From single‐chain folding to polymer nanoparticles via intramolecular quadruple hydrogen‐bonding interaction

Single‐chain folding via intramolecular noncovalent interaction is regarded as a facile mimicry of biomacromolecules. Single‐chain folding and intramolecular crosslinking is also an effective method to prepare polymer nanoparticles. In this study, poly(methyl methacrylate‐co?2‐ureido‐5‐deazapterines functionalized ethylene methacrylate) (P(MMA‐co‐EMA‐DeAP)) is synthesized via free radical polymerization. The single‐chain folding of P(MMA‐co‐EMA‐DeAP) and the formation of the nanoparticles in diluted solution (concentration <0.005 mg/mL) are achieved via supramolecular interaction and intramolecular collapsing during the disruption‐reformation process of the hydrogen bonding triggered by water. The size and the morphology of the nanoparticles are characterized by dynamic light scattering, transmission electron microscope, and atomic force microscope. The results show that the size of the nanoparticles depends on the molecular weight of the polymer and the loading of 2‐ureido‐5‐deazapterines functionalized ethylene methacrylate (EMA‐DeAP) on the polymer backbone. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1832–1840     

Thermo‐ and pH‐sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

Polymers consisting of poly(acrylic acid) (PAA) and statistical poly[(acrylic acid)‐co‐(tert‐butylacrylate)] (P(AA‐co‐tBA)), attached to both extremities of Jeffamine® (D series based on a poly(propylene oxide) (PPO) with one amine function at each end) using atom transfer radical polymerization (ATRP) are presented in this article. An original bifunctional amide‐based macroinitiator was first elaborated from Jeffamine®. tBA polymerization was subsequently initiated from this macroinitiator. This polymerization occurs in a well‐controlled manner leading to narrow molecular weights distribution. Amphiphilic copolymers were finally obtained after complete or partial hydrolysis of the PtBA blocks into PAA. The control of the partial hydrolysis of tBA units, conducted in a concentrated HCl/tetrahydrofuran mixture, is demonstrated. The properties of the triblock copolymers were preliminary investigated in aqueous solution by absorbance, DLS measurements and SEC/MALS/DV/DRI analysis as a function of temperature and pH modifications, providing evidences of thermo‐ and pH‐sensitive self‐assembly of the copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2606–2616     

Naphthalic anhydride derivatives: Structural effects on their initiating abilities in radical and/or cationic photopolymerizations under visible light

Only one naphthalic anhydride derivative has been reported as light sensitive photoinitiator, this prompted us to further explore the possibility to prepare a new family of photoinitiators based on this scaffold. Therefore, eight naphthalic Naphthalic anhydride derivatives (ANH1‐ANH8) have been prepared and combined with an iodonium salt (and optionally N‐vinylcarbazole) or an amine (and optionally 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine) to initiate the cationic polymerization of epoxides and the free radical polymerization of acrylates under different irradiation sources, that is, very soft halogen lamp (～ 12 mW cm^?2), laser diode at 405 nm (～1.5 mW cm^?2) or blue LED centered at 455 nm (80 mW cm^?2). The ANH6 based photoinitiating systems are particularly efficient for the cationic and the radical photopolymerizations, and even better than that of the well‐known camphorquinone based systems. The photochemical mechanisms associated with the chemical structure/photopolymerization efficiency relationships are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis, and electron spin resonance spin‐trapping techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2860–2866     

Suppressing the environmental dependence of the open‐circuit voltage in inverted polymer solar cells through a radical polymer anodic modifier

Developing stable, readily‐synthesized, and solution‐processable transparent conducting polymers for interfacial modifying layers in organic photovoltaic (OPV) devices has become of great importance. Here, the radical polymer, poly(2,2,6,6‐tetramethylpiperidinyloxy methacrylate (PTMA), is shown to not affect the absorption of the well‐studied poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) active layer when incorporated into inverted OPV devices, as it is highly transparent in the visible spectrum due to the non‐conjugated nature of the PTMA backbone. The inclusion of this radical polymer as an anode‐modifying layer enhanced the open‐circuit voltage and short‐circuit current density values over devices that did not contain an anodic modifier. Importantly, devices fabricated with the PTMA interlayer had performance metrics that were time‐independent over the entire course of multiples days of testing after exposing the OPV devices to ambient conditions. Furthermore, these high performance values were independent of the metal used as the top electrode contact in the inverted OPV devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 311–316     

Preparation of 17β‐estradiol‐imprinted material by surface‐initiated atom transfer radical polymerization and its application

A novel 17β‐estradiol molecularly imprinted polymer was grafted onto the surface of initiator‐immobilized silica by surface‐initiated atom transfer radical polymerization. The resulting molecularly imprinted polymer was characterized by elemental analysis and thermogravimetric analysis. The binding property of molecularly imprinted polymer for 17β‐estradiol was also studied with both static and dynamic methods. The results showed that the molecularly imprinted polymer possessed excellent recognition capacity for 17β‐estradiol (180.65 mg/g at 298 K), and also exhibited outstanding selectivity for 17β‐estradiol over the other competitive compounds (such as testosterone and progesterone). Then, the determination of trace 17β‐estradiol in beef samples was successfully developed by using molecularly imprinted polymer solid‐phase extraction coupled with high‐performance liquid chromatography. The limit of detection was 0.25 ng/mL, and the amount of 17β‐estradiol in beef samples was detected at 2.83 ng/g. This work proposed a sensitive, rapid, reliable, and convenient approach for the determination of trace 17β‐estradiol in complicated beef samples.     

