Syntheses of Optically Active Polyacrylates

ABSTRACT

Different secondary alcohols were resolved by lipase catalyzed transesterification using 2,3-butanedione monoxime acrylate as acrylating agent. The results showed that the reaction rates were the fastest among reactions reported until now. The effect of solvent on the transesterification rate was studied. The enantiomeric excess (ee) and enantiomeric purity (E value) of all the acrylate monomers were determined. The synthesized optically active acrylate monomers were polymerized by free radical polymerization technique.     

Stereospecific radical polymerization of optically active (S)-N-(2-hydroxy-1-phenylethyl) methacrylamide catalyzed by Lewis acids

The effects of Lewis acids, namely, rare earth metal trifluoromethanesulfonates, on the radical polymerization of (S)-N-(2-hydroxy-1-phenylethyl) methacrylamide were examined under various conditions. In the absence of Lewis acids, syndiotactic-rich polymers (r = 84%) were obtained, whereas in the presence of a catalytic amount of Lewis acids, the polymerization proceeded in an isotactic-specific manner (m up to 64%). Polymerization solvents strongly influenced the effect of the Lewis acids. The polymerization in n-butyl alcohol showed the highest isotactic selectivity, whereas the polymerization in DMSO showed no isotacticity-enhancing effect. Further increases in the Lewis acid concentration and the polymerization temperature did not produce clear effects on the tacticity of the polymers. The interaction between the monomer and Lewis acids was investigated, and the plausible mechanism of stereocontrol in the radical polymerization of (S)-HPEMA was analyzed based on the Lewis acid-monomer interaction.     

Phase Transfer Catalyzed Alkylation: An Efficient Protection of Acid Labile Hemiketals

The reaction of hemiketals (1–6) with sodium hydroxide and methyl iodide in the presence of TBAI as a catalyst furnished methoxy hemiketals (7–10) in more than 90% yield.     

Albumin-mediated asymmetric nitroaldol reaction of aromatic aldehydes with nitromethane in water

We succeeded in the asymmetric nitroaldol (Henry) reaction of aromatic aldehydes with nitromethane using human serum albumin (HSA) in water at neutral pH. The reaction of 4-nitrobenzaldehyde smoothly proceeded for 24 h at 30 °C to afford the corresponding (R)-2-nitro-1-(4-nitrophenyl)ethanol (27% ee). Lowering the reaction temperature to 0 °C improved the enantioselectivity (53% ee). Although the denatured HSA also catalyzed the coupling reaction, no enantioselectivity was observed. The reaction was also applicable to other substrates bearing various substitutions on the benzene ring, and the ee of (R)-1-(biphenyl-4-yl)-2-nitroethanol was up to 79% ee.     

激光光源线宽对外差探测性能的影响

本文根据统计理论分析了激光线宽对外差探测结果的影响, 并讨论了激光线宽对杨氏干涉条纹对比度的影响. 本文基于解析结果做了数值仿真, 所得结果表明激光线宽增加时, 外差探测方式仍可以检测到中频信号, 但在线宽较大时, 受噪声影响无法准确地提取到中频频率. 为验证理论分析结果, 使用线宽为1 MHz的激光光源进行了8.1 km外场实验, 实验结果与数值分析结论一致, 即不会因为线宽增加而无法检测到中频信号. 文中所得结论对于外差探测光源的选择有重要指导意义, 因此根据测量目标的特性和测量要求, 可按照文中结论评估光源的线宽指标.     

Frequency-selective quantitation of short-echo time 1H magnetic resonance spectra

Accurate and efficient filtering techniques are required to suppress large nuisance components present in short-echo time magnetic resonance (MR) spectra. This paper discusses two powerful filtering techniques used in long-echo time MR spectral quantitation, the maximum-phase FIR filter (MP-FIR) and the Hankel-Lanczos Singular Value Decomposition with Partial ReOrthogonalization (HLSVD-PRO), and shows that they can be applied to their more complex short-echo time spectral counterparts. Both filters are validated and compared through extensive simulations. Their properties are discussed. In particular, the capability of MP-FIR for dealing with macromolecular components is emphasized. Although this property does not make a large difference for long-echo time MR spectra, it can be important when quantifying short-echo time spectra.     

