Atom Transfer Radical Polymerization Polymerization Research Articles

A Team for the Low‐Temperature Bulk Depolymerization of Polymethacrylates

AbstractThis invited Team Profile was created by Athina Anastasaki of the Laboratory of Polymeric Materials at ETH Zurich, Switzerland. They recently published an article developing a low‐temperature and solvent‐free method to depolymerize polymers made by atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization. The key to the success of the approach was an efficient end‐group transformation of the polymers to macromonomer, which allowed up to 90 % monomer regeneration at low temperatures. “Solvent‐Free Chemical Recycling of Polymethacrylates Made by ATRP and RAFT Polymerization: High‐Yielding Depolymerization at Low Temperatures”, R. Whitfield, G. R. Jones, N. P. Truong, L. E. Manring, A. Anastasaki, Angew. Chem. Int. Ed. 2023, 62, e202309116.

A Team for the Low-Temperature Bulk Depolymerization of Polymethacrylates.

This invited Team Profile was created by Athina Anastasaki of the Laboratory of Polymeric Materials at ETH Zurich, Switzerland. They recently published an article developing a low-temperature and solvent-free method to depolymerize polymers made by atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. The key to the success of the approach was an efficient end-group transformation of the polymers to macromonomer, which allowed up to 90 % monomer regeneration at low temperatures. "Solvent-Free Chemical Recycling of Polymethacrylates Made by ATRP and RAFT Polymerization: High-Yielding Depolymerization at Low Temperatures", R. Whitfield, G. R. Jones, N. P. Truong, L. E. Manring, A. Anastasaki, Angew. Chem. Int. Ed. 2023, 62, e202309116.

Vitamin B12-catalyzed electro-polymerization for ultrasensitive RNA detection

Vitamin B12 being a natural catalyst in atom transfer radical polymerization (ATRP), has the advantages of mild reaction conditions, good biocompatibility and high catalytic efficiency. In this report, an electrochemical biosensor of the lung cancer biomarker microRNA-21 (miRNA-21) is designed for early screening of lung cancer with high sensitivity at the femtomolar level. In this approach, hairpin DNA with N3 end group was first attached to the electrode surface. When miRNA-21 was present and paired with hairpin DNA, the N3 group released and attached to the ATRP initiator through “click reaction”. Through eATRP, a large number of FerrocenylMethyl Methacrylate (FcMMA) monomers polymerized into long chains for signal amplification. These long chains had a distinct electrical signal in the square wave voltammetry (SWV), which can detect RNA with high sensitivity. The limit of detection (LOD) goes down to 1.010 fM after ATRP polymerization, which is lower than that of the majority of other ultra-sensitive RNA electrochemical assays. Results also show that the vitamin B12-based electrochemical biosensor is highly selective and suitable for RNA detection in complex biological samples.

A universal strategy for the construction of polymer brush hybrid non-glutaraldehyde heart valves with robust anti-biological contamination performance and improved endothelialization potential.

