Archive for the ‘Paper of the Week’ Category

Paper of the week:Roll-to-roll processable thermally reactive copolymers for polymer solar cells

Graphical abstract: Rapid flash annealing of thermally reactive copolymers in a roll-to-roll process for polymer solar cells

Light induced thermocleaving of a thermally reactive copolymer based on dithienylthiazolo[5,4-d]thiazole (DTZ) and silolodithiophene (SDT) in contact with the heat sensitive substrate polyethyleneterphthalate (PET) was effectively demonstrated with the use of high intensity pulsed light, delivered by a commercial photonic sintering system. Thermally labile ester groups are positioned on the DTZ unit of the copolymer that can be eliminated thermally for enhanced photochemical stability and advantages in terms of processing (solubility/insolubility switching). The photonic sintering system was successfully implemented in a full roll-to-roll process on flexible PET substrates and large-area polymer solar cell modules were prepared by solution processing of five layers under ambient conditions using the photonic sintering system for thermocleaving of the active layer. The PET foil did not show any deformation after exposure to the high intensity light only leaving the insoluble thermocleaved active layer. The active layer remained planar after light exposure thereby allowing the coating of supplementary material on top.

Rapid flash annealing of thermally reactive copolymers in a roll-to-roll process for polymer solar cells, Martin Helgesen ,  Jon Eggert Carlé ,  Birgitta Andreasen ,  Markus Hösel ,  Kion Norrman ,  Roar Søndergaard and Frederik C. Krebs Polym. Chem., 2012,3, 2649-2655.

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Paper of the week: Highly stable polymeric vesicles prepared by a simple coating method

Graphical abstract: Well-defined polymeric vesicles with high stability and modulation of cell uptake by a simple coating protocol

Amphiphilic polymers have been synthesised by controlled free radical polymerisation techniques. These polymers self-assemble into well-defined vesicles in aqueous conditions, enabling encapsulation of a model hydrophilic molecule. The polymeric vesicles show high stability against a range of aqueous conditions with marginal release of cargo, even in the presence of known cell-membrane disruptive polymers such as branched poly(ethylene imine) (b-PEI). This stability allows for inversion of the surface charge of the polymeric vesicles by a simple coating protocol leading to an enhanced uptake by mammalian cells.

Well-defined polymeric vesicles with high stability and modulation of cell uptake by a simple coating protocol Gökçen Yaşayan, Martin Redhead, Johannes P. Magnusson, Sebastian G. Spain, Stephanie Allen, Martyn Davies, Cameron Alexander and Francisco Fernández-Trillo Polym. Chem., 2012, 3, 2596-2604.

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Paper of the week: Nanoassemblies of surfactant-like peptide-amphiphiles

Graphical abstract: Controlled peptide coated nanostructures via the self-assembly of functional peptide building blocks

Molecular self-assembly mediated by noncovalent interactions, such as hydrogen bonding, hydrophobic and p-stacking interactions, provides important guidance for the construction of a new generation of biomaterials with various functions. Arising from the abundant examples of protein self-assembly existing in nature, peptide-based building blocks with the unique properties of good biocompatibility, chemical versatility and biological recognition abilities have been widely used to prepare a variety of functional biomaterials. In this paper, Zhang and co-workers designed and prepared a functional peptide sequence with membrane penetrating (eight continuous arginine residues) and tumor-targeting functions (GRGDS). Self-assembled GRGDS-based micelles loaded with the anti-tumor drug DOX and incubated with HeLa and COS-7 cells demonstrated tumor-targeting and membrane-penetrating abilities and delivered the drug into HeLa cells. The strategy reported in this study presents potential for the construction of biocompatible peptide-based biomaterials with favorable bioactivity.

Controlled peptide coated nanostructures via the self-assembly of functional peptide building blocks by Xiao-Ding Xu , Jing-Xiao Chen , Han Cheng , Xian-Zheng Zhang and Ren-Xi Zhuo Polym. Chem20123, 2479-2486.

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Paper of the week: Carbon nanotube-incorporated polymer hydrogels

Graphical abstract: Synthesis of single-walled carbon nanotube-incorporated polymer hydrogels via click chemistry

Electrically conductive hydrogels are soft, polymeric networks that combine hydrogels’ unique properties with electroactive polymers’ inherent conductivity. With this in mind, Changsik Song and co-workers reported the design of single-walled carbon nanotubes (SWNTs) incorporated into polyvinyl alcohol (PVA) hydrogels by Cu-catalyzed azide–alkyne cycloaddition reaction. This efficient and modular reaction allowed the production of hydrogels with cross-linker molecules of various properties such as hydrophilic or hydrophobic character. Control of cross-linking density and molecular transport inside the click hydrogels was demonstrated by measuring degrees of swelling and the electrochemical diffusion coefficient of an ionic solute. In addition, incorporation of single-walled carbon nanotubes into the click hydrogels aided the growth of poly(3,4-ethylenedioxythiophene), presumably due to their enhancement of electrical conductivity. SWNT-incorporated PVA hydrogels synthesized by click chemistry may be of great interest for use as electrically conductive hydrogels in biomedical applications.

