounds against the Gram-negative bacterium Escherichia coli. The antibacterial activity of the crude extract of E. alternifolia and of the isolated compounds against Gram-positive bacteria provides a Western scientific explanation of the therapeutic modality of this plant species in traditional Aboriginal medicinal practice.
Publisher: American Chemical Society (ACS)
Date: 11-1994
DOI: 10.1021/MA00101A008
Publisher: Elsevier BV
Date: 11-1981
Publisher: American Chemical Society (ACS)
Date: 23-02-2002
DOI: 10.1021/LA001801I
Publisher: SPIE
Date: 27-12-2006
DOI: 10.1117/12.696290
Publisher: Elsevier BV
Date: 15-04-2000
Publisher: IOP Publishing
Date: 12-05-2008
DOI: 10.1088/0957-4484/19/24/245704
Abstract: The deposition of plasma polymer coatings onto porous alumina (PA) membranes was investigated with the aim of adjusting the surface chemistry and the pore size of the membranes. PA membranes from commercial sources with a range of pore diameters (20, 100 and 200 nm) were used and modified by plasma polymerization using n-heptylamine (HA) monomer, which resulted in a chemically reactive polymer surface with amino groups. Heptylamine plasma polymer (HAPP) layers with a thickness less than the pore diameter do not span the pores but reduce their diameter. Accordingly, by adjusting the deposition time and thus the thickness of the plasma polymer coating, it is feasible to produce any desired pore diameter. The structural and chemical properties of modified membranes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and x-ray electron spectroscopy (XPS). The resultant PA membranes with specific surface chemistry and controlled pore size are applicable for molecular separation, cell culture, bioreactors, biosensing, drug delivery, and engineering complex composite membranes.
Publisher: American Chemical Society (ACS)
Date: 24-12-2008
DOI: 10.1021/LA802016B
Abstract: A block copolymer consisting of a phosphate-containing moiety (poly[2-(methacryloyloxy)ethyl phosphate], PMOEP) and a keto-containing moiety (poly[2-(acetoacetoxy)ethyl methacrylate], PAAEMA) showed good stability after attachment to an APS amine-modified glass slide, as did both of the respective homopolymers. The PAAEMA homopolymer can attach to the APS amine groups via covalent linkages, while the PMOEP homopolymer most likely attaches through electrostatic interactions involving deprotonated phosphate and protonated amine groups. To elucidate the conformation of the block copolymer after attachment, particularly with respect to the PMOEP segment orientation, principal component analysis (PCA) of time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra of the surface-attached polymer layers was performed. Comparison with the pure homopolymer spectra and interpretation after PCA indicate that the adsorbed conformation is not random. Rather, the copolymer is adsorbed in a conformation that preferentially exposes the PMOEP block toward the outer surface. We thus conclude that the most likely conformation of PMOEP-b-PAAEMA immobilized onto the APS-modified glass slide is via covalent interfacial linkages involving the PAAEMA block with the result that the surface is enriched in PMOEP tails. This in turn implies that under the conditions applied (dry DMF) the covalent coupling of keto groups to the amine groups of the aminated slide is more efficient than the proton transfer required for the generation of electrostatic attractions. This (partially) preferential orientation of the PMOEP-b-PAAEMA copolymer could have significant implications on interfacial interactions such as those involved in nucleation and the subsequent mineralization sequence of events in hydroxyapatite formation. The present study demonstrates that ToF-SIMS is a powerful tool not only for the investigation of the surface composition of adsorbed layers, but also for probing the molecular conformation of such adsorbed block copolymers, though care is required in the PCA analysis of multiple spectra.
Publisher: SPIE
Date: 06-04-2001
DOI: 10.1117/12.424405
Publisher: Wiley
Date: 2002
DOI: 10.1002/SIA.1446
Publisher: Oxford University Press (OUP)
Date: 29-10-2018
DOI: 10.1093/JAC/DKY437
Abstract: Fungal biofilms caused by Candida spp. are a major contributor to infections originating from infected biomaterial implants. Since echinocandin-class molecules interfere with the integrity of the fungal cell wall, it was hypothesized that surface-immobilized anidulafungin and micafungin could play a role in preventing fungal adhesion and biofilm formation on surfaces. Anidulafungin and micafungin were covalently coupled to biomaterial surfaces and washed. Surface-sensitive instrumental analysis quantitatively and qualitatively confirmed their presence. Analysis after washing experiments provided evidence of their covalent immobilization. The in vitro antifungal properties of surfaces were confirmed using static biofilm assays and fluorescence microscopy kinetic studies. Antifungal surface coatings eliminated 106 cfu/cm2 inoculations of Candida albicans and prevented biofilm formation and hyphal development on coated surfaces. Surfaces were successively exposed to fresh inoculum and were effective for at least five challenges in eliminating adherent yeasts. We have observed antifungal and anti-biofilm activity of surfaces bearing conjugated echinocandins, which operate through surface contact. The analytical and biological evidence suggests an antifungal mechanism for echinocandins that does not rely upon freely diffusing molecules.
Publisher: Wiley
Date: 07-2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2009
DOI: 10.1039/B904367E
Abstract: In this communication we demonstrate that in the initial stages of deposition of ultrathin plasma polymer films, both the growth rate and the chemical composition of the films are affected by the nature of the substrate which is an important question surprisingly neglected until now.
Publisher: Elsevier BV
Date: 04-2015
DOI: 10.1016/J.JEP.2015.01.033
Abstract: Australian Aboriginal people used crushed leaves of Geijera parviflora Lindl. both internally and externally for pain relief, including for toothache (Cribb and Cribb, 1981). This study tested the hypothesis that this traditional use might be at least in part explained by the presence of compounds with anti-inflammatory activity. A crude extract (95% EtOH) was prepared from powdered dried leaves. From the CH3Cl fraction of this extract compounds were isolated by bioassay-guided fractionation and tested for: (1) cytotoxicity in RAW 264.7 murine leukemic monocyte-macrophages, (2) prostaglandin E2 (PGE2) inhibitory activity in 3T3 Swiss albino mouse embryonic fibroblast cells, as well as (3) nitric oxide (NO) and (4) tumour necrosis factor alpha (TNFα) inhibitory activity in lipopolysaccharide (LPS)-stimulated RAW 264.7 cells. Isolated compounds were also tested for (5) antibacterial activity against a panel of Gram-positive (Staphylococcus aureus ATCC 29213 and ATCC 25923, Staphylococcus epidermidis ATCC 35984, biofilm-forming) and Gram-negative (Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853) strains by broth microdilution. Eleven compounds were isolated, including one new flavone and one new natural product, with a further four compounds reported from this species for the first time. Some of the compounds showed good anti-inflammatory activity in vitro. In particular, flindersine (1) and N-(acetoxymethyl) flindersine (3) inhibited PGE2 release with IC50 values of 5.0μM and 4.9μM, respectively, without any significant cytotoxicity. Several other compounds showed moderate inhibition of NO (5, 6, 7) and TNF-α (6), with IC50 in the low micromolar range however much of this apparent activity could be accounted for by the cytotoxicity of these compounds. None of the compounds showed anti-bacterial activity. The inhibition of PGE2, an important mediator of inflammation and pain, by flindersine and a derivative thereof, along with the moderate anti-inflammatory activity shown by several other compounds isolated from Geijera parviflora leaf extract, support the traditional use of this plant for pain relief by Australian Aboriginal people.
Publisher: IOP Publishing
Date: 13-09-2002
Publisher: Elsevier BV
Date: 1989
Publisher: Elsevier BV
Date: 1991
Publisher: IEEE
Date: 2006
Publisher: Wiley
Date: 11-2022
Publisher: Wiley
Date: 05-02-2008
Publisher: Wiley
Date: 09-12-2010
Abstract: Surfaces with micro‐ and nanometer‐scale patterns have many potential applications, particularly in lifescience. This article reports on a versatile, straightforward, and inexpensive approach for the creation of chemical patterns using fabricated binary colloid crystals, consisting of small and large particles, as masks for the deposition of an amino‐functionalised ultrathin film by plasma polymerization. After removal of the binary colloidal mask, the characterization techniques [scanning electron microscopy (SEM) and atomic force microscopy (AFM)] reveal a surface contrast that depicts an ability of the small particles to allow diffusion of the plasma to the substrate. A plasma‐polymer film is created under the small particles and the region of substrate in direct contact with the large particle remains uncoated. Numerous types of patterns and feature heights can be produced with good fidelity over areas of several cm 2 by appropriate tuning of the binary colloid crystal mask morphology and the plasma‐polymer deposition time. Finally, the amine groups of the patterned surface are used for covalent grafting poly(ethylene glycol) propionaldehyde (PEG‐PALD) by reductive amination under conditions of reduced solubility to produce a patterned surface for directed adsorption of protein. AFM investigations show that the proteins are preferentially attached to the nanometer‐scale regions of the pattern without PEG‐PALD.
