酰化

Most of these peptides are amidated at their C-terminals, which is essential for their full activities. The a-amide comes from posttranslational modification that is catalyzed by α-amidase (α-AE or PAM). The amidation reaction is a rate-limiting step in the biosynthesis of regulatory peptides.

大部分活性肽的C-端是酰胺化的，而且α-酰胺基为多肽的完全生物活性所必需；α-酰胺基来自多肽的翻译后加工，由α-酰胺化酶催化完成，是酰胺化多肽生物合成途径中的限述步骤。

To avoid the influence of ammonolysis, alcoholysis and hydrolysis on molecular structure identification, in this paper, derivational estimation is utilized to confirm molecular structures ofβ-naphthol-containing sulfonyl chloride intermediates. Then the structures of corresponding sulfonamide dyes are also confirmed by FTIR,~1H NMR and mass spectrometry.

为了避免磺酰氯化合物发生水解、醇解和胺解等衍生化反应影响磺酰氯化合物分子结构表征，本文采用衍生化反推法证明了β-萘酚结构磺酰氯化合物的分子结构，并利用红外光谱、核磁共振氢谱、质谱表征了含β-萘酚结构磺酰胺染料的分子结构。

The method involves exposing the cells to a compound having the formula I in which: w is a nucleic acid x is a non-amino acid or non-peptide nucleic acid binding group y is a spacer having a chain length equivalent to 1-30 carbon-carbon single covalent bonds or is absent R4 is H or halogen or CH2O-R3; and R1, R2 and R3 are the same or different and are either hydrogen, methyl, ethyl, alkyl, alkenyl, hydroxylated alkyl, hydroxylated alkenyl groups or ether containing alkyl, alkenyl, hydroxylated alkyl or hydroxylated alkenyl groups optionally being an acyl group having a carbon chain length equivalent to 3-24 carbon atoms saturated or unsaturated, with the proviso that at least one of R1, R2 or R3 includes a group having a carbon chain of 3-24 carbon atoms saturated or unsaturated, or to a compound having the formula II in which: w is a nucleic acid x is a non-amino acid or non-peptide nucleic acid binding group y is a space having a chain length equivalent to 1-30 carbon-carbon single covalent bonds or is absent, R5 is alkyl, alkenyl, hydroxylated alkyl, hydroxylated alkenyl group or ether containing alkyl, alkenyl, hydroxylated alkyl or hydroxylated alkenyl group optionally being an acyl group having a carbon chain length equivalent to 3-24 carbon atoms saturated or unsaturated, with the proviso that R5 includes a group having a carbon chain of 3-24 carbon atoms saturated or unsaturated.

该方法包括使细胞暴露于具有式的化合物，在式中：w是核酸，x是非氨基酸或者非肽核酸结合基团，y是具有等于1―30个碳―碳单共价键的链长的间隔基或者不存在，R4是H或者卤素或者CH2O－R3；R1、R2和R3是相同的或者不同的并且是氢、甲基、乙基、烷基、链烯基、羟基化烷基、羟基化链烯基或者包含烷基、链烯基、羟基化烷基或羟基化链烯基的醚，任选地是来源于具有等于3―24个碳原子的碳链长的饱和或不饱和脂肪酸的酰基，其条件是R1、R2或者R3的至少一个包括具有3―24个碳原子的饱和或不饱和碳链的基团，或者使细胞暴露于具有式的化合物，在式中：w是核酸，x是非氨基酸或者非肽核酸结合基团，y是具有等于1―30个碳―碳单共价键的链长的间隔基或者不存在，R5是烷基、链烯基、羟基化烷基、羟基化链烯基或者包含烷基、链烯基、羟基化烷基或羟基化链烯基的醚，任选地是具有等于3―24个碳原子的饱和或不饱和碳链的链长的酰基，其条件是R5包括具有3―24个碳原子的饱和或不饱和碳链的基团。

They are, 4 21-amidohydrocortisone Ba1～Ba4, 10 21-amidoprednisolone Bb1～Bb10, 4 21-amidomethylprednisolone Bc1～Bc4, 4 21-amidodexamethasone Bd1～Bd4, 1 21-amidobetamethasone Be1, 1 21-amidoRS Bf1, 1 21-amidocortisone Bg1, 1 21-amidoprednisone Bh1. The amido groups were acetamido, nicotinamido, hemesuccinamido, benzoylamido, methanesufonamido, or arylsufonylamido.

