London Dispersion Interactions inside Macrocycles
大环内的伦敦色散相互作用
基本信息
- 批准号:271456295
- 负责人:
- 金额:--
- 依托单位:
- 依托单位国家:德国
- 项目类别:Priority Programmes
- 财政年份:2015
- 资助国家:德国
- 起止时间:2014-12-31 至 2021-12-31
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
We propose to investigate the contribution of London dispersion interactions (LDI) to the molecular recognition process of macrocycles, prominently cucurbit[n|urils (CBn) and to the control of chemical reactions inside their inner cavity. CBn are water-soluble macrocyclic host molecules of the molecular container type, that is, they are able to encapsulate numerous organic guests inside their hydrophobic cavity. The driving force for binding inside the inner cavity of CBn is primarily traced back to a hydrophobic effect, but LDI present an important modulator. Out of the original six experimental lines of investigation, five will be further pursued in the second project phase: 1) Building up on our quantification of LDI in the binding of noble gases (He, Ne, Ar, Kr, and Xe) to the smallest CBn homologue, CB5, we plan to study the potential of different docking cations to modulate LDI in the resulting CB5•noble gas•cation complexes. 2) We will extend our investigation on the high-affinity binding of strongly polarizable borate clusters of the type (B12X12)2– to substituted carboranes, which in contrast to the dianionic borate clusters possess a neutral core. In order to dissect solvent effects from LDI, we will also study the solvent isotope effect for this type of complexes. 3) As an example of supramolecular catalysis, we have investigated the dimerization of cyclopentadiene inside CB7, for which we have found a million-fold rate enhancement; this study will be extended to methylcyclopentadiene to introduce chemoselectivity into the catalytic reaction. 4) We propose to assess the relative abundance of inclusion versus exclusion complexes in the gas phase as an interesting approach to study LDI. Through collaborations, we have started to investigate a series of organic ammonium ions with CB6 in the gas phase. For direct comparison, we already determined the binding constants of the ammonium ions to CB6 in water during the first phase of the priority programme. 5) The inversion process of CBn macrocycles in the gas phase will also be examined, which is thought to be driven by intramolecular LDI. Throughout the project, NMR spectroscopy, isothermal titration calorimetry, dye displacement titrations, organic synthesis and quantum-chemical calculations will be used to determine the binding affinities as well as thermodynamic parameters and, thus, to evaluate the importance of LDI.
本文研究了伦敦分散作用(LDI)对大环化合物分子识别过程的贡献,主要是葫芦[n|脲(CBN)和控制其内腔内的化学反应。CBN是分子容器类型的水溶性大环主体分子,也就是说,它们能够将许多有机客体包封在它们的疏水空腔内。CBN内腔内结合的驱动力主要追溯到疏水效应,但LDI是一个重要的调节剂。在最初的六个实验研究路线中,有五个将在第二项目阶段进一步进行:1)建立在我们对惰性气体(He,Ne,Ar,Kr和H2O)与最小的CBN同系物CB 5结合中的LDI的量化基础上,我们计划研究不同对接阳离子在所得CB 5·惰性气体·阳离子络合物中调节LDI的潜力。2)我们将扩大我们的调查上的强极化硼酸盐集群的类型(B12 X12)2-取代碳硼烷,这与双阴离子硼酸盐集群具有中性核心的高亲和力结合。为了剖析LDI的溶剂效应,我们还将研究这类配合物的溶剂同位素效应。3)作为超分子催化的一个例子,我们已经研究了CB 7内的环戊二烯的二聚反应,我们已经发现了百万倍的速率增强;这项研究将扩展到甲基环戊二烯引入催化反应的化学选择性。4)我们建议评估的相对丰度的包合物与排阻配合物在气相中作为一个有趣的方法来研究LDI。通过合作,我们已经开始研究一系列有机铵离子与CB 6在气相中的反应。为了直接比较,我们已经在优先计划的第一阶段确定了铵离子与水中CB 6的结合常数。5)CBN大环在气相中的反转过程也将被检查,这被认为是由分子内LDI驱动的。在整个项目中,NMR光谱,等温滴定量热法,染料置换滴定,有机合成和量子化学计算将用于确定结合亲和力以及热力学参数,从而评估LDI的重要性。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