Publisher: IOP Publishing
Date: 07-2016
Publisher: American Vacuum Society
Date: 12-2008
DOI: 10.1116/1.3046123
Abstract: The concurrent release of calcium phosphate and biomacromolecules may improve wound healing responses at the interface with ceramic materials of orthopaedic and dental implants. Hydrogel coatings consisting of a mixture of alginate and chitosan were doped and applied onto solid carriers with the aim of investigating their use as local delivery vehicles. Coatings containing both the model macromolecule FITC-dextran 70 kDa (FD 70) and dispersed calcium phosphate carbonate (CPC) nanoparticles were coated onto a solid, nonporous model substrate to study the concurrent release of FD 70 and calcium and phosphate ions from within the hydrogel. Hydrogel coatings containing only FD 70 were cast onto porous calcium phosphate coatings, similar to hydroxyapatite, to study the release of FD 70 from, and calcium and phosphate ions through, the hydrogel coating. Transmission electron microscopy showed good dispersion of the CPC nanoparticles, and scanning electron microscopy and atomic force microscopy showed that increased CPC loading resulted in an increase in surface roughness but to extents well below those affecting cell responses. The release of FD 70 from CPC-loaded coatings was similar to release from the hydrogel alone, although higher CPC loadings resulted in small changes. The release of FD 70 was better described by double or triple phase zero order release kinetics this complex time dependence indicates that in addition to outdiffusion, other, time-dependent factors apply, such as swelling of the gel, as expected from the known effects of calcium ions on alginate. Calcium and phosphate ions were also released, with similar release kinetics, through the hydrogel layer from the underlying CaP layer. In either case, release decreased to negligible levels after 3 days, suggesting that the systems of this study are suitable for short-term concurrent release of water-soluble biomacromolecules and calcium and phosphate ions.
Publisher: American Chemical Society (ACS)
Date: 12-06-2008
DOI: 10.1021/LA8002959
Abstract: Liposomes that are surface-bound to a biomaterial such as a contact lens are of interest for localized delivery of therapeutic agents, but it is not known whether such liposome layers are sufficiently robust. The stability of a dense, PEG-functionalized layer of liposomes, affinity-bound onto a multilayer coated surface, was tested under various stress conditions using colloid-probe atomic force miscroscopy (AFM). The different stress effects were generated by varying the applied normal load of the probe and the impinging fluid shear through different approach velocities and by varying the applied lateral forces by scanning under increasing force loads. The effect of applied forces (normal and lateral) was further investigated by coating the probe with a layer of albumin. The liposomes remained intact following the r ing of both protein-coated and uncoated probes under the normal and lateral loads. The low-fouling nature of these liposomes, with respect to nonspecific protein adsorption, was also demonstrated from the interaction force measurements which showed only weak adhesion from the protein layer during the contact period of the albumin-coated probe. The observed adhesive interactions were concluded to be a direct result of the applied load from the probe, during the force measurements, rather than from attraction of the protein molecules for the surface-bound liposomes. The low frictional response of the liposome layer indicated the viscoelastic nature of these molecules, which enabled liposome structure retention during the continuous load application. The demonstrated stability of the liposomes presents a system of viable and localized drug delivery in, for ex le, ophthalmic applications.
Publisher: Royal Society of Chemistry (RSC)
Date: 2014
DOI: 10.1039/C4RA01892C
Abstract: Novel, highly chlorinated surface coatings were produced via a one-step plasma polymerization (pp) of 1,1,1-trichloroethane (TCE), exhibiting excellent antimicrobial properties against the vigorously biofilm-forming bacterium Staphylococcus epidermidis .
Publisher: American Chemical Society (ACS)
Date: 12-07-2013
DOI: 10.1021/NP400376R
Abstract: Two novel alkaloids (parvifloranines A and B), possessing an unusual 11-carbon skeleton linked with amino acids, were isolated from Geijera parviflora, an endemic Australian Rutaceae. Their structures were elucidated by extensive spectroscopic measurements including 2D NMR analyses. Parvifloranine A was found to be a mixture of two enantiomers, (S)-1 and (R)-1, in a ratio of 1:4, based on their separation using a chiral column. Parvifloranine B is also believed to be a mixture of enantiomers. Proposed biosynthetic pathways are discussed. Parvifloranine A inhibited the synthesis of nitric oxide in LPS-stimulated RAW 264.7 macrophages with an IC50 value of 23.4 μM.
Publisher: American Vacuum Society
Date: 11-2021
DOI: 10.1116/6.0001099
Abstract: There are many reports of antimicrobial coatings bearing immobilized active agents on surfaces however, strong analytical evidence is required to verify that the agents are indeed covalently attached to the surface. In the absence of such evidence, antimicrobial activity could result from a release of active agents. We report a detailed assessment of antifungal surface coatings prepared using covalent attachment chemistries, with the aim of establishing a set of instrumental and biological evidence required to convincingly demonstrate antimicrobial activity due to nonreleasing, surface active compounds and to exclude the alternate possibility of activity due to release. The strongest biological evidence initially supporting permanent antifungal activity was the demonstration of the ability to reuse s les in multiple, sequential pathogen challenges. However, additional supporting evidence from washing studies and instrumental analysis is also required to probe the possibility of gradual desorption of strongly physisorbed compounds versus covalently attached compounds. Potent antifungal surface coatings were prepared from approved pharmaceutical compounds from the echinocandin drug class (caspofungin, anidulafungin, and micafungin) and assessed by microbiological tests and instrumental methods. Carbonyl diimidazole linking chemistry enabled covalent attachment of caspofungin, anidulafungin, and micafungin to plasma polymer surfaces, with antifungal surface activity likely caused by molecular orientations that present the lipophilic tail toward interfacing fungal cells. This study demonstrates the instrumental and biological evidence required to convincingly ascertain activity due to nonreleasing, surface active compounds and summarize these as three criteria for assessing other reports on surface-immobilized antimicrobial compounds.
Publisher: Elsevier BV
Date: 04-2010
Publisher: American Chemical Society (ACS)
Date: 04-12-2015
DOI: 10.1021/ACS.JNATPROD.5B00833
Abstract: The purpose of this study was to assess the biofilm-removing efficacy and inflammatory activity of a serrulatane diterpenoid, 8-hydroxyserrulat-14-en-19-oic acid (1), isolated from the Australian medicinal plant Eremophila neglecta. Biofilm breakup activity of compound 1 on established Staphylococcus epidermidis and Staphylococcus aureus biofilms was compared to the antiseptic chlorhexidine and antibiotic levofloxacin. In a time-course study, 1 was deposited onto polypropylene mesh to mimic a wound dressing and tested for biofilm removal. The ex-vivo cytotoxicity and effect on lipopolysaccharide-induced pro-inflammatory cytokine release were studied in mouse primary bone-marrow-derived macrophage (BMDM) cells. Compound 1 was effective in dispersing 12 h pre-established biofilms with a 7 log10 reduction of viable bacterial cell counts, but was less active against 24 h biofilms (approximately 2 log10 reduction). Compound-loaded mesh showed dosage-dependent biofilm-removing capability. In addition, compound 1 displayed a significant inhibitory effect on tumor necrosis factor alpha (TNF-α) and interleukin-6 (IL-6) secretion from BMDM cells, but interleukin-1 beta (IL-1β) secretion was not significant. The compound was not cytotoxic to BMDM cells at concentrations effective in removing biofilm and lowering cytokine release. These findings highlight the potential of this serrulatane diterpenoid to be further developed for applications in wound management.
Publisher: Royal Society of Chemistry (RSC)
Date: 2015
DOI: 10.1039/C5CC01722J
Abstract: We report a stable plasma polymer coating which releases nitric oxide, inhibiting bacterial growth without cytotoxic side effects.