包括：4个21-酰胺基氢化可的松（Ba1～Ba4），10个21-酰胺基氢化泼尼松（Bb1～Bb10），4个21-酰胺基甲泼尼龙（Bc1～Bc4），4个21-酰胺基地塞米松（Bd1～Bd4），1个21-酰胺基倍它美松（Be1），1个21-酰胺基RS（Bf1），1个21-酰胺基可的松（Bg1），1个21-酰胺基强的松（Bh1）。21-酰胺基分别为乙酰胺基、烟酰胺基、单琥珀酰胺基、苯甲酰胺基、甲烷磺酰胺基或取代苯磺酰胺基等。

This work, concentrated on the asymmetric allylation of aldehydes controlled by different chiral auxiliaries prepared from rotational pure tartaric acid, can be divided into three parts.The first part aims to review the developments of chiral drugs and asymmetric synthesis, from which derived the present research topic backgrounds and works.Synthesis and applications of allylation from aldehydes are the second part of the thesis. By optimizing the reaction conditions, such as solvents, temperature, time and chiral auxiliaries like N,N\'-dibenzyl tartamide, N,N\'-p-dimethylphenyl tartamide, N,N\'-o-dimethylphenyl tartamide, N,N\'-o-dichlorophenyl tartamide, N,N\'-a-dinaphyl tartamide, N,N\'-dicyclohexyl tartamide and N,N\'-diphenyl tartamide, ideal experimenttal conditions are obtained according to HPLC monitoring, as well as the auxiliaries\' recoveries experiments. Starting from benzaldehyde and 3-bromopropaldehyde, N,N\'-dibenzyl tartamide is considered the best auxiliary in this reaction.

本文介绍了醛的不对称烯丙基化反应，以光学纯酒石酸为原料，研究了不同构型手性配体在醛的烯丙基化反应中的立体选择性，全文共分三部分十个章节：第一部分对当前手性药物和手性技术进行了概述，并由此展开了本文的研究背景和任务；第二部分为有机合成部分，对醛的不对称烯丙基化反应进行了深入探讨，以苯甲醛为原料对反应条件进行优化，在优化的反应条件下对制备的七种可回收手性酰胺配体(N-苄基酒石酸二酰胺、N-对甲苯基酒石酸二酰胺、N-邻甲苯基酒石酸二酰胺、N-邻氯苯基酒石酸二酰胺、N-a-萘基酒石酸二酰胺、N-环己基酒石酸二酰胺和N-苯基酒石酸二酰胺)进行筛选，优化配体回收实验条件，最终确定出N-苄基酒石酸二酰胺在苯甲醛的不对称烯丙基化反应中具有较大优越性，结晶回收的手性配体光学纯度保持不变。

Seven of them have not been reported.Their structures were confirmed by IR,~1HNMR,MS,and element analysis. 4.Meanwhile,the green methylation procedure of imides was developed by using dimethyl carbonate as methylation reagent.A series of imides,for example,phthalimide,3,4-dibromo-maleimide and succincide were used for substrates.The effects of DABCO(1,4-diazabicyclo [2.2.2]octane)and DBU(1,8-diazabicyclo[5.4.0]undec-7-ene)as a catalyst in this kind of reactions were investigated.2-Bromo-3-(1-methylindolyl-3-yl)-1-methyl-1H-pyrrole-2,5-dione was prepared by using dimethyl carbonate,which further expanded the use of dimethyl carbonate,as a green agent in organic synthesis.

在以硫酸二甲酯为甲基化试剂对3，4-二溴马来酰亚胺进行N-甲基化反应合成3，4-二溴-N-甲基马来酰亚胺的同时，以碳酸二甲酯为甲基化试剂，对3，4-二溴马来酰亚胺、邻苯二甲酰亚胺、琥珀酰亚胺等酰亚胺类化合物的N-甲基化反应进行了研究；考察了1，4-二氮杂双环[2.2.2]辛烷，1，8-二氮杂双环[5.4.0]十一碳-7-烯、碳酸钾和四丁基溴化铵等作为催化剂对碳酸二甲酯N-甲基化反应的反应时间和收率等的影响，并应用碳酸二甲酯为甲基化试剂，合成了N-甲基-3-溴-4-(1-甲基-吲哚-3)-马来酰亚胺。

As a key step of the synthesis, the Friedel-crafts acylation was researched. And the optimal operation variables were determined through orthogonal experiment: when 0.lmol acetanilide, 0.26mol aluminum chloride, 0.12mol propionyl chloride and 200ml carbon disulfide are introduced, and the reaction time is 5 hour, the yield can be up to 57.3%. The solid super acid catalyst was preliminary studied. Four solid super acid catalysts were prepared to take the place of aluminum chloride, and it was indicated that AlCl3 acidic resin can better catalyze the Friedel-Crafts reaction of acetanilide.

