A Basic Study on Artificial Protease

按顺序确定锌（II）大环聚胺中的酸性，一种新型的碳基绑定锌（II）复合物被证明是一个很好的模型，可以在第二类麦芽糖和蛋白质中提取锌的作用（II）。锌的分离（II）-封闭碳基与8.41的pky-D2 a-D2和一种结果产品，一种enolate-bound复合体12被分离。Thus， zinc（II） ion demonstrated a thermodynamic effect to raise the acidity of the carbonyl methylene （ordinary pK-D2a-D2， ca。19）按10号命令。在equilibrium中，锌（II）复合物竞争激烈地生长了一个异构锌羟基复合物（ratio = 1 ： 3）在25°C的无规则解决方案。在更多的无氢条件下，将equilibrium转移到enolate-bound复合体，在纯甲基氯化萘解决方案中，只有enolate-bound复合体被制成。目前的发现是，在锌氧化物的存在中，可以产生近中性pH值将是有用的信息 ... More 以研究在明确的解决方案中得到的更多精炼锌-催化醇反应和酰胺-羟基反应。Moreover，一种脂蛋白锌（II）复合体已被合成和完全表征。它在共微溶液中被证明是锌复合体形式的锌-羟基碱碱pH值，而锌-羟基是4-硝基乙酸酯、磷酸二酯和磷酸二酯单烯氢化的核催化剂。本研究提出了一项建议，即脂蛋白锌复合体在现有的活性剂中可能是一种极端的候选人，用于处置神经气体。使用Amido Substrates （例如，乙酰苯胺、4-硝基乙酰苯胺、甘氨酸），如何，我们不能观察锌复合体中的酰胺羟基。Furthermore，我们证明了双（锌-cyclen）和三（锌-cyclen）是DNA测序选择性配体的一种新颖类型，其中有极高的效果与聚thymine组结合（例如，TpT and TpTpT） at？M concentrations。这些锌（II）-多大环环化合物及其修改方法将通过一种机制来确定广泛的生物化学和医学应用，尽管这些传统DNA-动机识别药物的机制有所不同。Less（低）

In order to determine the zinc(II) acidity in macrocyclic polyamine, a new carbonyl-bound zinc(II) complex was demonstrated to be a good model that serves to elucidate the role of zinc(II) in the class II aldolases and proteases. The deprotonation of the zinc(II)-bound carbonyl occurred with a pKィイD2aィエD2 of 8.41 and one of the resulting products, an enolate-bound complex 12 was separately isolated. Thus, zinc(II) ion demonstrated a thermodynamic effect to raise the acidity of the carbonyl methylene (ordinary pKィイD2aィエD2, ca. 19) by orders of 10. The deprotonation from the zinc(II) complex competitively yielded an isomeric zinc hydroxide complex in the equilibrium (ratio = 1 : 3) regardless of the aqueous solution at 25°C. In more anhydrous conditions, the equilibrium shifted to the enolate-bound complex and in pure MeCN solution only enolate-bound complex was formed. The present discovery that in the presence of zinc enolates can be generated near neutral pH would be useful informatio … More n in exploring more refined Zn-cataiytic aldol reactions and amide-hydrolysis reactions in aqueous solution.Moreover, a lipophilic zinc(II) complex has been synthesized and fully characterized. It was demonstrated that in co-micellar solution , the zinc complex forms Zn-hydroxideat alkaline pH. The Zn-hydroxide is the nucleophilic catalyst in the co-micelle for hydrolysis of 4-nitrophenyl acetate, phosphotriester and phosphodiester monoanion. This study suggests that the lipophilic zinc complex in the presence of the surfactant may be an extremely promising candidate for disposal of nerve gases. Using amido substrates (e.g., acetoanilide, 4-nitroacetoanilide, glycylgricine), however, we could not observe the amide hydrolysis by the zinc complex.Furthermore, we have demonstrated that bis(Zn-cyclen) and tris(Zn-cyclen) are novel types of DNA sequence-selective ligands, which are extremely efficient in bnding to poly-thymine group (e.g., TpT and TpTpT) at μM concentrations. These zinc(II)-polymacrocyclic complexes and their modifications would find wide biochemical and medicinal applications by a mechanism entirely different from those of conventional DNA-motif recognizing drugs. Less