摘要
“光合作用反应是地球上最为重要的化学反应”,并激发了许多生物学家和化学家们的浓厚兴趣。在大量有关光合作用过程的系统研究工作中,有相当数量的化学家从事着光合作用反应化学模型体系电子传递过程的研究。
本文综合运用UV-Vis、NMR、IR 、MS和XPS等分析方法,系统地研究了光合作用模型体系中对苯醌(BQ)、2,5-二氯对苯醌(DCBQ)及四氯对苯醌(CA)和咪唑(Im)物质在CH3CN溶液中的基态相互作用。并初步进行了时间分辨CIDNP技术的研究。
1、对苯醌 / 咪唑模型体系分子间相互作用的基态1H-NMR研究
通过对苯醌 / 咪唑模型体系分子间相互作用的基态1H-NMR研究,发现对苯醌和咪唑分子之间可能存在氢键作用。
2、对苯醌与咪唑在CH3CN溶液中的基态作用研究
对苯醌和咪唑在CH3CN溶液中首先快速形成BQ-Im CTC过渡态,然后生成对苯酚、2,5- 二咪唑取代基对苯醌。
3、四氯苯醌与咪唑及N-甲基咪唑的基态作用研究
首次发现四氯苯醌与咪唑在CH2Cl2溶液中形成1:2的CA-Im CTC,并对其进行了分离和表征。同时研究发现溶剂对反应的速度有一定的影响。四氯苯醌与N-甲基咪唑在CH2Cl2溶液中形成1:1的CA-NMIm CTC,并对其进行了分离、表征。
4、2,5-二氯对苯醌和咪唑在CH3CN溶液中的基态作用研究初探
该模型体系的UV-Vis和时间分辨1H-NMR实验表明,该反应体系除生成DCBQ-Im CTC外,还有其它键合物质生成。
5、时间分辨CIDNP (Time Resolved CIDNP)技术研究
在系统分析国内外时间分辨CIDNP的实验技术的基础上,初步在Varian Unity200 FT-NMR仪器上建立了时间分辨CIDNP实验装置。
Photosynthesis is the most chemical reaction on the earth, which excites the interest of biologists and chemists. During the lots of research of photosynthesis system, there are a large number of chemists who are engaged in the research of electron transfer procedures among the photosynthesis model system.
In this thesis, the interactions of p-benzoquinone, 2,5-dicholorbenzoquinone and Tetrachloro-p-benzoquinone with imidazole which are the basic photosynthesis model system were studied by UV-Vis, NMR, IR, MS and XPS analytical methods under ground state systematicly. At the same time, the Time-Resolved CIDNP technique was also investigated . The main results were obtained as following:
1. 1H-NMR study of p-benzoquinone / imidazole model system under ground state
P-benzoquinone / imidazole model system was studied under ground state by 1H-NMR method. The hydrogen bonding between p-benzoquinone and imidazole was observed under ground state.
2. Study of interaction of p-benzoquinone with imidazole in CH3CN under ground state
The results show that the reaction of p-benzoquinone with imidazole undergoes a charge transfer complex transition state at first, then produces hydroquinone and 2,5-Bis (imidazol-1-yl) hydroquinone.
3. Study of interaction of tetrachloro-p-benzoquinone with imidazole and N-methylimidazole under ground state
1:2 CA-Im CTC was observed in the reaction of tetrachloro-p-benzoquinone with imidazole in CH2Cl2 for the first time. The CA-Im CTC was isolated and
characterized. At the same time, the interaction of tetrachloro-p-benzoquinone with N-methylimidazole under ground state was also investigated, the result shows that 1:1 CA-NMIm CTC was formed. During the whole experiments there were no solvent polarity effects.
4. Preliminary study of interaction of 2,5-dicholorbenzoquinone with imidazole in CH3CN under ground state
The UV-Vis and time-resolved 1H-NMR experiments show that the reaction of 2,5-dicholorbenzoquinone with imidazole is much complicated. Not only CTC ,but also other products were formed.
5. Investigation on the Time-Resolved CIDNP technique
The preliminary Time-Resolved CIDNP device was established on the Varian Unity200 FT-NMR spectrometer.
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