The flavonoid‐based macromolecule initiator was prepared for the first time by the transesterification reaction of naringin with 2‐bromoisobutyryl bromide. In accordance with the “grafting from” methodology, a naringin‐based copolymer brush with a polar naringenine‐7‐rhamnosidoglucoside core and an amphiphilic poly(methyl methacrylate)‐block‐poly(N‐isopropylacrylamide) (PMMA‐b‐PNIPAM) side chains was synthesized for the first time via a simplified electrochemically mediated ATRP (seATRP), utilizing only 40 ppm of catalytic complex. The rate of the polymerizations was controlled by applying optimal potential or current values during preparative electrolysis to prevent the possibility of intermolecular coupling of the growing polymer brushes. Naturally derived polymer brushes showed narrow molecular weight distributions (Đ = 1.06−1.08). 1H NMR spectral results confirm the formation of citrus‐based polymer brushes. These new naringin‐based polymer materials may find biomedical applications as thermo‐sensitive drug delivery systems, membranes, and biologically active thin films in tissue engineering. 相似文献
D ‐/L ‐Peptides such as gramicidin A (gA) adopt unique dimeric β‐helical structures of different topologies. To overcome their conformational promiscuity and enrich individual components, a dynamic combinatorial approach assisted by thiol tags was developed. This method led to identification of the preferential formation of antiparallel dimers under a broad range of conditions, which was independent of peptide side‐chain polarity. Exclusive formation of an antiparallel cyclic dimer was achieved in the presence of cesium ions. 相似文献
We report the synthesis of monomers for atom‐transfer radical polymerization (ATRP) and a reversible addition‐fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT‐containing polymers are suitable for rapid amide‐forming ligations for both post‐polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star‐shaped block copolymers. In addition, we applied post‐polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT‐containing copolymer. Cellular assays revealed that the polymer–antibiotic conjugate is biocompatible and provides efficient light‐controlled release of the antibiotic on demand. 相似文献
The novel hydrophobic coating material was received for the first time by a two‐step synthetic route. Firstly, the 15‐functional brominated macroinitiator was prepared by the esterification methodology. Next step covers synthesis of star‐like polymers by poly(n‐butyl acrylate) (PBA) arms polymerization via three low‐ppm atom transfer radical polymerization (ATRP) approaches including application of copper and silver wire in SARA and ARGET ATRP, respectively, as driving forces in redox cycle of catalyst, and an external stimulus in the form of electric current (seATRP) as the third approach in copper(II) regeneration system. As expected, the electrochemically mediated technique allows synthesis of tannic acid‐inspired coating polymers in precisely controlled manner during the entire polymerization process, proved by linear first‐order kinetics plot in contrast to above‐mentioned methods, low dispersity (Ð = 1.18) of star‐shaped polymers, and high efficiency of initiation (?i = 81%) determined after detaching of polymers side arms. Macromolecules received by all low‐ppm ATRP solutions were characterized by preserved chain‐end functionality (theoretical dead chain fraction; DCFtheo <1%). Adhesive and hydrophobic properties of received polymer materials were investigated by contact angles (θ) and free surface energy (FSE) calculations. Prepared polymer films besides excellent hydrophobic properties have great potential as a self‐healing solution. 相似文献
Low‐bandgap conjugated copolymers based on a donor–acceptor structure have been synthesised via palladium‐complex catalysed direct arylation polymerisation. Initially, we report the optimisation of the synthesis of poly(cyclopentadithiophene‐alt‐benzothiadiazole) (PCPDTBT) formed between cyclopentadithiophene and dibromobenzothiadiazole units. The polymerisation condition has been optimised, which affords high‐molecular‐weight polymers of up to Mn = 70 k using N‐methylpyrrolidone as a solvent. The polymers are used to fabricate organic photovoltaic devices and the best performing PCPDTBT device exhibits a moderate improvement over devices fabricated using the related polymer via Suzuki coupling. Similar polymerisation conditions have also been applied for other monomer units. 相似文献
In Alzheimer’s disease, amyloid‐β (Aβ) peptides aggregate into extracellular fibrillar deposits. Although these deposits may not be the prime cause of the neurodegeneration that characterizes this disease, inhibition or dissolution of amyloid fibril formation by Aβ peptides is likely to affect its development. ThT fluorescence measurements and AFM images showed that the natural antibiotic gramicidin S significantly inhibited Aβ amyloid formation in vitro and could dissolve amyloids that had formed in the absence of the antibiotic. In silico docking suggested that gramicidin S, a cyclic decapeptide that adopts a β‐sheet conformation, binds to the Aβ peptide hairpin‐stacked fibril through β‐sheet interactions. This may explain why gramicidin S reduces fibril formation. Analogues of gramicidin S were also tested. An analogue with a potency that was four‐times higher than that of the natural product was identified. 相似文献
Summary: A novel hydroxyl‐functionalised initiator for atom transfer radical polymerisation (ATRP) was synthesised by esterification reaction of a non‐reducing sugar, meso‐inositol. Due to steric hindrance, one of the six hydroxyl groups present in the sugar was not derivatised to the corresponding 2‐bromoisobutyrate. The macroinitiator was used in ambient temperature ATRP of a hydrophobic monomer, methyl methacrylate (MMA) and a hydrophilic monomer, oligoethylene glycol methacrylate (OEGMA) using tri(ethylene glycol) monomethyl ether (TEGMME) as the polymerisation solvent and CuCl/CuCl2/PMDETA as the catalytic system. Under these conditions, polymerisation proceeded on to high conversion while maintaining low polydispersity giving well‐defined five‐arm star polymers. Hydrolysis under basic conditions was carried out to deduce the number of linear chains that were attached to the sugar.
Potentiometric Ag+ sensors were prepared by galvanostatic electropolymerization of 3,4‐ethylenedioxythiophene (EDOT) and pyrrole (Py) on glassy carbon electrodes by using sulfonated calixarenes as doping ions. Poly(3,4‐ethylenedioxythiophene) (PEDOT) and polypyrrole (PPy) doped with p‐sulfonic calix[4]arene (C4S), p‐sulfonic calix[6]arene (C6S) and p‐sulfonic calix[8]arene (C8S) were compared. PEDOT and PPy doped with poly(styrene sulfonate) (PSS) were also included for comparison. The analytical performance of the conducting polymer‐based Ag+ sensors was studied by potentiometric measurements. All conducting polymer and dopant combinations showed sensitivity and selectivity to Ag+ compared to several alkali, alkaline‐earth, and transition‐metal cations. The type of the conducting polymer used for the fabrication of the electrodes was found to have a more significant effect on the selectivity of the electrodes to Ag+ than the ring size of the sulfonated calixarenes used as dopants. Selected conducting polymer‐based sensors were studied by cyclic voltammetry (CV) and energy dispersive analysis of X‐rays (EDAX) measurements. Results from the EDAX measurements show that both PEDOT‐ and PPy‐based membranes accumulate silver. 相似文献
Summary: The communication provides a novel and alternative route to generate chemically tethered binary polymer‐brush pattern through two‐step surface‐initiated atomic‐transfer radical polymerization (SI‐ATRP). Polymer brush‐1 was prepared by SI‐ATRP, passivated by a reaction with NaN3, and etched with UV irradiation through a transmission electron microscopy grid to create exposed sites for the subsequently attached initiator on which polymer brush‐2 was grown.
Schematic representation of the resultant binary polymer brush patterns. 相似文献