新型手性氨基酸烯砜的合成

以苯亚磺酸钠和3-氯-2-甲基-1丙烯为原料,经偶联、氯化、溴化,之后再与氨基酸胺化反应合成得到了两个新型手性氨基酸烯砜化合物。所获得化合物的结构经HR-MS,1H,13C和/或DEPT NMR验证。     

新的氨基酸受体的合成和分子识别性质研究

从双氨基甲基手性双环胍出发,经三步反应合成了由稳定的共价键桥联双环胍、氮杂冠醚和萘环的氨基酸受体1.液-液竞争萃取和^1HNMR实验表明受体对氨基酸两性离子具有较好的侧链选择性和对映选择性,能够选择性地将L-芳香族氨基酸从水相转移到二氯甲烷有机相。     

Synthesis and property of novel amino acid‐based polymers by self‐polyaddition of monomers containing both oxetanyl and carboxyl groups

A new synthetic strategy for polymers containing amino acids in the main chain was developed. Monomers N‐oxetanylalanine (N‐Oxe‐Ala‐COOH), N‐oxetanylglutamic acid (N‐Oxe‐Glu‐COOH), and N‐oxetanyllysine (N‐Oxe‐Lys‐COOH) containing both oxetanyl and carboxyl groups were synthesized, and self‐polyaddition and self‐copolyaddition of these monomers afforded the corresponding polymers containing amino acids in the main chain [poly(_OxAla), poly(_OxLys), poly(_OxGlu), poly(_OxAla‐co‐_OxGlu), poly(_OxGlu‐co‐_OxLys), and poly(_OxAla‐co‐_OxLys)] with molecular weight in the range of 920–6620, in satisfactory yields. The physical properties, such as solubility, glass transition temperature, and thermal stability, were consistent with the amount of carboxyl groups at the chain ends. Biodegradability of the polymers was examined by the biochemical oxygen demand method; the decomposition ratios of poly(_OxAla) and poly(_OxAla‐co‐_OxGlu) were about 60%, whereas that of poly(_OxGlu) was nearly 100% after 28 days. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

N-二异丙氧磷酰化氨基酸的合成

以亚磷酸二异丙酯为磷酰化试剂、次氯酸钠为氯代试剂首次对20种常见的α-氨基酸进行了磷酰化.通过添加适量四丁基溴化铵为相转移催化剂,使用过量的亚磷酸二异丙酯以补偿其在强碱环境中的水解,从而提高了反应产率.所得产物经核磁共振谱、红外光谱和质谱鉴定结构并分析总结了该类化合物的谱图特征规律.     

Synthesis of jasplakinolide analogues containing a novel omega-amino acid

The synthesis of the omega-amino acid 4 is described utilizing a two-dimensional synthesis strategy combined with an enzymatic differentiation of homotopic ester groups. The amino acid 4 features two non-bonded interactions that result in conformational constraints on a cyclic construct. This amino acid was incorporated into the four macrolactams 17, 22, 31, and 37. The ring in 17 and 22 is 18-membered, whereas 31 and 37 have a 19-membered ring. The pairs with the same ring size differ in a N-methyl group. For the larger macrolactams (31 and 37) conformational analysis showed that the macrocyclic rings are somewhat more rigid than in the natural lead, the depsipeptide jasplakinolide. Nevertheless, their conformations are comparable to the natural product. There are no intramolecular hydrogen bonds, neither is the cis-rotamer populated in the N-methyl compound 37. Due to the increased flexibility of the smaller macrolactams 17 and 22 and signal overlap, a distinct solution structure could not be obtained for these compounds. The amino acid 4 should be useful for restricting the conformation of other small peptides.     

Synthesis,characterization and cytotoxicity of platinum(II) complexes containing reduced amino acid ester Schiff bases

Nine platinum(II) complexes containing reduced amino acid ester Schiff bases were synthesized and characterized using spectroscopy (¹H NMR, ¹³C NMR, infrared), elemental analysis and molar conductivity. The interaction of these complexes with salmon sperm DNA was investigated by means of ultraviolet and circular dichroism spectroscopies. The potential antitumor activity of all compounds was tested in vitro on HeLa and A549 tumor cell lines. Almost all the complexes exhibited better cytotoxic activity than cisplatin against these cell lines.     

