有机合成反应中副反应的影响因素讨论

有机合成反应中副反应的产生和控制是反应成败的一个关键因素。对有机合成反应中常见副反应产生的过程进行了分析和总结,并讨论了传质、传热、加料方式、原料配比等合成工艺条件与这些副反应产生的相关性。可帮助学生更好地理解和分析有机合成反应工艺条件的选择和控制。     

A Glycan Array-Based Assay for the Identification and Characterization of Plant Glycosyltransferases

Growing plants with modified cell wall compositions is a promising strategy to improve resistance to pathogens, increase biomass digestibility, and tune other important properties. In order to alter biomass architecture, a detailed knowledge of cell wall structure and biosynthesis is a prerequisite. We report here a glycan array-based assay for the high-throughput identification and characterization of plant cell wall biosynthetic glycosyltransferases (GTs). We demonstrate that different heterologously expressed galactosyl-, fucosyl-, and xylosyltransferases can transfer azido-functionalized sugar nucleotide donors to selected synthetic plant cell wall oligosaccharides on the array and that the transferred monosaccharides can be visualized “on chip” by a 1,3-dipolar cycloaddition reaction with an alkynyl-modified dye. The opportunity to simultaneously screen thousands of combinations of putative GTs, nucleotide sugar donors, and oligosaccharide acceptors will dramatically accelerate plant cell wall biosynthesis research.     

用林邦的副反应思想处理滴定曲线和终点误差

本文用林邦的副反应思想处理离子平衡及滴定分析中的一些问题 ,试图把 4种反应平衡和 4种滴定方法在数学模型上进行统一 ,以达到节省教学学时和提高教学质量的目的     

丝组二肽所含基团在其切割DNA反应中的作用

近 2 0年来 ,人工核酸切割试剂的研究一直是化学、生物化学和分子生物学中最为活跃的前沿领域之一[1,2 ] .人工核酸切割试剂可以在足迹技术和核酸高级结构的研究中用作高分辨率的化学探针 ,还可以用于合成定点切割试剂[3] .后者又被称为人工工具酶 ,是一种非常重要的分子生物学工具 ,在疾病的基因治疗、反义 PCR技术等领域中都具有重要的应用 .人工核酸切割试剂的切割机理主要有自由基机理和磷酸酯水解机理两大类 .相对于自由基机理 ,水解机理具有许多优点 ,使得水解型切割试剂具有更为广泛的应用 .对于 DNA,目前文献报道的水解型人工切…     

A Glycan Array‐Based Assay for the Identification and Characterization of Plant Glycosyltransferases

Growing plants with modified cell wall compositions is a promising strategy to improve resistance to pathogens, increase biomass digestibility, and tune other important properties. In order to alter biomass architecture, a detailed knowledge of cell wall structure and biosynthesis is a prerequisite. We report here a glycan array‐based assay for the high‐throughput identification and characterization of plant cell wall biosynthetic glycosyltransferases (GTs). We demonstrate that different heterologously expressed galactosyl‐, fucosyl‐, and xylosyltransferases can transfer azido‐functionalized sugar nucleotide donors to selected synthetic plant cell wall oligosaccharides on the array and that the transferred monosaccharides can be visualized “on chip” by a 1,3‐dipolar cycloaddition reaction with an alkynyl‐modified dye. The opportunity to simultaneously screen thousands of combinations of putative GTs, nucleotide sugar donors, and oligosaccharide acceptors will dramatically accelerate plant cell wall biosynthesis research.     

用林邦的副反应思想处理滴定分析

以林邦的副反应思想为理论基础,创新滴定分析理论,整合滴定分析内容,统一"四大滴定"分析,并讨论了滴定分析的教学方法和学习方法。     

Carbodiimide-Mediated Beckmann Rearrangement of Oxyma-B as a Side Reaction in Peptide Synthesis

The suppression of side reactions is one of the most important objectives in peptide synthesis, where highly reactive compounds are involved. Recently, the violuric acid derivative Oxyma-B was introduced into peptide synthesis protocols as a promising additive to efficiently control the optical purity of the amino acids prone to racemization. However, we discovered a side reaction involving the Beckmann rearrangement of Oxyma-B during the coupling reaction, which compromises the yield and purity of the target peptides. Here, we present the investigation of the mechanism of this rearrangement and the optimization of the coupling reaction conditions to control it. These results can be taken into account for the design of novel efficient oxime-based coupling reagents.     