基于阿秒抖动光纤锁模激光器的时钟同步

光纤锁模激光器结构简单, 运转稳定, 且输出的超短脉冲序列具有极高的时钟稳定性, 在抽运探测、脉冲相干合成等要求高精度时钟同步的前沿领域有着广阔的应用前景. 本文通过激光器腔内的电光调制器进行反馈控制, 实现了两台光纤锁模激光器之间的紧密时钟信号同步; 并且通过平衡光学互相关方法, 对残余的时钟误差信号进行了测量, 分辨率达到了13 as. 通过优化激光器的腔内动力学过程及反馈环路的参数, 在[1 Hz, 10 MHz]的积分区间内得到了109 as的残余时钟误差, 对应单台激光器的平均时间抖动为77 as.     

稀有气体卤化物准分子激光器工作气体实时补给技术

为延长稀有气体卤化物准分子激光器工作气体使用寿命,在原有供气设备基础上增加了工作气体实时补给技术.该技术采用FPGA控制系统将逐步提高放电电压、补充卤素气体和更换部分混合气体等操作有效组合起来.随着激光脉冲能量的下降,逐步提高放电电压;当放电电压达到最大值时,开始补充卤素气体,并恢复放电电压;当补充卤素气体效果不明显时,更换部分混合工作气体.将该技术应用于医用型ArF准分子激光器中进行实验研究,结果表明:在没有使用工作气体实时补给技术的情况下,激光器累计工作14.38 h后,输出单脉冲激光能量下降了17.2％;采用工作气体实时补给技术后,激光器输出能量下降速率明显降低,累计工作14.38 h,其单脉冲能量下降率能控制在3％范围内.因此,采用该技术可延长激光器工作气体的使用寿命、提高输出激光能量稳定性、减少停机次数并降低运行成本.     

New optically active poly(amide–imide)s from N-trimellitylimido-l-amino acid and 1,2-bis[4-aminophenoxy]ethane in the main chain: Synthesis and characterization

Six new optically active poly(amide–imide)s (PAIs) with good inherent viscosities were synthesized from the direct polycondensation reaction of N-trimellitylimido-l-amino acids with 1,2-bis[4-aminophenoxy]ethane by direct polycondensation in a medium consisting of N-methyl-2-pyrrolidone (NMP)/triphenyl phosphite (TPP)/calcium chloride (CaCl₂)/pyridine (py). Diamine was synthesized by using a two-step reaction. At first 1,2-bis[4-nitrophenoxy]ethane was prepared from the reaction of two equimolars 4-nitrophenol and one equimolar 1,2-dibromo ethane and the dinitro compound was reduced by using Pd/C. Also N-trimellitylimido-l-amino acids were synthesized by the condensation reaction of trimellitic anhydride with two equimolars of various l-amino acids in acetic acid solution. The polymerization reactions produced a series of optically active PAIs with a high yield and good inherent viscosity. The resulted polymers were fully characterized by means of FTIR and ¹H NMR spectroscopy, elemental analyses, inherent viscosity, specific rotation, solubility tests, thermogravimetric analysis (TGA), and a derivative of thermogravimetric (DTG) analysis.     

低泵浦功率的遥泵放大在超长跨距密集波分复用系统中的应用

针对长跨距密集波分复用系统中喇曼放大入纤泵浦功率过大的问题,将遥泵放大器（RP-EDFA）引入到系统中,通过对共纤RP-EDFA的噪音性能及其优化设计的研究,在理论上计算比较了RP-EDFA系统和后向喇曼放大系统在不同泵浦功率水平下的光信噪比和非线性相移,表明遥泵放大技术有效降低了入纤泵浦的功率水平,更适合长跨距应用.运用遥泵放大技术,对一个典型的长跨距系统进行系统Q值的模拟,结果表明：在 220 mW泵浦功率水平下可以实现跨距为 167 km的40×11.6 Gbit/s系统1000 km传输,Q值裕量4.4 dB.