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Macromolecular Rapid Communications

Philipp Weis, Si Wu
Azobenzene-containing macromolecules (azo-macromolecules) such as azobenzene-containing polymers (azopolymers) and azobenzene-functionalized biomacromolecules are photoswitchable macromolecules. Trans-to-cis photoisomerization in conventional azo-macromolecules is induced by ultraviolet (UV) light. However, UV light cannot penetrate deeply into issue and has a very small fraction in sunlight. Therefore, conventional azo-macromolecules are problematic for biomedical and solar-energy-related applications. In this Feature Article, the strategies for constructing visible and near-infrared (NIR) light-responsive azo-macromolecules are reviewed, and the potential applications of visible- and NIR-light-responsive azo-macromolecules in biomedicine and solar energy conversion are highlighted...
June 23, 2017: Macromolecular Rapid Communications
Janos Balogh, Antsar Rih Hlil, Ibrahim El-Zoghbi, Muhammad Ghufran Rafique, Dalila Chouikhi, Mohammed Al-Hashimi, Hassan S Bazzi
This paper reports the efficient synthesis of the first class of polyisobutylene(PIB)-supported palladium-PEPPSI precatalyst (PEPPSI = pyridine-enhanced precatalyst preparation, stabilization, and initiation). The new complexes are employed in Buchwald-Hartwig amination of aryl chlorides and are found to be reasonably active in the titled cross-coupling reaction. The supported catalysts are tested in polar (1,4-dioxane and 1,2-dimethoxyethane) as well as in aliphatic reaction media (toluene and n-heptane) and display superior activity in the highly lipophilic solvent (n-heptane)...
June 19, 2017: Macromolecular Rapid Communications
Long Fei Fan, Min Zhi Rong, Ming Qiu Zhang, Xu Dong Chen
The present communication reports a novel strategy to fabricate reversible shape-memory polymer that operates without the aid of external force on the basis of a two-phase structure design. The proof-of-concept material, crosslinked styrene-butadiene-styrene block copolymer (SBS, dispersed phase)/polycaprolactone-based polyurethane (PU, continuous phase) blend, possesses a closely connected microphase separation structure. That is, SBS phases are chemically bonded to crosslinked PU by means of a single crosslinking agent and two-step crosslinking process for increasing integrity of the system...
June 19, 2017: Macromolecular Rapid Communications
Tong Qin, Yue Zang, Wei-Yun Bai, Kai Yao, Yun-Xiang Xu
A novel ladder-type donor pyran-bridged indacenodithiophene (IDTP) is developed by introducing two oxygen atoms into indacenodithiophene unit. IDTP possesses a twisted backbone and leads to facially asymmetric arrangement of side chains, resulting in enhanced local π-π stacking of according polymer poly[(5,5,11,11-tetrakis(4-octylphenyl)-5,11-dihydrothieno[2',3':5,6]pyrano[3,4-g]thieno[3,2-c]isochromene)-alt-4,7-(5-fluoro-2,1,3-benzothiadiazole)] (PIDTP)-FBT, which shows extended absorption range. Moreover, oxygen atoms render deeper highest occupied molecular orbital (HOMO) levels of poly[indacenodithiophene-alt-4,7-(5-fluoro-2,1,3-benzothiadiazole)] (PIDTP)-FBT compared with PIDT-FBT, therefore bringing a higher open-circuit voltage (Voc )...
June 19, 2017: Macromolecular Rapid Communications
Yuhao Wang, Svetlana A Sukhishvili
Spontaneous formation of polymer nanoparticles of well-defined, <100 nm sizes with controlled solid/hollow morphology and fluorescent properties is reported. The nanoparticle formation is assisted by temperature-triggered nucleation of an amphiphilic polymer-poly(N-isopropylacrylamide) (PNIPAM)-and mediated by hydrogen bonding of the emerged nuclei with tannic acid (TA). The pH of solution and TA/PNIPAM ratios are explored as parameters that define TA/PNIPAM assembly. Well-defined nanoparticles are formed in a wide range of neutral pH when the TA/PNIPAM ratio exceeds its critical, pH-dependent value...
