Experimental Study of Nonadiabatic Dynamics in Photoinduced Reactions of Complexes

配合物光诱导反应非绝热动力学的实验研究

• 批准号: EP/C539648/1
• 负责人: Andrew Hudson
• 金额: $ 30.96万
• 依托单位: University of Bristol
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2006
• 资助国家: 英国
• 起止时间: 2006 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FC539648%2F1
• 关键词: Experimental; Study; Nonadiabatic; Dynamics; Photoinduced

During a collision between atoms or molecules, the momentum of the heavy nuclei might be expected to supply the driving force (or energy) for a reaction to take place. Subsequently, the redistribution of electrons between the nuclei of the atoms or molecules leads to the formation or breaking of chemical bonds. This explanation is justified by the much heavier mass of the nuclei compared with electrons. However, there are examples in chemistry where it is the motion of electrons that drive the nuclei on the course of a chemical transformation. The result is the formation of a product that might otherwise have been unexpected. It is the object of this work to examine the mechanism for these processes. Two representative examples of these reactions will be described below. These involve the chemistry of a drug used to treat cancer and a rather unusual reaction mechanism.(1) Photodynamic Therapy: an experimental treatment for patients with cancer and other diseases.Oxygen molecules are absorbed in the blood and tissue of a human body. The transfer of energy to these molecules will generate a highly reactive form of oxygen that can be used for the destruction of diseased cells. This can be achieved in collisions between oxygen and another highly-energetic molecule. This other molecule is a drug that has been administered to a patient and it has been activated by the absorption of energy from light. A suitable source of light is a laser and, using a fibre-optic light guide inserted into the patient's body, the light can be delivered directly to the drug in the location of a tumor.(2) The Harpooning Reaction: the reactions of alkali metals (i.e. Li, Na, K) with halogens (fluorine, chlorine, bromine molecules).The mechanism of this reaction involves the transfer of an electron from an alkali-metal atom to a halogen molecule. This event has been referred to as harpooning because it is observed whilst the atom and molecules are widely spaced apart. The electrostatic attraction of the ion pair formed by the transfer of an electron (the harpoon ) results in the halogen molecule being reeled Into the alkali metal. This research is aimed at discovering fundamental information about the electron-transfer event and it will be extended to chemical processes involving charge-transfer from metal centres of biological molecules.In a sub-discipline of Chemistry referred to as Physical Chemistry, the principles of Physics are used to study chemical reactions. The same approach will be applied in this work using examples of chemical reactions involving molecules or mechanisms of interest in biology and medicine. This is a novel approach to the study of this field and it will provide unique and original data.

在原子或分子之间的碰撞过程中，重核的动量可能会为反应的发生提供驱动力（或能量）。随后，原子或分子的核之间的电子重新分布导致化学键的形成或断裂。原子核的质量要比电子重得多，这一解释是合理的。然而，在化学中有这样的例子，在化学转化过程中，是电子的运动驱动原子核。其结果是形成了一种可能是意想不到的产品。这是这项工作的目的是检查这些过程的机制。下面将描述这些反应的两个代表性示例。这些涉及用于治疗癌症的药物的化学和一种相当不寻常的反应机制。(1)光动力疗法：对癌症和其他疾病患者的实验性治疗。氧分子被人体的血液和组织吸收。能量转移到这些分子将产生一种高活性形式的氧，可用于破坏病变细胞。这可以通过氧气和另一种高能分子之间的碰撞来实现。另一种分子是一种药物，它已经被施用于患者，并通过吸收来自光的能量而被激活。合适的光源是激光器，并且使用插入患者体内的光纤光导，光可以直接递送到肿瘤位置中的药物。(2)鱼叉反应：碱金属（即Li、Na、K）与卤素（氟、氯、溴分子）的反应。该反应的机理涉及电子从碱金属原子转移到卤素分子。这种现象被称为鱼叉，因为它是在原子和分子被广泛地分开时观察到的。由电子转移形成的离子对的静电引力（鱼叉）导致卤素分子被卷入碱金属中。该研究旨在发现有关电子转移事件的基本信息，并将扩展到涉及生物分子金属中心电荷转移的化学过程。在化学的一个分支学科中，称为物理化学，物理学原理用于研究化学反应。同样的方法将应用于这项工作中，使用涉及生物学和医学中感兴趣的分子或机制的化学反应的例子。这是一个新的方法来研究这一领域，它将提供独特的和原始的数据。

项目成果

Jet-cooled spectroscopy of porphyrins

卟啉的喷射冷却光谱

• 发表时间: 2009
• 期刊: Journal of Porphyrins and Phthalocyanines
• 影响因子: 1.5
• 作者: N/a Beames

Comparison of the resonance-enhanced multiphoton ionization spectra of pyrrole and 2,5-dimethylpyrrole: Building toward an understanding of the electronic structure and photochemistry of porphyrins.

吡咯和 2,5-二甲基吡咯的共振增强多光子电离光谱的比较：加深对卟啉电子结构和光化学的理解。

• DOI: 10.1063/1.3257681
• 发表时间: 2009
• 期刊: The Journal of chemical physics
• 作者: Beames JM