Dynamic combinatorial chemistry.
Dynamic combinatorial chemistry.
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DOI：
10.1002/chin.200648268
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发表时间：
2006-09
期刊：
影响因子：
62.1
通讯作者：
P. Corbett;J. Leclaire;Laurent Vial;Kevin R. West;Jean-Luc Wietor;J. Sanders;S. Otto
中科院分区：
文献类型：
--
作者：
P. Corbett;J. Leclaire;Laurent Vial;Kevin R. West;Jean-Luc Wietor;J. Sanders;S. Otto
动态组合化学是指在热力学控制下的组合化学，即在动态组合库（DCL）中，所有组分都处于平衡状态。这需要库成员通过可逆的化学过程相互转化，这可能涉及共价键或非共价相互作用，包括金属配体配位（见第2节）。动态组合化学的独特之处在于库的组成由每个库成员在特定实验条件下的热力学稳定性决定。这使得DCL在识别热力学最小值方面成为强大的工具，这在许多不同的背景下都很有用。一个应用是在具有不同构象特性的结构（折叠体）的混合物中鉴定最稳定的结构（图1a）。具有最有利的内部非共价相互作用的那些结构将被稳定化，并优先于缺乏这种稳定化的那些文库成员形成（见第4.5节）。特定文库成员的稳定化也可以通过文库成员之间的分子间非共价相互作用发生，文库组成偏向于形成稳定组装体或聚集体的那些成员（图1b）。虽然这种方法很少受到关注（见4.4节），但它具有发现自组装分子的真实的潜力，包括互锁结构和新的软材料。DCL中的热力学控制意味着改变实验条件可以诱导文库组成的变化;也就是说，动态组合文库将对外部影响做出响应。原则上，这种响应性可以以多种方式利用：例如，用于发现具有强烈温度或压力依赖性的化合物或对光或电场或磁场有反应的化合物。朱塞佩和莱恩
Dynamic combinatorial chemistry is defined as combinatorial chemistry under thermodynamic control; that is, in a dynamic combinatorial library (DCL), all constituents are in equilibrium. This requires the interconversion of library members into one another through a reversible chemical process, which can involve covalent bonds or noncovalent interactions including metal-ligand coordination (see section 2).Dynamic combinatorial chemistry is unique in that the composition of the library is determined by the thermodynamic stability of each of the library members under the particular conditions of the experiment. This makes DCLs powerful tools in identifying thermodynamic minima, which is useful in a number of different contexts. One application is the identification of the most stable structure in mixtures of structures with different conformational properties (foldamers)(Figure 1a). Those structures that have the most favorable internal noncovalent interactions will be stabilized and formed in preference over those library members that lack such stabilization (see section 4.5). Stabilization of specific library members can also take place through intermolecular noncovalent interactions between library members, the library composition being biased toward those members that form stable assemblies or aggregates (Figure 1b). Although this approach has received little attention (see section 4.4), it has real potential for the discovery of self-assembling molecules including interlocked architectures and new soft materials. Thermodynamic control in DCLs implies that changing the conditions of the experiment can induce changes in the library composition; that is, dynamic combinatorial libraries will respond to external influences. In principle, this responsiveness can be exploited in numerous fashions: for instance, for the discovery of compounds with strongly temperatureor pressure-dependent properties or compounds that respond to light or electric or magnetic fields. Giuseppone and Lehn