新型光动力化合物5-氨基乙酰丙酸的化学合成与应用

综述了20世纪90年代以来以杂环物质衍生物、β酮酯类化合物及其他化合物为原料合成5-氨基乙酰丙酸(ALA)的研究进展.评述了以糠胺、四氢糠胺、5-羟甲基-2-糠醛、乙酰丙酸、丁二酸单乙酯酰氯、单甲酯丁二酸和甘氨酸为原料的合成方法以及部分合成方法的优缺点及工业应用前景.介绍了ALA在农业领域作为无公害绿色除草剂、杀虫剂、落叶剂、植物生长调节剂等的应用,及其在医学领域和有机合成中的应用.     

氨基酸表面活性剂的合成、性质及工业应用（续完）

正7毒性传统表面活性剂,特别是阳离子表面活性剂对水生生物具有很强的毒性。其急性毒性是由于表面活性剂在细胞-水界面处的吸附-离子相互作用现象。降低表面活性剂的cmc通常导致表面活性剂更强的界面吸附,通常导致其急性毒性升高。表面活性剂疏水链的长度增加也导致表面活性剂急性毒性增大。大部分AAS为对人体和环境(特别是对海洋生物)低毒或无毒,使其适合做为食品成分、药物     

A new strategy for the synthesis of dinucleotides loaded with glycosylated amino acids--investigations on in vitro non-natural amino acid mutagenesis for glycoprotein synthesis

The in vitro non-natural amino acid mutagenesis method provides the opportunity to introduce non-natural amino acids site-specifically into proteins. To this end, a chemically synthesised aminoacylated dinucleotide is enzymatically ligated to a truncated suppressor transfer RNA. The loaded suppressor tRNA is then used in translation reactions to read an internal stop codon. Here we report an advanced and general strategy for the synthesis of the aminoacyl dinucleotide. The protecting group pattern developed for the dinucleotide facilitates highly efficient aminoacylation, followed by one-step global deprotection. The strategy was applied to the synthesis of dinucleotides loaded with 2-acetamido-2-deoxy-glycosylated amino acids, including N- and O-beta-glycosides and O- and C-alpha-glycosides of amino acids, thus enabling the extension of in vitro non-natural amino acid mutagenesis towards the synthesis of natural glycoproteins of high biological interest. We demonstrate the incorporation of the glycosylamino acids--although with low suppression efficiency--into the human interleukin granulocyte-colony stimulating factor (hG-CSF), as verified by the ELISA technique.     

Trichloroisocyanuric acid,a new and efficient catalyst for the synthesis of dihydropyrimidinones

An efficient three-component synthesis of 3,4-dihydropyrimidinones using trichloroisocyanuric acid (TCCA) as a mild, homogeneous and neutral catalyst for Biginelli reaction in ethanol or DMF under reflux condition and microwave irradiation is described. Yields are excellent in either of the two conditions.     

新固体酸催化合成己二酸二丁酯绿色新工艺

研究了应用自制“T 40 0”催化合成己二酸二丁酯的绿色新工艺。“T 40 0”是某一无机盐经 40 0℃焙烧制得一种水不溶的新型固体酸催化剂 ,吸附吡啶的红外光谱表明 :催化剂表面形成了新的Br nsted酸中心。此催化剂对己二酸和正丁醇的酯化活性高、无副反应、沉降较快、易与产物分离等特点 ,并得到合成己二酸二丁酯的绿色新工艺条件如下 :己二酸 0 .1mol,正丁醇 0 .35mol,催化剂 0 .6g ,反应温度 15 0℃ ,反应时间 10 0min ,在此条件下收率可达 99%以上。     

Natural antioxidants produced in oxidized lipid/amino acid browning reactions

1-Substituted pyrroles (1 and2) and1-substituted 2-(1′-hydroxypropyl)pyrroles (3–5) were produced in reactions between a lipid peroxidation product, 4,5(E)-epoxy-2(E)-heptenal, and the amino acid lysine. The antioxidative activity of compounds1–5 was studied. Oxidative stability was evaluated in refined soybean oil containing compounds1–5, butylated hydroxytoluene (BHT),n-propyl gallate orl-lysine, at concentrations of 50–200 ppm. Oils were either oxidized at 60°C and oxidation products determined by the thiobarbituric acid-reactive substances assay, or they were oxidized at 110°C by the Rancimat method. Although both methods gave similar results, greater differences were observed at 60°C than at 110°C. Addition of compounds1–5,l-lysine, BHT, and propyl gallate significantly (P<0.01) protected the oil against oxidation. The effectiveness order found was:l-lysine << compounds3–4 < compounds1–2 < compound5 ≈ BHT << propyl gallate.     

