ORCID Profile
0000-0002-3828-5481
Current Organisation
University of Miami
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Publisher: Wiley
Date: 10-11-2021
Abstract: Dynamic materials (DMs) or dynamers have potential applications across a broad range of material science challenges. These applications include sustainable materials as a part of the circular plastics economy, advanced materials with tailored high stress properties and biomedical agents. DMs are comprised of polymers that crosslinked through reversible covalent and noncovalent linking groups. This group provides reversible bonds, which impart properties such as (re)healing, adaptability, toughness into a material. The nature of the linker dictates the dynamer's stability and dynamic properties, although for many applications one linker alone cannot give materials with complex multiresponsive functions. The combination of multiple dynamic linkers can introduce complementary functionalities into a single material. This combination of linkers enhances the collective material properties by matching their strengths and offsetting the weaknesses, or by selecting linkers for specific functions, such as one linker for rapid exchange and the other to respond to external stimuli. This contribution highlights the possibilities and unique features of materials containing multiple dynamic linkers, reviewing both fundamental discoveries of materials possessing multiple dynamic bonds and applications facilitated by the presence of multiple linking group chemistry.
Publisher: American Chemical Society (ACS)
Date: 04-03-2021
Publisher: Elsevier BV
Date: 2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3LP00012E
Abstract: Multiple architectural pathways are developed towards self-healable responsive polymer nanocomposites using CNT reinforcement and multiple dynamic chemistries. These materials contribute to applications in smart lighting systems and custom resistors.
Publisher: American Chemical Society (ACS)
Date: 20-02-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8OB00397A
Abstract: The thermally driven exchange of thiol-Michael adducts is investigated, elucidating the underlying mechanism of this dynamic covalent process.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1PY01129D
Abstract: The choice and mixture of chain transfer agent in reversible addition/fragmentation chain transfer polymerization has been used to modulate the dispersity and architecture of vinyl ketone polymers and their copolymers.
Publisher: Wiley
Date: 10-05-2019
Publisher: American Chemical Society (ACS)
Date: 24-03-2021
DOI: 10.1021/ACSMACROLETT.1C00046
Abstract: In the past decade, photochemistry has emerged as a growing area in organic and polymer chemistry. Use of light to drive polymerization has advantages by imparting spatial and temporal control over the reaction. Photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization (PET-RAFT) has emerged as an excellent technique for developing well-defined polymers from a variety of functional monomers. However, the mechanism, of electron versus energy transfer is debated in the literature, with conflicting reports on the underlying process. This perspective focuses on the mechanistic aspects of PET-RAFT, in particular, the electron versus energy transfer pathways. The different mechanisms are evaluated, including evidence for one versus the other mechanisms. The current literature has not reached a consensus across all PET-RAFT processes, but rather, each catalytic system has unique characteristics.
Publisher: American Chemical Society (ACS)
Date: 22-03-2021
Publisher: Wiley
Date: 25-07-2019
Abstract: The power of chemical light generation (chemiluminescence) is used to drive polymerization reactions. A biphasic reaction is developed such that light‐generating reactions are confined to the organic phase and photopolymerization occurs in the aqueous phase. Well‐defined RAFT‐capped polymers are synthesized and the kinetics are shown to be dictated by light generation.
Publisher: American Chemical Society (ACS)
Date: 18-08-2022
Publisher: Wiley
Date: 02-11-2022
Abstract: Dynamic bonds introduce unique properties such as self‐healing, recyclability, shape memory, and malleability to polymers. Significant efforts have been made to synthesize a variety of dynamic linkers, creating a erse library of materials. In addition to the development of new dynamic chemistries, fine‐tuning of dynamic bonds has emerged as a technique to modulate dynamic properties. This Review highlights approaches for controlling the timescales of dynamic bonds in polymers. Particularly, eight dynamic bonds are considered, including urea/urethanes, boronic esters, Thiol–Michael exchange, Diels–Alder adducts, transesterification, imine bonds, coordination bonds, and hydrogen bonding. This Review emphasizes how structural modifications and external factors have been used as tools to tune the dynamic character of materials. Finally, this Review proposes strategies for tailoring the timescales of dynamic bonds in polymer materials through both kinetic effects and modulating bond thermodynamics.