数据更新时间:{{ journalArticles.updateTime }}
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
数据更新时间:{{ journalArticles.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ monograph.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ sciAawards.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ conferencePapers.updateTime }}
{{ item.title }}
- 作者:
{{ item.author }}
数据更新时间:{{ patent.updateTime }}
Professor Dr. Werner Nau其他文献
Professor Dr. Werner Nau的其他文献
{{
item.title }}
{{ item.translation_title }}
- DOI:
{{ item.doi }} - 发表时间:
{{ item.publish_year }} - 期刊:
- 影响因子:{{ item.factor }}
- 作者:
{{ item.authors }} - 通讯作者:
{{ item.author }}
{{ truncateString('Professor Dr. Werner Nau', 18)}}的其他基金
Fluorescence techniques applied to root-state detection in protein folding
荧光技术应用于蛋白质折叠根态检测
- 批准号:
321602882 - 财政年份:2016
- 资助金额:
-- - 项目类别:
Research Grants
Polypeptide dynamics and structure studied simultaneously by collision-induced fluorescence quenching and resonance energy transfer in the 10-Å domain
通过碰撞诱导的荧光猝灭和 10-Å 域中的共振能量转移同时研究多肽动力学和结构
- 批准号:
168513691 - 财政年份:2010
- 资助金额:
-- - 项目类别:
Research Grants
Supramolecular tandem assays for monitoring enzymatic activity
用于监测酶活性的超分子串联测定
- 批准号:
106373163 - 财政年份:2008
- 资助金额:
-- - 项目类别:
Research Grants
相似海外基金
New Extensions to Symmetry-adapted Perturbation Theory: Spin Splittings, Explicitly Correlated Dispersion, and Intramolecular Interactions
对称适应微扰理论的新扩展:自旋分裂、显式相关色散和分子内相互作用
- 批准号:
1955328 - 财政年份:2020
- 资助金额:
-- - 项目类别:
Standard Grant
Dispersion interactions in fluorinated biopolymers
氟化生物聚合物中的分散相互作用
- 批准号:
398048621 - 财政年份:2018
- 资助金额:
-- - 项目类别:
Priority Programmes
Investigation and modelling of dispersion interactions in electronically excited states and the effects of dispersion interactions on electronic excitations
电子激发态色散相互作用的研究和建模以及色散相互作用对电子激发的影响
- 批准号:
398047156 - 财政年份:2018
- 资助金额:
-- - 项目类别:
Priority Programmes
Investigation of London Dispersion Interactions with Azobenzene Switches
伦敦色散与偶氮苯开关相互作用的研究
- 批准号:
397692616 - 财政年份:2018
- 资助金额:
-- - 项目类别:
Priority Programmes
Modeling Dispersion Interactions in Chemistry
化学中的分散相互作用建模
- 批准号:
526665-2018 - 财政年份:2018
- 资助金额:
-- - 项目类别:
University Undergraduate Student Research Awards
Computer modeling of London dispersion interactions
伦敦色散相互作用的计算机建模
- 批准号:
512448-2017 - 财政年份:2017
- 资助金额:
-- - 项目类别:
University Undergraduate Student Research Awards
Accurate and Efficient Modeling of Biomolecular Ionic Interactions: Charge Redistribution, Polarization and Dispersion
生物分子离子相互作用的准确有效的建模:电荷重新分布、极化和色散
- 批准号:
9083227 - 财政年份:2016
- 资助金额:
-- - 项目类别:
Heavy main group elements as dispersion energy donors - experimental and theoretical studies of bismuth compounds with bismuth-pi-interactions as structure determining component
作为色散能量供体的重主族元素 - 以铋-π-相互作用作为结构决定组分的铋化合物的实验和理论研究
- 批准号:
271339741 - 财政年份:2015
- 资助金额:
-- - 项目类别:
Priority Programmes
Understanding the Role of Dispersion Interactions in the Mechanical Properties of Molecular Crystals
了解色散相互作用在分子晶体机械性能中的作用
- 批准号:
271390424 - 财政年份:2015
- 资助金额:
-- - 项目类别:
Priority Programmes
SPP 1807: Control of London Dispersion Interactions in Molecular Chemistry
SPP 1807:分子化学中伦敦分散体相互作用的控制
- 批准号:
255533046 - 财政年份:2015
- 资助金额:
-- - 项目类别:
Priority Programmes