Parent Copolymer Research Articles

Fluorescein Isothiocyanate Labelled PCL‐PEG‐PCL Copolymer as Delivery System of Capsaicin

AbstractAmphiphilic block copolymers, made of biocompatible polycaprolactone (PCL) and polyethylene glycol (PEG), due to their ability to self‐assemble in water into nanoscopic micelles, have been largely exploited for drug delivery systems (DDS). This study introduces a novel approach by synthesizing a fluorescein isothiocyanate FITC‐labelled PCL‐PEG‐PCL triblock copolymer, with the aim to develop a drug delivery system for natural bioactive. As a proof of concept, the FITC‐labelled PCL‐PEG‐PCL copolymer is applied for the preparation of micelles encapsulating into the core capsaicin (CP), a pungent alkaloid found in chili peppers with diverse therapeutic applications. Challenges associated with CP′s solubility, bioavailability, and stability are addressed using this DDS. Comprehensive characterization of FITC‐labelled copolymer is conducted using a range of analytical techniques, including nuclear magnetic resonance (NMR), dynamic light scattering (DLS), high‐performance liquid chromatography (HPLC), Fourier‐transform infrared spectroscopy (FTIR), fluorescence, and confocal laser scanning microscopy (CLSM). Key properties such as critical micelle concentration, CP loading, and release behavior are thoroughly investigated and compared with the characteristics of the unlabeled parent copolymer. This research pioneers the investigation of PCL‐PEG‐PCL triblock copolymers for CP delivery, along with the use of FITC‐labelled variants, opening new avenues for research in drug delivery and nanomedicine.

Well‐Defined Tetrazole‐Functional Copolymers as Macromolecular Ligands for Luminescent Ir(III) and Re(I) Metal Species: Synthesis, Photophysical Properties and Application in Bioimaging

AbstractWell‐defined copolymers containing luminescent iridium and hybrid iridium/rhenium fragments are prepared utilizing parent poly(n‐butyl acrylamide‐co‐N‐(1H‐tetrazol‐5‐yl) acrylamide) as macromolecular chelating species. The parent (co)polymers are prepared via the modification of a precursor poly(pentafluorophenyl acrylate) (polyPFPA) homopolymer, prepared by reversible addition‐fragmentation chain transfer polymerization, with n‐butylamine and 5‐aminotetrazole. Reaction of the parent copolymers with [Ir2(ppy)4(μ−Cl2)] (ppy = 2‐phenylpyridine) yields modified copolymers containing the Ir(ppy)2 fragment as a pendent group. Attachment of the Ir species is confirmed by a combination of photophysical studies, UV–Vis spectroscopy, and visually under irradiation with UV light. Importantly, it is demonstrated that the chelation of the Ir(ppy)2 fragment to a polymeric scaffold does not impact the fundamental photophysical properties of the Ir species. Attachment of a second luminescent metal species, Re(CO)3(phen) (phen = 1,10‐phenanthroline), gives hybrid materials containing Re(I) and Ir(III). The photophysical properties of these hybrid materials are consistent with the presence of both metal species and indicate the occurrence of energy transfer phenomena from the polymer‐bound Ir to Re metal centers. Finally, it is demonstrated that the Ir modified polymers and the Ir/Re hybrid materials offer potential in tissue imaging applications with scope to tune both luminescent properties and biological specificity as evidenced from preliminary brain tissue staining experiments.