Publisher: Elsevier BV
Date: 09-2017
DOI: 10.1016/J.BIOMATERIALS.2017.05.009
Abstract: One of the most significant hurdles to the affordable, accessible delivery of cell therapy is the cost and difficulty of expanding cells to clinically relevant numbers. Immunotherapy to prevent autoimmune disease, tolerate organ transplants or target cancer critically relies on the expansion of specialized T cell populations. We have designed 3D-printed cell culture lattices with highly organized micron-scale architectures, functionalized via plasma polymerization to bind monoclonal antibodies that trigger cell proliferation. This 3D technology platform facilitate the expansion of therapeutic human T cell subsets, including regulatory, effector, and cytotoxic T cells while maintaining the correct phenotype. Lentiviral gene delivery to T cells is enhanced in the presence of the lattices. Incorporation of the lattice format into existing cell culture vessels such as the G-Rex system is feasible. This cell expansion platform is user-friendly and expedites cell recovery and scale-up, making it ideal for translating T cell therapies from bench to bedside.
Publisher: Elsevier
Date: 2016
Publisher: Elsevier BV
Date: 03-1995
Publisher: Elsevier BV
Date: 10-2011
Publisher: Elsevier BV
Date: 1988
Publisher: Elsevier BV
Date: 11-2014
Publisher: Wiley
Date: 13-01-2014
Publisher: Elsevier BV
Date: 08-1999
Publisher: American Chemical Society (ACS)
Date: 15-02-2016
Abstract: Controlling the release kinetics from a drug carrier is crucial to maintain a drug's therapeutic window. We report the use of biodegradable porous silicon microparticles (pSi MPs) loaded with the anticancer drug c hothecin, followed by a plasma polymer overcoating using a loudspeaker plasma reactor. Homogenous "Teflon-like" coatings were achieved by tumbling the particles by playing AC/DC's song "Thunderstruck". The overcoating resulted in a markedly slower release of the cytotoxic drug, and this effect correlated positively with the plasma polymer coating times, ranging from 2-fold up to more than 100-fold. Ultimately, upon characterizing and verifying pSi MP production, loading, and coating with analytical methods such as time-of-flight secondary ion mass spectrometry, scanning electron microscopy, thermal gravimetry, water contact angle measurements, and fluorescence microscopy, human neuroblastoma cells were challenged with pSi MPs in an in vitro assay, revealing a significant time delay in cell death onset.
Publisher: Elsevier BV
Date: 2012
DOI: 10.1016/J.ACTBIO.2011.09.001
Abstract: Polyfunctional T cell responses are increasingly underpinning new and improved vaccination regimens. Studies of the nature and extent of these T cell responses may be facilitated if specific T cell populations can be assessed from mixed populations by ligand-mediated capture in a solid-state assay format. Accordingly, we report here the development of a novel strategy for the solid-state capture and real-time activation analyses of in idual cognate T cells which utilizes a spontaneous self-assembly process for generating multimers of biotinylated class I major histocompatibility-peptide complex (MHCp) directly on the solid-state assay surface while also ensuring stability by covalent interfacial binding. The capture surface was constructed by the fabrication of multilayer coatings onto standard slides. The first layer was a thin polymer coating with surface aldehyde groups, onto which streptavidin was covalently immobilized, followed by the docking of multimers of biotinylated MHCp or biotinylated anti-CD45.1 monoclonal antibody. The high binding strength at each step of this immobilization sequence aims to ensure that artefacts such as (partial) detachment, or displacement by proteins from solution, would not interfere with the intended biological assays. The multilayer coating steps were monitored by X-ray photoelectron spectroscopy data indicated that the MHCp proteins self-assembled in a multimeric form onto the streptavidin surface. Immobilized multimeric MHCp demonstrated the capacity to bind and retain antigen-specific T cells from mixed populations of cells onto the solid carrier. Furthermore, real-time confocal microscopic detection and quantification of subsequent calcium flux using paired fluorescent ratiometric probes facilitated the analysis of in idual T cell response profiles, as well as population analyses using a combination of in idual T cell events.
Publisher: Wiley
Date: 27-03-2023
Abstract: Plasma polymers from glycidol vapors are of interest for direct covalent grafting of molecules bearing amine or thiol groups. The question of whether pulsed plasma operation might lead to a higher surface density of epoxide groups and a higher density of grafted molecules is studied using the antifungal drug caspofungin. X‐ray photoelectron spectroscopy and Time of flight‐secondary ions mass spectrometry analysis followed by caspofungin grafting revealed that both continuous wave and pulsed plasmas led to surface epoxides but with higher densities upon pulsing. Investigations into stability suggested that glycidol plasma polymer coatings were still able to immobilize caspofungin after 2 years of storage, making them suitable for applications where grafting of molecules needs to be done immediately before usage of a device.
Publisher: American Chemical Society (ACS)
Date: 07-08-2008
DOI: 10.1021/JP803678W
Abstract: Plasma polymers deposited from n-heptylamine onto silicon wafers have been found to form a porous microstructure when immersed in water and other solvents, with pores of dimensions and densities that vary considerably between coatings deposited under different plasma conditions. This solvent-induced pore formation was found to correlate with the observed percentage of extractable material. With low radio frequency (rf) power inputs, the resultant softer coatings possess considerably more extractable material than coatings deposited at higher applied power levels. The porosity is thus proposed to result from the formation of voids created by the extraction of soluble low-molecular-weight polymeric material, which produces shrinkage stress that the coating, firmly attached to the substrate, cannot relieve by macroscopic contraction. The microscopic contraction of plasma polymer volume creates voids that appear to span the entire film thickness. The effect of aging plasma polymers in air was also investigated. For films deposited at low power it led to reduced extraction of soluble material and different pore morphology, whereas for films deposited at higher rf power levels, the extracted amounts and pore formation were the same for aged coatings. It was also found that the density of surface amine groups was lower for films deposited under the two lowest power settings, in contrast to the commonly held belief that the use of minimal applied rf power aids retention of functional groups. These porous plasma polymer coatings with surface groups suitable for further interfacial chemical immobilization reactions may be useful for various membrane and biotechnology applications.
Publisher: American Vacuum Society
Date: 05-2022
DOI: 10.1116/6.0001746
Abstract: Cardiovascular disease is a leading cause of death worldwide however, despite substantial advances in medical device surface modifications, no synthetic coatings have so far matched the native endothelium as the optimal hemocompatible surface for blood-contacting implants. A promising strategy for rapid restoration of the endothelium on blood-contacting biomedical devices entails attracting circulating endothelial cells or their progenitors, via immobilized cell-capture molecules for ex le, anti-CD34 antibody to attract CD34+ endothelial colony-forming cells (ECFCs). Inherent is the assumption that the cells attracted to the biomaterial surface are bound exclusively via a specific CD34 binding. However, serum proteins might adsorb in-between or on the top of antibody molecules and attract ECFCs via other binding mechanisms. Here, we studied whether a surface with immobilized anti-CD34 antibodies attracts ECFCs via a specific CD34 binding or a nonspecific (non-CD34) binding. To minimize serum protein adsorption, a fouling-resistant layer of hyperbranched polyglycerol (HPG) was used as a “blank slate,” onto which anti-CD34 antibodies were immobilized via aldehyde-amine coupling reaction after oxidation of terminal diols to aldehydes. An isotype antibody, mIgG1, was surface-immobilized analogously and was used as the control for antigen-binding specificity. Cell binding was also measured on the HPG hydrogel layer before and after oxidation. The surface analysis methods, x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry, were used to verify the intended surface chemistries and revealed that the surface coverage of antibodies was sparse, yet the anti-CD34 antibody grafted surface-bound ECFCs very effectively. Moreover, it still captured the ECFCs after BSA passivation. However, cells also attached to oxidized HPG and immobilized mIgG1, though in much lower amounts. While our results confirm the effectiveness of attracting ECFCs via surface-bound anti-CD34 antibodies, our observation of a nonspecific binding component highlights the importance of considering its consequences in future studies.
