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首页> 外文学位 >Part I. Construction and stereochemical analysis of chiral carbinols. Part II. Development of a system to study kinetic effects in polyvalent binding to clustered carbohydrates.
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Part I. Construction and stereochemical analysis of chiral carbinols. Part II. Development of a system to study kinetic effects in polyvalent binding to clustered carbohydrates.

机译：第一部分手性甲醇的构建和立体化学分析。第二部分开发了一种研究多价结合成簇的碳水化合物的动力学效应的系统。

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Assigning absolute configuration of molecules continues to be a major problem. Contradictory results have come from two of the most known methods, the exciton coupling circular dichroism (ECCD) method and the Mosher ester NMR analysis, for the configuration of C2 of Chromomycin A3 (CRA3). We have established the absolute stereochemistry of the key structural motif of CRA3 by using a combination of molecular modeling, solution 1H NMR, and X-ray crystallography. Our results explain why it is difficult to assign stereochemistry based on solution methods alone and suggest that a comparison of calculated and experimental optical rotatory dispersion (ORD) data provides the most straightforward way to assign the absolute configuration.; While a number of model systems have been designed for the study of polyvalent interaction, most of them focus on enhancement in binding avidities by carbohydrate clustering. We have designed a new model system, which allows for investigations of both kinetic details and thermodynamic effects of a polyvalent binding process. Using a glycosylated heptameric ion channel derived from the alpha-hemolysin pore, both the rate and binding constants for the interaction between Bauhinia purpurea (BP) lectin and the natural ligand disaccharide were measured. This system also provides a method to explore the effects of systematic changes in linker length and structure in polyvalent binding and will form a basis for construction of stochastic biosensors which can be used for detecting toxins, viruses, bacteria, and whole cells.; beta-Hydroxy amino acids are an important class of compounds ubiquitously occurring in nature. Due to their importance as building blocks of many bioactive natural products, an efficient synthetic route to this class of compounds is critical for both biological and chemical studies. We have synthesized requisite beta-hydroxy-tyrosine derivatives using an Evans asymmetric aldol condensation procedure for research directed towards construction of a new hybrid antibiotic and elucidation of the role of an enzyme NovJ/K in novobiosin biosynthesis. Also described herein is our exploration of the possibility of accessing beta-hydroxy amino acids by direct oxidation at the benzylic position of tyrosine.
机译：分配分子的绝对构型仍然是主要问题。对于铬霉素A3（CRA3）的C2构型，两种最著名的方法（激子偶合圆二色性（ECCD）方法和Mosher酯NMR分析）产生了矛盾的结果。我们已经通过使用分子建模，溶液1H NMR和X射线晶体学的组合建立了CRA3关键结构基序的绝对立体化学。我们的结果解释了为什么仅基于溶液方法很难分配立体化学，并且建议比较计算得出的旋光色散和实验旋光色散（ORD）数据可以最直接地分配绝对构型。尽管已经设计了许多用于研究多价相互作用的模型系统，但大多数模型系统着重于通过碳水化合物聚类提高结合亲和力。我们设计了一个新的模型系统，该系统可以研究多价结合过程的动力学细节和热力学效应。使用衍生自α-溶血素孔的糖基化七聚体离子通道，测量了紫荆花（BP）凝集素与天然配体二糖之间相互作用的速率和结合常数。该系统还提供了一种方法，以探索接头长度和结构在多价结合中系统变化的影响，并将为构建可用于检测毒素，病毒，细菌和整个细胞的随机生物传感器奠定基础。 β-羟基氨基酸是自然界普遍存在的重要一类化合物。由于它们作为许多具有生物活性的天然产物的重要组成部分，因此有效合成此类化合物的途径对于生物学和化学研究均至关重要。我们已经使用Evans不对称醛醇缩合方法合成了必需的β-羟基酪氨酸衍生物，用于针对新型杂合抗生素的构建以及酶Novov / K在新生物素生物合成中的作用的研究。本文还描述了我们探索在酪氨酸的苄基位置通过直接氧化获得β-羟基氨基酸的可能性。

著录项

  • 作者

    Nam, Joonwoo.;

  • 作者单位

    Princeton University.;

  • 授予单位 Princeton University.;
  • 学科 Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2004
  • 页码 274 p.
  • 总页数 274
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
  • 关键词

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