头孢菌素氨解和酶解过程中质子磁共振谱的变化
Changes in proton-magnetic-resonance spectra during aminolysis and enzymic hydrolysis of cephalosporins.
作者信息
Hamilton-Miller J M, Richards E, Abraham E P
出版信息
Biochem J. 1970 Feb;116(3):385-95. doi: 10.1042/bj1160385.
Abstract
- Changes in proton-magnetic-resonance spectra were followed during the reaction of cephalosporins, deacetylcephalosporins, deacetoxycephalosporins and a Delta(2)-cephalosporin with ND(3) in D(2)O. 2. Changes in proton-magnetic-resonance spectra were also followed during the hydrolysis of a cephalosporin and a deacetylcephalosporin in D(2)O with a beta-lactamase. 3. Structures for the reaction products are proposed. 4. The signals obtained after aminolysis of the beta-lactam ring of a cephalosporin indicate that the reaction is accompanied by expulsion of the acetoxy group as acetate, formation of a double bond in the Delta(4)-position and the appearance of an exocyclic methylene group. 5. Aminolysis of deacetyl- and deacetoxycephalosporins can occur without immediate structural changes in the dihydrothiazine ring. 6. In contrast, the ring structure of the first product of enzymic hydrolysis of a deacetylcephalosporin is apparently identical with that of the product of aminolysis of the cephalosporin itself.
摘要
- 在头孢菌素、去乙酰头孢菌素、去乙酰氧基头孢菌素和一种Δ(2)-头孢菌素与重水（D₂O）中的ND₃反应过程中，对质子磁共振谱的变化进行了跟踪。2. 在重水（D₂O）中，用β-内酰胺酶对一种头孢菌素和一种去乙酰头孢菌素进行水解时，也对质子磁共振谱的变化进行了跟踪。3. 提出了反应产物的结构。4. 头孢菌素的β-内酰胺环氨解后得到的信号表明，该反应伴随着乙酰氧基以乙酸盐形式排出、在Δ(4)位形成双键以及出现环外亚甲基。5. 去乙酰和去乙酰氧基头孢菌素的氨解可以在二氢噻嗪环没有立即发生结构变化的情况下发生。6. 相比之下，去乙酰头孢菌素酶促水解的首个产物的环结构显然与头孢菌素本身氨解产物的环结构相同。
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Cephalosporinase and penicillinase activities of a beta-lactamase from Pseudomonas pyocyanea.铜绿假单胞菌β-内酰胺酶的头孢菌素酶和青霉素酶活性
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