Publisher: American Chemical Society (ACS)
Date: 17-06-2009
DOI: 10.1021/LA900703E
Abstract: Covalently grafted poly(ethylene oxide) coatings have been widely studied for use in biomedical applications, particularly for the reduction of protein and other biomolecule adsorption. However, many of these studies have not characterized the hydrated structure of the coatings. This new study uses a combination of silica colloid probe interaction force measurements using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) in order to determine the grafting density and hydrated layer structure of monomethoxy poly(ethylene oxide) aldehyde layers, covalently grafted onto amine plasma polymer surfaces, and their interactions with silica surfaces. For high grafting densities, purely repulsive interactions were measured as expected for densely grafted polymer brushes. These interactions could be described by theoretical expectations for compression of one polymer brush layer. However, at lower grafting densities, attractive interactions were observed at larger separation distances, originating from bridging interactions due to adsorption of the PEO chains on the surface of the silica colloid probe. This is a new finding indicating that the coupled PEO molecules have sufficient conformational freedom to interact strongly with an adjacent surface or, for ex le, protein molecules for which there is an affinity. The attractive interactions could be removed by grafting an additional PEO layer onto the silica colloid probe. Protein adsorption measurements confirmed that at high grafting densities, the amount of adsorbed protein on the PEO grafted surfaces was greatly reduced, to the order of the detection limit for the XPS technique.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C6RA28491D
Abstract: We demonstrate the applicability of colloid-probe AFM to detect different surface chemistries on binary colloidal crystal layers of different chemical and protein patterns.
Publisher: Wiley
Date: 07-2022
Publisher: Royal Society of Chemistry (RSC)
Date: 2011
DOI: 10.1039/C1JM10317B
Publisher: Royal Society of Chemistry (RSC)
Date: 2013
DOI: 10.1039/C2BM00143H
Publisher: Elsevier BV
Date: 06-1982
Publisher: Elsevier BV
Date: 08-1976
Publisher: Elsevier BV
Date: 11-2020
Publisher: American Chemical Society (ACS)
Date: 17-04-2004
DOI: 10.1021/BM049941K
Abstract: Surface-immobilized liposome layers are of interest for various potential applications such as localized drug delivery, but their characterization is challenging. We have employed an AFM method and fluorescent dye release to analyze anchored liposomes. In addition, we studied whether the liposomes are surface-bound solely via specific interaction (NeutrAvidin/biotin) or whether physisorptive binding also plays a role. Liposomes containing PEG-biotin lipids were affinity bound to NeutrAvidin molecules which had been immobilized onto solid supports via three different hydrogel interlayers. After liposome docking, approaching the surface with a colloid probe mounted onto an AFM cantilever showed considerable compression behavior, consistent with expectation based on intact, deformable liposomes but not lipid bilayers, thus showing that disruption of liposomes did not occur upon immobilization onto these support surfaces. Plastic deformation suggestive of liposome disruption on compression was not observed. The kinetics of fluorescent dye release also demonstrated that intact liposomes had been successfully immobilized onto all three supports. Blocking surface-immobilized NeutrAvidin molecules with excess biotin in solution before exposure to liposomes showed that the docking of liposomes was dependent largely but not exclusively on biotin-NeutrAvidin affinity binding, with evidence for some nonspecific physisorption, as the extent of liposome binding onto blocked NeutrAvidin surfaces was appreciably lower than for unblocked surfaces but not zero. Finally, consecutive addition of further NeutrAvidin and liposome layers enabled fabrication of multilayers, and this was clearly seen in AFM compressibility and fluorescent dye release measurements.
Publisher: Elsevier BV
Date: 04-2006
Publisher: American Chemical Society (ACS)
Date: 19-04-2012
DOI: 10.1021/AM300128N
Abstract: The deposition of a thin film layer by plasma polymerization enables the surface functionalization of a wide range of substrate materials for biointerfacial interactions. Plasma polymers can surface-bind proteins specifically via covalent linkages or nonspecifically through other irreversible adsorption mechanisms key questions are whether covalent chemisorption has indeed occurred, and whether the protein retains functionality. Here the mode of surface binding of streptavidin and the biotin binding functionality of the bound streptavidin layer are studied on plasma polymer (pp) surfaces deposited using propionaldehyde and ethanol that were plasma polymerized at different powers (P) to investigate possible mechanisms for protein binding to a range of different surface chemistries. As expected, with pp surfaces composed principally of aldehyde groups, protein conjugation appears to be specific (chemisorption) allowing the immobilization of streptavidin (SAV) molecules retaining the ability to bind biotinylated probes. To contrast with this, we present the first study of protein adsorption to ethanol pp surfaces prepared at different P. This provides an investigation into retention of the hydroxyl functionality in the pp at low P and its effect on protein adsorption. Adsorption of human serum albumin (HSA) to ethanol pp was similar to that on propionaldehyde pp except at low P (5 W) where hydroxyl group retention and hydration presumably has a role in reducing protein adsorption. Although we observed SAV adsorption to ethanol pp surfaces at all P, interestingly, the protein lost its ability to bind biotinylated probes. Thus we suggest that irreversible, nonspecific adsorption of protein on ethanol pp surfaces results in apparent protein denaturation despite the hydrophilic nature of the ethanol pp surface. We conclude by making inferences between the pp structure as measured by X-ray photoelectron spectroscopy (XPS) and the related protein adsorption mechanisms.
Publisher: American Chemical Society (ACS)
Date: 05-08-2008
DOI: 10.1021/LA801140U
Abstract: A novel plasma functionalization process based on the pulsed plasma polymerization of allyl glycidyl ether is reported for the generation of robust and highly reactive epoxy-functionalized surfaces with well-defined chemical properties. Using a multitechnique approach including X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), infrared spectroscopy (FT-IR), atomic force microscopy (AFM) and ellipsometry, the effect of the plasma deposition parameters on the creation and retention of epoxy surface functionalities was characterized systematically. Under optimal plasma polymerization conditions (duty cycle: 1 ms/20 ms and 1 ms/200 ms), reactive uniform films with a high level of reproducibility were prepared and successfully used to covalently immobilize the model protein lysozyme. Surface derivatization was also carried out with ethanolamine to probe for epoxy groups. The ethanolamine blocked surface resisted nonspecific adsorption of lysozyme. Lysozyme immobilization was also done via microcontact printing. These results show that allyl glycidyl ether plasma polymer layers are an attractive strategy to produce a reactive epoxy functionalized surface on a wide range of substrate materials for biochip and other biotechnology applications.
Publisher: American Chemical Society (ACS)
Date: 15-12-2007
DOI: 10.1021/AC701720Y
Abstract: Furanone compounds (fimbrolides) have attracted interest as antibacterial compounds for use in human health care, for instance, as an antibacterial coating for medical devices to combat device-centered infections. To ensure effectiveness for extended periods of time, they must be immobilized covalently onto a device surface in this study, this was done via azide/nitrene chemistry and photochemical coupling. However, the detection and quantification of surface-immobilized small molecules such as furanones presents a considerable analytical challenge, yet is necessary for optimization of coatings and reliable interpretation of biological responses. We have utilized the surface sensitivity and chemical specificity of time-of-flight secondary ion mass spectrometry (TOF-SIMS) to characterize each step of the grafting sequence. On account of the complexity of the data, principal component analysis (PCA) was used to interpret and compare spectra. The results demonstrate the utility of TOF-SIMS with PCA for the detection of the surface-grafted small molecules azidoaniline and a brominated furanone imaging of the bromine ion peaks also enabled assessment of grafting uniformity. Thus, successful multilayer coating and furanone grafting was observed, and substantial and uniform coverage of furanone molecules on the surface. Even multiple grafting steps involving, in the present case, two low molecular weight compounds can readily be disentangled by PCA. The utility of TOF-SIMS analysis with PCA is particularly well illustrated in the present case by the grafting of the furanone molecules, which did not yield a singular unique peak in the positive ion mass spectra, whereas the collective spectral changes elucidated by PCA provided unambiguous verification of successful grafting of this low molecular weight compound.
Publisher: Wiley
Date: 10-01-2011
DOI: 10.1002/BIP.21584
Abstract: The well-characterized small heat-shock protein, alphaB-crystallin, acts as a molecular chaperone by interacting with unfolding proteins to prevent their aggregation and precipitation. Structural perturbation (e.g., partial unfolding) enhances the in vitro chaperone activity of alphaB-crystallin. Proteins often undergo structural perturbations at the surface of a synthetic material, which may alter their biological activity. This study investigated the activity of alphaB-crystallin when covalently bound to a support surface alphaB-crystallin was immobilized onto a range of solid material surfaces, and its characteristics and chaperone activity were assessed. Immobilization was achieved via a plasma-deposited thin polymeric interlayer containing aldehyde surface groups and reductive amination, leading to the covalent binding of alphaB-crystallin lysine residues to the surface aldehyde groups via Schiff-base linkages. Immobilized alphaB-crystallin was characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and quartz crystal microgravimetry, which showed that 300 ng cm(-2) (dry mass) of oligomeric alphaB-crystallin was bound to the surface. Immobilized alphaB-crystallin exhibited a significant enhancement (up to 5000-fold, when compared with the equivalent activity of alphaB-crystallin in solution) of its chaperone activity against various proteins undergoing both amorphous and amyloid fibril forms of aggregation. The enhanced molecular chaperone activity of immobilized alphaB-crystallin has potential applications in preventing protein misfolding, including against amyloid disease processes, such as dialysis-related amyloidosis, and for biodiagnostic detection of misfolded proteins.
