Experimental Studies of the Structures, Energetics, and Reactions of Gas Phase Self-Assembled Biomolecular Ionic Complexes
气相自组装生物分子离子配合物的结构、能量学和反应的实验研究
基本信息
- 批准号:RGPIN-2014-04429
- 负责人:
- 金额:$ 3.93万
- 依托单位:
- 依托单位国家:加拿大
- 项目类别:Discovery Grants Program - Individual
- 财政年份:2017
- 资助国家:加拿大
- 起止时间:2017-01-01 至 2018-12-31
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
Studies of complexes composed of metal cations and amino acids or DNA bases are important for our understanding of the physical chemistry of self-assembled biomaterials. The structures also have biological relevance in terms of, for example, telomere research. Part of the work proposed is to study the intrinsic structures, energetics, and spectroscopy of G-tetrads that compose G-quadruplexes—tracts of guanine residues at the ends of DNA strands which are an important part of the telomere. The assembley of these G-quadruplexes are typically initiated by metal cations. 9-ethylguanine (9-eG) is an ideal model for the nucleic acid as the 9-position is blocked, as it is in nucleic acids. Preliminary experimental work on (9eG)4M+ (M=Li+, Na+, K+, and Cs+) has revealed a remarkable stability of the (9eG)4Na+ complexes which theory shows us are square planar. In contrast, complexes with the other metal ions are non-planar, probably due to competition between hydrogen bonding between the nucleic acids and metal-ion/molecule interactions. Much more work is required to fully understand the balance of intermolecular forces that bind these structures. For example, what is the effect on structure stability and reactivity of metal cations with higher oxidation states such as the alkali earth, transition, and lanthanide metals. This research will also lead to valuable information on metal ion induced defects in nucleic acids. We plan to study the structures and energetics of higher order structures such as (9eG)8M+ and [(9eG)12M2]2+ of significance to biological and supramolecular materials research. The construction of these complexes relies on molecular recognition and self-assembly processes that occur in DNA, RNA, and proteins etc. Supramolecular complexes of the other nucleic acid bases as well as those composed of a mixture of bases will be studied. This research will have an impact health and cancer research, providing fundamental knowledge of the makeup of these biological complexes.We will carry out research on polymetallic cation-peptide supramolecular assemblies. We have done preliminary CID studies on complexes such as [Ca5(GlyGly-H)8]2+ and have also begun to model them. Our current picture has the five Ca2+ ions in a plane bridged by oxygen atoms of the peptide, similar to proposed structures of naturally occurring clusters such as ferritin and the oxygen-evolving complex of photosystem II. We propose to compare the structures, energetics and reactivities of self-assembled complexes composed of different metals and larger, varied peptides in the gas phase.These studies will be augmented by research on smaller components of the supramolecular clusters, such as metal cation-bound dimers of amino acids, DNA bases, and carbohydrates.A new tunable IR laser, far more powerful than our current one is on order. This laser will allow us to record IRMPD spectra on G-tetrads and other strongly-bound species which was not possible with our current laser. With this new laser, our spectral range increases down to 2400 cm-1 (from 3200 cm-1) allowing us to spectroscopically characterize the fundamentally important and very intense hydrogen bonded N-H stretching bands. Besides IRMPD spectroscopy and computational techniques to determine structures of gaseous ions we will use energy-resolved CID, CID coupled with isotopic substitution, blackbody infrared radiative dissociation coupled with master equation modeling to determine binding energies, and radiative association with kinetic modeling to study bimolecular ion-molecule reactions. We are also adding simulated annealing to our repertoire of techniques to help ensure we have explored the full geometric space of our large clusters.