June 12, 2017: Macromolecular Rapid Communications
Jingyan Zhang, Haiou Zhou, Hao Liu, Jinming Hu, Shiyong Liu
Well-defined β-cyclodextrin (β-CD)-terminated double hydrophilic diblock copolymers (DHBCs), β-CD- poly(di(ethylene glycol) methyl ether methacrylate) (PMEO2 MA)-b-poly(2-(diethylamino)ethyl methacrylate) (PDEA) (BP1) and β-CD-PDEA-b-PMEO2 MA (BP2), are synthesized via sequential atom transfer radical polymerizations of di(ethylene glycol) methyl ether methacrylate and 2-(diethylamino)ethyl methacrylate using alkynyl-functionalized initiator, followed by click reactions with an excess of mono-azido-substituted β-cyclodextrin (β-CD-N3 )...
June 12, 2017: Macromolecular Rapid Communications
Jianbing Huang, Decai Li, Hui Liang, Jiang Lu
Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained...
June 12, 2017: Macromolecular Rapid Communications
S Allazetta, A Negro, M P Lutolf
A droplet microfluidics strategy to rapidly synthesize, process, and screen up to hundreds of thousands of compositionally distinct synthetic hydrogels is presented. By programming the flow rates of multiple microfluidic inlet channels supplying individual hydrogel building blocks, microgel compositions and properties are systematically modulated. The use of fluorescent labels as proxies for the physical and chemical properties of the microgel permits the rapid screening and discovery of specific formulations through fluorescence microscopy or flow cytometry...
June 12, 2017: Macromolecular Rapid Communications
Huaqiang Ju, Fengbo Zhu, Hao Xing, Zi Liang Wu, Feihe Huang
Herein a facile method is reported to prepare polymer gels based on the formation of acylhydrazone bond under mild conditions. A pillar[5]arene derivative appended with ten hydrazide groups provides multiple sites for the reaction with the aldehyde groups of bis(p-formylphenyl) sebacate in the presence of a small amount of HCl as the catalyst in dimethyl sulfoxide (DMSO), producing transparent polymer organogels. The mechanical properties of gels can be easily tuned by the molar ratio of the reactant compounds...
June 6, 2017: Macromolecular Rapid Communications
Yi-Jen Han, Ying-Ling Liu
In this work, the incorporation of a 2,2,6,6-tetramethylpiperydinyl-1-oxyl (TEMPO) group to a benzoxazine ring is performed using a one-pot synthesis for the preparation of TEMPO-functionalized benzoxazine compounds and polymers as reactive and crosslinkable initiators for nitroxide-mediated polymerization (NMP). The TEMPO-functionalization reaction of benzoxazine, traced with (1) H NMR, is conducted with sequential radical transfer and coupling reactions. Moreover, polystyrene-grafted polybenzoxazine copolymers are prepared with the TEMPO-benzoxazine initiator and NMP of styrene...
June 5, 2017: Macromolecular Rapid Communications
Dan-Wei Zhang, Hui Wang, Zhan-Ting Li
Conjugated polymers may be induced by intra- and/or intermolecular non-covalent forces to fold into helical conformations. Helices formed by aromatic amide, hydrazide, and urea polymers possess a well-organized cavity and depth, which is defined by their degree of polymerization. Driving forces may be intramolecular hydrogen bonding and/or solvophobicity, or guest induction. The resulting long helices represent a new class of unimacromolecular dynamic tubular architectures that exhibit unique properties or functions in, for example, molecular recognition, chirality transfer, and ion transporting...
June 1, 2017: Macromolecular Rapid Communications
Jianbo Tan, Dongdong Liu, Chundong Huang, Xueliang Li, Jun He, Qin Xu, Li Zhang
Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization...
May 31, 2017: Macromolecular Rapid Communications
Justin J Chung, Brian S T Sum, Siwei Li, Molly M Stevens, Theoni K Georgiou, Julian R Jones
Hybrids with a silica network covalently bonded to a polymer are promising materials for bone repair. Previous work on synthesizing methyl methacrylate (MMA) based copolymers by reversible addition-fragmentation chain transfer (RAFT) polymerization gives high tailorability of mechanical properties since sophisticated polymer structures can be designed. However, more flexible hybrids would be beneficial. Here, n-butyl methacrylate (BMA) and methyl acrylate (MA) based hybrids are produced. Unlike MMA, BMA and MA hybrids do not show plastic deformation, and BMA hybrid has strain to failure of 33%...