Publisher: Elsevier BV
Date: 1980
Publisher: American Chemical Society (ACS)
Date: 08-01-2014
DOI: 10.1021/AM405143E
Abstract: The characterization of variations in the chemical composition and ensuing mechanical properties across the thickness of coatings with continuously varying compositions through their thickness (graded coatings) presents considerable challenges for current analytical techniques in materials science. We report here the direct imaging of nanomechanical and chemical gradients across cross-sections of an organosilicone coating fabricated via microwave plasma enhanced chemical vapor deposition (PECVD). Cross-sectional nanoindentation was used to determine the mechanical properties of uniform and graded organosilicone coatings. Both hardness and modulus across the coatings were directly measured. Additionally, "modulus mapping" on cross-sections was used to map the complex modulus. For the graded coating, it was found that variations in the complex modulus was predominantly due to varying storage modulus. It was observed that at the interface with the substrate there was a low storage modulus, which linearly increased to a relatively high storage modulus at the surface. It is proposed that the increase in stiffness, from the substrate interface to the outer surface, is due to the increasing content of a cross-linked O-Si-O network. This mechanical gradient has been linked to a change in the Si:O ratio via direct compositional mapping using ToF-SIMS. Direct mapping of the mechanical and compositional gradients across these protective coatings provides insight into the changes in properties with depth and supports optimization of the critical mechanical performance of PECVD graded coatings.
Publisher: Wiley
Date: 11-08-2011
Publisher: American Chemical Society (ACS)
Date: 03-05-2017
DOI: 10.1021/ACS.BIOMAC.6B01687
Abstract: The propensity of glycosaminoglycans to mediate cell-cell and cell-matrix interactions opens the door to capture cells, including circulating blood cells, onto biomaterial substrates. Chondroitin sulfate (CS)-B is of particular interest, since it interacts with the receptor (EGF)-like module-containing mucin-like hormone receptor-like 2 precursor (EMR2) displayed on the surface of leukocytes and endothelial progenitor cells. Herein, CS-B and its isomer CS-A were covalently immobilized onto heptylamine plasma polymer films via three different binding chemistries to develop platform technology for the capture of EMR2 expressing cells onto solid carriers. Surface characterization verified the successful immobilization of both glycosaminoglycans. The EMR2 expressing human myeloid cell line U937 preferentially bound onto CS-B-modified substrates, and U937 cells preincubated with CS-B in solution exhibited reduced affinity for the substrate. The direct capture of hematopoietic and blood-circulating endothelial cell types via a glycosaminoglycan-binding surface receptor opens an unexplored route for the development of biomaterials targeted at these cell types.
Publisher: American Vacuum Society
Date: 06-2007
DOI: 10.1116/1.2751126
Abstract: The localized availability of bioactive biomolecules directly at the implant/tissue interface presents a promising strategy for improved wound healing and thus biointegration. Bioactive molecules that cannot be incorporated into the bulk material of a device may be delivered from a compatible surface coating, while the reservoir capacity of thin surface coatings is limited, they offer localized delivery over the first few critical hours or days of wound healing. In this study an alginate/chitosan hydrogel has been utilized as the basis for nanoscale eluting coatings to provide a hydrophilic yet water insoluble surface delivery system. The release characteristics of these hydrogel coatings were measured by employing the model molecules-fluorescein isothiocyanate dextran [FD molecular weights (MWs) 4, 70, and 2000 kDa], fluorescein isothiocyanate albumin, and rhodamine. Scanning electron microscopy and atomic force microscopy were used to study the morphology of the hydrogel coatings on model substrates, and ellipsometry was employed for measuring the coating thickness. On silicon wafers, the coatings were of good uniformity and conformal, with a thickness of approximately 120 nm and a rms roughness of 3.0 nm. A model porous substrate, paper, which afforded deep pore penetration of the hydrogel, was used to mimic hydroxyapatite. The release of FD was observed to be dependent on the MW, the release medium, charge, and surface roughness. Sustained release was recorded for FD 70 and FD 2000 with yields of about 90% and 75%, respectively, into simulated body fluid within 26 days. Concurrent elution of different molecules from one hydrogel coating was demonstrated. The observed elution profiles were fitted to release kinetics such as the Korsmeyer-Peppas model or first order release.
Publisher: American Chemical Society (ACS)
Date: 11-1991
DOI: 10.1021/LA00059A015
Publisher: Elsevier BV
Date: 10-2011
DOI: 10.1016/J.CBPA.2011.07.012
Abstract: The chemical composition of the surface layers of synthetic biomaterials used for human medical devices and in biotechnology plays a key role in determining interfacial interactions between biological media (such as protein solutions, cells, tissue) and the synthetic material. Accordingly, considerable research efforts focus on improving the 'biocompatibility' of biomaterials by applying various surface modification and thin film coating approaches. Here we focus on the patterning of surface chemistries, often designed to exercise spatial control over events such as cell attachment and spreading. Secondly, we review recent developments in chemical characterisation of biomaterials surfaces, which is essential both for verifying the success of intended surface modification strategies and for reliable interpretation of observed biological responses. Biomaterials surface analysis by imaging ToF-SIMS and XPS and compositional depth profiling are discussed, as is the emerging complementary technique of Metastable Induced Electron Spectroscopy.
Publisher: SPIE
Date: 19-11-2001
DOI: 10.1117/12.454587
Publisher: SPIE
Date: 19-11-2001
DOI: 10.1117/12.454588
Publisher: Elsevier BV
Date: 09-2018
Publisher: Elsevier BV
Date: 02-1982
Publisher: Elsevier BV
Date: 08-2013
Publisher: Wiley
Date: 20-09-2022
Abstract: Plasma polymers have long been of interest as thin film coatings on biomedical devices and products, to generate desirable surface properties for favorable bio‐interfacial interactions. Plasma polymers have also been used as platforms for the covalent immobilization of bioactive molecules. More recently, additional aspects have been investigated, such as selective prevention of adhesion of microbial pathogens, either via plasma polymers per se or including antimicrobial drugs. Plasma polymers have also been investigated for the release of silver ions and small organic molecules. Complementing low‐pressure plasma approaches, processes at atmospheric pressure have attracted interest recently, including for nano/biocomposite coatings. This contribution reviews the use of plasma polymers for intended biomedical applications, with a focus on more recent topic areas.
Publisher: American Chemical Society (ACS)
Date: 27-01-2012
DOI: 10.1021/LA204714P
Abstract: Surface density gradients of streptavidin (SAV) were created on solid surfaces and demonstrated functionality as a bioconjugation platform. The surface density of immobilized streptavidin steadily increased in one dimension from 0 to 235 ng cm(-2) over a distance of 10 mm. The density of coupled protein was controlled by its immobilization onto a polymer surface bearing a gradient of aldehyde group density, onto which SAV was covalently linked using spontaneous imine bond formation between surface aldehyde functional groups and primary amine groups on the protein. As a control, human serum albumin was immobilized in the same manner. The gradient density of aldehyde groups was created using a method of simultaneous plasma copolymerization of ethanol and propionaldehyde. Control over the surface density of aldehyde groups was achieved by manipulating the flow rates of these vapors while moving a mask across substrates during plasma discharge. Immobilized SAV was able to bind biotinylated probes, indicating that the protein retained its functionality after being immobilized. This plasma polymerization technique conveniently allows virtually any substrate to be equipped with tunable protein gradients and provides a widely applicable method for bioconjugation to study effects arising from controllable surface densities of proteins.
