A pH- and temperature-sensitive macrocyclic graft copolymer composed of PEO ring and multi-poly(2-(dimethylamino) ethyl methacrylate) lateral chains

A novel method for the synthesis of macrocyclic graft copolymers was developed through combination of anionic ring-opening polymerization (AROP) and atom transfer radical polymerization (ATRP). A linear α,ω-dihydroxyl poly(ethylene oxide) with pendant acetal protected hydroxyl groups (l-poly(EO-co-EEGE)) was prepared first by the anionic copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE). Then l-poly(EO-co-EEGE) was cyclized. The crude cyclized product containing the linear byproduct was hydrolyzed and purified by being treated with α-CD. The pure cyclic copolymer [c-poly(EO-co-Gly)] was esterified by reaction with 2-bromoisobutyryl bromide, and then used as ATRP macroinitiators to initiate polymerization of 2-(dimethylamino) ethyl methacrylate (DMAEMA), and a series of pH- and temperature-sensitive macrocyclic graft copolymers composed of a hydrophilic PEO as the ring and PDMAEMA as side chains (c-PEO-g-PDMAEMA) were obtained. The behavior of pH- and temperature-sensitive macrocyclic copolymers was studied in aqueous solution by fluorescence and dynamic light scattering (DLS). The critical micellization pH values of macrocyclic graft copolymers and their corresponding linear graft copolymers (l-PEO-g-PDMAEMA) were measured. Under the same conditions, the cyclic graft copolymer with the shorter side chains gave the higher critical micellization pH value. The c-PEO-g-PDMAEMA showed the lower critical micellization pH value than the corresponding l-PEO-g-PDMAEMA. The average hydrodynamic diameters (D _h) of the micelles were measured by DLS with the variation of the aqueous solution pH value and temperature.     

Poly[bis(μ‐4‐benzoyl‐1‐isonicotinoylthiosemicarbazide‐κ2N:S)dichloridocadmium(II)]

The asymmetric unit of the title complex, [CdCl₂(C₁₄H₁₂N₄O₂S)₂]_n, consists of one Cd^II ion located on the crystallographic inversion centre, one 4‐benzoyl‐1‐isonicotinoylthiosemicarbazide ligand and one chloride ligand. The central Cd^II ion adopts a distorted octahedral coordination geometry formed by two pyridyl N atoms of two ligands, two S atoms of two other ligands and two chloride ligands. The thiosemicarbazide ligands act as bridges, linking the metal ions into a two‐dimensional layered structure parallel to the bc plane. Intermolecular N—H...O hydrogen bonds and C—H...π interactions exist between adjacent layers.     

新型β-二酚卟啉光敏剂合成及其与DNA作用

以β-硝基卟啉为原料,分别与2,3-萘二酚或邻苯二酚直接反应,制备了6个新型β-二酚取代卟啉光敏药物,通过UV,~1H NMR,IR,MS,元素分析等手段对化合物进行了结构表征并初步探讨了反应机理.DNA凝胶电泳实验表明,该类光敏剂对pBR322质粒DNA具有很好的光敏切割作用,作为光敏剂或其前体具有很好的应用前景.     

Mechanistic and kinetic investigations of N2H4 + OH reaction

The reaction of N₂H₄ with OH has been investigated by quantum chemical methods. The results show that hydrogen abstraction mechanism is more feasible than substitution mechanism thermodynamically. The calculated rate constants agree with the available experimental data. The calculated results show that the variational effect is small at lower temperature region, while it becomes significant at higher temperature region. On the other hand, the small‐curvature tunneling effect may play an important role in the temperature range 220?3000 K. Moreover, the calculated rate constants show negative temperature dependence at the temperatures below 500 K, which is in accordance with Vaghjiani's report that slightly negative temperature dependence is found over the temperature range of 258?637 K. The mechanism of the major product (N₂H₃) with OH has also been investigated theoretically to understand the title reaction thoroughly. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Study of fragmentation pathways of lithiated α,β‐unsaturated thioesters by electrospray ionization mass spectrometry