Publisher: American Chemical Society (ACS)
Date: 16-09-2021
Publisher: Wiley
Date: 26-04-2019
Publisher: Wiley
Date: 06-05-2021
Abstract: Covalent adaptable networks (CANs) based on the thiol–Michael (TM) linkages can be thermal and pH responsive. Here, a new vinyl‐sulfone‐based thiol–Michael crosslinker is synthesized and incorporated into acrylate‐based CANs to achieve stable materials with dynamic properties. Because of the reversible TM linkages, excellent temperature‐responsive re‐healing and malleability properties are achieved. In addition, for the first time, a photoresponsive coumarin moiety is incorporated with TM‐based CANs to introduce light‐mediated reconfigureability and postpolymerization crosslinking. Overall, these materials can be on demand dynamic in response to heat and light but can retain mechanical stability at ambient condition.
Publisher: American Chemical Society (ACS)
Date: 25-01-2017
DOI: 10.1021/JACS.6B11643
Publisher: American Chemical Society (ACS)
Date: 27-04-2022
Publisher: Wiley
Date: 23-04-2019
Abstract: Dynamic covalent bonds (DCBs) have received significant attention over the past decade. These are covalent bonds that are capable of exchanging or switching between several molecules. Particular focus has recently been on utilizing these DCBs in polymeric materials. Introduction of DCBs into a polymer material provides it with powerful properties including self-healing, shape-memory properties, increased toughness, and ability to relax stresses as well as to change from one macromolecular architecture to another. This Minireview summarizes commonly used powerful DCBs formed by simple, often "click" reactions, and highlights the powerful materials that can result. Challenges and potential future developments are also discussed.
Publisher: Wiley
Date: 29-05-2021
Abstract: Protein‐polymer bioconjugates present a way to make enzymes more efficient and robust for industrial and medicinal applications. While much work has focused on mono‐functional conjugates, that is, conjugates with one type of polymer attached such as poly(ethylene glycol) or poly( N ‐isopropylacrylamide), there is a practical interest in gaining additional functionality by synthesizing well‐defined bifunctional conjugates in a hetero‐arm star copolymer architecture with protein as the core. Using ubiquitin as a model protein, a synthetic scheme is developed to attach two different polymers (oligo(ethylene oxide) methacrylate and N,N‐dimethylacrylamide) directly to the protein surface, using orthogonal conjugation chemistries and grafting‐from by photochemical living radical polymerization techniques. The additional complexity arising from attempts to selectively modify multiple sites led to decreased polymerization performance and indicates that initiators for continuous activator regeneration atom transfer radical polymerization and reversible addition‐fragmentation chain transfer polymerization are not well‐suited to bifunctional bioconjugates applications under the studied conditions. Nonetheless, the polymerization conditions preserve the native fold of the ubiquitin and enable production of a hetero‐arm star protein‐polymer bioconjugate.
Publisher: American Chemical Society (ACS)
Date: 09-08-2022
Publisher: American Chemical Society (ACS)
Date: 14-06-2021
Publisher: Wiley
Date: 14-11-2022
DOI: 10.1002/POL.20220539
Abstract: Coronavirus disease 2019 (COVID‐19) has significantly impacted human health, the global economy, and society. Viruses residing on common surfaces represent a potential source of contamination for the general population. Spike binding peptide 1, SBP1 is a 23 amino acid peptide, which has micromolar binding affinity (1.3 μM) towards the spike protein receptor‐binding domain. We hypothesize that if we can covalently immobilize this SBP1 peptide in a covalent crosslinked network system, we can develop a surface that would preferentially bind spike protein and, therefore, which could limit viral spread. A series of covalently crosslinked networks of hydroxy ethyl acrylate (HEA) with different primary chain lengths and crosslinker density was prepared. Later, this network system was functionalized using 2% SBP1 peptide. Our study found that with a shorter chain length and lower crosslinker density, the HEA network system alone could capture almost 80% of the spike protein. We reported that the efficiency could be enhanced almost by 17% with higher crosslinker density.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9PY01387C
Abstract: Controlled polymerization is used to make well defined polymers that are assembled into dynamic interpenetrated network materials. Self-healing, toughness and stress relaxation are imparted into the material through the dynamic linkages.
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3PY00912B
Publisher: Springer Science and Business Media LLC
Date: 18-10-2021
Publisher: American Chemical Society (ACS)
Date: 26-01-2022
Publisher: American Chemical Society (ACS)
Date: 21-09-2022
DOI: 10.1021/ACS.BIOMAC.2C00441
Abstract: The thermophilic cellulase Cel5a from Fervidobacterium nodosum ( Fn Cel5a) was conjugated with neutral, cationic, and anionic polymers of increasing molecular weights. The enzymatic activity toward an anionic soluble cellulose derivative, thermal stability, and functional chemical stability of these bioconjugates were investigated. The results suggest that increasing polymer chain length for polymers compatible with the substrate enhances the positive impact of polymer conjugation on enzymatic activity. Activity enhancements of nearly 100% were observed for bioconjugates with N , N -dimethyl acrylamide (DMAm) and N , N -dimethyl acrylamide-2-( N , N -dimethylamino)ethyl methacrylate (DMAm/DMAEMA) due to proposed polymer-substrate compatibility enabled by potential noncovalent interactions. Double conjugation of two functionally distinct polymers to wild-type and mutated Fn Cel5a using two conjugation methods was achieved. These doubly conjugated bioconjugates exhibited similar thermal stability to the unmodified wild-type enzyme, although enzymatic activity initially gained from conjugation was lost, suggesting that chain length may be a better tool for bioconjugate activity modulation than double conjugation.