Publisher: Elsevier BV
Date: 04-2013
Publisher: Informa UK Limited
Date: 1992
Publisher: Wiley
Date: 18-10-2006
DOI: 10.1002/SIA.2387
Publisher: American Chemical Society (ACS)
Date: 07-2008
DOI: 10.1021/LA801619V
Abstract: Porous silicon has received considerable interest in recent years in a range of biomedical applications, with its performance determined by surface chemistry. In this work, we investigate the PEGylation of porous silicon wafers using click chemistry. The porous silicon wafer surface chemistry was monitored at each stage of the reaction via photoacoustic Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, whereas sessile drop contact angle and model protein adsorption measurements were used to characterize the final PEGylated surface. This work highlights the simplicity of click-chemistry-based functionalization in tailoring the porous silicon surface chemistry and controlling protein-porous silicon interactions.
Publisher: Informa UK Limited
Date: 1995
Publisher: American Chemical Society (ACS)
Date: 28-08-2008
DOI: 10.1021/LA801359W
Abstract: Biomimetic coatings offer exciting options to modulate the biocompatibility of biomaterials. The challenge is to create surfaces that undergo specific interactions with cells without promoting nonspecific fouling. This work reports an innovative approach toward biomimetic surfaces based on the covalent immobilization of a carboxylate terminated PEGylated hyaluronan (HA-PEG) onto plasma functionalized NiTi alloy surfaces. The metal substrates were aminated via two different plasma functionalization processes. Hyaluronan, a natural glycosaminoglycan and the major constituent of the extracellular matrix, was grafted to the substrates by reaction of the surface amines with the carboxylic acid terminated PEG spacer using carbodiimide chemistry. The surface modification was monitored at each step by X-ray photoelectron spectroscopy (XPS). HA-immobilized surfaces displayed increased hydrophilicity and reduced fouling, compared to bare surfaces, when exposed to human platelets (PLT) in an in vitro assay with radiolabeled platelets (204.1 +/- 123.8 x 10 (3) PLT/cm (2) vs 538.5 +/- 100.5 x 10 (3) PLT/cm (2) for bare metal, p < 0.05). Using a robust plasma patterning technique, microstructured hyaluronan surfaces were successfully created as demonstrated by XPS chemical imaging. The bioactive surfaces described present unique features, which result from the synergy between the intrinsic biological properties of hyaluronan and the chemical composition and morphology of the polymer layer immobilized on a metal surface.
Publisher: Wiley
Date: 03-02-2012
Publisher: Wiley
Date: 07-12-2020
Publisher: Informa UK Limited
Date: 09-2009
DOI: 10.1586/ERD.09.36
Abstract: Despite considerable research and development efforts, the problem of infections related to biomedical devices and implants persists. Bacteria evidently can readily colonize surfaces of synthetic materials, such as those used for the fabrication of catheters, hip and knee implants, and many other devices. As the growing colony encapsulates itself with a protective exocellular bacterial polysaccharide layer, the biofilm becomes much harder to combat than circulating bacteria. Thus, there is a strong need to mitigate bacterial colonization by equipping the surfaces of biomedical devices and implants with features such as surface chemistry and surface roughness that are unfavorable for bacterial attachment. Here we review a number of strategies used for the design of antibacterial coatings. We also discuss specific issues that arise from using various types of coatings.
Publisher: American Chemical Society (ACS)
Date: 25-10-2013
DOI: 10.1021/BM401128R
Abstract: We have synthesized a series of copolymers containing both positively charged (amine, guanidine) and hydrophobic side chains ( hiphilic antimicrobial peptide mimics). To investigate the structure-activity relationships of these polymers, low polydispersity polymethacrylates of varying but uniform molecular weight and composition were synthesized, using a reversible addition-fragmentation chain transfer (RAFT) approach. In a facile second reaction, pendant amine groups were converted to guanidines, allowing for direct comparison of cation structure on activity and toxicity. The guanidine copolymers were much more active against Staphylococcus epidermidis and Candida albicans compared to the amine analogues. Activity against Staphylococcus epidermidis in the presence of fetal bovine serum was only maintained for guanidine copolymers. Selectivity for bacterial over mammalian cells was assessed using hemolytic and hemagglutination toxicity assays. Guanidine copolymers of low to moderate molecular weight and hydrophobicity had high antimicrobial activity with low toxicity. Optimum properties appear to be a balance between charge density, hydrophobic character, and polymer chain length. In conclusion, a suite of guanidine copolymers has been identified that represent a new class of antimicrobial polymers with high potency and low toxicity.
Publisher: Royal Society of Chemistry (RSC)
Date: 2012
DOI: 10.1039/C2JM30210A
Publisher: MDPI AG
Date: 08-01-2021
Abstract: To combat infections on biomedical devices, antimicrobial coatings have attracted considerable attention, including coatings comprising naturally occurring antimicrobial peptides (AMPs). In this study the aim was to explore performance upon extended challenge by bacteria growing in media above s les. The AMPs LL37, Magainin 2, and Parasin 1 were selected on the basis of well-known membrane disruption activity in solution and were covalently grafted onto a plasma polymer platform, which enables application of this multilayer coating strategy to a wide range of biomaterials. Detailed surface analyses were performed to verify the intended outcomes of the coating sequence. S les were challenged by incubation in bacterial growth media for 5 and 20 h. Compared with the control plasma polymer surface, all three grafted AMP coatings showed considerable reductions in bacterial colonization even at the high bacterial challenge of initial seeding at 1 × 107 CFU, but there were increasing numbers of dead bacteria attached to the surface. All three grafted AMP coatings were found to be non-toxic to primary fibroblasts. These coatings thus could be useful to produce antibacterial surface coatings for biomaterials, though possible consequences arising from the presence of dead bacteria need to be studied further, and compared to non-fouling coatings that avoid attachment of dead bacteria.
Publisher: American Chemical Society (ACS)
Date: 09-06-2005
DOI: 10.1021/LA050386X
Abstract: Adsorbed layers of "comb-type" copolymers consisting of PEG chains grafted onto a poly(l-lysine) (PLL) backbone on niobium oxide substrates were studied by colloid-probe AFM in order to characterize the interfacial forces associated with coatings of varying architectures (PEG/PLL ratios and PEG chain lengths) and their relevance to protein resistance. The steric and electrostatic forces measured varied substantially with the architecture of the PLL-g-PEG copolymers. Varying the ionic strength of the buffer solutions enabled discrimination between electrostatic and steric-entropic contributions to the net interfacial force. For high PEG grafting densities the steric component was most prominent, but at low ionic strengths and high grafting densities, a repulsive electrostatic surface force was also observed its origin was assigned to the niobia charges beneath the copolymer, as insufficient protonated amine groups in the PLL backbone were available for compensation of the oxide surface charges. For lower grafting densities and lower ionic strengths there was a substantial attractive electrostatic contribution arising from interaction of the electrical double layer arising from the protonated amine groups, with that of the silica probe surface (as under low ionic strength conditions, the electrical double layer was thicker than the PEG layer). For these PLL-g-PEG coatings the net interfacial force can thus be a markedly varying superposition of electrostatic and steric-entropic contributions, depending on various factors. The force curves correlate with protein adsorption data, demonstrating the utility of AFM colloid-probe force measurements for quantitative analysis of surface forces and how they determine interfacial interactions with proteins. Such characterization of the net interfacial forces is essential to elucidate the multiple types of interfacial forces relevant to the interactions between PLL-g-PEG coatings and proteins and to advance interpretation of protein adsorption or repellence beyond the oversimplified steric barrier model in particular, our data demonstrate the importance of an ionic-strength-dependent minimum PEG layer thickness to screen the electrostatic interactions of charged interfaces.
Publisher: Elsevier BV
Date: 12-2002
DOI: 10.1016/S0142-9612(02)00228-4
Abstract: The highly sensitive surface analytical techniques X-ray photoelectron spectroscopy (XPS) and time-of-flight static secondary ion mass spectrometry (ToF-SIMS) were used to test the resistance of poly(ethylene glycol) (PEG) coatings towards adsorption of lysozyme (LYS) and fibronectin (FN). PEG coatings were prepared by grafting methoxy-terminated aldehyde-PEG (MW 5000 Da) onto two amino-functionalised surfaces with different amine group densities, generated by radio frequency glow discharge polymerisation of n-heptylamine and allylamine. Grafting was performed at the lower critical solution temperature to maximise the graft density of the PEG chains. XPS showed that the grafted density of PEG chains was slightly higher on the allylamine surface. XPS detected no adsorption of either protein on either PEG coating. ToF-SIMS analysis, on the other hand, found, in the positive ion spectra, minute but statistically significant signals assignable to amino acid fragment ions from both proteins adsorbed to the lower density PEG coating and from LYS but not FN on the higher density PEG coating. Negative ion spectra contained relatively more intense protein fragment ion signals for the lower density PEG coating but no changes assignable to adsorbed proteins on the higher density PEG coating. These results demonstrate the importance of utilising highly sensitive techniques to study protein adsorption on surfaces intended to be protein resistant, and that both positive and negative ion ToF-SIMS spectra should be acquired to probe for possible very low levels of protein adsorption.