May 31, 2017: Macromolecular Rapid Communications
Sanjib Banerjee, Vincent Ladmiral, Antoine Debuigne, Christophe Detrembleur, S M Wahidur Rahaman, Rinaldo Poli, Bruno Ameduri
Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly(VAc-alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (≤1.24) and molar masses up to 57 000 g mol(-1) . These copolymers have a precise 1:1 alternating structure over a wide range of comonomer feed compositions...
May 31, 2017: Macromolecular Rapid Communications
Lin Qu, Peng Sun, Ying Wu, Ke Zhang, Zhengping Liu
An efficient metal-free homodifunctional bimolecular ring-closure method is developed for the formation of cyclic polymers by combining reversible addition-fragmentation chain transfer (RAFT) polymerization and self-accelerating click reaction. In this approach, α,ω-homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, well-defined cyclic polymers are then prepared using the self-accelerating double strain-promoted azide-alkyne click (DSPAAC) reaction to ring-close the azide end-functionalized homodifunctional linear polymer precursors...
May 31, 2017: Macromolecular Rapid Communications
Hao Zeng, Owies M Wani, Piotr Wasylczyk, Arri Priimagi
Liquid crystal elastomers are among the best candidates for artificial muscles, and the materials of choice when constructing microscale robotic systems. Recently, significant efforts are dedicated to designing stimuli-responsive actuators that can reproduce the shape-change of soft bodies of animals by means of proper external energy source. However, transferring material deformation efficiently into autonomous robotic locomotion remains a challenge. This paper reports on a miniature inching robot fabricated from a monolithic liquid crystal elastomer film, which upon visible-light excitation is capable of mimicking caterpillar locomotion on different substrates like a blazed grating and a paper surface...
May 31, 2017: Macromolecular Rapid Communications
Sivaprakash Shanmugam, Jiangtao Xu, Cyrille Boyer
Recently, visible-light-regulated polymerization has been gaining popularity, as it opens a range of new opportunities for the synthesis of functional polymers and materials. Here, the most recent developments in this field are summarized, which is the use of photocatalysts and catalyst-free approaches to mediate polymerization upon photoexcitation. These catalysts can transfer an electron or energy to activate an initiator. The recent achievements in light-regulated atom-transfer radical polymerization, reversible addition-fragmentation chain-transfer polymerization, ring-opening metathesis polymerization, cobalt-mediated radical polymerization, iodine-mediated radical polymerization, and living cationic polymerization are reviewed...
May 26, 2017: Macromolecular Rapid Communications
Hui Li, Peng Yang, Parasmani Pageni, Chuanbing Tang
Metal-containing polymer hydrogels have attracted increasing interest in recent years due to their outstanding properties such as biocompatibility, recoverability, self-healing, and/or redox activity. In this short review, methods for the preparation of metal-containing polymer hydrogels are introduced and an overview of these hydrogels with various functionalities is given. It is hoped that this short update can stimulate innovative ideas to promote the research of metal-containing hydrogels in the communities...
May 26, 2017: Macromolecular Rapid Communications
Ansheng Liang, Xiaoyan Zhou, Wenqiao Zhou, Tao Wan, Luhai Wang, Chengjun Pan, Lei Wang
Three conjugated polymers with alkyl chains of different lengths are designed and synthesized, and their structure-property relationship as organic thermoelectric materials is systematically elucidated. All three polymers show similar photophysical properties, thermal properties, and mechanical properties; however, their thermoelectric performance is influenced by the length of their side chains. The length of the alkyl chain significantly influences the electrical conductivity of the conjugated polymers, and polymers with a short alkyl chain exhibit better conductivity than those with a long alkyl chain...
May 24, 2017: Macromolecular Rapid Communications
Zhi-Chao Jiang, Yao-Yu Xiao, Yang Kang, Bang-Jing Li, Sheng Zhang
Moisture or water has the advantages of being green, inexpensive, and moderate. However, it is challenging to endow water-induced shape memory property and self-healing capability to one single polymer because of the conflicting structural requirement of the two types of materials. In this study, this problem is solved through introducing two kinds of supramolecular interactions into semi-interpenetrating polymer networks (semi-IPNs). The hydrogen bonds function as water-sensitive switches, making the materials show moisture-induced shape memory effect...
May 23, 2017: Macromolecular Rapid Communications
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