ESR and calculations on electronic structure of phenalenyl and phenalenyl derivative radicals

Calculations on electronic structure of the perinaphthenyl radical and phenalenyl derivative radicals responsible for the composition of the ESR spectrum of marine diesel under heating were performed to obtain support for the experimental ESR results. The parameters calculated were the hyperfine coupling constants (A), which were then used for comparison with the experimental data. The energy‐minimized structures were obtained using the density functional theory method. In all cases, the symmetry system was taken into account in theoretical calculations. The differences between experimental and theoretical values were below 7% for nearest hydrogens in molecules, named hyperfine coupling constant A (first neighbors) and 18% for farthest hydrogens atoms named hyperfine coupling constants A′ (second neighbors), for all structures analyzed. Copyright © 2014 John Wiley & Sons, Ltd.     

Optically Active Helical Vinylterphenyl Polymers: Chiral Teleinduction in Radical Polymerization and Tunable Stereomutation

Helical vinyl aromatic polymers are emerging as interesting chiral materials due to their dynamic tailorability, synthetic simplicity, and outstanding chemical and physical stabilities. This Personal Account discusses long‐range chirality transfer in the radical polymerization of vinylterphenyl monomers and tunable stereomutation of the resultant polymers. It begins with a general introduction to the design, synthesis, and characterization of helical poly{(+)‐2,5‐bis[4′‐((S)‐2‐methylbutyloxy)phenyl]styrene}, the first one of this series of polymers. Then, long‐range chirality transfer during radical polymerization of terphenyl‐based vinyl monomers is explained. After that, the chiroptical property control of the resultant polymers by means of the transition from kinetically controlled conformation to thermodynamically controlled conformation and external stimulus is described. This Personal Account concludes by discussing the advantages and disadvantages of the strategy of using vinylterphenyls to obtain optically active helical polymers and providing a short outlook, especially emphasizing the importance of tacticity on the chiroptical properties of polymers.     

对流层大气NO3与N2O5的实地测量

大气硝基(NO₃)自由基和五氧化二氮(N₂O₅)是对流层大气化学反应的核心物种,对于理解大气氧化性、二次有机气溶胶生成、活性卤素化学和全球硫素循环等对流层大气化学研究的关键问题具有重要意义。大气NO₃自由基和N₂O反应活性高、大气寿命短、浓度低,其定量分析非常具有挑战性。本文总结了大气NO₃自由基与N₂O₅的实地测量方法,并对差分光学吸收光谱(DOAS)、腔衰荡光谱(CRDS)、腔增强光谱(CEAS)、激光诱导荧光光谱(LIF)、电子顺磁共振谱(MIESR)和化学离子化质谱(CIMS)等六类技术方法的准确度、精确度、时间分辨率、测量干扰、标定方法和系统稳定性等方面进行了系统比较。综合分析认为吸收光谱法是对流层NO₃自由基与N₂O₅测量技术的发展方向,其中近期发展起来的腔技术(CRDS和CEAS)显示出较好的应用潜力。但是我国实际大气环境中普遍存在高浓度的颗粒物污染,如何在高颗粒物条件下实现NO₃自由基与N₂O₅的精密准确测量具有挑战性。本文进一步归纳了NO₃自由基与N₂O₅在城市、森林、自由大气和海洋海岸等典型大气环境条件下的浓度水平和主要科学发现,探讨了一些亟待解决的问题和可能的重点研究方向。     

水介质中ATRP法制备PDMAEMA及其温敏性

在30℃下以溴化亚铜-溴化铜混合物为催化剂,五甲基二乙烯三胺(PMDETA)为配体,在水介质中利用原子转移自由基聚合法(ATRP)合成聚合度达到300的聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)。核磁共振结果显示,聚合反应符合一级反应动力学描述。利用紫外可见分光光度计(UV-Vis)表征该聚合物的温敏性,结果表明,随着PDMAEMA聚合物链长的增加,其最低临界溶解温度(LCST)可降低至31.4℃。     

Synthesis of a PEG-PNIPAm thermosensitive dendritic copolymer and investigation of its self-association

A Novel thermosensitive dendritic copolymer based on polyethylene glycol(PEG) and poly(Nisopropylacrylamide)(PNIPAm) with a cloud point(CP) around 36 ?C was successfully synthesized by preparation of a dendritic polyol and followed by atom transfer radical polymerization(ATRP) of N-isopropylacrylamide. The dendritic copolymer was characterized using gel-permeation chromatography(GPC), FTIR and 1H-NMR spectroscopy. The selfassociation behavior of the copolymer in aqueous medium was investigated by dynamic light scattering(DLS) and transmission electron microscopy(TEM). These investigations confirmed that the dendritic copolymer showed different association behaviors at various temperatures.