Self‐assembly of block copolymers with an alkoxysilane‐based core‐forming block: A comparison of synthetic approaches

Polymerization‐induced self‐assembly (PISA) has become the preferred method of preparing self‐assembled nano‐objects based on amphiphilic block copolymers. The PISA methodology has also been extended to the realization of colloidal nanocomposites, such as polymer–silica hybrid particles. In this work, we compare two methods to prepare nanoparticles based on self‐assembly of block copolymers bearing a core‐forming block with a reactive alkoxysilane moiety (3‐(trimethoxysilyl)propyl methacrylate, MPS), namely (i) RAFT emulsion polymerization using a hydrophilic macroRAFT agent and (ii) solution‐phase self‐assembly upon slow addition of a selective solvent. Emulsion polymerization under both ab initio and seeded conditions were studied, as well the use of different initiating systems. Effective and reproducible chain extension (and hence PISA) of MPS via thermally initiated RAFT emulsion polymerization was compromised due to the hydrolysis and polycondensation of MPS occurring under the reaction conditions employed. A more successful approach to block copolymer self‐assembly was achieved via polymerization in a good solvent for both blocks (1,4‐dioxane) followed by the slow addition of water, yielding spherical nanoparticles that increased in size as the length of the solvophobic block was increased. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 420–429     

Solvent‐free Synthesis of Water‐Soluble New Pyridinium Amines: Spectroscopic Characterization,Biological Screening,and Interaction Study with DNA

New water‐soluble pyridinium amines ( 2–8 ) were obtained by the solid‐state reactions of 4‐chloro‐1‐methylpyridin‐1‐ium triflate ( 1 ) and various primary aromatic amines. These compounds were characterized by ¹H , ¹³C NMR , FTIR , UV –vis, and fluorescence spectroscopic methods along with single‐crystal X‐ray structure determination. The interaction potentials of all newly synthesized compounds with calf thymus DNA (CT‐DNA ) were investigated by UV –vis and florescence spectroscopy accompanied by docking studies. UV –vis spectroscopy indicated that the binding of compounds with CT‐DNA takes place via the intercalative mode. The compounds were also screened for their potential as antioxidants and enzyme inhibition agents. Some compounds displayed excellent butyrylcholine and acetylcholine esterase inhibition activities and were effective in scavenging the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH ) radical in a dose‐dependent manner comparable to a standard.     

A degradable atom transfer radical polymerization inimer: Synthesis,polymerization, and cleavage of the resulting polymer products

A novel degradable inimer for atom transfer radical polymerization (ATRP), 2‐(6‐(2‐((2‐bromo‐2‐methylpropanoyl)oxy)ethyl)pyridin‐2‐yl)ethyl methacrylate (PyDEBrMΑ), was synthesized by the two‐step esterification of 2,6‐pyridinediethanol, first with α‐bromoisobutyryl bromide in order to introduce the initiator moiety, and then with methacryloyl chloride in order to introduce the monomer moiety. PyDEBrMA was subsequently used to initiate the self‐condensing ATRP of methyl methacrylate (MMA) to obtain a hyperbranched MMA homopolymer which could be cleaved at the PyDEBrMA residue either by treatment under mildly alkaline hydrolysis conditions (sodium deuteroxide in d₆‐DMSO at room temperature) or thermolysis at 150 °C. The lability of the PyDEBrMA residue arises from the presence in its structure of two 2‐(pyridin‐2‐yl)ethyl ester moieties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2831–2839     

Boroxine Nanotubes: Moisture‐Sensitive Morphological Transformation and Guest Release

Boroxines, (R‐BO)₃, which can be easily synthesized via a dehydration reaction of boronic acids, R–B(OH)₂, selectively self‐assemble in toluene into nanofibers, nanorods, nanotapes, and nanotubes, depending on the aromatic substituent (R). Spectroscopic measurements show that the nanotube consists of a J‐aggregate of the boroxine. Humidification converts the morphology from the nanotube to a sheet as a result of the hydrolysis of the boroxine components and subsequent molecular‐packing rearrangement from the J‐aggregate to an H‐aggregate. Such a transformation leads to the compulsive release of guest molecules encapsulated in the hollow cylinder of the nanotube. The hydrolysis and the molecular‐packing rearrangement described above are suppressed by coordination of pyridine to the boron atom, with the resulting moiety acting as a Lewis acid of the boroxine component. The pyridine‐coordinated nanotube is transformed into a helical coil by humidification. Guest release during the nanotube‐to‐helical‐coil transformation is much slower than during the nanotube‐to‐sheet transformation, but faster than from a nanotube that did not undergo morphological transformation. The storage and release of guest molecules from the boroxine nanotubes can be precisely controlled by adjusting the moisture level and the concentration of Lewis bases, such as amines.     

物理层安全中的最优中继选择及协同干扰策略

本文提出了一种以协同干扰为基础,结合了最优中继选择和功率分配的物理层安全方案.该方案针对分布式天线的场景,从中间节点中选择一个最佳的节点作为中继,剩余的其他节点作为协同干扰节点.中继节点使用放大转发策略.本文同时提出了协同干扰节点的波束成形算法.另外,我们还推导出了中继节点和协同干扰节点之间的功率分配的闭式解.最后,本文还给出了相关的仿真结果,证实了新提出的方案比传统方案能获得更高的安全容量.     

10.6 μm脉冲激光对多晶硅探测器干扰损伤实验

用10.6 μm脉冲CO2激光辐照多晶硅光电探测器,进行了干扰与损伤阈值实验研究,得到了对多晶硅探测器的干扰、损伤阈值;分析了不同干扰能量的干扰效果,研究了干扰损伤机理,依据受干扰程度对干扰等级进行了划分;通过干扰激光能量与干扰光斑面积的关系,重度饱和后探测器随时间恢复情况,探讨了各干扰等级下10.6 μm脉冲激光对红外成像系统的干扰效果。