Synthesis of single-walled carbon nanotube-incorporated polymer hydrogels via click chemistry by Rebecca Eunji Lee, Jiyoung Park, Sung Gap Im and Changsik Song Polym. Chem20123, 2451-2455.

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Paper of the week: Degradable copolymers by ring-opening and reverse addition–fragmentation chain transfer polymerization

Graphical abstract: Degradable graft copolymers by ring-opening and reverse addition–fragmentation chain transfer polymerization

Polymers with a diverse range of properties and applications can be prepared by tailoring polymer topology and composition. Among these polymer architectures, the preparation of graft copolymers has been intensely investigated. In this context, researchers at Warwick University reported on the synthesis and controlled ring-opening polymerization (ROP) of a six membered cyclic carbonate monomer with pendant reversible addition–fragmentation chain transfer (RAFT) functionality. The growth of fast propagating monomers (methyl acrylate, tetrahydropyran acrylate and N-isopropylacrylamide) from the obtained RAFT-functional poly(carbonate)s resulted in the formation of well-defined graft copolymers with a biodegradable backbone. Importantly, control of solution and thermal properties was achieved through variation of graft length, grafting density and grafting monomer. In addition, the preparation and self-assembly of a PNiPAm graft copolymer provided a convenient route to novel thermoresponsive biodegradable micelles.

Degradable graft copolymers by ring-opening and reverseaddition–fragmentation chain transfer polymerization by Rebecca J. Williams, Rachel K. O’Reilly and Andrew P. Dove Polym. Chem20123, 2156-2164.

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Paper of the week: water-dispersible silver-decorated polymer vesicles and micelles with antibacterial efficacy

Graphical abstract: Preparation of water-dispersible silver-decorated polymer vesicles and micelles with excellent antibacterial efficacy

It is well known that silver nanoparticles have excellent antibacterial activities. However, to prepare well-defined, water-dispersible and long-term stable silver nanoparticles still remains a challenge. Presented in this paper are the design and preparation of new water-dispersible silver-decorated polymer vesicles and micelles based on a new kind of amphiphilic block-statistical copolymer synthesized by ATRP: poly(ethylene oxide)-block-poly(2-(dimethylamino)ethyl methacrylate-stat-t-butyl acrylate) (PEO-b-P(DMA-stat-tBA)) and its partially hydrolyzed derivative, poly(ethylene oxide)-block-poly(2-(dimethylamino)ethyl methacrylate-stat-acrylic acid) (PEO-b-P(DMA-stat-AA)). Poly(DMA) is introduced for the coordination of Ag+ ions to form silver nanoparticles in situ upon reduction, whereas poly(AA) is designed to serve the scaffold for the silver nanoparticle formation in the micelle core by electrostatic interactions with Ag+ ions. Those water-dispersible silver-decorated polymer micelles and vesicles showed excellent antibacterial efficacy against Escherichia coli (E. coli) with quite low minimum inhibitory concentration and minimum bactericidal concentration.

Preparation of water-dispersible silver-decorated polymer vesicles and micelles with excellent antibacterial efficacy by Hang Lu, Lang Fan, Qiuming Liu, Jingren Wei, Tianbin Renand Jianzhong Du Polym. Chem. 2012, 3, 2217-2227.

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Paper of the Week: Design of a platform for the preparation of libraries of functional polymer brushes

Graphical abstract: Synthesis and post-polymerization modification of poly(pentafluorophenyl methacrylate) brushes

Post-polymerization modification is a powerful strategy to endow polymers with functional groups that cannot be incorporated via direct polymerization. In this paper, Klok and co-workers explored the reversible addition–fragmentation chain transfer polymerization (RAFT) of pentafluorophenyl methacrylate (PFMA) to prepare active ester containing polymer brushes and investigated the feasibility and versatility of these reactive thin polymer films towards post-polymerization modification with a variety of amines. Except for the secondary amine diisopropylamine, the sterically demanding aminomethylanthracene and aniline, post-polymerization modification with all other investigated amines proceeded with near to quantitative conversion within 2–20 hours. The high reactivity towards a broad range of amines, combined with a good hydrolytic stability and solubility/swellability in a range of organic solvents makes the PPFMA brushes a very attractive platform for the rapid synthesis of diverse libraries of functional polymer brushes via post-polymerization modification.

Synthesis and post-polymerization modification of poly(pentafluorophenyl methacrylate) brushes by Kemal Arda Günay, Nicolas Schüwer and Harm-Anton Klok Polym. Chem. 20123, 2186-2192.

