胶束介质中的α－氨基酸合成

胶束介质中的α－氨基酸合成余孝其，蓝仲蔽，赵华明（四川大学化学系成都６１００６４）关键词逆向胶束，α－氨基酸，合成氨基酸是人体所必需的营养物质，也是医药、食品等工业重要的基本原料，与人类有着密切的联系。α－氨基酸的合成方法很多，可利用醛与氯仿在碱性条...     

Ni（Ⅱ）螯合物在氨基酸合成中的应用

Ni(Ⅱ)螯合物诱导合成氨基酸是氨基酸合成方法中一类新颖且有工业生产价值的合成方法.从合成方法学、络合金属离子的优选、配体的改进、卤代片段的选择、合成氨基酸种类等方面介绍该合成方法的研究进展.     

Ni(II)螯合物在氨基酸合成中的应用

Ni(II)螯合物诱导合成氨基酸是氨基酸合成方法中一类新颖且有工业生产价值的合成方法. 从合成方法学 、络合金属离子的优选、配体的改进、卤代片段的选择、合成氨基酸种类等方面介绍该合成方法的研究进 展.     

光学活性双氨基酸的合成

光学活性的双氨基酸作为一类非天然的氨基酸合成子, 在医药、农药和肽类合成中有着重要的作用. 评述了近年来关于光学活性双氨基酸合成的进展.     

钯催化的酰胺羰基化反应

酰胺羰基化的发现为氨基酸及其衍生物的合成提供了一个新方法。该合成方法 步骤简洁，只需一步即可从醛、酰胺-氧化碳合成N-酰基氨基酸，而且该反应是原 子经济型反应。与钴催化的酰胺羰基化相比，钯催化的反应条件更为温和，催化效 率也大为提高，对基团有更广普的适应性。简述近所来这一领域的新进展。     

吸附型“人工肝”辅助材料的合成及其性能研究Ⅰ大孔吸附树脂对芳香氨基酸的吸附性能

合成了苯乙烯型大孔吸附剂（MacroreticularAdsorbentMA）测定其孔结构参数，考察吸附剂对芳香氨基酸的吸附性能。实验结果表明，MA－2型吸附剂对芳香氨基酸具有特异性吸附，而对支链氨基酸吸附为非特异性吸附，其血液相容性良好。     

β-氨基酸的合成: 等当体方法的应用

β-氨基酸是一类在药物开发和生物研究中有广泛应用的中间体. 由等当体合成β-氨基酸的方法具有结构定制、合成产物丰富、直观等特点, 是β-氨基酸合成领域中不可或缺的合成方法. 重点介绍近年来该领域具有代表性的工作.     

α-氨基酸的不对称合成

α氨基酸的不对称合成是合成方法学中的重要组成部分,由此而发展出来的方法成为不对称合成领域中的典范。本文着重从合成方法学角度出发,总结了α－氨基酸不对称合成的最新进展。     

合成位阻肽的偶合试剂研究

本文综述了合成含N-烷基氨基酸或α，α-二取代氨基酸位阻肽的偶合试剂研究新进展，并对这些新的偶合试剂及偶合方法的优点和不足予以评述。     

电化学合成氨基酸类化合物的研究进展（英文）

氨基酸类化合物在现代医药化学研究和药物设计开发方面具有非常重要的作用,一直以来,开发高效的合成方法学来制备这些氨基酸类化合物的研究吸引了化学家们广泛的研究兴趣.另一方面,近些年电化学反应逐渐兴起成为一种绿色可再生的合成手段,是有机合成化学领域的研究热点,其在氨基酸的合成方面的应用也受到了极大的关注.本综述第一次较为系统全面地总结了近些年有关电化学手段合成氨基酸的研究进展,讨论了这些电化学方法在合成氨基酸类化合物方面的实际应用的可行性、具备的优势以及存在的一些局限,为氨基酸绿色合成方面的研究提供了一定的参考.     

Incorporation of β‐Silicon‐β3‐Amino Acids in the Antimicrobial Peptide Alamethicin Provides a 20‐Fold Increase in Membrane Permeabilization

Incorporation of silicon‐containing amino acids in peptides is known to endow the peptide with desirable properties such as improved proteolytic stability and increased lipophilicity. In the presented study, we demonstrate that incorporation of β‐silicon‐β3‐amino acids into the antimicrobial peptide alamethicin provides the peptide with improved membrane permeabilizing properties. A robust synthetic procedure for the construction of β‐silicon‐β3‐amino acids was developed and the amino acid analogues were incorporated into alamethicin at different positions of the hydrophobic face of the amphipathic helix by using SPPS. The incorporation was shown to provide up to 20‐fold increase in calcein release as compared with wild‐type alamethicin.     

Peptide-Chain Elongation Using Unprotected Amino Acids in a Micro-Flow Reactor

Conventional peptide synthesis requires a deprotection step after each amidation step, which decreases synthetic efficiency. Therefore, peptide synthesis using unprotected amino acids is considered an ideal approach. Here, we report peptide chain elongation using unprotected amino acids via a mixed carbonic anhydride. Micro-flow technology enabled rapid mixing of an organic layer containing a protected amino acid or dipeptide and an aqueous layer containing an unprotected amino acid or dipeptide to accelerate the desired amidation, and this approach successfully suppressed undesired racemization/epimerization (≤0.4 %). Various di-, tri-, and tetra-peptides were obtained in good to high yields. This is the first report on peptide chain elongation that proceeds without severe racemization from unprotected amino acids using inexpensive, nonexplosive, less wasteful, and less toxic reagents.     