Self-assembly of Li single-ion-conducting block copolymers for improved conductivity and viscoelastic properties

Single-ion conducting polyelectrolytes (SICPs) with mobile Li cation have recently gathered significant attention as an “ideal” electrolyte for safe solid-state rechargeable lithium batteries, because they eliminate salt concentration gradients and concentration overpotentials, allowing transference number (tLi+) values close to unity. In this work, a series of single ion conducting block copolymers, namely [(LiM)n-r-(PEGM)m]-b-(PhEtM)k (A-b-B), is synthesized via reversible addition-fragmentation chain transfer (RAFT) copolymerization of 1-[3-(methacryloyloxy)propylsulfonyl]-(trifluoromethanesulfonyl)imide (LiM), poly(ethylene glycol)methyl ether methacrylate (PEGM) and 2-phenylethyl methacrylate (PhEtM) with controlled PEGM:LiM ratio, molecular weights (Mn = 25.8 ÷ 85.9 kDa) and narrow polydispersity (Mw/Mn = 1.12 ÷ 1.21). The bulk ionic conductivity, solid-state morphology and thermal properties of block copolymers are studied as a function of their composition. Block copolymers having molecular weights in the range of 46 ÷ 63 kDa and any ratio of PEGM:LiM (from 3:1 to 7:1) tend to evolve in quasi-hexagonally-packed cylinders, while copolymers with higher molecular weights (Mn > 74 kDa) and the ratio of PEGM:LiM = 5:1 and MA/MB ≤ 2.0 show lamellar phase separation. The lamellar long-range ordering in poly[(LiM17-r-PEGM86)-b-PhEtM131] and poly[(LiM17-r-PEGM86)-b-PhEtM194] results not only in the improved viscoelastic (mechanical) performance compared to parent copolymer poly[LiM17-r-PEGM86] (complex viscosity = 2.5 × 108 mPa s and 8.7 × 104 mPa s at 25 °C, respectively), but also in the demonstration of sufficiently high ionic conductivity despite the decrease in Li+ amount (σ = 3.8 × 10−7 and 4.1 × 10−7 S/cm at 25 °C, correspondingly). The selected poly[(LiM17-r-PEGM86)-b-PhEtM131] further shows high tLi+ (0.96 at 70 °C) and wide electrochemical stability (4.4 V vs. Li+/Li at 70 °C), which results in reversible and stable cycling at high specific capacities (up to 150 and 118 mAh g−1 at C/20 and C/5 rates, respectively) when assembled in lab-scale truly-solid-state Li metal cells with Li/copolymer/LiFePO4 configuration.

Investigation of structural and electrical properties of nickel chloride doped pyrrole aniline copolymer

Chemical oxidative copolymerization has been employed for the synthesis of pyrrole and aniline copolymer at room temperature, in equal proportion. The prepared copolymer was undoped and then further doped with 10% NiCl2 using immersion method. Structural characterization of self-doped, undoped and doped copolymer was performed using FTIR, WAXD and SEM techniques. Results reveal the modifications in the original copolymer structure accompanied by various shifts in the band positions and appearance of the new bands in IR spectrum due to doping. The X-ray diffractograms reveals presence of modified and shifted peaks indicating the changes due to doping. The scanning electron micrographs of undoped and doped copolymers show globular structure due to doping when compared with that of the parent copolymer. In addition, using two probe methods the dc electrical conductivity of these samples was recorded in the temperature range of 313 K to 673 K, at a field of 27 V/cm. The log σ Versus 1/T plots of the self-doped and doped samples display the transformation of the sample at a given temperature from metallic to semi conducting and vice versa. The I-V plots for the self-doped and doped copolymer has also been plotted at a fixed temperature of 323 K which shows linear behavior of the samples. The conductivity measurements show reduction in conductivity of prepared samples thereby suggesting the presence of bipolarons as charge carrier. The results confirm the effect of doping on the copolymer properties.

Physicochemical Properties and Biological Performance of Polymethacrylate Based Gene Delivery Vector Systems: Influence of Amino Functionalities.