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Paper of the Week: Synthesis and charge-transporting properties of electron-deficient CN2–fluorene based D–A copolymers

Graphical abstract: Synthesis and charge-transporting properties of electron-deficient CN2–fluorene based D–A copolymers

The past decade has witnessed extensive concentration on the synthesis of conjugated polymers and their applications for organic electronic devices due to their low-cost, light-weight, and flexibility compared to their inorganic semiconductor counterparts. Donor–acceptor (D–A) copolymerization is a currently common strategy to design and synthesize potential semiconducting copolymers. In this study, Yao and co-workers reported on the synthesis of four D–A copolymers on the basis of a novel acceptor (A) unit of 9-fluorenylidene malononitrile (CN2–Fluorene) and four common donor (D) units of 9-alkylfluorene (P1), benzodithiophene (P2), bithiophene (P3), and dithienopyrrole (P4). These four copolymers exhibit a weak ICT absorption edge up to 800 nm. The HOMO energy levels of the copolymers are finely tuned by the donor units, while the LUMO energy levels of the copolymers are highly depressed and determined by the CN2–Fluorene unit. The hole mobility of P3 is measured as 1.43 x 10-3 cm2.V-1.s-1 under ambient conditions and that of P2 and P4 is on the order of 10-4 cm2.V-1.s-1. The results reveal that CN2–Fluorene is a new electron-acceptor unit and may be incorporated with proper electron-donors when designing semiconducting D–A copolymers.

Synthesis and charge-transporting properties of electron-deficient CN2–fluorene based D–A copolymers by Jianhua Huang, Yan Zhao, Xunlei Ding, Hui Jia, Bo Jiang, Zhiguo Zhang, Chuanlang Zhan, Shenggui He, Qibing Pei, Yongfang Li, Yunqi Liu and Jiannian Yao Polym. Chem. 20123, 2170-2177.

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Paper of the Week: Stimuli-responsive cholesterol conjugated polymers

Graphical abstract: Synthesis, self-assembly and stimuli responsive properties of cholesterol conjugated polymers

Reversible addition–fragmentation chain transfer (RAFT) polymerization was used to generate well-defined pH-responsive biofunctional polymers as potential ‘smart’ gene delivery systems. A series of five poly(dimethylamino ethyl methacrylate-co-cholesteryl methacrylate) P(DMAEMA-co-CMA) statistical copolymers, with similar molecular weights and varying cholesterol content, were prepared. The syntheses, compositions and molecular weight distributions for P(DMAEMA-co-CMA) were monitored by nuclear magnetic resonance (NMR), solid-state NMR and gel permeation chromatography (GPC) evidencing well-defined polymeric structures with narrow polydispersities. Aqueous solution properties of the copolymers were investigated using turbidimetry and light scattering to determine hydrodynamic diameters and zeta potentials associated with the phase transition behaviour of P(DMAEMA-co-CMA) copolymers. UV-Visible spectroscopy was used to investigate the pH-responsive behaviour of copolymers. Hydrodynamic radii were measured in the range 10–30 nm (pH, temperature dependent) by dynamic light scattering (DLS). Charge studies indicated that P(DMAEMA-co-CMA) polymers have an overall cationic charge, mediated by pH. Potentiometric studies revealed that the buffering capacity and pKa values of polymers were dependent on cholesterol content as well as on cationic charge. The buffering capacity increased with increasing charge ratio, overall demonstrating transitions in the pH endosomal region for all five copolymeric structures. Cell viability assay showed that the copolymers displayed increasing cytotoxicity with decreasing number of cholesterol moieties. These preliminary results show the potential of these well-defined P(DMAEMA-co-CMA) polymers as in vitro siRNA delivery agents.

Synthesis, self-assembly and stimuli responsive properties of cholesterol conjugated polymers by Sema Sevimli,  Sharon Sagnella,  Maria Kavallaris,  Volga Bulmus and Thomas P. Davis Polym. Chem. 2012, 3, 2057-2069.

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Paper of the Week: Hyperbranched polythioether-ynes by thiol-halogen click-like coupling and thiol-yne click polymerization

Fast and scalable production of hyperbranched polythioether-ynes was achieved by applying sequential click chemistry (SCC) via couple-monomer methodology (CMM). As a typical example, thiol-halogen click-like reaction employing strong base, KOH and thiol-yne click reaction via UV irradiation were used for precursor preparation and polymerization, respectively. Two series of hyperbranched polythioether-ynes employing two kinds of di-thiols with different reactivity have been prepared within 10 h and characterized with 1H NMR spectroscopy and gel permeation chromatography. The hyperbranched polymers (HPs) derived from 1,6-hexanedithiol reached high weight-average molecular weight (Mw) of 230500, high weight-average degree of polymerization (DPw) of 1224 and high degree of branching (DB) of 0.82–0.68. Postmodification of abundant alkyne terminal groups afford HPs with a greatly enhanced DB of 0.96. Heat-initiated polymerization was also attempted. The present study clearly demonstrates the robustness of application of SCC technique in the CMM strategy for fast, scalable preparation of multifunctional HPs.

Fast and scalable production of hyperbranched polythioether-ynes by a combination of thiol-halogen click-like coupling and thiol-yne click polymerization by Jin Han, Bo Zhao, Aijin Tang, Yanqin Gao and Chao Gao Polym. Chem., 2012, 3, 1918-1925

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