对合成路线中的Friedel-Crafts酰基化反应进行了研究，运用正交实验设计确定了最佳工艺条件：当乙酰苯胺用量为0.1mol时，AlCl_3用量为0.26mol、丙酰氯用量为0.12mol、溶剂用量为200ml、反应时间为5h，产率可达到57.3％；对于固体超强酸催化剂进行了初步研究，合成了四种催化剂，其中负载AlCl_3强酸性树脂对于乙酰苯胺的Friedel-Crafts酰基化具有一定的催化活性。

In this paper, firstly using natural fatty acids including lauric acid, myristic acid, palmitic acid etc. and disproportionated rosin as starting materials, the acyl reaction of starting materials with SOCl_2 respectively, and then using Schotten-Baumann condensation: on the reaction conditions of alkalescence, condensation of acylchloride with amino acid (sarcosine, glycine, alanine etc.), and then acidification, saltation. A series of anionic surfactants of N-acyl amino: sodium N-fatty acyl sarcosinate (SFS-12, SFS-14, SFS-16); sodiun N-fatty acyl glycinate(SFG-12, SFG-14, SFG-16); sodium N-fatty acyl alaninate(SFA-12, SFA-14, SFA-16)and sodium N-disproportionated rosinoyl aminatewere prepared. During the preparation of N-acylamino acid, the reaction conditions of acylchloride with amino acid condensation were identified by optimizing the synthetic conditions of N-lauroyl sarcosine: mol ratio of amino acid to acylchloride 2:1, reaction taken place in a solvent composed by acetone/water 2:1, acylchloride and 20% NaOH were slowly added to the reaction mixture at the same time while maintaining the pH at 9~10, after completion of adding maintaining reacting for 2.5h at 25℃.

首先以月桂酸、肉豆蔻酸、棕榈酸等天然脂肪酸和歧化松香为原料，与氯化亚砜反应制得酰氯，然后采用Schotten-Baumann 缩合法路线，即在碱性条件下，酰氯和氨基酸(肌氨酸、甘氨酸、丙氨酸等)缩合，经过酸化、成盐，合成一系列氨基酸型阴离子表面活性剂：脂肪酰肌氨酸钠，即月桂酰肌氨酸钠(SFS-12)、肉豆蔻酰肌氨酸钠(SFS-14)、棕榈酰肌氨酸钠(SFS-16)；脂肪酰甘氨酸钠，即月桂酰甘氨酸钠(SFG-12)、肉豆蔻酰甘氨酸钠(SFG-14)、棕榈酰甘氨酸钠(SFG-16)；脂肪酰丙氨酸钠，即月桂酰丙氨酸钠(SFA-12)、肉豆蔻酰丙氨酸钠(SFA-14)、棕榈酰丙氨酸钠(SFA-16)；N-歧化松香酰基氨基酸钠(sodium N-disproportionated rosinoyl aminate)，即N-歧化松香酰基肌氨酸钠(sodium N-disproportionated rosinoyl sarcosinate ，简称SDRS)、N-歧化松香酰基甘氨酸钠(sodium N-disproportionated rosinoyl glycinate，简称SDRG)、N-歧化松香酰基丙氨酸钠(sodium N-disproportionated rosinoyl alaninate，简称SDRA)。

Based on the-references on the thermal imidization of polyand the polymer composition analysis,the thermal imidization mechanism of SMA with aniline was demonstrated to be a two-stage consecutive reaction,in which a second-order reversible ring-opening reaction of SMA to produce poly(styrene-co-N-phenyl-maleamic acid)and a first-order irreversible intrachain ring-closing reaction to form SNPMI were involved.

论文首先参考聚酰胺酸热环化反应，并通过SMA酰亚胺化产物的组成分析，确定了SMA与苯胺的热酰亚胺化反应机理为一个包含由SMA生成苯乙烯—N-苯基马来酰胺酸共聚物的二级可逆开环反应以及由SNPMA生成苯乙烯—N-苯基马来酰亚胺共聚物的一级不可逆分子内闭环反应在内的串联反应过程，其中第二步SNPMA闭环反应为控制步骤。

This hyperacetylation causes cell cycle arrest and cell death in cancer cells but not in normal cells.

这种高度乙酰化造成癌症细胞的细胞周期阻断和细胞死亡，而不造成正常细胞的细胞周期阻断和细胞死亡。

The labia have now been sutured together almost completely.The drains and the Foley catheter come out at the top.

此刻阴唇已经几乎完全的缝在一起了，排除多余淤血体液的管子和Foley导管从顶端冒出来。

To get the business done, I suggest we split the difference in price.

为了做成这笔生意，我建议我们在价格上大家各让一半。