Controlling the outcome of overacylation of N-protected aminooxyacetic acid during the synthesis of an aminooxy-peptide for chemical ligation

An aminooxy-containing peptide, the nucleophile partner for oxime ligations, is usually grafted on a NH₂-peptide resin by activating a protected aminooxyacetic acid as an active ester. Here, we have shown that its subsequent coupling to NH₂-peptide resin competes with the overacylation of the -NH-O- nitrogen and that the overacylation level increases with the basicity of the reaction mixture. Moreover, we found that overacylation is prevented when the COOH of the Aoa-derivatives is engaged in an amide bond.     

Detecting and Analyzing Politically-Themed Stocks Using Text Mining Techniques and Transfer Entropy—Focus on the Republic of Korea’s Case

Politically-themed stocks mainly refer to stocks that benefit from the policies of politicians. This study gave the empirical analysis of the politically-themed stocks in the Republic of Korea and constructed politically-themed stock networks based on the Republic of Korea’s politically-themed stocks, derived mainly from politicians. To select politically-themed stocks, we calculated the daily politician sentiment index (PSI), which means politicians’ daily reputation using politicians’ search volume data and sentiment analysis results from politician-related text data. Additionally, we selected politically-themed stock candidates from politician-related search volume data. To measure causal relationships, we adopted entropy-based measures. We determined politically-themed stocks based on causal relationships from the rates of change of the PSI to their abnormal returns. To illustrate causal relationships between politically-themed stocks, we constructed politically-themed stock networks based on causal relationships using entropy-based approaches. Moreover, we experimented using politically-themed stocks in real-world situations from the schematized networks, focusing on politically-themed stock networks’ dynamic changes. We verified that the investment strategy using the PSI and politically-themed stocks that we selected could benchmark the main stock market indices such as the KOSPI and KOSDAQ around political events.     

Novel Approach to Two-Component Analysis Based on the Generalized Calibration Strategy

The generalized calibration strategy (GCS), developed and previously applied to chemical analysis, has been adapted to two-component (2C) analysis. According to the 2C-GCS procedure, a set of 10 calibration solutions containing a sample and standards of two analytes in well-defined composition was diluted. The measurements performed at a given dilution stage allow the concentration of both analytes in a sample to be evaluated with six apparent concentrations calculated with various mathematical approaches. As a result, the method allows the detection, examination, and elimination of nonlinear and interference effects with multiplicative and additive characteristics. To perform 2C-GCS automatically and effectively, a dedicated flow sequential injection system was designed to be fully controlled by a computer. Caffeine and paracetamol were determined in synthetic and pharmaceutical samples using this calibration approach. The analytes were determined with good precision and accuracy with low consumption of sample and standard solutions. On the basis of this experimental model, the influence of effects and tendencies in the examined analytical system was detected and evaluated.     

[4 1]及[3 2]会聚式四氢呋喃环合成策略在天然产物全合成中的应用进展

四氢呋喃环广泛存在于具有生物活性的天然产物结构当中,立体选择性地构筑四氢呋喃环往往成为这些天然产物全合成研究中的关键。本文归纳了已有全合成报道中的四氢呋喃环成环策略,以实例展示了其中的会聚式合成策略在近年的发展。相比于直线型的分子内关环策略,以[4+1]、[3+2]为代表的会聚式四氢呋喃关环策略往往能够使全合成的整体路线更加简洁高效,更符合全合成研究领域的发展趋势。     

Sequential native chemical ligation utilizing peptide thioacids derived from newly developed Fmoc-based synthetic method

The first facile Fmoc-based synthetic procedure for peptide thioacids was developed. Successful application of the resulting thioacids to sequential native chemical ligation (NCL) in the N to C direction was achieved. Conversion of the peptide thioacids to the corresponding thioesters with Ellman's reagent followed by NCL in the presence of tris(2-carboxyethyl)phosphine (TCEP) and thiophenol was accomplished in a one-pot manner.     

Open tubular capillary electrochromatography: A useful microreactor for collagen I glycation and interaction studies with low-density lipoprotein particles

Diabetes, a multifunctional disease and a major cause of morbidity and mortality in the industrialized countries, strongly associates with the development and progression of atherosclerosis. One of the consequences of high level of glucose in the blood circulation is glycation of long-lived proteins, such as collagen I, the most abundant component of the extracellular matrix (ECM) in the arterial wall. Glycation is a long-lasting process that involves the reaction between a carbonyl group of the sugar and an amino group of the protein, usually a lysine residue. This reaction generates an Amadori product that may evolve in advanced glycation end products (AGEs). AGEs, as reactive molecules, can provoke cross-linking of collagen I fibrils. Since binding of low-density lipoproteins (LDLs) to the ECM of the inner layer of the arterial wall, the intima, has been implicated to be involved in the onset of the development of an atherosclerotic plaque, collagen modifications, which can affect the affinity of native and oxidized LDL for collagen I, can promote the entrapment of LDLs in the intima and accelerate the progression of atherosclerosis.In this study, open tubular capillary electrochromatography is proposed as a new microreactor to study in situ glycation of collagen I. The kinetics of glycation was first investigated in a fused silica collagen I-coated capillary. Dimethyl sulphoxide, injected as an electroosmotic flow marker, gave information about the charge of coating. Native and oxidized LDL, and selected peptide fragments from apolipoprotein B-100, the protein covering LDL particles, were injected as marker compounds to clarify the interactions between LDLs and the glycated collagen I coating. The method proposed is simple and inexpensive, since only small amounts of collagen and LDL are required. Atomic force microscopy images complemented our studies, highlighting the difference between unmodified and glycated collagen I surfaces.     

基于TSP问题的一种改进遗传算法

针对传统遗传算法(GA)在解决旅行商问题(TSP)时存在的不足,对初始种群的选取方式和算子的选取进行了改进,设计出了一种能够较好的求解出TSP问题的最优解的算法.计算机仿真实验验证了该算法的有效性.     

基于社团结构的负载传输优化策略研究

研究表明网络社团结构特征对负载传输有影响,明显社团结构特征会降低网络的承载能力.由于最短路由策略在选择路由时有一定的随机性,本文提出了一种基于社团结构的负载传输策略,减少最短路由经过的社团数量,从而降低社团边缘节点的介数.实验结果显示,该策略在保证最短路由小世界特性的同时,提升了网络的承载能力,社团划分得越准确传输优化策略效果越显著. 关键词： 优化路由策略 社团结构 复杂网络 负载传输     

与资本市场收益变动相关的最优再保险策略

本文在假定资本市场变动与保险公司资本收益变动存在相关性的情况下,研究了保险公司最优再保险策略问题.利用HJB-变分不等方程,获得了最优再保险策略和最小破产概率的显示表达式,推广了文献[3]的结果.     

A hybrid of adjustable trust-region and nonmonotone algorithms for unconstrained optimization

This study devotes to incorporating a nonmonotone strategy with an automatically adjusted trust-region radius to propose a more efficient hybrid of trust-region approaches for unconstrained optimization. The primary objective of the paper is to introduce a more relaxed trust-region approach based on a novel extension in trust-region ratio and radius. The next aim is to employ stronger nonmonotone strategies, i.e. bigger trust-region ratios, far from the optimizer and weaker nonmonotone strategies, i.e. smaller trust-region ratios, close to the optimizer. The global convergence to first-order stationary points as well as the local superlinear and quadratic convergence rates are also proved under some reasonable conditions. Some preliminary numerical results and comparisons are also reported.