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.     

新型荧光试剂N-9-吖啶基氨基乙酸的合成及其光谱性质

新型荧光试剂N-9-吖啶基氨基乙酸的合成及其光谱性质     

Synthesis and characterization of polyesteramides derived from an oxazoline-functional alcohol and dicarboxylic acid anhydrides

Novel polyesteramides were synthesized by copolymerization in bulk of 5-(4,5-dihydro-1,3-oxazol-2-yl)-1-pentanol and various cyclic dicarboxylic acid anhydrides at temperatures varying between 120 and 200°C. The polymers resulting from polycondensation were characterized by means of ¹H–NMR, FTIR, MALDI–TOF–MS, SEC, and DSC. The glass transition temperatures, T_g, of the copolymers were varied between −28 and +31°C as a function of the anhydride type. Molecular weights, M_w, were dependent on reaction temperature, reaction time, and anhydride type. Spectroscopic investigation of reaction products and esteramide model compounds provided evidence for imide by-product formation, which accounts for the low degree of polymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3367–3376, 1999     

氨基酸酯-烷基醚混合取代聚膦腈的合成与表征

聚膦腈高聚物,因其良好的生物相容性而用作生物医用材料。若在其侧链引入对热(如烷氧基醚)或对pH值敏感和可生物降解的基团(如氨基酸酯),则可得到具有环境敏感性和可生物降解性能的高聚物,这些高聚物可望作为药物载体,用于药物的控制释放。     

微波辐射在合成沙利度胺的铵盐类衍生物中的应用

沙利度胺(Thalidomide)又名反应停,化学名称为N-2-(2,6-二氧-3-哌啶基)-邻苯二甲酰亚胺[N-2-(2,6-dioxo-3-piperidinyl)-phthalidomide],是一种合成类谷氨酸衍生物,曾因致畸副作用而一度停止对其的研究[1].但上个世纪末期,Sampaio[2]等曾报道,沙利度胺可抑制体外LPS刺激原代人体单核细胞生成TNF-α,Kenyon[3]等的研究表明(S)-沙利度胺有着很强的抑制血管生成作用,再度引发了科学界对沙利度胺及其相关衍生物的研究兴趣.     

Synthesis of meta- and paracyclophanes containing unsaturated amino acid residues

[7.7], [8.8], [9.9] and [13.13] Paracyclophanes and [9.9] and [13.13] metacyclophanes containing two unsaturated amino acid residues have been synthesised. An X-ray crystallographic study of three of the paracyclophanes and molecular modelling of two paracyclophanes and two metacyclophanes revealed two main structural types. The ‘staggered’ structure appears to be favoured by longer hydrocarbon chains, whilst the ‘barrel’ structure appears to be more accessible to compounds containing shorter hydrocarbon chains. The [9.9] paracyclophane has been hydrogenated and deprotected to give a saturated amino acid, and an alternative approach to key aldehydes is reported.     

Synthesis of polyamides and polyureas containing leucine–tyrosine linkages

Monomers with leucine–tyrosine linkages were synthesized using diphenyl phosphoryl azide as a coupling reagent. Leucyltyrosylpoly(propylene glycol) bis(2-aminopropyl ether) tyrosylleucine (monomer 1 ) has a longer spacer: poly(propylene glycol) bis(2-aminopropyl ether) (Jeffamine® D-400), and leucyltyrosyliminohexamethyleneiminotyrosylleucine (monomer 2 ) has a shorter spacer: hexamethylenediamine. Polyureas from monomers 1 and 2 with hexamethylene diisocyanate and methylenedi-p-phenyl diisocyanate were synthesized. Polyamide, polyesteramide from monomer 2 were synthesized. The characterization of these polymers using ¹H-NMR, ¹³C-NMR, solid-state ¹³C-NMR, IR, GPC, and also thermal analysis are presented. © 1997 John Wiley & Sons, Inc.     