Physicochemical characteristics and biological performance of polyplexes based on two identical copolymers bearing tertiary amino or quaternary ammonium groups are evaluated and compared. Poly(2-(dimethylamino)ethyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate) block copolymer (PDMAEMA-b-POEGMA) is synthesized by reversible addition fragmentation chain transfer polymerization. The tertiary amines of PDMAEMA are converted to quaternary ammonium groups by quaternization with methyl iodide. The two copolymers spontaneously formed well-defined polyplexes with DNA. The size, zeta potential, molar mass, aggregation number, and morphology of the polyplex particles are determined. The parent PDMAEMA-b-POEGMA exhibits larger buffering capacity, whereas the corresponding quaternized copolymer (QPDMAEMA-b-POEGMA) displays stronger binding affinity to DNA, yielding invariably larger in size and molar mass particles bearing greater number of DNA molecules per particle. Experiments revealed that QPDMAEMA-b-POEGMA is more effective in transfecting pEGFP-N1 than the parent copolymer, attributed to the larger size, molar mass, and DNA cargo, as well as to the effective cellular traffic, which dominated over the enhanced ability for endo-lysosomal escape of PDMAEMA-b-POEGMA.

Rapid Generation of Block Copolymer Libraries Using Automated Chromatographic Separation.

A versatile and scalable strategy is reported for the rapid generation of block copolymer libraries spanning a wide range of compositions starting from a single parent copolymer. This strategy employs automated and operationally simple chromatographic separation that is demonstrated to be applicable to a variety of block copolymer chemistries on multigram scales with excellent mass recovery. The corresponding phase diagrams exhibit increased compositional resolution compared to those traditionally constructed via multiple, individual block copolymer syntheses. Increased uniformity and lower dispersity of the chromatographic libraries lead to differences in the location of order-order transitions and observable morphologies, highlighting the influence of dispersity on the self-assembly of block copolymers. Significantly, this separation technique greatly simplifies the exploration of block copolymer phase space across a range of compositions, monomer pairs, and molecular weights (up to 50000 amu), producing materials with increased control and homogeneity when compared to conventional strategies.

Rheology of sodium and zinc ionomers: Effects of neutralization and valency

Using a parallel-plate rheometer equipped with a partitioned plate and the Sentmanat extensional rheometer fixture, a full rheological characterization of several commercial ionomers (sodium and zinc) and their corresponding parent copolymers has been carried out. Particular emphasis has been placed on the distribution of the relaxation times to identify the characteristic times, such as reptation, Rouse, and lifetime of associations that are associated with entanglements, ionic and hydrogen bonding associations. As such, scaling laws have been used to calculate the order of magnitude of these characteristic times that are important parameters to gain a better understanding of their rheological behavior. To study the effects of ionic reversible associations, the commercial ionomers were completely un-neutralized and their rheological behavior was compared directly with their associative counterparts. The rheological comparison included the linear viscoelastic moduli, the damping function, and extensional rheology, demonstrating the significant effects of ionic interactions. Moreover, the rheological properties of sodium and zinc ionomers are also compared addressing the effect of valency of ions (Na+ vs Zn++).

Relation between the Electronic Properties of Regioregular Donor-Acceptor Terpolymers and Their Binary Copolymers.

By analyzing the optical band gap and energy levels of seven different regioregular terpolymers in which two different electron-rich donor moieties are alternating with a common electron-deficient acceptor unit along the backbone, we establish a direct correlation with the properties of the corresponding binary copolymers in which one donor and one acceptor are combined. For this study, we use diketopyrrolopyrrole as the common acceptor and different π-conjugated aromatic oligomers as donors. We find that the optical band gap and frontier orbital energies of the terpolymers are the arithmetic average of those of the parent copolymers with remarkable accuracy. The same relationship is also found for the open-circuit voltage of the bulk heterojunction solar cells made with the ter- and copolymers in combination with [6,6]-phenyl-C71-butyric acid methyl ester. Comparison of these findings with data in the literature suggests that this is a universal rule that can be used as a tool when designing new π-conjugated polymers. The experimental results are supported by a semiempirical quantum chemical model that accurately describes the energy levels of the terpolymers after parametrization on the energy levels of the copolymers and also provides a theoretical explanation for the observed arithmetic relations.