Non-reductive coupling of branched amino fatty acid esters with mono and disaccharides: synthesis of a new class of alkyl glycosylamines

A new class of alkyl glycosylamines, using methyl 9- ( 1 ) or methyl 12-aminooctadecanoate ( 2 ) and carbohydrates (glucose ( 3a ), galactose ( 3b ), lactose ( 3c ), and maltose ( 3d ), has been synthesized. In order to accomplish the binding of the amino fatty acid esters 1–2 with carbohydrates 3a–d the method described by Helferich, which is using peracetylated carbohydrate bromides, was employed. The yields ranged between 26 and 55%. The chemical structures were identified using ¹H and ¹³C NMR-spectroscopy including 2D techniques and FT-IR. The critical micelle concentrations and the surface tension profiles of these N-Alkyl-D -glycosides in water were determined.     

Synthesis and solution properties of a new pH-responsive polymer containing amino acid residues

The amine salt, N,N-diallyl-N-carboethoxymethylammonium chloride was cyclopolymerized in water using ammonium persulfate as an initiator to afford a cationic polyelectrolyte which on acidic hydrolysis of the pendant ester groups gave the corresponding cationic acid salt (CAS). The CAS was converted into an anionic polyelectrolyte (APE) and polybetaine (PB). The solution properties of the APE having two basic functionalities were investigated in detail by potentiometric and viscometric techniques. Basicity constants of the amine as well as the carboxylate groups in APE are ‘apparent’ and as such follow the modified Henderson-Hasselbalch equation; as the degree of protonation (α) of the whole macromolecule increases, the protonation of the amine nitrogens and carboxylate groups becomes increasingly more difficult and easier, respectively. While the APE, PB and CAS were found to be soluble in salt-free water, the corresponding PB and CAS of the SO₂ copolymers of the amine salt 1 were found to be insoluble in water.     

Thermal alteration of a cyclic fatty acid produced by a flaxseed extract

Methyl 8-[2-(cis-pent-2′-enyl)-3-oxo-cis-cyclopent-4-enyl] octanoate (I) is the methyl ester of a cyclic fatty acid synthesized enzymically from an incubation of linolenic acid with an extract of flaxseed (Linum usitatissimum L.). A proposed trivial name for I is methyl 12-oxo-cis-10, 15-phytodienoate (12-oxo-PDA). The evidence presented indicated that compound I has thecis configuration of the carbon chains with respect to the cyclopentenone ring. Treatment with acid, base, or heat isomerized I to a second product (II) that has thetrans configuration of the carbon chains. Prolonged heat treatment of II yielded a third cyclic product, methyl 12-oxo-9(13),cis-15-phytodienoate (III).     

氯磺酸合成新工艺的开发与应用

1气相法合成工艺氯磺酸是三氧化硫的延伸产品,国内现有的氯磺酸生产装置均使用三氧化硫气体(如一次转化出口炉气、加热蒸发发烟硫酸产生纯SO_3,气体配用二次转化出口炉气、加热蒸发发烟硫酸产生的纯SO_3气体等),与来自曼海姆法硫酸钾装置的氯化氢气体[(?)(HCl)≥30%]或者氯碱装置氯化氢气体[(?)(HCl)约95%]或者硫酸-盐酸氯化氢发生装置氯化氢气体[(?)(HCl)约100%]在130～230℃下反应,合成气态氯磺酸,再经过冷凝分离得到液态氯磺酸产品。气相法合成工艺存在的问题主要有:a.尾气     

对羟基苯乙酸-N,N-二甲氨基甲酰甲酯合成工艺优化研究

采用对羟基苯乙酸、氯代乙酰二甲胺、三乙胺为原料经反应合成对羟基苯乙酸-N,N-二甲基氨基甲酰甲酯。合成优化工艺条件为:n(对羟基苯乙酸)∶n(氯代乙酰二甲胺)=1∶1.0,n(对羟基苯乙酸)∶n(三乙胺)=1∶1.5,反应时间12 h,反应温度60℃,产率81%,纯度98%左右。     

Characterization of a prostaglandin-like metabolite of linolenic acid produced by a flaxseed extract

One of the products formed upon incubation of linolenic acid (cis9,12,15-octadecatrienoic acid) with an extract of flaxseed acetone powder has been characterized as 8-[2-(cis-pent-2′-enyl)-3-oxo-cis-cyclopent-4-enyl]octanoic acid. The cyclopentenone ring structure of this acid is analogous to that of the A-type prostaglandins produced in mammalian systems.     

多肽合成中氨基酸活化酯的制备研究

氨基酸活化反应对合成多肽的产率及纯度具有重要影响。以芴甲氧羰基-缬氨酸为研究对象,首次采用反相高效液相色谱法检测活化反应过程,建立了芴甲氧羰基-缬氨酸活化酯的分析方法,优化了氨基酸活化酯的制备条件,并引入了新的用于Fmoc策略合成多肽的溶剂体系——四氢呋喃。结果表明:溶剂和活化试剂对活化酯的产率影响显著;活化酯制备的最佳反应条件为n(Fmoc-Val-OH)∶n(HOBt)∶n(DCC)=1∶1∶1.2,溶剂为THF,反应温度为25℃。     

Aspartic acid in a new role: Synthesis and application of a pH-responsive cyclopolymer containing residues of the amino acid