With the intensification of the aging population and the development of transcatheter heart valve replacement technology (THVR), clinical demand for bioprosthetic valves is increasing rapidly. However, commercial bioprosthetic heart valves (BHVs), mainly manufactured from glutaraldehyde cross-linked porcine or bovine pericardium, generally undergo degeneration within 10-15 years due to calcification, thrombosis and poor biocompatibility, which are closely related to glutaraldehyde cross-linking. In addition, endocarditis caused by post-implantation bacterial infection also accelerates the failure of BHVs. Herein, a functional cross-linking agent bromo bicyclic-oxazolidine (OX-Br) has been designed and synthesized to crosslink BHVs and construct a bio-functionalization scaffold for subsequent in-situ atom transfer radical polymerization (ATRP). The porcine pericardium cross-linked by OX-Br (OX-PP) exhibits better biocompatibility and anti-calcification property than the glutaraldehyde-treated porcine pericardium (Glut-PP) as well as comparable physical and structural stability to Glut-PP. Furthermore, the resistance to biological contamination especially bacterial infection of OX-PP along with anti-thrombus and endothelialization need to be enhanced to reduce the risk of implantation failure due to infection. Therefore, amphiphilic polymer brush is grafted to OX-PP through in-situ ATRP polymerization to prepare polymer brush hybrid BHV material SA@OX-PP. SA@OX-PP has been demonstrated to significantly resist biological contamination including plasma proteins, bacteria, platelets, thrombus and calcium, and facilitate the proliferation of endothelial cells, resulting in reduced risk of thrombosis, calcification and endocarditis. Altogether, the proposed crosslinking and functionalization strategy synergistically achieves the improvement of stability, endothelialization potential, anti-calcification and anti-biofouling performances for BHVs, which would resist the degeneration and prolong the lifespan of BHVs. The facile and practical strategy has great potential for clinical application in fabricating functional polymer hybrid BHVs or other tissue-based cardiac biomaterials. STATEMENT OF SIGNIFICANCE: Bioprosthetic heart valves (BHVs) are widely used in valve replacements for severe heart valve disease, and clinical demand is increasing year over year. Unfortunately, the commercial BHVs, mainly cross-linked by glutaraldehyde, can serve for only 10-15 years because of calcification, thrombus, biological contamination, and difficulties in endothelialization. Many studies have been conducted to explore non-glutaraldehyde crosslinkers, but few can meet high requirements in all aspects. A new crosslinker, OX-Br, has been developed for BHVs. It can not only crosslink BHVs but also serve as a reactive site for in-situ ATRP polymerization and construct a bio-functionalization platform for subsequent modification. The proposed crosslinking and functionalization strategy synergistically achieves the high requirements for stability, biocompability, endothelialization, anti-calcification, and anti-biofouling propeties of BHVs.

Preparation of Supramolecular Miktoarm Star Copolymers with a Zinc Phthalocyanine Core through ATRP and RAFT Polymerization.

Topological polymers have attracted considerable attention owing to their unique chemical and physical properties. This study demonstrates the formation of novel supramolecular miktoarm star copolymers with a zinc phthalocyanine (ZnPc) core using metal-ligand coordination interactions. Various linear polymers with pyridyl end groups, poly(methyl methacrylate), poly(vinyl acetate) and poly(N-vinyl carbazole), are prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. This facilitates coordination to the ZnPc core of 4-armed star-shaped polystyrene prepared via atom-transfer radical polymerization (ATRP). Furthermore, the formation of a 1:1 complex of a ZnPc molecule and pyridyl group of the chain-transfer agent for RAFT is confirmed by absorption spectral studies and 1 H NMR spectroscopic analyses. The concept of supramolecular complexation can be extended to the preparation of AB4 -type supramolecular miktoarm star-shaped copolymers with functional cores.

Preparation of coumarin polymer grafted nanocellulose films to form high performance, photoresponsive barrier layers

AbstractHydrophobically modified cellulose is prepared in this research by conducting atom transfer radical polymerization (ATRP) of methacrylate substituted coumarin monomer on initiator grafted cellulose. The photocrosslinking of uniformly grafted coumarin on cellulose surface is applied to improve the water vapor barrier property of the film. The water vapor transmission rate (WVTR) of films prepared from modified cellulose with varying grafting density, grammage, and photocrosslinking time is studied. By increasing the amount of crosslinking within the grafted cellulose film, we succeeded in reducing WVTR. The WVTR is reduced from 160 to 20 g/m2/day using a sheet of 60 g/m2 after crosslinking. The effect of grafting density on WVTR is also analyzed to observe that the higher the grafting density, lower the WVTR of the sheet both before and after crosslinking. Furthermore, free ATRP polymerization (without cellulose) and polymerization using a sacrificial initiator of the monomer are conducted to estimate the dispersity of the polymer on cellulose. The monomer, free polymer and cellulose grafted polymers are analyzed for the composition, thermal, morphology, photoresponsive behavior, and polymerization quantification using NMR, FTIR, UV–Vis, TGA DSC, GPC, SEM, ICP‐MS. It is concluded that the inter and intramolecular photo dimerization of coumarin molecules forms a hydrophobic crosslinked hyper network in the polymer sheet, which improves its barrier property.

High‐efficient surface tailoring via reverse atom transfer radical polymerization and reversible addition‐fragmentation chain‐transfer polymerization in an aqueous system initiated by a monocenter redox pair

AbstractThe commonly used multi‐center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert‐butyl hydroperoxide groups and ascorbic acid (SiO2‐TBHP/AsAc) was applied to substitute the commonly used initiation method of R‐supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high‐efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X‐ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high‐efficient” surface tailoring of various materials.