Synthesis and Properties of Thermotropic Poly(oxybenzoate-co-oxynaphthoate) Copolyester Modified by a Third AB Type Monomer

The synthesis and modification of high performance thermotropic liquid crystal polyesters (TLCP) are still being investigated due to their excellent properties. In this study modification of poly(oxybenzoate-co-oxynaphthoate) (P-HBA/HNA), a random copolymer of 4-hydroxybenzoic acid (HBA) and 6-hydroxy-2-naphthoic acid (HNA), by 5 mol% of one of three AB type monomers (AB type monomers are those who have hydroxy and carboxylic end groups), vanillic acid (VA), 4-hydroxyphenylacetic acid (HPA) and 4-hydroxycinnamic acid (HCA), was conducted. The influence of the AB type third monomer on the liquid crystal properties, melting behavior, thermal stability, microstructure and fiber morphology of the resulting modified terpolyesters was comparatively studied relative to the parent copolymer. When 5 mol% of the HBA units were replaced, the resulting terpolyesters had much lower melting temperatures and could be easily melt processed, while the modified terpolyesters exhibited higher melting and glass transition temperatures when 5 mol% of the HNA units were replaced. Weaker melting peaks and larger melting ranges were observed for the modified terpolyesters, attributed to the existence of nonperiodic layer crystallites caused by the modifiers. The obtained terpolyesters showed good thermal stability and could be melt processed in a broad nematic phase temperature region. The molecular chain packing of the modified terpolyesters was almost destroyed by the third AB type reactants. Fibers prepared from the resulting terpolyesters exhibited well developed fibrillar structure and higher orientation factors, indicating that modification of the P-HBA/HNA by using the AB type monomers to improve its properties would be useful.

Role of molecular weight and hydrophobicity of amphiphilic tri-block copolymers in temperature-dependent co-micellization process and drug solubility

The binary P123 + F108, + F98, + F88, + F68, + F87 and + P84 systems were used to systematically explore the effect of molecular weight and hydrophobicity of Pluronic on the tendency of cooperative binding between parent copolymers and solubility of drug (ibuprofen) in these mixed Pluronic systems. Temperature-dependent co-micellization process in these systems was carefully investigated by using high sensitivity differential scanning calorimeter (HSDSC), dynamic light scattering (DLS) and small angle X-ray scattering (SAXS). All the HSDSC thermograms for these systems consistently exhibit two endothermic (micellization) peaks apart by at least 13.3 °C. It was evidenced that micelles are mainly formed by P123, the copolymer with a lower critical micelle temperature (CMT), at low temperatures. Raising temperature would dehydrate the other Pluronic with a higher CMT to be integrated into the neat P123 micelles developed at low temperatures. When the temperature is further increased beyond the second endothermic peak, the mixed micelles with a two-shell structure and characteristic corona lengths of their parent copolymers are observed to prove the existence of cooperative binding between parent copolymers. All the binary mixed Pluronic systems used in this study exhibit cooperative binding to form unimodal distribution of mixed micelles, except the P123 + F68 system. The SAXS results show that P123 + F68 system at 65 °C exhibits bimodal distribution of aggregates with coexisting of neat F68 micelles (65% in number) and P123 + F68 mixed micelles (35% in number). It is interesting to find out that P123 and F68 with distinct polypropylene oxide (PPO) moieties (i.e., a difference of 37 PO units) would exhibit very weak cooperative binding to partially form mixed micelles. Addition of ibuprofen in the P123 + F68 system would substantially enhance the cooperative binding between P123 and F68 to form bimodal distribution of aggregates with coexisting of neat F68 micelles (drops down to 30% in number) and P123 + F68 mixed micelles (increases up to 70% in number). For the systems with ibuprofen incorporated, SAXS results demonstrate that the drug is mainly encapsulated in the core of neat micelles developed at low temperatures. The solubility of ibuprofen in the 0.5 wt% P123 + 0.368 wt% P84 system is as high as 2.62 mg/ml, which is 114 times more than that in pure water at 37 °C.

