Thioether‐Bearing Hyperbranched Polyether Polyols with Methionine‐Like Side‐Chains: A Versatile Platform for Orthogonal Functionalization

The synthesis of thioether‐bearing hyperbranched polyether polyols based on an AB/AB₂ type copolymerization (cyclic latent monomers) is introduced. The polymers are prepared by anionic ring‐opening multibranching copolymerization of glycidol and 2‐(methylthio)ethyl glycidyl ether (MTEGE), which is conveniently accessible in a single etherification step. Slow monomer addition provides control over molecular weights. Moderate dispersities (Đ = 1.48–1.85) are obtained, given the hyperbranched structure. In situ ¹H NMR copolymerization kinetics reveal reactivity ratios of r _G = 3.7 and r _MTEGE = 0.27. Using slow monomer addition, copolymer composition can be systematically varied, allowing for the adjustment of the hydroxyl/thioether ratio, the degree of branching (DB = 0.36–0.48), thermal properties, and cloud point temperatures in aqueous solution in the range of 29–75 °C. Thioether oxidation to sulfoxides enables to tailor the copolymers' solubility profile. Use of these copolymers as a versatile, multifunctional platform for orthogonal modification is highlighted. The methyl sulfide groups can be selectively alkoxylated, using propylene oxide, allyl glycidyl ether, or furfuryl glycidyl ether, resulting in functional hyperbranched polyelectrolytes. Reaction of the alcohol groups with benzyl isocyanate demonstrates successful orthogonal functionalization.

     

正交试验结合响应面法优化诃子多糖提取工艺

采用正交试验结合响应面法优化诃子多糖的提取工艺,以诃子多糖的提取率为指标,以固液比、提取温度、提取时间和提取次数为因素,正交试验初步筛选工艺参数,响应面法做进一步优化.结果表明,多糖提取的最佳工艺条件为固液比1∶28,提取温度69℃,提取时间1h,提取次数3次,各项指标相对误差均小于2%,应用响应面法可减少诃子多糖提取时间.     

扰动m-增生算子的零集

本文对Ｋａｒｔｓａｔｏｓ提出的一个问题给出了完整的回答并减弱了Ｋａｒｔｓａｔｏｓ定理的条件,     

有限局部环上对称矩阵的计数定理(I)

设$A_{n}(R)$是有限局部环$Z/p^{k}Z$上$n$阶对称矩阵的集合, 这里$n\geq 2$. $p$是大于$2$素数, $p\equiv1({\rm mod}4)$ 且$k>1$. 通过确定有限局部环$Z/p^{k}Z$上对称矩阵的标准型, 计算出$A_{n}(R)$在线性群${\rm GL}_{n}(R)$作用下的轨道数, 从而计算出由特定对称矩阵确定的正交群的阶以及与特定对称矩阵在同一轨道的对称矩阵的阶.     

基于数字相干叠加的相干光正交频分复用系统中光纤非线性容忍性研究

光正交频分复用系统中的光纤非线性效应制约着系统进一步的扩容. 针对此问题, 提出一种数字相干叠加的方法, 用于提高相干光正交频分复用系统对光纤非线性的容忍性. 仿真中, 5通道的波分复用下偏振复用相干光正交频分复用系统的每个通道传输四进制正交振幅调制映射的71.53 Gbit/s信号在光纤中传输400 km. 首先, 通道间隔为25 GHz, 与传统相干光正交频分复用系统相比, 色散补偿前后, 使用数字相干叠加的相干光正交频分复用系统的信噪比分别提升了6.02 dB和9.05 dB, 最佳入纤光功率均增大了2 dB; 其次, 通道间隔为50 GHz, 色散补偿前后, 信噪比分别提升了4.9 dB和8.75 dB. 通过理论推导及仿真, 验证了所提方法能有效消除相干光正交频分复用系统的一阶非线性失真, 进而提高系统对光纤非线性的容忍性.     

基于动态混沌映射的三维加密正交频分复用无源光网络

提出了一种基于混沌映射的三维加密正交频分复用无源光网络保密通信系统.该系统通过相关性检测锁定收发端混沌系统参数,实现收发双方混沌系统同步;并利用同步混沌系统生成密钥,实现符号扰动以及二重子载波加密.该加密方案的密钥空间超过10~(86),能够有效对抗穷举攻击.实验实现了13.3 Gb/s基于64进制正交幅度调制的加密正交频分复用信号在25 km标准单模光纤中的传输,并完成了信息的有效解密.     

RATE OF INTRA-MOLECULAR CONTACT FORMATION IN SHORT TWO-DIMENSIONAL COMPACT POLYMERS CHAINS

It is important to know the rate of intra-molecular contact formation in proteins in order to understand how proteins fold clearly. Here we investigate the rate of intra-molecular contact formation in short two-dimensional compact polymer chains by calculating the probability distribution p(r) of end-to-end distance r using the enumeration calculation method and HP model on two-dimensional square lattice. The probability distribution of end-to-end distance p(r) of short two-dimensional compact polymers chains may consist of two parts, i.e. p(r) = p1(r) p2(r), where p1(r) and p2(r) are different for small r. The rate of contact formation decreases monotonically with the number of bonds N, and the rate approximately conforms to the scaling relation of k(N) ∝ N-α. Here the value of α increases with the contact radius a and it also depends on the percentage of H (hydrophobic) residues in the sequences of compact chains and the energy parameters of εHH, εHP and εPP . Some comparisons of theoretical predictions with experimental results are also made. This investigation may help us to understand the protein folding.     

N-二茂铁甲基丁胺的合成

以二茂铁甲醛和正丁胺为原料,经缩合、还原反应制得N-二茂铁甲基丁胺。采用连续操作的方法,用正交实验确定了反应的最佳条件:二茂铁甲醛10 mmol,n(FcCHO)∶n(n-C4H9NH2)∶n(KBH4)=1.0∶1.4∶1.4;于(65±2)℃缩合反应6 h;于(55±2)℃还原反应8 h,产率可达77.8%。在最佳条件下实验规模放大50倍,收率达80.5%,纯度达99.5%。     

A Novel Preprocessing Algorithm for Three-Way HPLC Data

Orthogonal signal correction (OSC) was a data preprocessing algorithm. It ensured that the filtered information was irrelevant to concentration data while using it to filter the noise from the original data. This paper extended the OSC application range from two-way data to three-way data. Two drug data sets, Enoxacin, Norfloxacin, Ciprofloxacin and Betamethasone, cortisone acetate, prednisone acetate, showed that the application of the OSC algorithm to three-way HPLC data was feasible and needed further research.     

Difluorocarbene-Induced Ring-Opening Difluoromethylation-Halogenation of Cyclic (Thio)Ethers with TMSCF2X (X=Br,Cl)**

The ring-opening difluoromethylation-halogenation of cyclic (thio)ethers is reported through a simple strategy relying on carbon-chalcogen bond activation with difluorocarbene. The reaction proceeds through in situ protonation of the previously little-known difluoromethylene oxonium or sulfonium ylide intermediate followed by ring-opening with halide ion to afford halogenated acyclic difluoromethyl (thio)ethers that can then be employed for further elaboration. TMSCF₂X (X=Br, Cl) are unique reagents to achieve this synthetic purpose, which serve as both the difluorocarbene source and the halide ion source.