High sensitive electrochemical methamphetamine detection in serum and urine via atom transfer radical polymerization signal amplification

Herein we designed a highly sensitive and selective biosensor for methamphetamine (METH) detection based on aptamer recognition probe and atom transfer radical polymerization (ATRP) signal amplification strategy. In this experiment, METH aptamer and its complementary DNA strand were first attached to the electrode surface. In the presence of METH, the prioritized conjugation between METH and the aptamer will take one strand of DNA from the double-stranded DNA, so that the third segment of azide-modified DNA could be successfully modified onto the electrode surface. Through click chemistry and ATRP polymerization, the monomers with ferrocene were polymerized into a long chain, and the signal was amplified, then high-sensitivity detection of METH can be carried out. The result showed that the sensor could detect METH as low as 17 fM, which is about two orders of magnitude lower than that by traditional METH detection methods. Moreover, when different concentrations of METH were added to serum and urine, the recovery rate of the biosensor was as high as 93%. Therefore, using nucleic acid aptamer as capture probe and ATRP as signal amplification strategy can provide a promising application platform for sensitive detection of low concentration toxicants.

Kinetics of MMA Atom Transfer Radical Polymerization Initiated by Reducing Agent in Stirred Batch Emulsion Reactor

AbstractAb initio emulsion atom transfer radical polymerization (ATRP) differs from regular emulsion polymerization because the kinetic and thermodynamic aspects of each process are very unlikely alike. This paper presents a kinetic analysis of activator generated by electron transfer (AGET) ATRP of methyl methacrylate (MMA) in a stirred emulsion reactor. The focus of the study is to assess the variation of the monomer content in the organic phase and the rate polymerization for different reaction temperatures, as well as the impact of surfactant content and stirring speed on latex stability. Poly(methyl methacrylate) (PMMA) polymer samples are analyzed by means of gravimetry, dynamic light scattering, gel permeation chromatography, and HNMR techniques to determine monomer conversion, polymer particle diameter, molecular weight distribution, and polymer molecular structure, respectively. The results show the production of PMMA of narrow polydispersity index (Ð) and low molar mass (Mn) for MMA conversion around 60% and detect two‐regions instead of a three‐regions trend of rate of polymerization (Rp) as conventional emulsion polymerization. The reaction rate increases during the nucleation stage and then flattens over an invariant trend which confirms a living feature of the AGET ATRP polymerization. The average number of radicals per latex particle (ñ) is also debated.

Radical Lifetimes in Atom Transfer Radical Polymerization: A Monte Carlo and Deterministic Investigation

Mean radical lifetimes and fluctuations in lifetime are shown to decrease with conversion and polydispersity index for atom transfer radical polymerization (ATRP) of both methyl methacrylate and styrene. In the first study of its kind, a comprehensive investigation of radical lifetimes in both ATRP and conventional free-radical polymerizations is reported using a kinetic Monte Carlo model. Quantile–quantile plots show the radical lifetimes to be exponentially distributed with equal mean and standard deviation. Radical lifetimes are shown to be thousands of times longer in conventional free-radical polymerization compared with ATRP. Reduced mean radical lifetimes and fluctuations offer a new perspective on the ATRP mechanism. Reduction in radical lifetime fluctuations ensures less variability in the number of monomer units added during the propagation steps and keeps the polydispersity index low. Deterministic models are used along with the kinetic Monte Carlo model to investigate several facets of these polymerization systems and are validated against experimental data.

Visualization of Atom Transfer Radical Polymerization by Aggregation-Induced Emission Technology.

Aggregation-induced emission (AIE) technology has been demonstrated to be a facile approach for in-situ monitoring atom transfer radical polymerization (ATRP). A series of tertraphenyl ethylene (TPE)-containing α-bromo compounds were synthesized and applied as ATRP initiators. The photoluminescent (PL) emission of the polymerization system is proved to be sensitive to the local viscosity owing to the AIE characteristics of TPE. Linear relationships between the resulting molecular weight Mn and PL intensity were observed in several polymerization systems with different monomers, indicating the variability of this technique. Compared to physical blending, the chemical bonding of the TPE group in the chain end has higher sensitivity and accuracy to the polymer segments and the surrounding environment. This work promoted the combination of the AIE technique and controlled living radical polymerization, and introduced such an optical research platform to the ATRP polymerization process.

