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1.
蛋白质磷酸化是细胞内调节酶功能的一种重要的翻译后修饰 .蛋白质内酪氨酸磷酰化是目前所知道的在细胞应答外界刺激时最主要的信号传导方式 [1] .文献 [2 ]报道的酪氨酸 O-磷酰化的方法是基于亚磷酰胺化学 ,包含亚磷酸化和氧化两步 .我们在 O-磷酰化多肽的合成研究中发现 ,应用 Atherton-Todd反应可以有效地进行酪氨酸 O-磷酰化 .Atherton- Todd反应是指二烷基亚磷酸酯在四氯化碳和有机碱 (如三乙胺 )存在下转变成二烷基磷酰氯 ,从而进行胺、亚胺及肟的磷酰化 .该法曾被有效地用于在弱碱性水溶液中合成 N - (二烷基磷酰 )氨基酸和小肽 [… 相似文献
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以壳寡糖(COS)为原料, 二乙基亚磷酸酯(DEPH)为磷酰化试剂, 通过改变反应体系中三乙胺(TEA)的用量控制二乙基磷酰基的进攻位点, 实现了2-N和3,6-O位点二乙基亚磷酰化壳寡糖衍生物的合成, 制备了N-二乙氧磷酰化壳寡糖及N,O,O-二乙氧磷酰化壳寡糖, 并采用单一变量法对合成条件进行了优化, 用31P NMR对产物进行了跟踪分析. 合成N-二乙氧磷酰化壳寡糖的最优反应条件为2 g COS, nCOS∶nTEA=1∶6, nCOS∶nDEPH=1∶3, 滴加DEPH和CCl4的时间为2 h, 低温反应2 h, 在该优化条件下产物的磷含量为1.50%(质量分数). 合成N,O,O-二乙氧磷酰化壳寡糖的最优反应条件为2 g COS, nCOS∶nTEA=1∶6, nCOS∶nDEPH=1∶5, 滴加DEPH和CCl4 的时间2 h, 低温反应4 h, 常温反应8 h, 在该优化条件下产物的磷含量为3.42%. 对合成反应的可能机理进行了推测. 相似文献
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用MNDO方法对磷酰化丝氨酸仿生化反应机理中所形成的六配位磷中间体(3)可能的3个异构体的结构及其反应活性进行了研究.在六配位磷中间体3的6根键中,丝氨酸的羧基氧O3与磷之间的键最弱,最易断裂生成新的五配位磷中间体4,4的P_N键断裂得到磷酰基的N→O转位反应产物5.对于六配位磷中间体3中的两个异丙氧基,位于丝氨酸侧链羟基O6对面的异丙氧基较另一个易于离去(约低37kJ/mol)并得到中间体6,接着甲醇从O6对面新产生的空隙进攻中间体6中的磷,生成磷上酯交换产物9.六配位磷中间体机理比较好地解释了实验中所发现的磷酰化丝、苏氨酸仿生化反应的多样性和复杂性. 相似文献
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寡肽类化合物一般具有较强的生物活性,多数可作为药物或药物前体,因此成为人们的研究热点之一.目前寡肽的合成方法主要有液相法、固相法及酶促合成法,这些合成方法往往需要对氨基酸的活性基团进行选择性保护,步骤繁琐.近期研究发现,在水-醇体系中α-氨基酸被磷酰化为N-磷酰-α-氨基酸后,可发生自组装聚合肽反应;在无水条件下,N,O-二(三甲基硅基)-α-氨基酸可与磷酰化试剂如O,O-亚苯基磷酰氯反应生成N-磷酰-α-氨基酸,后者也可通过自组装反应得到二~八肽,但这些N-磷酰-α-氨基酸的制备均需使用有机磷试剂.我们发现,在无机磷试剂如PCl5等辅助下,α-氨基酸同样可以发生自组装反应,得到一系列寡聚肽,这既可为寡聚肽的合成提供一种新的方法,同时,因无机磷试剂在原始地球条件下更可能存在,因而对于揭示多肽及蛋白质的起源具有重要意义.氨基酸的自组装反应具有链锁反应的特点,因此必须控制反应条件实现对反应的控制。 相似文献
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设计合成了5种新型正电子发射断层显像剂[O-(2-[18F]氟乙基)-L-酪氨酸的前体化合物:N-叔丁氧羰基-O-(2-甲磺酰/对硝基苯磺酰)-氧乙基-L-酪氨酸甲酯(9a,11a)和N-叔丁氧羰基-O-(2-甲磺酰/对甲苯磺酰/对硝基苯磺酰)-氧乙基-L-酪氨酸叔丁酯(9b,10b,11b)。 这些化合物以L-酪氨酸为原料,先与甲醇发生酯化反应或与乙酸叔丁酯进行酯交换,再用叔丁氧羰基保护氨基,最后以碳酸钾为碱、18-冠-6为相转移催化剂与乙二醇的磺酸酯在丙酮溶液中加热回流形成目标化合物,总收率为30%~67%。 相似文献
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以L-苯丙氨酸或L-亮氨酸为起始原料,经过氨基保护和羧基酯化得到N-苄氧羰基-L-广苯丙氨酸-对硝基苯酯(4a)或N-苄氧羰基-L-亮氨酸-对硝基苯酯(4b);4在三乙胺作用下与L-组氨酸甲酯盐酸盐缩合得到直链二肽N-苄氧羰基-L-苯丙氨酸-L-组氨酸甲酯(5a)或N-苄氧羰基-L-亮氨酸-L-组氨酸甲酯(5b);Pd/C催化5脱掉保护基后在微波辐射下,经环化反应合成了手性催化剂环二肽(6a或6b),其结构经1H NMR和IR表征.重点考察了由5合成6的反应条件.结果表明,以甲醇为溶剂,于65 W辐射120 min,6a和6b的产率分别达到90%和68%. 相似文献
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本文报道某些两可阴离子磷酰化反应的区域选择性.苯基丙酮双阴离子与二乙基磷酰氯反应,除O-磷酰化产物的顺,反异构体外,还得两个C-磷酰化产物.烯丙基苯碳阴离子与二乙基磷酰氯反应未获得预期产物,苯乙酮的环已胺Schiff碱作为两可阴离子,在磷酰化反应中可获得以C-磷酰化为主的三种产物.本文对双阴离子的化学结构与磷酰化反应区域选择性的影响作了讨论. 相似文献
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The dissociation of deprotonated peptides containing hydroxyl side chains was studied by electrospray ionization coupled with Fourier transform ion cyclotron resonance (ESI-FTICR) via sustained off-resonance irradiation collision induced dissociation (SORI-CID). Dissociation under post-source decay (PSD) conditions was performed by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF). This work included hexapeptides with one residue of serine, threonine, or tyrosine and five inert alanine