Publisher: MDPI AG
Date: 31-03-2019
DOI: 10.3390/ANTIBIOTICS8020034
Abstract: Plant metabolites that have shown activity against bacteria and/or environmental fungi represent valuable leads for the identification and development of novel drugs against clinically important human pathogenic fungi. Plants from the genus Eremophila were highly valued in traditional Australian Aboriginal medicinal practices, and E. alternifolia was the most prized among them. As antibacterial activity of extracts from E. alternifolia has been documented, this study addresses the question whether there is also activity against infectious fungal human pathogens. Compounds from leaf-extracts were purified and identified by 1- and 2-D NMR. These were then tested by disk diffusion and broth microdilution assays against ten clinically and environmentally relevant yeast and mould species. The most potent activity was observed with the diterpene compound, 8,19-dihydroxyserrulat-14-ene against Cryptococcus gattii and Cryptococcus neoformans, with minimum inhibition concentrations (MIC) comparable to those of Amphotericin B. This compound also exhibited activity against six Candida species. Combined with previous studies showing an antibacterial effect, this finding could explain a broad antimicrobial effect from Eremophila extracts in their traditional medicinal usage. The discovery of potent antifungal compounds from Eremophila extracts is a promising development in the search for desperately needed antifungal compounds particularly for Cryptococcus infections.
Publisher: Informa UK Limited
Date: 1994
Abstract: The attachment and growth of human endothelial cells and fibroblasts was studied on polymer surfaces fabricated by the polymerization of volatile amine and amide compounds in a low pressure gas plasma, and by the treatment of various surfaces in ammonia plasmas, which served to increase the nitrogen content of the surface layers. Infrared spectra showed the presence of amide groups, including those cases where the volatile compound ('monomer') did not contain oxygen. The performance of the surfaces in cell attachment correlated with the surface hydrophilicity and the nitrogen content, although for the latter a fair degree of scatter indicated that a more complex relationship applies. All these surfaces supported the attachment and growth of human cells. Generally, amide plasma polymers were best but the in idual monomer and the plasma parameters also played a role. From comparisons of the various surfaces, it is suggested that the amide group is the main promoter of cell attachment in nitrogen-containing plasma surfaces.
Publisher: Wiley
Date: 04-10-2011
Publisher: Wiley
Date: 06-1994
Publisher: Elsevier BV
Date: 02-1997
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7RA03897F
Abstract: We report a facile, one-step, aqueous surface bioconjugation approach for producing an antifungal surface coating that prevents the formation of fungal biofilms.
Publisher: Public Library of Science (PLoS)
Date: 02-06-2016
Publisher: Public Library of Science (PLoS)
Date: 14-12-2015
Publisher: American Chemical Society (ACS)
Date: 06-12-2011
DOI: 10.1021/AM201320A
Abstract: Targeted delivery and controlled local release of drugs has a number of advantages over conventional systemic drug delivery approaches. Novel platforms for local delivery from solid drug carriers are needed to satisfy the requirements of various medical applications, in particular for the incorporation and release of hydrophilic drugs from a solid carrier material. We have utilized the plasma polymerization of n-heptylamine for the generation of two thin coated layers that serve two distinct purposes. First, an n-heptylamine plasma polymer layer is applied onto the surface of the solid carrier material in order to facilitate spreading of the drug, which is applied by solvent casting levofloxacin in ethanol was used for this study. A second n-heptylamine plasma polymer coating then serves as a thin barrier coating to control the release. We show that the rate of release can be adjusted via the thickness of the plasma polymer overlayer. We also show that this modality of controlled release of levofloxacin completely inhibits Methicillin-resistant Staphylococcus aureus (MRSA) colonization and biofilm formation on and near the coated biomaterial surface.
Publisher: Royal Society of Chemistry (RSC)
Date: 2010
DOI: 10.1039/C0JM01419B
Publisher: Elsevier BV
Date: 2000
Publisher: MDPI AG
Date: 28-09-2021
DOI: 10.3390/ANTIBIOTICS8020063
Abstract: Plants in the Australian genus Eremophila (Scrophulariaceae) have attracted considerable recent attention for their antimicrobial compounds, which possess a wide range of chemical structures. As they are typically associated with the oily-waxy resin layer covering leaves and green branchlets, and Eremophila lucida is prominent among the species containing a pronounced sticky resin layer, this species was considered of interest for assessing its antibacterial constituents. The n-hexane fraction of the crude acetone extract of the leaves exhibited antibacterial activity against Staphylococcus aureus. Isolation led to the known compounds cembratriene, (3Z, 7E, 11Z)-15-hydroxycembra-3,7,11-trien-19-oic acid (1), the sesquiterpenoid, farnesal (2) and the viscidane diterpenoid, 5α-hydroxyviscida-3,14-dien-20-oic acid (3). The purified compounds were tested for antibacterial activity with 2 and 3 showing moderate antibacterial activity against Gram-positive bacteria.
Publisher: SAGE Publications
Date: 04-1990
DOI: 10.1177/088391159000500203
Abstract: Poly(2-hydroxyethyl methacrylate) (pHEMA) surfaces etched by H 2 SO 4 , chloric acid (HClO 4 /KClO 3 ), and HF, were analyzed by electron spectros copy (XPS) to study the surface chemical changes that led to good attachment and growth of endothelial cells on the sulfuric acid treated surface, but not on the others. Sulfonation did not occur. With all three acid treatments, the domi nant chemical structures on the new surfaces were not free methacrylic acid groups that might have been produced by hydrolysis of the ester groups. Some of the several possible reactions between the acids and the pHEMA surface are not consistent with the XPS analyses. The acid treated surfaces contain mainly hydroxyl, ether and ester groups, and one or several among these enhance cell attachment and growth. Also, our data indicate caution in using XPS data as predictors of biomedical performance.
Publisher: Wiley
Date: 2006
DOI: 10.1002/SIA.2363
Publisher: Elsevier BV
Date: 11-2010
DOI: 10.1016/J.JHIN.2010.07.001
Abstract: Established methods for cleaning and sterilising biomedical devices may achieve removal of bioburden only at the macroscopic level while leaving behind molecular levels of contamination (mainly proteinaceous). This is of particular concern if the residue might contain prions. We investigated at the molecular level the removal of model and real-life proteinaceous contamination from model and practical surfaces by air plasma (ionised air) treatment. The surface-sensitive technique of X-ray photoelectron spectroscopy (XPS) was used to assess the removal of proteinaceous contamination, with the nitrogen (N1s) photoelectron signal as its marker. Model proteinaceous contamination (bovine serum albumin) adsorbed on to a model surface (silicon wafer) and the residual proteinaceous contamination resulting from incubating surgical stainless steel (a practical biomaterial) in whole human blood exhibited strong N1s signals [16.8 and 18.5 atomic percent (at.%), respectively] after thorough washing. After 5min air plasma treatment, XPS detected no nitrogen on the s le surfaces, indicating complete removal of proteinaceous contamination, down to the estimated XPS detection limit 10ng/cm(2). Applying the same plasma treatment, the 7.7at.% nitrogen observed on a clinically cleaned dental bur was reduced to a level reflective of new, as-received burs. Contact angle measurements and atomic force microscopy also indicated complete molecular-level removal of the proteinaceous contamination upon air plasma treatment. This study demonstrates the effectiveness of air plasma treatment for removing proteinaceous contamination from both model and practical surfaces and offers a method for ensuring that no molecular residual contamination such as prions is transferred upon re-use of surgical and dental instruments.