Ultrasensitive aptamer fluorometric detection of IFN-γ by dual atom transfer radical polymerization amplification

Exploiting biological detection methods with high selectivity and sensitivity has been an urgent demand for low abundance biomolecules. Herein, an ultrasensitive aptamer fluorometric method of protein detection was fabricated via a sequential dual atom transfer radical polymerization (ATRP). For the first time, surface-initiated dual ATRP was utilized to make the fluorometric signal amplification for gamma-interferon (IFN-γ) protein assay. Two aptamers are used as protein probes, which can form a high stable and selective “aptamer/ protein/aptamer” sandwich structure. One aptamer probe is attached on superparamagnetic nanoparticle via surface self-assembled, the other one is linked with initiators of dual ATRP amplification by click chemistry formed triazole group. With large numbers of fluorescein-o-acrylate grown directly on a nanoparticle surface, a convenient “aptamer/protein/aptamer-polymer” supersandwich sensor was fabricated. Under optimal conditions, IFN-γ can be assayed with detection limit down to 0.178 fM in PBS buffer (equals to 1.072 ˣ103 IFN-γ molecules). Even in complex human serum, IFN-γ can also be detected with the limit of 1.54 fM, equals to 9.275 ˣ103 IFN-γ molecules. Results show a great potential in real ultrasensitive protein detection for its high selectivity, efficiency and stability. Besides, this proposed sensing method, which combines the advantages of superparamagnetic nanomaterial and chemically catalyzed surface-initiated dual ATRP polymerization, compared to the traditional signal amplify methods, is novel, more convenient, simpler and enzyme-free cascade amplification.

Grafting strategies for the synthesis of active DNase I polymer biohybrids

Protein polymer hybrids play an increasingly important role in therapeutics and biocatalysis. Synthesis of these biohybrids can be achieved by either the grafting-from or grafting-to strategy and are generally thought to be interchangeable. Therefore, when choosing between these two strategies the decision is usually based on polymer accessibility and purification preference. However, in this study, we demonstrated that the choice of the polymer ligation strategy played a significant role in the stability and bioactivity of the final hybrid. Our goal was to prepare a thermally stable DNase I polymer hybrid by utilizing either synthetic strategies. We found that the grafting-from strategy using reversible addition-fragmentation chain transfer polymerization (RAFT) or atom transfer radical polymerization (ATRP) yielded DNase I biohybrids with no activity. Control reactions were used to demonstrate inherent protein deactivation caused by the grafting-from conditions for either ATRP or RAFT polymerization. The grafting-to method yielded active and thermally stable DNase I biohybrids.

Synthesis of non-amphiphilic block copolymer with S-trityl-cysteine and pyrene units by ATRP polymerization: characterization and fluorescence study

A new diblock copolymer, 1-methylpyrene isobutyrate–poly(methyl methacrylate–block-N-acryloyl-S-trityl-cysteine)-Br (Py–PMMA–b-ATCys-Br), was synthesized by atom transfer radical polymerization (ATRP) of N-acryloyl-S-trityl-L-cysteine monomer (ATCys) with 1-methylpyrene isobutyrate–poly(methyl methacrylate)–Br as a macroinitiator. The diblock copolymer and its precursor were characterized by 1H and 13C NMR spectroscopy, fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), gel permeation chromatography (GPC), and glass transition temperatures (Tg) measurements. Fluorescence properties of the diblock copolymer were investigated using various quenching (Cu2+, Hg2+, Fe2+, Fe3+, Co2+, Ni2+ and Pb2+) in dimethylformamide solutions, the more efficient quenchers being the Cu2+, Hg2+, Fe2+, and Fe3+ ions. In addition, the effect of in situ photogenerated silver nanoparticles on the copolymer fluorescence was also investigated.

Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer.