Unexpected Side Reaction in the Intermolecular N-H Insertion of Phenyl Diazoacetates with Arylamines

Unexpected side reaction is discovered from the N-H insertion of phenyl diazoacetates with arylamines in the presence of Rh2(OAc)4 catalyst. This side reaction is not evident with copper catalysts such as Cu(acac)2 or Cu(OTf)2. Good yield of the N-H insertion was obtained by using 0.2% of copper catalyst.     

Polarization Curve of a Porous Hydrophobized Electrode for Electrosynthesis Involving a Side Electrochemical Reaction

A polarization curve, suggested for electrosynthesis in a porous hydrophobized electrode operating in an inner-kinetic mode at a current efficiency for the target product below 100%, depends on the balance between exchange currents and slopes of the side and target reactions and the difference between the equilibrium potential of the side reaction and the steady-state electrode potential. At different slopes of the side and the target reactions, the current efficiency depends on the polarization. Experimental and calculated data satisfactory agree.     

基于Endo-M N175Q糖链转移反应与丙酮富集糖肽的LC-MS分析糖蛋白N-糖链

基于化学酶标记和丙酮富集糖肽方法,建立了一种可靠、有效、简单的糖蛋白N-糖链分析方法。以唾液酸糖肽(SGP)为模型糖肽,比较了样品中丙酮加入量对SGP的富集效果,最终选择加入样品体积5倍量的丙酮。用丙酮富集经胰蛋白处理的核糖核酸酶B(RNase B)酶解液中的糖肽,以富集分离得到的糖肽(糖基供体)和PDPZ-Boc-Asn-GlcNAc(糖基受体)作为酶反应底物,进行Endo-M N175Q的转糖基反应,得到PDPZBoc-Asn-GlcNAc-N-糖链标记物。采用YMC C18色谱柱为分析柱,10 mmol/L甲酸铵-乙腈为流动相梯度洗脱,经液相色谱-串联质谱(LC-MS)检测得到5种高甘露糖型糖链。结果表明,丙酮可有效地富集大量肽和少量糖肽混合溶液中的糖肽,Endo-M N175Q可将天然糖肽的糖链转移到PDPZ-Boc-Asn-GlcNAc受体上。将该方法应用于胎球蛋白N-糖链分析,检测到5种复杂型N-糖链。该研究为各种糖蛋白N-糖链检测提供了新的分析方法。     

Reaction Mechanism for the Removal of NOx by Wet Scrubbing Using Urea Solution: Determination of Main and Side Reaction Paths

Secondary problems, such as the occurrence of side reactions and the accumulation of by-products, are a major challenge in the application of wet denitrification technology through urea solution. We revealed the formation mechanism of urea nitrate and clarified the main and side reaction paths and key intermediates of denitrification. Urea nitrate would be separated from urea absorption solution only when the concentration product of [urea], [H⁺] and [NO₃⁻] was greater than 0.87~1.22 mol³/L³. The effects of the urea concentration (5–20%) and reaction temperature (30–70 °C) on the denitrification efficiency could be ignored. Improving the oxidation degree of the flue gas promoted the removal of nitrogen oxides. The alkaline condition was beneficial to the dissolution process, while the acidic condition was beneficial to the reaction process. As a whole, the alkaline condition was the preferred process parameter. The research results could guide the optimization of process conditions in theory, improve the operation efficiency of the denitrification reactor and avoid the occurrence of side reactions.     

Protein-Templated Hit Identification through an Ugi Four-Component Reaction**

Kinetic target-guided synthesis represents an efficient hit-identification strategy, in which the protein assembles its own inhibitors from a pool of complementary building blocks via an irreversible reaction. Herein, we pioneered an in situ Ugi reaction for the identification of novel inhibitors of a model enzyme and binders for an important drug target, namely, the aspartic protease endothiapepsin and the bacterial β-sliding clamp DnaN, respectively. Highly sensitive mass-spectrometry methods enabled monitoring of the protein-templated reaction of four complementary reaction partners, which occurred in a background-free manner for endothiapepsin or with a clear amplification of two binders in the presence of DnaN. The Ugi products we identified show low micromolar activity on endothiapepsin or moderate affinity for the β-sliding clamp. We succeeded in expanding the portfolio of chemical reactions and biological targets and demonstrated the efficiency and sensitivity of this approach, which can find application on any drug target.     