Publisher: American Chemical Society (ACS)
Date: 20-05-2006
DOI: 10.1021/LA0602766
Abstract: The electrostatic adsorption onto charged surfaces of comb copolymers comprising a polyelectrolyte backbone and pendent PEG side chains, such as poly(l-lysine)-g-poly(ethylene glycol) (PLL-g-PEG), has in previous studies provided protein-repellent thin coatings, particularly on metal oxide surfaces. A drawback of this approach is, however, the instability of such adsorbed layers under extreme pH values or high ionic strength. We have overcome this limitation in the present study by covalently immobilizing PLL-g-PEG copolymers onto aldehyde plasma-modified substrates. Silicon wafers, optical waveguide chips, and perfluorinated ethylene-co-propylene (FEP) polymer substrates were first coated with a thin plasma polymer layer using a propionaldehyde plasma, followed by covalent immobilization of PLL-g-PEG via reductive amination between amine groups of the PLL backbone with aldehyde groups on the plasma-deposited interlayer. The stability in high salt media and the protein resistance of different molecular architectures of immobilized PLL-g-PEG layers were quantitatively investigated by XPS, an optical waveguide technique (OWLS), and ToF-SIMS. The adsorption of bovine serum albumin was found to be below the detection limit (<2 ng/cm(2)), as for electrostatically adsorbed PLL-g-PEG layers. However, after 24 h of exposure of covalently immobilized layers of PLL-g-PEG to high ionic strength buffer (2400 mM NaCl), no significant change in the protein resistance was observed, whereas under the same conditions electrostatically adsorbed PLL-g-PEG coatings lost their protein resistance. Moreover, covalent immobilization via an aldehyde plasma interlayer enabled the application of PLL-g-PEG layers onto substrates such as FEP onto which electrostatic binding is not possible. These findings create a generic platform for the covalent immobilization of PLL-g-PEG onto a wide variety of substrates.
Publisher: Elsevier BV
Date: 05-2002
DOI: 10.1016/S0142-9612(01)00334-9
Abstract: The effects of pinning density, chain length, and 'cloud point' (CP) versus non-CP grafting conditions have been studied on the ability of polyethylene glycol (PEG) layers to minimize adsorption from a multicomponent (lysozyme, human serum albumin (HSA), IgG and lactoferrin) protein solution. Methoxy-terminated aldehyde-PEG (M-PEG, MW 5000) and dialdehyde-PEG (PEG(ald)2, MW 3400) were grafted by reductive amination onto two surfaces of different amine group density, generated by radiofrequency glow discharge (r.f.g.d.) deposition of n-heptylamine (HA) (low density) or allylamine (AlA) (high density) r.f.g.d. polymer layers. The PEG graft density was varied also by increasing the temperature and salt (K2SO4) content of the grafting solution it reached a maximum at the CP of the PEGs. The CP reaction conditions were critical for producing PEG layers capable of minimizing protein adsorption. X-ray photoelectron spectroscopy (XPS) showed that under these conditions, PEG(ald)2 produced a thick linear PEG layer, most likely by aldol condensation. Protein adsorption was assessed using XPS and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) in the surface mode (Surface-MALDI-MS). Coatings grafted at non-CP conditions showed some protein adsorption, as did the HA/M-PEG layer grafted at the CP. On the other hand, no protein adsorption was detected on the HA/PEG(ald)2, AlA/M-PEG, and AlA/PEG(ald)2 surfaces when grafted at the CP. Thus, the effects of pinning density and chain length are interrelated, but the key factor is optimization of PEG chain density by use of the CP conditions, provided that a sufficient density of pinning sites exists.
Publisher: Ovid Technologies (Wolters Kluwer Health)
Date: 07-2008
Publisher: Wiley
Date: 02-09-2014
Publisher: CSIRO Publishing
Date: 2012
DOI: 10.1071/CH11311
Abstract: We have developed a novel method for activating T-cells on material surfaces that enable in idual and population-based analyses of intracellular calcium flux, as a quantitative measure of T-cell receptor engagement. Functionalized material surfaces were created using a plasma-polymerized foundation layer to immobilize stimulatory T-cell ligands, which could induce T-cell receptor-dependent calcium flux in naive T-cells. Real-time confocal microscopic detection and quantification of calcium flux using paired fluorescent ratiometric probes facilitated the tracking and analysis of response profiles of in idual T-cells, as well as population analyses using a combination of in idual T-cell events. This type of combined analysis cannot be achieved using traditional population-based flow cytometric approaches, and thus provides a logical step towards developing the capacity to assess the magnitude and quality of inherently heterogeneous effector T-cell responses to antigenic challenge.
Publisher: Elsevier BV
Date: 1991
Publisher: Elsevier BV
Date: 12-2012
Publisher: American Chemical Society (ACS)
Date: 17-07-2009
DOI: 10.1021/AC9009337
Abstract: Stimuli-responsive materials show considerable promise for applications that require control over biomolecule interactions at solid material interfaces. Graft coatings of poly(N-isopropylacrylamide) (pNIPAM) are of interest for biomedical and biotechnological applications due to their temperature-dependent switching of surface properties between adhesive and nonadhesive states for cells and proteins. The characterization of protein adsorption to these switchable coatings is a formidable task since switching not only influences the affinity for proteins but at the same time induces a significant change in the coating. Here, the highly sensitive analytical technique of time-of-flight-secondary ion mass spectrometry (TOF-SIMS) combined with principal component analysis (PCA) was used for the characterization of protein adsorption onto pNIPAM coatings prepared by free radical polymerization onto surface-bound polymerizable groups. Adsorption of bovine serum albumin and lysozyme onto pNIPAM coatings from phosphate buffered solutions was investigated at temperatures above and below the polymer's lower critical solution temperature (LCST). Below the LCST, no adsorbed proteins could be detected even with this ultrasensitive method. Whereas above the LCST, adsorbed protein was detected in amounts corresponding at less than the monolayer. PCA loadings plots showed that adventitious contaminants, which might lead to confounding or misleading spectral changes upon protein exposure, were not observed.
Publisher: Oxford University Press (OUP)
Date: 11-2011
DOI: 10.1111/J.1365-2672.2011.05174.X
Abstract: To determine the antibacterial spectrum and cytotoxic activities of serrulatane compounds from the Australian plant Eremophila neglecta. Antimicrobial activities of serrulatane compounds 8,19-dihydroxyserrulat-14-ene (1) and 8-hydroxyserrulat-14-en-19-oic acid (2) were tested against Gram-negative and Gram-positive bacteria including human and veterinary pathogens and some multidrug-resistant isolates. Minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) of the compounds were determined by broth microdilution assay. Both compounds exhibited antibacterial activity against all Gram-positive test strains. They showed antimycobacterial activity against isolates of Mycobacterium fortuitum and Mycobacterium chelonae. Of the five Gram-negative bacteria tested, only Moraxella catarrhalis showed susceptibility to the compounds. Cytotoxic activities were tested in the Vero cell line. Compound 1 showed more activity than 2 in both antibacterial and cytotoxicity assays with cytotoxicity at concentrations similar to the MBC. Serrulatane compounds showed significant activity against medically important bacteria, with 1 exhibiting stronger antibacterial activity. However, they also displayed toxicity to mammalian cells. Serrulatanes are of interest as novel antibacterial compounds for use in biomedical applications this study reports data obtained with a range of bacterial strains and mammalian cells, essential for assessing the capabilities and limitations of potential applicability of these compounds.
Publisher: Elsevier BV
Date: 04-1982
Publisher: American Chemical Society (ACS)
Date: 09-09-2009
DOI: 10.1021/AC901882Z
Publisher: Springer Science and Business Media LLC
Date: 2000
Publisher: Elsevier BV
Date: 09-2004
Publisher: Elsevier BV
Date: 09-2004
Publisher: American Chemical Society (ACS)
Date: 11-11-2019
DOI: 10.1021/ACS.JPCLETT.9B02855
Abstract: Deposition chemistry from plasma is highly dependent on both the chemistry of the ions arriving at surfaces and the ion energy. Typically, when measuring the energy distribution of ions arriving at surfaces from plasma, it is assumed that the distributions are the same for all ionic species. Using ethyl acetate as a representative organic precursor molecule, we have measured the ion chemistry and ion energy as a function of pressure and power. We show that at low pressure (<2 Pa) this assumption is valid however, at elevated pressures ion-molecule collisions close to the deposition surface affect both the energy and chemistry of these ions. Smaller ions are formed close to the surface and have lower energy than larger ionic species which are formed in the bulk of the plasma. The changes in plasma chemistry therefore are closely linked to the physics of the plasma-surface interface.
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Funder: Australian Research Council
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Funder: Australian Research Council
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Funder: Australian Research Council
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Funder: Australian Research Council
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Funder: Australian Research Council
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