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  本文選題：β-環(huán)糊精復(fù)合物　切入點：α-氨基酸及其酯化物側(cè)鏈　出處：《高等學(xué)�；瘜W(xué)學(xué)報》2017年05期

【摘要】：為了探索α-氨基酸及其酯化物的側(cè)鏈R基團對其與環(huán)糊精非共價復(fù)合物結(jié)合強度的影響,將一定摩爾比的β-環(huán)糊精(β-CD)分別與L型正纈氨酸(n-Val)、亮氨酸(Leu)、苯丙氨酸(Phe)、天冬氨酸(Asp)、天冬氨酸-4-芐酯(Asp-4-benzyl ester)和天冬氨酸-4-叔丁酯(Asp-4-t-butyl ester)在室溫下混合,反應(yīng)平衡后采用電噴霧電離質(zhì)譜進行競爭反應(yīng)檢測,并以改進的質(zhì)譜滴定結(jié)合曲線擬合法計算結(jié)合常數(shù).結(jié)果表明,它們均可形成摩爾比為1∶1的非共價復(fù)合物.在2組競爭反應(yīng)中,復(fù)合物的結(jié)合強度順序分別為[β-CD∶Asp-4-benzyl ester+H]~+[β-CD∶Asp-4-t-butyl ester+H]~+[β-CD∶Asp+H]~+以及[β-CD∶Phe+H]~+[β-CD∶Leu+H]~+[β-CD∶n-Val+H]~+.質(zhì)譜滴定曲線擬合法測得[β-CD∶n-Val+H]~+,[β-CD∶Asp+H]~+,[β-CD∶Asp-4-t-butyl ester+H]~+,[β-CD∶Asp-4-benzyl ester+H]~+,[β-CD∶Leu+H]~+和[β-CD∶Phe+H]~+的穩(wěn)定常數(shù)(lgK_(st))分別為1.81,2.54,3.14,3.26,3.36和3.67,結(jié)合強度依次增強.競爭反應(yīng)的定性分析結(jié)果與質(zhì)譜滴定定量法測得結(jié)合強度結(jié)果的趨勢一致.由于所選用的α-氨基酸及其酯化物客體的羧基端(—COOH)和氨基端(—NH_2)均相同,且都為親水基團,僅有側(cè)鏈R基團不同,因此在溶液中客體分子受疏水驅(qū)動與β-CD主體靠近并結(jié)合時,側(cè)鏈R基團的疏水力和極性2個因素起重要作用.由于客體分子體積小,其碳端的羧基還可與β-CD大口或小口邊緣的羥基形成氫鍵,使復(fù)合物更加穩(wěn)定.
[Abstract]:In order to explore the effect of side chain R group of 偽 -amino acid and its ester on the binding strength of 偽 -amino acid and its side chain R group to cyclodextrin noncovalent complex, 尾 -cyclodextrin (尾 -CD) was mixed with L-type valine n-Valan, leucine leucine, phenylalanine Phehe, Asp-4-benzyl aspartate, Asp-4-benzyl esterat and Asp-4-t-butyl esterat at room temperature, respectively. After reaction equilibrium, the competitive reaction was detected by electrospray ionization mass spectrometry, and the binding constant was calculated by the improved mass spectrometry titration and curve fitting method. They all form noncovalent complexes with a molar ratio of 1:1. In two groups of competitive reactions, The order of binding strength of the complexes is [尾 -CDAsp-4-benzyl ester H] ~ [尾 -CD: Asp-4-t-butyl ester H] ~ [尾 -CDAsp-4-butyl ester H] and [尾 -CDAsp-4-benzyl ester H] ~ ~ [尾 -CDAsp-4-benzyl ester H] ~ ~ [尾 -CDAsp-4-benzyl ester H] ~ [尾 -CDAsp-4-benzyl ester H] and [尾 -CDAsp-4-benzAsp H] ~, [尾 -CDAsp-4-benzAsp H] and [尾 -CDPHE H] ~ and [尾 -CDPHE H] and [尾 -CDPHE H] and [尾 -CDAsp-4-benzyl ester H] ~, [尾 -CDAsp-4--butyl ester H], [尾 -CDAsp-4-benzyl ester H], [尾 -CDAsp-4-benzyl ester H], [尾 -CDAsp-4-benzyl ester H] and [尾 -CDPHE H] and [尾 -CDPHE H] and 尾 -CDPHE H respectively. The results of qualitative analysis of the competitive reaction were consistent with the results obtained by quantitative mass spectrometry titration. Because the 偽 -amino acid and its ester guest carboxyl terminal (COOH) and amino terminal (NH2) were the same, They are hydrophilic groups, only the side chain R groups are different, so the hydrophobic force and polarity of the side chain R group play an important role when the guest molecules are driven by hydrophobic force and bound to 尾 -CD host in solution. The carboxyl group of the carbon terminal can also form a hydrogen bond with the hydroxyl group at the big or small mouth edge of 尾 -CD, which makes the complex more stable.
【作者單位】： 復(fù)旦大學(xué)化學(xué)系激光化學(xué)研究所;
【基金】：國家十二五重大科學(xué)儀器專項(批準(zhǔn)號:2011YQ14015006)資助~~
【分類號】：O636.12;O657.63

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