A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

Grafting of a Stimuli Responsive Polymer on Nanolayered Coextruded PS/PCL Films by Surface Initiated Polymerization

A simple method of preparing stimuli‐responsive polystyrene (PS)/polycaprolactone (PCL) nanolayered films with by growing poly(N‐isopropylacrylamide) (PNIPAM) brush on the surface by surface‐initiated polymerization is reported. Atom transfer radical polymerization (ATRP) initiator with a benzophenone moiety is attached onto the surface by UV irradiation. After ATRP polymerization, PNIPAM brush films with varying thicknesses are produced. X‐ray photoelectron spectroscopy (XPS) confirms the successful deposition of initiator and grafting of the polymer. Moreover, the behavior of the brush film as a function of temperature is demonstrated by contact angle experiments. Photopatterning is also achieved by using a photomask and is confirmed by Fourier Transform Infrared (FTIR) imaging.image

A Synthetic and Multispectroscopic Speciation Analysis of Controlled Radical Polymerization Mediated by Amine–Bis(phenolate)iron Complexes

The mechanism of reversible-deactivation radical polymerization (RDRP) mediated by chloro-substituted amine–bis(phenolate)iron complexes was studied via a combination of Mossbauer, EPR, NMR, and online Vis/NIR spectroscopy. It was found that styrene polymerization operates via an atom-transfer radical polymerization (ATRP) mechanism when alkyl halide is present, whereas an interplay between ATRP and organometallic-mediated radical polymerization (OMRP) equilibria occurs during MMA polymerization. The preparation of the amine–bis(phenolate)iron(II) complex, [O2NN′]FeII, allowed polymerizations to be performed under an OMRP-only regime free of alkyl halide that yields dispersities as low as 1.29 for MMA polymerization.

Controlled synthesis of photosensitive graft copolymers with high azobenzene-chromophore loading densities in the main and side chains by combining ATRP and ADMET polymerization

Photosensitive graft copolymers containing azobenzene chromophores in the main and side chains were successfully synthesized by combining living atom transfer radical polymerization (ATRP) and acyclic diene metathesis (ADMET) chemistry based on the results of proper heterodifunctional inimer and azobenzene monomer design. The precise copolymer architectural features were manipulated by combining the macromonomer technique and the macroinitiator method. The as-prepared copolymer containing azobenzene chromophores in the main and side chains showed unique reversible isomerization processes, suggesting that the photoisomerization of azobenzene chromophores occured mainly in one of the two types of azobenzene groups in the main or side chains with similar probabilities due to their main and side-on structure.

Well-controlled atom transfer radical polymerizations of acrylates using recyclable niobium complex nanoparticle as photocatalyst under visible light irradiation

Niobium complex was successfully introduced into atom transfer radical polymerization (ATRP) system as a new kind of recyclable photocatalyst. The niobium complex acted as photocatalyst that could be activated by the photoredox reaction under visible light irradiation and ethyl 2-bromoisobutyrate (EBiB) was used as initiator. Successful ATRP polymerizations of acrylates were realized. The well-defined polymers with controlled molecular weight and narrow polydispersity index (PDI) (Mw/Mn = 1.16–1.30) could be achieved when the feed ratio of photocatalyst to EBiB was controlled properly. It was also found that the polymerization is highly responsive to light initiation, therefore, the polymerization can be controlled on or off at ease. In addition, the photocatalyst can be recycled and reused to initiate the polymerization for many times without significant compromisation of the initiation efficiency.

A combining signal amplification of atom transfer radical polymerization and redox polymerization for visual biomolecules detection

A novel combination of atom transfer radical polymerization (ATRP) and redox polymerization is here used to allow instrument-free visualization of special biomolecules for which dynamic polymer growth is used in signal amplification. In this method, the convenient and mild redox polymerization-assisted amplification with cerium ammonium (IV) nitrate as oxidant at the second stage was achieved by directly using the hydroxyl groups from poly(hydroxyethyl methacrylate) (PHEMA) synthesized via ATRP at the first stage. The brushed polymers poly(hydroxylethyl methacrylate)-branched-poly (acrylamide) (PHEMA-branched-PAM) prepared by successive ATRP and redox polymerization in situ drastically grew up at the detected biomolecules spot to improve the visibility of biomolecule and simplify the detection procedure. With the proposed strategy, the signal amplification of streptavidin (SA) as model detected biomolecule was investigated on two different substrates such as silicon wafer and gold, respectively. As a result, detection limit of SA was demonstrated on the gold substrates where binding of 1.0 ng/mL SA was differentiable from the background using ellipsometry. Moreover, binding of 0.5 nmol/L DNA led to visually distinguishable spots on the gold surface under mild condition. The proposed method exhibited an efficient amplification performance for molecules detection, and paved a new way for visual diagnosis of biomolecules. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2791–2799