Insight into functionalized DMN-co-GMA copolymers

Suspension–emulsion polymerization was applied to obtain porous microspheres of 2,3-epoxypropyl methacrylate (GMA) cross-linked with 1,4-di(methacryloyloxymethyl)-naphthalene (DMN). In the next step, the porous methacrylate network was modified by subsequent reaction with diethylenetriamine. The newly obtained functionalized material was characterized in detail. After the process of modification, a drop in the value of specific surface area of the functionalized copolymers was observed. Their thermal behavior was monitored by TG/DSC/FTIR methods in inert and oxidative conditions. The reaction with diethylenetriamine resulted in the decrease in thermal resistance of the obtained porous microspheres. Initial decomposition temperatures (IDTs) established in helium atmosphere fell down from 258–269 °C for parent copolymers to 206–220 °C for modified ones. The same situation was observed in synthetic air atmosphere. IDTs decreased from 249–269 to 207–230 °C. Moreover, the thermal decomposition of the functionalized microspheres exhibited multistage decomposition patterns different from parent GMA-DMN copolymers.

Nonlinear rheology of poly(ethylene-co-methacrylic acid) ionomers

Using a parallel-plate rheometer equipped with a partitioned plate, and the Sentmanat extensional rheometer fixture, a full rheological characterization of several commercial ionomers and their corresponding parent copolymers has been carried out. Particular emphasis has been placed on the distribution of the relaxation times to identify the characteristic times, such as reptation, Rouse, and sticky-Rouse, that are associated with the characteristic lifetime of the ionic and hydrogen bonding associations. As such, scaling laws have been used to calculate the order of magnitude of the lifetimes of associations and the association energy that are important parameters to gain a better understanding of their rheological behavior. To study the effects of ionic associations, the commercial ionomers were completely unneutralized and their rheological behavior was compared directly with their associative counterparts. The rheological comparison included the linear viscoelastic moduli, the damping function, steady shear, and extensional rheology demonstrating the significant effects of ionic interactions.

Preparation of photodynamic P(MMA-co-MAA) composite nanofibers doped with MMT: A facile method for increasing antimicrobial efficiency

We report the preparation of photodynamic materials from electrospun nanofibers of P(MMA-co-MAA) co-polymer that were doped with montmorillonite (MMT), and further functionalized with the cationic photosensitizer methylene blue (MB). The resultant composite nanofibers were characterized by spectroscopic (infrared, UV − vis, fluorescence) and physical (SEM/TEM, gravimetric) methods. Addition of MMT (0–6 wt%) in the electrospinning process increased the adsorption of the methylene blue photosensitizer from 21.5 mg (67.1 μmol)/g P(MMA-co-MAA) parent copolymer to 30.0 mg (93.8 μmol)/g P(MMA-co-MAA)/MMT-6 composite nanofibers. The MB-decorated P(MMA-co-MAA)/MMT-6 composite nanofibers showed a 99.997% (4.8 log units) and 97% (1.8 log units) reduction in CFU/mL against Staphylococcus aureus (ATCC-6538) and Escherichia coli strain 8099, respectively, after visible light illumination (LED lamp, 30 min, 35 ± 5 mW/cm2), demonstrating that the increased photosensitizer loading attributable to MMT doping led to a 1–2 log unit increase in photodynamic inactivation efficacy over the non-doped MB-decorated P(MMA-co-MAA) parent copolymer (99.9% and 84% reduction for S. aureus and E. coli, respectively). The results demonstrate that MMT and similar additives may be a universal method for increasing the adsorption capacity of cationic photosensitizers in electrospun nanofibers, thereby generating materials with improved photodynamic inactivation efficacy without significantly changing the fiber morphology, cost, or ease of production.

Synergistic Effect of Binary Mixed-Pluronic Systems on Temperature Dependent Self-assembly Process and Drug Solubility.