A genetically encoded metallocene containing amino acid

Redox active amino acids, cofactors, and metal ions are involved in a large number of catalytic, electron transfer, and regulatory processes in biology. Consequently, the ability to engineer redox active centers at defined sites in proteins would facilitate both the study and manipulation of a wide range of biological processes. Recently, we demonstrated that the redox active amino acid 3,4-dihydroxyphenylalanine could be efficiently and selectively incorporated into proteins in Escherichia coli using a nonsense codon and a corresponding orthogonal tRNA/aminoacyl-tRNA synthetase pair. We now report that ferrocene derivative 1 can be genetically encoded in Saccharomyces cerevisiae (S. cerevisiae) in good yield in response to the amber codon, TAG.     

位点特异、拓扑结构明确的蛋白质-聚氨基酸偶联物的简洁合成

发展位点特异且具有明确拓扑结构的蛋白质-高分子偶联物是高分子和化学生物学领域共同面对的挑战之一.在聚合物末端精确引入一个或多个具有特殊反应活性的生物正交官能团是实现位点特异生物偶联的关键前提.这一过程通常比较低效、需要多步骤的官能团转化、聚合后修饰以及保护脱保护,费时且繁琐.最近,通过在聚合过程中原位生成官能团,以一锅-两步的过程得到可直接用于蛋白质偶联的异遥爪聚合物,从而实现了多种不同拓扑结构的蛋白质-聚氨基酸偶联物的快速构筑.这一简洁的合成路线实现了以前尚未获得的头-尾相接的环状偶联物的制备,使这些偶联物表现出了很强的体外酶稳定性以及热稳定性.该工作是蛋白质-高分子偶联化学的一次创新的尝试;同时,利用该方法所制备的偶联物在蛋白质药物领域具有广阔的应用前景.     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

Syntheses and radical polymerizations of optically active (meth)acrylamides having amino acid moieties

Syntheses and radical polymerizations of several (meth)acrylamides having L -amino acid moieties were examined. The monomers were prepared by the reactions of L -amino acid ester hydrochlorides with (meth)acryloyl chloride in the presence of triethylamine in satisfactory yields. Radical polymerizations of the monomers were carried out in the presence of AIBN (1 mol %) in bulk and in several solvents to afford the corresponding polymers in satisfactory yield. The glass transition temperatures and specific rotations of the polymers depended on the substituents of the L -amino acid moieties. Nearly the same specific rotations were observed for the monomers and the model compounds of the polymer units, N-pivaloyl amino acid methyl esters. On the contrary, the specific rotations of the polymers shifted to the negative direction in ca. 30°. The interaction between the polymer side chains might affect the changes in the specific rotations from monomers to polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2619–2629, 1997     

Synthesis of novel ionic polymers containing arsonic acid group

Synthesis of ortho‐ and para‐acryloylaminophenylarsonic acids (o‐AAPHA and p‐AAPHA) monomers and their homopolymers, useful as ion‐exchange materials, are reported. Both the monomers and homopolymers are synthesized with >90% yield. The structures of the new compounds are determined by NMR and FTIR spectroscopy. Molecular weights of the polymers are determined from light scattering measurements and found to be M_w = 38,759 g/mol for o‐AAPHA polymer and M_w = 31,347 g/mol for p‐AAPHA polymer. Good thermal stability of the new compounds derived from their intra‐ or intermolecular hydrogen bondings suggests their applications as proton‐exchange membrane at high temperatures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1627–1634, 2006     

光学活性含硅氨基酸的合成

光学纯的硅取代氨基酸是一类非天然的手性氨基酸合成子，在药物，植物保护 剂和精细化学品的合成具有极为广阔的应用前景，其合成方法包括化学不对称合成 及化学合成外消旋体－生物学拆分两种，综述了该方面的研究进展。