The fragmentation pathways of lithiated α,β‐unsaturated thioesters with different substituents were investigated by electrospray ionization tandem mass spectrometry (ESI‐MS/MS) in positive ion mode. In mass spectrometry of the α,β‐unsaturated thioesters, Ar‐CH?CH‐CO‐S‐Ph, loss of PhSLi and elimination of a thiophenol were the two major fragmentation reactions of the lithiated molecules. The elemental compositions of all the ions were confirmed by high‐resolution Fourier transform ion cyclotron resonance tandem mass spectrometry (FTICR‐MS/MS). The thioesters studied here were para‐monosubstituted on the phenyl ring of cinnamoyl and the electron‐withdrawing groups favored loss of a thiophenol, whereas the electron‐releasing groups strongly favored the competing reaction leading to the loss of PhSLi to form a cinnamoyl cation, Ar‐CH?CHCO⁺. The intensity ratios of the two competitive product ions were well correlated with the σ substituent constants. The mechanisms of these two competing routes were further investigated by density functional theory (DFT) calculations. Copyright © 2010 John Wiley & Sons, Ltd.     

Formaldehyde removal by Rayon-based activated carbon fibers modified by <Emphasis Type="Italic">P</Emphasis>-aminobenzoic acid

We impregnated Rayon-based activated carbon fibers (ACFs) by p-aminobenzoic acid (PABA) and systematically investigated their porous structure, surface chemistry, and formaldehyde removal behavior. Using standard nitrogen adsorption analysis, we found that the specific surface area, the micropore volume, and the total pore volume decreased with increasing concentration of PABA. Through elemental analysis and X-ray photoelectron spectroscopy, it was found that some nitrogen-containing functional groups presented on the surface of modified Rayon ACFs. The modified Rayon-based ACFs showed much higher adsorption capacity and longer breakthrough time for formaldehyde than did as-prepared Rayon-based ACF. We proposed that the improvement of formaldehyde removal by modified ACFs was attributed to the combined effects of physisorption contributed by pore structures and chemisorption contributed by the N-containing functional groups, whereas there was only physisorption between the as-prepared ACF and formaldehyde molecules.     

基于FPGA的PPM调制解调系统设计

光通信技术的蓬勃发展对调制解调技术提出了更高的要求,脉冲位置调制（PPM）有较高的平均功率利用率,传输速率以及较强的抗干扰能力,能够很好地满足实际需求。从脉冲位置调制的基本原理出发,基于FPGA对PPM调制解调系统进行设计,特别是对PPM的帧同步进行详细说明,并用Verilog HDL语言对系统进行时序仿真,验证了设计的正确性。     

医疗内窥镜影像系统的设计与实现

设计并实现了消化内镜影像系统的常用功能,并增加了病变图像的二次采集,典型病例库的维护以及“所见即所得”的报告生成方式,提高了诊断效率。并对系统进行了全面的测试,保证了系统的稳定性和功能完备性。     

直调型正交频分复用多模光纤链路性能研究

正交频分复用(OFDM)技术可应用在多模光纤(MMF)通信系统中实现短距离高速信息传输.文章提出利用光学角谱法计算MMF模式色散,结合OFDM原理构建直接调制型MMF传输的理论模型,并且数值分析了传输速率和误码率(BER)等系统重要性能指标.计算结果表明,系统接收机BER为10-3时,对应同步光纤网络中的信号带宽标准OC-768(40 Gbit/s)信号,其传输距离可达2.5 km以上.     

基于ARM7的太阳能控制器的设计与现实

本文阐述了太阳能光伏电池的工作原理以及伏安特性,提供了一套完善的太阳能控制器电路.该电路采用了目前最流行的ARM芯片为控制核心,来实时监控光伏两端电压、蓄电池两端电压以及充电电流和放电电流.从而控制整个电路的工作状态.