The reaction between diallylamine and dimethyl maleate afforded the Michael addition product dimethyl N,N-diallylaspartate [(CH₂CH–CH₂)₂NCH(CO₂Me)CH₂CO₂Me] I, which upon treatment with dry HCl and ester hydrolysis with aqueous HCl gave its hydrochloride salt [(CH₂CH–CH₂)₂NH⁺CH(CO₂Me)CH₂CO₂Me Cl⁻] II and N,N-diallylaspartic acid hydrochloride [(CH₂CH–CH₂)₂NH⁺CH(CO₂H)CH₂CO₂H Cl⁻] III, respectively. The new monomers II and III underwent cyclopolymerization to give, respectively, cationic polyelectrolytes (CPEs) poly(II) and poly(III). Under the influence of pH, triprotic acid (+) poly(III) was equilibrated to water-insoluble diprotic polyzwitterionic acid (±) IV, water-soluble monoprotic poly(zwitterion–anion) (± −) V, and its conjugate base polydianion (=) VI. The protonation constants of the carboxyl group and trivalent nitrogen in VI have been determined. A 20-ppm concentration of IV is effective in inhibiting the precipitation of CaSO₄ from its supersaturated solution with an ≈ 100% scale inhibition efficiency for a duration of 50 h at 40 °C. The aqueous two-phase systems (ATPSs) of VI and polyoxyethylene have been studied. The transformation of water-soluble VI to insoluble IV makes it a recycling ATPS as it can be recycled by precipitation at a lower pH.     

Chemical synthesis and characterization of self-doped N-propanesulfonic acid polyaniline derivatives

In chemical oxidative homopolymerization of aniline-N-propanesulfonic acid, ammonium persulfate has been used as an oxidant to obtain water-soluble and self-acid-doped polyanilines. Copolymerization of aniline-N-propanesulfonic acid with aniline, using three feed molar ratios of comonomers has been studied, as well. The polymers and copolymers had moderate molecular weights and were soluble in water and polar solvents. They have been obtained in self-acid-doped form, as has been evidenced by UV?CVis spectroscopy, as green-colored materials, and can be de-doped with alkaline solutions. The propanesulfonic groups had not cleaved during the oxidative polymerization and the atomic ratio between nitrogen and sulfur atoms (N/S) was determined by X-ray photoelectron spectroscopy which was consistent with the chemical structure. The chemical structures and morphologies of the homo- and copolymers have been studied by FTIR, ¹HNMR, UV?CVis, thermogravimetric analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction methods. The X-ray diffraction patterns of the homo- and copolymers have showed a high degree of crystallinity which can be explained by the ionic interaction between propanesulfonate anions and the amine nitrogen atoms of the main chain, resulting in the layering structure of the polyaniline chains. Electrical conductivity of the homopolymer determined at room temperature on pressed pellet was 0.0038?S/cm, while the copolymers show higher conductivities compared with homopolymer.     

二硫代苯甲酸合成新工艺研究

合成了重要的RAFT聚合链转移剂二硫代苯甲酸。探索出最佳合成方法并且利用正交设计方法重点研究了原料摩尔比、搅拌方式、氯化卞滴加时间对反应收率的影响。结果表明,硫与氯化卞的最佳摩尔比为2.11∶1,在反应瓶中加入少许玻璃珠磁力搅拌,加料时间为60~80min时,收率最高达到55%,远高于文献的报道(40%)。用IR和1H NMR表征了产物结构。     

二氯亚砜-甲醇溶液中合成氨基酸甲酯盐酸盐的研究

分别以5种氨基酸为原料,通过在二氯亚砜-甲醇溶液中反应,合成了L-酪氨酸甲酯盐酸盐、甘氨酸甲酯盐酸盐、L-丙氨酸甲酯盐酸盐、L-丝氨酸甲酯盐酸盐、L-苯丙氨酸甲酯盐酸盐等5种稳定的氨基酸甲酯盐酸盐。与现有的合成方法相比,本法操作简便,反应时间短,产物纯度较高,不需进一步提纯,产率可达92.6%～97.6%。     

氨基酸基质下碳酸钙的仿生合成

依据仿生合成的原理,以甘氨酸和酪氨酸作为有机基质,以尿素和氯化钙为原料,通过简单的水热合成法制备了碳酸钙晶体;利用XRD,SEM对产物进行表征,结果发现在不添加有机基质的溶液中得到树枝状的文石相碳酸钙晶体,添加甘氨酸溶液中得到方解石相碳酸钙,添加酪氨酸溶液中得到的方解石相和文石相碳酸钙混合晶体.并对碳酸钙晶须生长机理和两种氨基酸与碳酸钙的作用机理进行了初步探讨,氨基酸在水溶液中解离的带电荷的氨基和羧基对碳酸钙晶体成核和晶体生长起重要的作用,促进了方解石的成核生长;不同氨基酸等电点不同,R基结构不同也影响了碳酸钙晶体的最终形貌.