Reaction of a Programmable Glycan Presentation of Glycodendrimersomes and Cells with Engineered Human Lectins To Show the Sugar Functionality of the Cell Surface

Chemical and biological tools are harnessed to investigate the impact of spatial factors for functional pairing of human lectins with counterreceptors. The homodimeric adhesion/growth‐regulatory galectin‐1 and a set of covalently linked homo‐oligomers from di‐ to tetramers serve as proof‐of‐principle test cases. Glycodendrimersomes provide a versatile and sensitive diagnostic platform to reveal thresholds for ligand density and protein concentration in aggregation assays (trans ‐activity), irrespective of linker length between lectin domains. Monitoring the affinity of cell binding and ensuing tumor growth inhibition reveal the linker length to be a bidirectional switch for cis ‐activity. The discovery that two aspects of lectin functionality (trans ‐ versus cis ‐activity) respond non‐uniformly to a structural change underscores the power of combining synthetic and biological tools to advance understanding of the sugar functionality of the cell surface.     

Identification of Pairs of Organophosphorus Warfare Agents through Cholinesterase Reaction

Construction of Detehit (nerve-agent detector), a colorimetric biosensor of nerve agents, enables its utilization for selective analysis of nerve agents based on the different ability of nucleophilic reagents to reactivate enzyme-inhibitor complexes in the phase before dealkylation. For this purpose mono- and bispyridinium aldoximes, common in treatment of nerve agent poisoning, are used.

For a positive identification of a pair of organophosphates, a neural network analysis was used. The analysis was processed based on spectral data of the intensity of color changes of the surface of a cotton cloth reaction zone with immobilized and stabilized enzyme acetylcholinesterase. Color changes are based on Ellman's reaction. Intensity of these changes depends on activity of the enzyme after inhibition and reactivation of enzyme-inhibitor complex. The following nerve agents were identified: sarin, soman, tabun, cyclosarin, VX, and R-33.     

Identification of the Reaction Mechanism of Linear Irreversible Sequential Reactions

Kinetics and Catalysis - The article shows how the analysis of limited kinetic data (separate kinetic curves or even parts of them) for the set of sequential reactions with close values of the rate...     

Synthesis of D-Glucose-based Azacrown Ethers with Phosphinoxidoalkyl Side Chains and Their Application to an Enantioselective Reaction

Five chiral -D-glucose-based monoaza-15-crown-5 ethers with phosphinoxidoalkyl side chains of one to five carbon atoms (5a–e)have been synthesised. The cation binding ability of the new lariat ethers was evaluated bythe picrate extraction method. The substituents at the nitrogen atom were not a major influenceon the cation extraction ability of the azacrown ether; the compounds showed, however, a significant asymmetric induction as phase transfer catalysts in the Michael addition of2-nitropropane to chalcone (95% ee).     

由酸效应系数计算pH值的新方法

基于酸效应系数αL(H)与溶液酸度的关系,建立了一种由αL(H)手工计算pH值的新方法.该方法无需解高次方程,仅需对lgαL(H)及相关pKa作加减运算、复杂体系也只需增加少量以10为底的乘方运算及常用对数运算即可.因而方法简便,计算误差可预先设置,本文控制不超过5%.     

电喷雾电离质谱鉴定合成莱克多巴胺的副反应产物

采用电喷雾电离质谱(ESI-MS)结合碰撞诱导解离(CA)技术分析了合成莱克多巴胺(Ractopamine)产品溶液中目标化合物和副反应产物。根据一级和二级质谱图确定了反应副产物的化学结构,4种副产物分别为Ractopamine脱去水分子、再氢化及烃羟基甲醚化和乙醚化而形成的。质谱方法提供的分子量、分子结构信息对改进反应条件、减少副反应发生、提高产品收率具有指导作用。     

Communication: An Unusual Side Reaction in the Perallylation of a Glucoside Brought About by Sodium Hydride

We are presently working on the combination of carbohydrate and dendrimer chemistry, both to develop the synthesis of multivalent glycomimetics and to prepare novel dendrimers with advantageous properties. In the course of this work we have used saccharides as oligofunctional core molecules for the synthesis of carbohydrate-centered dendrimers¹ and carbohydrate-centered glycoclusters.²     

Three-in-One: Miniature Models of Natural Acyl-Transfer Systems Enable Vector-Selective Reaction on the Primary Side of Cyclodextrins

Miniature models of acyl-transfer systems in cells, which were composed by replacing the protein, coenzyme, and substrate with CD, functional group, and CD, respectively, and combining them all together in one, displayed definite role-sharing and exact cooperation of the functional groups and hydrophobic cavity, and thus enabled the regio-specific reaction.