Mixed Pluronic micelles from very hydrophobic and very hydrophilic copolymers were selected to scrutinize the synergistic effect on the self-assembly process as well as the solubilization capacity of ibuprofen. The tendency of mixing behavior between parent copolymers was systematically examined from two perspectives: different block chain lengths at same hydrophilicity (L92 + F108, +F98, +F88, and +F68), as well as various hydrophobicities at the same PPO moiety (L92 + F88, +F87, and +P84). Temperature-dependent micellization in these binary systems was clearly inspected by the combined use of high sensitivity differential scanning calorimeter (HSDSC) and dynamic light scattering (DLS). Changes in heat capacity and size of aggregates at different temperatures during the whole micellization process were simultaneously observed and examined. While distinction of block chain length between parent copolymers increases, the monodispersity of the binary Pluronic systems decreases. However, parent copolymers with distinct PPO moieties do not affirmatively lead to non-cooperative binding, such as the L92 + P84 system. The addition of ibuprofen promotes micellization as well as stabilizes aggregates in the solution. The partial replacement of the hydrophilic Pluronic by a more hydrophobic Pluronic L92 would increase the total hydrophobicity of mixed Pluronics used in the system to substantially enhance the solubility of ibuprofen. The solubility of ibuprofen in the 0.5 wt % L92 + 0.368 wt % P84 system is as high as 4.29 mg/mL, which is 1.4 times more than that of the 0.868 wt % P84 system and 147 times more than that in pure water at 37 °C.

Inducing hardening and healability in poly(ethylene-co-acrylic acid) via blending with complementary low molecular weight additives.

The design and synthesis of low molecular weight additives based on self-assembling nitroarylurea units, and their compatibility with poly(ethylene-co-acrylic acid) copolymers are reported. The self-assembly properties of the low molecular weight additives have been demonstrated in a series of gelation studies. Upon blending at low percentage weights (≤5%) with poly(ethylene-co-acrylic acid) the additives were capable of increasing the stress and strain to failure when compared to the parent copolymer. By varying the percentage weight of the additive as well as the type of additive the mechanical properties of poly(ethylene-co-acrylic acid) could be tailored. Finally, the healability characteristics of the blends were improved when compared to the original polymer via the introduction of a supramolecular ‘network within a network’.

Intramolecular Quaternization as Folding Strategy for the Synthesis of Catalytically Active Imidazolium-Based Single Chain Nanoparticles.

A novel synthetic strategy to single chain nanoparticles (SCNP) based on a previously unexplored intramolecular reaction as a means to autonomously fold a parent copolymer precursor is reported. The latter is a statistical styrenic-type copolymer synthesized by RAFT polymerization and is composed of four different comonomer units, including styrene, grafted poly(ethylene oxide) chains, and antagonist benzimidazol- and chlorobenzyl-based units. The two latter functions are reacted together by a quaternization reaction to spark the folding process, creating imidazolium-based cross-link points. Formation of SCNP with a hydrodynamic diameter <10 nm is established by a combination of different characterization techniques. A subsequent metathesis step for exchanging chloride anions by acetate ones of imidazolium moieties enables a use of SCNP for the organocatalyzed benzoin condensation, thanks to the ability of imidazolium acetate to generate SCNP-supported N-heterocyclic carbenes as organocatalysts.

Orthogonal thiol-ene 'click' reactions: a powerful combination for fabrication and functionalization of patterned hydrogels.

A combination of 'orthogonal' thiol-ene 'click' reactions is utilized for fabrication and functionalization of micro-patterned hydrogels. A furan-protected maleimide-containing parent copolymer is partially activated via the retro Diels-Alder reaction to obtain an 'orthogonally' functionalizable copolymer, where the different functional groups can be exploited for multi-functionalization or fabrication of functional hydrogels using combination of the nucleophilic and radical thiol-ene reactions.