Publisher: Royal Society of Chemistry (RSC)
Date: 2017
DOI: 10.1039/C7PY01356F
Abstract: Thiol-maleimide adducts are incorporated as crosslinkers into polymer networks and act as pH-responsive and thermoresponsive dynamic crosslinkers, imparting malleability and self-healing properties into the material.
Publisher: American Chemical Society (ACS)
Date: 07-01-2019
DOI: 10.1021/ACSMACROLETT.8B00819
Abstract: Dynamic nucleophilic exchange of quaternary anilinium salts has been incorporated into rehealable and malleable polymeric materials that can be activated under mild (60 °C) thermal stimulus. The mechanism of dynamic exchange between quaternary anilinium salt and free aniline was assessed in small-molecule model experiments. The dynamic exchange was found to be dissociative in nature, due to the indirect S
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3SM00394A
Abstract: Soft 3D-printable adhesive elastomers with self-healing capabilities were formulated. These materials were 3D printed into complex structures and used to modify soft robots for shape-selective lifting.
Publisher: American Chemical Society (ACS)
Date: 08-01-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2023
DOI: 10.1039/D3PY00217A
Abstract: Polymer networks based on phenyl vinyl ketone were synthesized. The introduction of a second network enhanced the control over the material's photodegradation, as well as modulating the mechanical properties.
Publisher: American Chemical Society (ACS)
Date: 26-10-2021
Publisher: American Chemical Society (ACS)
Date: 23-04-2918
Publisher: American Chemical Society (ACS)
Date: 10-01-2023
DOI: 10.1021/JACS.2C11757
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2CC01223E
Abstract: Aromatic foldamer based networks are developed, where the foldamer unit acts as a molecular spring. Energy dissipation increases with the number of turns in the foldamer, consistent with mechanical unfolding of the molecular spring.
Publisher: American Chemical Society (ACS)
Date: 14-04-2017
DOI: 10.1021/ACSMACROLETT.7B00172
Abstract: Doubly dynamic polymer networks were synthesized with two distinct exchangeable cross-linkers. The first linker is highly dynamic and rapidly exchanging hydrogen bonded 2-ureido-4[1
Publisher: Wiley
Date: 21-06-2021
DOI: 10.1002/POL.20210386
Abstract: An enduring question is: what is the simplest and easiest way to obtain tailored polymers? This communication explores a robust photoiniferter polymerization with only two active ingredients that requires no prior deoxygenation and can be performed on the milliliter scale or sub‐milliliter scale. Rather than leaving headspace in the polymerization vessel or scaling reactions up to fill the vessel, this approach fills the headspace of the reaction vessel with mineral oil or inert solvents. This approach can also be applied to polar monomers in aqueous media, using oil as the inert solvent, or to hydrophobic monomers with water as the inert solvent. This method removes enough ambient oxygen that the photoiniferter reaction proceeds with no deoxygenation step, and achieves high conversion and good molecular weight control in 10–20 h in both aqueous and organic solvents. Complex polymer architectures such as multiblock copolymers and gradient polymers were successfully synthesized by this approach.
Publisher: MDPI AG
Date: 05-07-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9MH01938C
Abstract: Surprisingly, a few seconds–minutes of compression at room temperature can increase the rate of dynamic bond exchange as measured by better self-healing, even for thermoresponsive dynamic bonds which do not exchange under ambient conditions.
Publisher: Wiley
Date: 28-05-2023
Abstract: ortho ‐Phenylenes are one of the simplest classes of aromatic foldamers, adopting helical geometries because of aromatic stacking interactions. The folding and misfolding of ortho ‐phenylenes are slow on the NMR timescale at or below room temperature, allowing detection of folding states using 1 H NMR spectroscopy. Herein, an ortho ‐phenylene hexamer is coupled with a RAFT chain transfer agent (CTA) on each repeat unit. A variety of acrylic monomers are polymerized onto the CTA‐functionalized ortho ‐phenylene using PET‐RAFT to yield functionalized star polymers with ortho‐ phenylene cores. The steric bulk of the acrylate monomer units as well as the chain length of each arm of the star polymer is varied. 1 H NMR spectroscopy shows that the folding of the ortho ‐phenylenes do not vary, providing a robust helical core for star polymer systems.