residues. During SORI-CID and PSD, dissociation of [M-H](-) yielded c- and y-ions. Side-chain losses of formaldehyde (HCHO) from serine-containing peptides, acetaldehyde (CH(3)CHO) from threonine-containing peptides, and 4-methylene-2,5-cycohexadienone (C(7)H(6)O) from tyrosine-containing peptides were generally observed in the negative ion PSD and SORI-CID spectra. Side-chain loss occurs much less from tyrosine-containing peptides than from serine- and threonine-containing peptides. This is probably due to the bulky side chain of tyrosine, resulting in steric hindrance and poor geometry for dissociation reactions. Additionally, a selective cleavage leading to the elimination of the C-terminal residue from [M-H](-) was observed from the peptides with serine and threonine at the C-terminus. This cleavage does not occur in the dissociation of peptides with an amide group at the C-terminus or peptides with neutral or basic residues at the C-terminus. It also does not occur with tyrosine at the C-terminus. Both the C-terminal carboxylic acid group and the hydroxyl side chain of the C-terminal residue must play important roles in the mechanism of C-terminal residue loss. A mechanism involving both the C-terminal carboxylic acid group and a hydroxyl side chain of serine and threonine is proposed. 相似文献
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JianChenZHANG ShuXiaCAO XiaoLiYANG YuFenZHAO 《中国化学快报》2004,15(6):646-648
three kinds of N-(diisopropyloxyphosphoryl) amino acids containing hydroxyl group were prepared in high yield by using diisopropyl phosphite as the phosphorylating agent, sodium hypochlorite as the chlorinating agent and tetrabutyl ammonium bromide as the phase transfer catalyst in basic aqueous media. 相似文献
14.
Electrospray tandem mass spectrometric studies of phosphopeptides and phosphopeptide analogues 总被引:3,自引:0,他引:3
A set of synthetic phosphopeptides and phosphopeptide analogues was studied by tandem nano-electrospray mass spectrometry. The influence of the collision offset and of the charge state of the molecular ion on phosphate-specific fragmentation processes was investigated in detail. H--D exchange experiments and structural considerations support a six-centered transition being present in the neutral loss of H3PO4 from serine, threonine and homoserine phosphopeptides, where the C-alpha hydrogen of serine or threonine or the C-beta hydrogen of homoserine is transferred to the protonated phosphate group. Neutral loss of H3PO4 at moderate collision offset potential represents a very abundant fragmentation process for serine, threonine and homoserine phosphopeptides. The most specific feature for discrimination of these phosphopeptides from tyrosine phosphopeptides is the m/z 79:97 ratio in the negative ion product spectra, which is consistently elevated in tyrosine phosphopeptides as compared with serine, threonine and homoserine phosphopeptides. The fragment ions of methylphosphono- and H-phosphonopeptides can be explained by the same mechanisms as are applicable to phosphopeptides. 相似文献
15.
