Selective activation of chemical bonds by active coherent THz spectrometry

通过主动相干太赫兹光谱选择性激活化学键

• 批准号: EP/I014845/1
• 负责人: Robert Donnan
• 金额: $ 31.45万
• 依托单位: Queen Mary University of London
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2010
• 资助国家: 英国
• 起止时间: 2010 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FI014845%2F1
• 关键词: Selective; activation; chemical; bonds; active

'Dial-a-Molecule' is a current EPSRC Grand Challenge. It seeks to tackle questions of the kind: 'How can we reliably predict how to convert one molecule into another?' 'How can we carry out a series of reactions sequentially?' and 'Can we invert modular reactions and/or reactors which can be linked to a myriad of ways to provide complex synthesis?' It has been estimated that achieving the reality of 'Dial-a-Molecule' may take 20 - 40 years to realise. The adventure of this project is to investigate the very real possibility of dramatically bringing this time-frame forward to 5 years distant from now by answering these questions through activation of specific chemical bonds in any given molecule. The consequences of being able to do so would be profound and far-reaching! - new reactions, potential for complete control of outcomes in product synthesis e.g. in C-H activation/oxidation. How can this be done? - by exploiting very recent state-of-the-art developments in electronic engineering to generating high-power terahertz (sub-millimetre wavelength) radiation and to bring it into the world of synthetic organic chemistry. The apparatus that embodies this sophisticated development is called a vector network analyser. Its special features, that are vital to supporting the aims of solving long-standing problems in organic synthesis, is that it generates and receives (phase) stable, widely-tunable radiation spanning many octaves. The resolution in tuning is hyper-fine, being on the order of a million-fold higher than conventional spectrometers (that are broadly based around thermal sources of radiation for their measurement operation). These unique features of the vector-network-analyser offer the potential reality for 'dialing' into the energy required to activate a given chemical bond in a molecule and not, say, an immediate neighbouring bond! Importantly the vector network analyser can be operated to immediately scan the aftermath of a stimulated reaction to investigate what reaction products may have resulted and in what quantity. The activation and scan events may be variably-controlled to range from a second to sub-microsecond time scales as required. An important consequence associated with being able to selectively trigger selective reaction processes with high precision is to eliminate the yield of waste products. Stages in conventional organic synthesis typically yield waste that is 1000s of time the mass of the desired product. Eliminating this waste translates into reduced consumption of energy both in generation and disposal. Over the 18 months of this project the burden of work will be: to design and manufacture a reaction vessel that simultaneously satisfies radiation and chemical constraints; and to systematically trial the programmable capability of the vector network analyser in service of promoting 'dialed' reactions of organic synthesis.

“Dial-a-Molecule”是目前EPSRC的大挑战。它试图解决这样的问题：“我们如何可靠地预测如何将一种分子转化为另一种分子？”我们怎样才能按顺序进行一系列的反应呢？我们能否将模块化反应和/或反应器颠倒过来，使其与无数种方法相联系，从而提供复杂的合成？据估计，实现“拨打分子”的现实可能需要20 - 40年的时间。这个项目的冒险是通过激活任何给定分子中的特定化学键来回答这些问题，从而研究将这一时间框架戏剧性地提前到5年的非常真实的可能性。一旦能够做到这一点，其影响将是深远的！- 新的反应，完全控制产物合成结果的潜力，例如C-H活化/氧化。如何才能做到这一点？- 通过利用电子工程的最新发展，产生高功率太赫兹（亚毫米波长）辐射，并将其带入合成有机化学的世界。体现这一复杂发展的仪器被称为矢量网络分析仪。它的特殊功能对于支持解决有机合成中长期存在的问题至关重要，因为它产生和接收（相位）稳定，可广泛调谐的辐射，跨越许多倍频程。调谐的分辨率是超精细的，比传统的光谱仪（其测量操作广泛地基于辐射的热源）高一百万倍。矢量网络分析仪的这些独特功能为“拨号”激活分子中给定的化学键而不是直接相邻键所需的能量提供了潜在的现实！重要的是，可以操作矢量网络分析仪以立即扫描刺激反应的后果，以研究可能产生的反应产物和数量。激活和扫描事件可以根据需要可变地控制为从秒到亚微秒的时间尺度。与能够以高精度选择性地触发选择性反应过程相关的重要结果是消除了废产物的产率。常规有机合成中的阶段通常产生的废物是所需产物质量的1000倍。消除这种废物转化为减少能源消耗的产生和处置。在这个项目的18个月的工作负担将是：设计和制造一个反应容器，同时满足辐射和化学约束;并系统地测试矢量网络分析仪的可编程能力，以促进有机合成的“拨号”反应。

项目成果

Terahertz spectral domain computational analysis of hydration shell of proteins with increasingly complex tertiary structure.

• DOI: 10.1021/jp407580y
• 发表时间: 2013-12
• 期刊: The journal of physical chemistry. B
• 作者: O. Sushko;R. Dubrovka;R. Donnan

Atomic and vibrational origins of mechanical toughness in bioactive cement during setting.

• DOI: 10.1038/ncomms9631
• 发表时间: 2015-11-09
• 期刊: Nature communications
• 影响因子: 16.6
• 作者: Tian KV;Yang B;Yue Y;Bowron DT;Mayers J;Donnan RS;Dobó-Nagy C;Nicholson JW;Fang DC;Greer AL;Chass GA;Greaves GN
• 通讯作者: Greaves GN

Bacillus spores and their relevant chemicals studied by terahertz time domain spectroscopy

• DOI: 10.1016/j.cplett.2013.12.061
• 发表时间: 2014-01
• 期刊: Chemical Physics Letters
• 影响因子: 2.8
• 作者: Jianhua Tang;Bin Yang;I. Llewellyn;R. R. Cutler-R.;R. Donnan

Erratum: "Sub-terahertz spectroscopy reveals that proteins influence the properties of water at greater distances than previously detected" [J. Chem. Phys. 142, 055101 (2015)].

• DOI: 10.1063/1.4913416
• 发表时间: 2015-02
• 期刊: The Journal of chemical physics
• 作者: O. Sushko;R. Dubrovka;R. Donnan