Publisher: American Chemical Society (ACS)
Date: 27-08-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0ME00015A
Abstract: A series of network materials containing dynamic hydrogen bonded and dynamic covalent Diels–Alder units are developed, with a focus on engineering the materials mechanical and self healing properties by tuning the underlying polymer's structure.
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C8PY00947C
Abstract: Synthesis of precision polymers crosslinked with dynamic thiol-Michael adducts is developed, and the materials are characterized to determine structure–property relationships.
Publisher: American Chemical Society (ACS)
Date: 27-02-2023
DOI: 10.1021/JACS.3C00668
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00602B
Abstract: Polymer based solid-state materials capable of disrupting lipid-bilayers are developed. The materials are mechanically robust and capable of outperforming a 10% small-molecule surfactant and modify filter materials.
Publisher: American Chemical Society (ACS)
Date: 13-03-2018
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0SC02200D
Abstract: Protein–polymer conjugates are explored using magnetic resonance methods to investigate the conformations of the polymer relative to the protein's surface.
Publisher: Wiley
Date: 28-08-2019
DOI: 10.1002/POLA.29475
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8CC09823A
Abstract: Non-equilibrium covalently crosslinked hydrogels are synthesized using carbodiimide fueled coupling of carboxylic acids to anhydrides which eventually dissipate by hydrolysis.
Publisher: American Chemical Society (ACS)
Date: 18-10-2021
DOI: 10.1021/JACS.1C08654
Abstract: Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most powerful reversible deactivation radical polymerization (RDRP) processes. Rate retardation is prevalent in RAFT and occurs when polymerization rates deviate from ideal conventional radical polymerization kinetics. Herein, we explore beyond what was initially thought to be the culprit of rate retardation: dithiobenzoate chain transfer agents (CTA) with more active monomers (MAMs). Remarkably, polymerizations showed that rate retardation occurs in systems encompassing the use of trithiocarbonates and xanthates CTAs with varying monomeric activities. Both the simple slow fragmentation and intermediate radical termination models show that retardation of all these systems can be described by using a single relationship for a variety of monomer reactivity and CTAs, suggesting rate retardation is a universal phenomenon of varying severity, independent of CTA composition and monomeric activity level.
Publisher: American Chemical Society (ACS)
Date: 09-09-2022
Publisher: American Chemical Society (ACS)
Date: 09-05-2022
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY01086C
Abstract: Substituent effects on the dithiobenzoate moiety of RAFT iniferters are investigated. Donating groups accelerate the iniferter process, while withdrawing groups slow it. The unique efficiency of the methoxydithiobenzoate iniferter was uncovered.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D2PY00575A
Abstract: Triply interpenetrated networks were made with a unique dynamic linker in each network. The linkers were hydrogen bonds, boronic esters and Diels–Alder adducts. Triply dynamic materials had superior properties compared to doubly dynamic analogues.
Publisher: American Chemical Society (ACS)
Date: 12-02-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8PY01399C
Abstract: This review article discusses the impact of polymer modification on bioconjugate performance, including both activity and stability, with a focus on how the polymer structure and functionality impact these parameters.
Publisher: American Chemical Society (ACS)
Date: 27-10-2023
Publisher: Wiley
Date: 17-05-2018
Abstract: This review article highlights recent developments in the field of photochemistry and photochemical reversible deactivation radical polymerization applied to aqueous polymerizations. Photochemistry is a topic of significant interest in the fields of organic, polymer, and materials chemistry because it allows challenging reactions to be performed under mild conditions. Aqueous polymerization is of significant interest because water is an environmentally benign solvent, and the use of water enables complex polymer self-assembly and bioconjugation processes to occur. This review focuses on powerful new developments in photochemical aqueous polymerization reactions and their applications to the synthesis of well-defined polymer nano-objects and bioconjugates. It is anticipated that these aqueous photopolymerizations will enable the next generation of self-assembled structures and biohybrid materials to be developed under mild and environmentally friendly conditions.
Publisher: Royal Society of Chemistry (RSC)
Date: 2022
DOI: 10.1039/D1PY01331A
Abstract: A general model is developed for the distribution of polymers made with reversible deactivation. The model is applied to a range of experimental systems including RAFT, cationic and ATRP.