Ramapanicker Ramesh Kavita De Shipra Gupta Srinivasan Chandrasekaran 《Journal of Chemical Sciences》2008,120(1):163-173
Propargyloxycarbonyl group is used as a protecting group for the hydroxyl groups of serine, threonine and tyrosine. The propargyloxycarbonyl
derivatives of these hydroxy amino acids are stable to acidic and basic reagents commonly employed in peptide synthesis. The
deprotection of the O-Poc derivatives using tetrathiomolybdate does not affect commonly used protecting groups such as N-Boc, N-Cbz, N-Fmoc, methyl and benzyl esters. The di-and tripeptides synthesized using O-Poc derivatives of serine, threonine and tyrosine are stable, isolable compounds and give the hydroxy peptides in good yields
when treated with tetrathiomolybdate. 相似文献
16.
Ekeroth J Borgh A Konradsson P Liedberg B 《Journal of colloid and interface science》2002,254(2):322-330
The synthesis of a series of thiols containing phosphorylated and non-phosphorylated serine, threonine, and tyrosine amino acid residues is described. The synthesized molecules, based on 3-mercaptopropionic acid, were assembled onto gold and subsequently characterized using infrared reflection-absorption spectroscopy, ellipsometry, X-ray photoelectron spectroscopy, and contact angle goniometry. The ellipsometric analysis indicates that they form densely packed and well-oriented monolayers on gold, with thicknesses that are in good agreement with estimated values from space-filling models. The bulky and space-demanding phosphorylated threonine analog was, however, found to be an exception. The increase in layer thickness when adding a phosphate group to the threonine is only 35% of that observed for the two other analogs. A detailed infrared examination of the influence of cation coordination to the phosphorylated serine analog using calcium and magnesium reveals structural similarities to those of the inorganic phosphate compound calcium hydroxy apatite. We furthermore discuss the application of these monolayers as soft templates for biomineralization. 相似文献
17.
We have successfully designed and synthesized new fluorogenic probes that specifically target different classes of protein phosphatases. The fluorescence profiles of the probes have been studied using 12 different phosphatases, and results showed that, besides alkaline and tyrosine phosphatases, our probes were able to detect serine/threonine as well as acid phosphatases. 相似文献
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Aurelio L Box JS Brownlee RT Hughes AB Sleebs MM 《The Journal of organic chemistry》2003,68(7):2652-2667
N-Methyl amino acids occur in many natural products. Experimental strategies are presented for a unified approach to the synthesis of N-methyl derivatives through 5-oxazolidinones of the 20 common l-amino acids. The amino acids with reactive side chains that required protecting groups or devoted syntheses for side chain construction for N-methylation to proceed included serine, threonine, tyrosine, cysteine, methionine, tryptophan, asparagine, histidine, and arginine. The studies have provided improved methods for the preparation of N-methyl serine, threonine, and tyrosine. All 20 of the common l-amino acids are now available in suitable forms for solid or solution-phase peptide synthesis. 相似文献
20.
Stefanie Mädler Claudia Bich David Touboul Renato Zenobi 《Journal of mass spectrometry : JMS》2009,44(5):694-706
Structure elucidation of tertiary or quaternary protein structures by chemical cross‐linking and mass spectrometry (MS) has recently gained importance. To locate the cross‐linker modification, dedicated software is applied to analyze the mass or tandem mass spectra (MS/MS). Such software requires information on target amino acids to limit the data analysis time. The most commonly used homobifunctional N‐hydroxy succinimide (NHS) esters are often described as reactive exclusively towards primary amines, although side reactions with tyrosine and serine have been reported. Our goal was to systematically study the reactivity of NHS esters and derive some general rules for their attack of nucleophilic amino acid side chains in peptides. We therefore studied the cross‐linking reactions of synthesized and commercial model peptides with disuccinimidyl suberate (DSS). The first reaction site in all cases was expectedly the α‐NH2‐group of the N‐terminus or the ε‐NH2‐group of lysine. As soon as additional cross‐linkers were attached or loops were formed, other amino acids were also involved in the reaction. In addition to the primary amino groups, serine, threonine and tyrosine showed significant reactivity due to the effect of neighboring amino acids by intermediate or permanent Type‐1 cross‐link formation. The reactivity is highly dependent on the pH and on adjacent amino acids. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献