Benzothiadiazole-pyrrolo[3,4-b]dithieno[2,3-f:3′,2′-h]quinoxalindione-based random terpolymer incorporating strong and weak electron accepting [1,2,5]thiadiazolo[3,4g]quinoxalinefor polymer solar cells

We report the synthesis of a D-A random terpolymer denoted as P2 consists of one thiophene donor unit and three acceptor benzothiadiazole (BT), pyrrolodithienoquinoxalinedione (PDQD) and thiadiazoloquinoxaline (TDQ) units by Stille-coupling reaction and investigated its optical and electrochemical properties. We have compared its properties with the parent copolymer P1. The P2 exhibits bandgap of about 1.18 eV which is lower than that of P1 (1.50 eV), indicating strength of accepting units controls both the optical and electrochemical bandgap. We have used terpolymer P2 as electron donor along with [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) as electron acceptor for the fabrication of solution processed bulk heterojunction polymer solar cells (PSCs). PSC based on an optimized P2:PC71BM (1:2 by weight) active layer processed with 3v % DIO/DCB solution, displayed a power conversion efficiency (PCE) of 7.22%, which is higher than that for P1 based polymer solar cell (PCE = 6.56%) processed under same conditions. The higher value of PCE for P2:PC71BM may be related to more favorable phase separated morphology of active layer as compared to P1:PC71BM, beneficial for the exciton dissociation and charge transport, as evidenced from the larger hole mobility.

Radical‐medicated end‐group transformation of amphiphilic methacrylate random copolymers for modulation of antimicrobial and hemolytic activities

ABSTRACTThis work describes synthesis of antimicrobial methacrylate copolymers by reversible addition‐fragmentation chain transfer (RAFT) polymerization and examines the versatility of this approach for improving chemical optimization to create potent, non‐toxic antimicrobial polymers. Specifically, this study focuses on the radical‐mediated transformation of end group of antimicrobial peptide‐mimetic polymer. RAFT polymerization using 2‐cyano‐2‐yl‐dithiobenzoate provided a statistical methacrylate copolymer consisting of aminobutyl and ethyl groups in the side chains. The following radical‐mediated modification using free radical initiators successfully transformed the ω‐end group of parent copolymer from dithiobenzoate to a cyanoisobutyl or aminoethyl cyanopentanoate group without any significant changes to the polymer molecular weight. In general, the parent polymer and variants showed a broad spectrum of activity against a panel of bacteria, but low hemolytic activity against human red blood cells. The parent copolymer with the dithiobenzoate end‐group showed highest antimicrobial and hemolytic activities as compared with other copolymers. The copolymers caused membrane depolarization in Staphylococcus aureus, while the ability of copolymers for membrane disruption is not dependent on the end‐group structures. The synthetic route reported in this study will be useful for further study of the role of polymer end‐groups in the antimicrobial activity of copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 304–312

Pyrene functionalized side chain alanine and histidine containing copolyacrylates prepared by free radical copolymerization

ABSTRACTAn optically active copolyacrylate, poly(N‐acryloyl‐L‐alanine‐co‐N‐acryloyl‐L‐histidine), is prepared by classical radical copolymerization of N‐acryloyl‐L‐alanine and N‐acryloyl‐L‐histidine, and further chemically modified with 1‐pyrene‐methanol. The structures of the synthesized compounds are confirmed by spectral analysis (FTIR, 1H/13C‐NMR, UV, fluorescence spectroscopy), thermal methods, and molecular weight measurements. Also, their optical activity is studied using circular dichroism (CD) spectroscopy and optical rotation measurements. The specific rotation values reveal that the direction of rotation of the parent copolymer is dictated by the monomer containing L‐alanine. CD data suggest negative and positive Cotton effects regarding the monomers with amino acids. In the case of the unmodified copolymer it is noted the changes of ellipticity values with increasing pH while the random‐coil conformation is preserved, which makes it suitable as a pH‐responsive system. Photochemical and photophysical investigations reveal that the pyrene‐functionalized chiroptical copolyacrylate can be used as a fluorescent chemosensor for the detection of nitro‐derivatives in organic media. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44457.