Publisher: American Chemical Society (ACS)
Date: 21-01-2020
Publisher: Elsevier BV
Date: 02-2023
Publisher: Royal Society of Chemistry (RSC)
Date: 2018
DOI: 10.1039/C7PY01398A
Abstract: Photolabile amine protecting groups are combined with RAFT polymerization to create well-defined amine containing polymers, which is typically a challenge for RAFT polymerization.
Publisher: American Chemical Society (ACS)
Date: 22-01-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0MA00143K
Abstract: Diels–Alder based dynamic polymer materials are reinforced with carbon nanotubes, to give materials with self-healing properties from the dynamic matrix and with enhanced mechanical and electrical properties from the carbon nanotubes.
Publisher: American Chemical Society (ACS)
Date: 07-09-2022
DOI: 10.1021/ACSMACROLETT.2C00448
Abstract: Photoinduced electron/energy transfer (PET)-reversible addition-fragmentation chain transfer polymerization (RAFT) and conventional photoinitiated RAFT were used to synthesize polymer networks. In this study, two different metal catalysts, namely, tris[2-phenylpyridinato-C2,N]iridium(III) (Ir(ppy) 3 ) and zinc tetraphenylporphyrin (ZnTPP), were selected to generate two different catalytic pathways, one with Ir(ppy) 3 proceeding through an energy-transfer pathway and one with ZnTPP proceeding through an electron-transfer pathway. These PET-RAFT systems were contrasted against a conventional photoinitated RAFT process. Mechanically robust materials were generated. Using bulk swelling ratios and degradable cross-linkers, the homogeneity of the networks was evaluated. Especially at high primary chain length and cross-link density, the PET-RAFT systems generated more uniform networks than those made by conventional RAFT, with the electron transfer-based ZnTPP giving superior results to those of Ir(ppy) 3 . The ability to deactivate radicals either by RAFT exchange or reversible coupling in PET RAFT was proposed as the mechanism that gave better control in PET-RAFT systems.
Publisher: American Chemical Society (ACS)
Date: 16-06-2020
Publisher: American Chemical Society (ACS)
Date: 12-01-2017
DOI: 10.1021/ACS.JPCLETT.6B02894
Abstract: Thermodynamic properties of protein unfolding have been extensively studied however, the methods used have typically required significant preparation time and high protein concentrations. Here we present a facile, simple, and parallelized differential scanning fluorimetry (DSF) method that enables thermodynamic parameters of protein unfolding to be extracted. This method assumes a two-state, reversible protein unfolding mechanism and provides the capacity to quickly analyze the biophysical mechanisms of changes in protein stability and to more thoroughly characterize the effect of mutations, additives, inhibitors, or pH. We show the utility of the DSF method by analyzing the thermal denaturation of lysozyme, carbonic anhydrase, chymotrypsin, horseradish peroxidase, and cellulase enzymes. Compared with similar biophysical analyses by circular dichroism, DSF allows for determination of thermodynamic parameters of unfolding while providing greater than 24-fold reduction in experimental time. This study opens the door to rapid characterization of protein stability on low concentration protein s les.
Publisher: American Chemical Society (ACS)
Date: 17-06-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/D0PY00823K
Abstract: Here we report a simple and versatile batch methodology to tailor polymer dispersity utilizing PET-RAFT polymerization.
Publisher: American Chemical Society (ACS)
Date: 05-10-2017
DOI: 10.1021/ACS.BIOCONJCHEM.7B00518
Abstract: A thermophilic cellulase, FnCel5a, from Fervidobacterium nodosum was conjugated with various functional polymers including cationic, anionic, and strongly and weakly hydrogen bonding polymers. The activity of FnCel5a toward a high-molecular-weight carboxymethyl cellulose substrate was enhanced by polymer conjugation. Activity enhancements of 50% or greater observed for acrylamide and mixed N,N-dimethyl acrylamide-2-(N,N-dimethylamino)ethyl methacrylate polymers, suggesting that the greatest enhancements were caused by polymers capable of noncovalent interactions with the substrate. The conjugates were found to have nearly identical thermodynamic stability to the native enzyme, as assessed by free energy (ΔG), enthalpy (ΔH), and entropy (TΔS) parameters extracted from differential scanning fluorimetry. Polymers tended to confer comparable tolerance to high concentrations of dimethylformamide, with longer polymers typically enabling higher activity relative to shorter polymers. The new FnCel5a conjugates represent an advance in the production of cellulases that maintain activity at high temperatures or in the presence of denaturing organic solvents.
Publisher: American Chemical Society (ACS)
Date: 03-11-2021
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1PY00198A
Abstract: Dynamic single and interpenetrated materials were developed, with post polymerization network exchange enhancing the material properties.
No related grants have been discovered for Dominik Konkolewicz.