研究金属阳离子与氨基酸或DNA碱基形成的络合物对于我们理解自组装生物材料的物理化学具有重要意义。例如,在端粒研究方面,这些结构还具有生物学相关性。建议的部分工作是研究组成G-四链的G-四联体的内在结构、能量学和光谱--DNA链末端的鸟嘌呤残基是端粒的重要组成部分。这些G-四链体的组装通常是由金属阳离子引发的。9-乙基鸟嘌呤(9-Eg)是核酸的理想模型,因为9-位被封闭,就像在核酸中一样。对(9EG)~4M~+(M=Li~+,Na~+,K~+和Cs~+)的初步实验工作表明,(9EG)~4Na~+络合物具有显著的稳定性。相反,与其他金属离子的络合物是非平面的,可能是由于核酸之间的氢键和金属-离子/分子相互作用之间的竞争。要完全理解束缚这些结构的分子间力的平衡,还需要做更多的工作。例如,具有较高氧化态的金属阳离子,如碱土金属、过渡金属和稀土金属,对结构稳定性和反应活性有什么影响。这项研究还将带来关于金属离子引起的核酸缺陷的有价值的信息。我们计划研究(9EG)8M+和[(9EG)12M2]2+等高阶结构的结构和能量学,这对生物和超分子材料的研究具有重要意义。这些复合体的构建依赖于DNA、RNA和蛋白质等发生的分子识别和自组装过程。我们将研究其他核酸碱基的超分子复合体以及由碱基混合物组成的超分子复合体。这项研究将对健康和癌症研究产生影响,为这些生物复合体的组成提供基础知识。我们将开展多金属阳离子-多肽超分子组装的研究。我们已经对[Ca5(GlyGly-H)8]2+等配合物进行了初步的CID研究,并开始对它们进行模型化。我们目前的图景是五个钙离子在一个平面上被多肽的氧原子连接起来,类似于天然存在的簇的结构,如铁蛋白和光系统II的放氧复合体。我们建议比较由不同金属和更大、不同的多肽在气相中组成的自组装复合体的结构、能量和反应性。这些研究将通过对超分子簇中较小成分的研究来加强,如氨基酸、DNA碱基和碳水化合物的金属阳离子结合二聚体。一种新的可调谐红外激光器正在订购中,其功率远远超过我们目前的激光。这台激光将使我们能够记录G-四分体和其他强结合物种上的IRMPD光谱,这是我们目前的激光所不可能做到的。有了这台新的激光,我们的光谱范围从3200厘米-1增加到2400厘米-1,使我们能够从光谱上表征基本重要和非常强烈的氢键N-H伸缩带。除了IRMPD光谱和计算技术外,我们还将使用能量分辨CID、CID与同位素取代耦合、黑体红外辐射解离与主方程模型耦合来确定结合能,以及辐射缔合与动力学模型来研究双分子离子-分子反应。我们还将模拟退火法添加到我们的技术库中,以帮助确保我们已经探索了大型星系团的完整几何空间。
项目成果
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Fridgen, Travis的其他文献
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{{ truncateString('Fridgen, Travis', 18)}}的其他基金
The Physical Chemistry-Structures, Energetics, and Reactions-of Self Assembled Metal Cationized Complexes in the Gas Phase
气相自组装金属阳离子配合物的物理化学——结构、能量和反应
- 批准号:
RGPIN-2019-05260 - 财政年份:2022
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
The Physical Chemistry-Structures, Energetics, and Reactions-of Self Assembled Metal Cationized Complexes in the Gas Phase
气相自组装金属阳离子配合物的物理化学——结构、能量和反应
- 批准号:
RGPIN-2019-05260 - 财政年份:2021
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
The Physical Chemistry-Structures, Energetics, and Reactions-of Self Assembled Metal Cationized Complexes in the Gas Phase
气相自组装金属阳离子配合物的物理化学——结构、能量和反应
- 批准号:
RGPIN-2019-05260 - 财政年份:2020
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
The Physical Chemistry-Structures, Energetics, and Reactions-of Self Assembled Metal Cationized Complexes in the Gas Phase
气相自组装金属阳离子配合物的物理化学——结构、能量和反应
- 批准号:
RGPIN-2019-05260 - 财政年份:2019
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
Experimental Studies of the Structures, Energetics, and Reactions of Gas Phase Self-Assembled Biomolecular Ionic Complexes
气相自组装生物分子离子配合物的结构、能量学和反应的实验研究
- 批准号:
RGPIN-2014-04429 - 财政年份:2018
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
Experimental Studies of the Structures, Energetics, and Reactions of Gas Phase Self-Assembled Biomolecular Ionic Complexes
气相自组装生物分子离子配合物的结构、能量学和反应的实验研究
- 批准号:
RGPIN-2014-04429 - 财政年份:2016
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
Experimental Studies of the Structures, Energetics, and Reactions of Gas Phase Self-Assembled Biomolecular Ionic Complexes
气相自组装生物分子离子配合物的结构、能量学和反应的实验研究
- 批准号:
RGPIN-2014-04429 - 财政年份:2015
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
Experimental Studies of the Structures, Energetics, and Reactions of Gas Phase Self-Assembled Biomolecular Ionic Complexes
气相自组装生物分子离子配合物的结构、能量学和反应的实验研究
- 批准号:
RGPIN-2014-04429 - 财政年份:2014
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
Structures, reactivities and energetics of ion-molecule complexes
离子-分子配合物的结构、反应性和能量学
- 批准号:
327041-2009 - 财政年份:2013
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
Structures, reactivities and energetics of ion-molecule complexes
离子-分子配合物的结构、反应性和能量学
- 批准号:
327041-2009 - 财政年份:2012
- 资助金额:
$ 3.93万 - 项目类别:
Discovery Grants Program - Individual
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