Click chemistry inspired synthesis of ferrocene amino acids and other derivatives

This work reports the synthesis of a wide range of ferrocenyl-amino acids and other derivatives in excellent yield. Diverse amino acid containing azides were synthesized and ligated to ferrocene employing click reaction to access ferrocenyl amino acids. Chiral alcohols, esters, diols, amines containing azido group were tagged to ferrocene via click reaction to generate ferrocene derived chiral derivatives. A novel strategy for direct incorporation of ferrocene into a peptide and a new route to 1, 1′disubstituted ferrocene amino acid derivative are reported.     

Ribosomal synthesis of unnatural peptides

Combinatorial libraries of non-biological polymers and drug-like peptides could in principle be synthesized from unnatural amino acids by exploiting the broad substrate specificity of the ribosome. The ribosomal synthesis of such libraries would allow rare functional molecules to be identified using technologies developed for the in vitro selection of peptides and proteins. Here, we use a reconstituted E. coli translation system to simultaneously re-assign 35 of the 61 sense codons to 12 unnatural amino acid analogues. This reprogrammed genetic code was used to direct the synthesis of a single peptide containing 10 different unnatural amino acids. This system is compatible with mRNA-display, enabling the synthesis of unnatural peptide libraries of 10(14) unique members for the in vitro selection of functional unnatural molecules. We also show that the chemical space sampled by these libraries can be expanded using mutant aminoacyl-tRNA synthetases for the incorporation of additional unnatural amino acids or by the specific posttranslational chemical derivitization of reactive groups with small molecules. This system represents a first step toward a platform for the synthesis by enzymatic tRNA aminoacylation and ribosomal translation of cyclic peptides comprised of unnatural amino acids that are similar to the nonribosomal peptides.     

Application of DEPBT on the Synthesis of the Protected Dipeptides Containing Histidine with Unprotected Imidazole Group by Solution Method

3- (Diethoxyphosphoryloxy)- 1,2,3-benzotriazln-4 (3H)-one (DE-PBT) was an organophosphorus coupling reagent developed by our group. It was an effective coupling reagent for the synthesis of protected peptides containing Tyr, Ser and Thr with unprotected hydroxy group on their side chain. The further study of the synthesis of a series of protected dipeptides containing hisfidine with unprotected imidazole group using DEPBT is reported. During the synthetic procedure, the imidazole group of histidine did not need to be protected. When the carboxyl components were N-protected aromatic amino acids or basic amino acids, the yields were relatively high (63%--81%). However,when the carboxyl components were N-protected acidic amino acids, the yields were relatively low (47%--48%). The results expanded the application of DEPBT on the synthesis of bioactive peptides containing histidine.     

Efficient copper-catalyzed synthesis of poly-N-heterocycles containing amino acid residues

An efficient copper-catalyzed method has been developed for the synthesis of poly-N-heterocycles containing amino acid residues. The protocol uses readily available 2-halobenzamides containing amino acids and their methyl esters, substituted phenylacetonitriles, and malononitrile as the starting materials and the reactions were performed well under mild conditions. The method should provide a novel and useful strategy for synthesis of N-heterocyclic compounds.     

Determination of glycine,alanine, and leucine at different solution ph with the aid of donnan potential sensors based on hybrid membranes

The cross sensitive sensors whose analytical signal is the Donnan potential (PD-sensors) were developed for the determination of the amino acids glycine, alanine, and leucine in acidic and alkaline solutions. Hybrid materials based on perfluorinated sulfo cation-exchange membranes Nafion and MF-4SC with incorporated zirconium dioxide and silicon dioxide nanoparticles, including those with modified surfaces containing proton-acceptor groups, were used in the PD-sensors. The sensitivity of the PD-sensors to hydronium ions, which interfere with the determination of amino acids at pH < 7, was considerably decreased due to the use of the membranes obtained by an in situ method that contained silicon dioxide nanoparticles with amine-containing groups. The greatest sensitivity of the PD-sensors to the anions of amino acids at pH > 7 and the smallest sensitivity to the cations K⁺ were observed in hybrid membranes, which combined an increased rate of anion transfer and a low moisture capacity. The use of the PD-sensors based on hybrid membranes makes it possible to determine the cations, anions, and zwitterions of amino acids over a wide range of pH with a sufficiently high accuracy.     

Synthesis and properties of MIDA boronate containing aromatic amino acids: new peptide building blocks

Herein, we report the synthesis of novel phenylalanine and tyrosine derivatives containing a N-methyliminodiacetic acid boronate group. These compounds can be prepared enantiomerically pure, they are stable to column chromatography and they can be stored in air for two months without degradation occurring. This new class of boronate containing aromatic amino acids has potential applications in both peptide chemistry and natural product synthesis.     

New stable backbone linker resins for solid-phase peptide synthesis

[reaction: see text] Two new 4-methoxybenzaldehyde backbone linker resins were developed for the solid-phase synthesis of peptides. The linkers are very stable during the cleavage of common protecting groups for amines (Fmoc, Boc) and carboxylic acids (Me, All, tBu) in peptide synthesis. Cleavage from the resin with refluxing TFA is sufficiently mild for peptides containing polar and nonpolar amino acids.     

卤代苯丙氨酸衍生物的合成与拆分

以苯胺类化合物为起始原料,经重氮化、丙烯酸加成、氨解等过程合成了5种消旋苯环取代苯丙氨酸衍生物,并采用α-糜蛋白酶和枯草杆菌蛋白酶对所有氨基酸进行了拆分,通过IR,¹HNMR,元素分析和旋光等技术进行表征.其中4种氨基酸未见文献报道.