某些光合作用模型体系的光激发与基态相互作用的磁共振研究
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摘要
光合作用是地球上最重要的化学反应。多年来，人们非常重视对伴随光合作用而产生的光致电子转移的研究。本文采用化学诱导动态核极化(CIDNP)和电子自旋共振(ESR)等方法，针对光合作用模型体系的光激发电子转移和基态相互作用以及跨膜电子传递反应动力学等问题，从反应机理及动力学等角度进行了探索性研究。
1．卟啉苯醌模型体系的光诱导反应机理探索
通过对比研究卟啉／苯醌／CD_3OD、苯醌／CD_3OD体系的CIDNP和ESR波谱，提出一个激发态苯醌与质子给体间的光诱导氢转移自由基反应新机理。
2．卟啉／苯醌／咪唑模型体系的光诱导反应机理探索
利用不同波长的光源(汞灯、镝灯)，在不同的溶剂(非质子溶剂C_6D_6、质子溶剂CDCl_3／CD_3OD)中对卟啉／苯醌／咪唑及其相关体系进行了光—CIDNP研究，发现卟啉／苯醌／咪唑体系均出现了强的发射极化信号，认为该体系发生了二次电子转移反应。
3．咪唑／醌模型体系的基态分子间相互作用的初探
分别进行了咪唑／苯醌、咪唑／四氯苯醌、咪唑／泛醌等体系基态NMR实验，发现加入醌后咪唑中—NH基团上H原子的化学位移和峰形都有较大的
北京化工大学硕士学位论文
改变，我f门认为咪哇和酿之间可能存在着分子间氢键作用。
4.跨膜电子传递反应动力学的探索
用ESR方法初步探讨了TPP汇心DAC与I称灯DODAC两种单层囊泡间
的光诱导电子转移反应，获得了长寿命的电荷分离态，为光合作用模拟提供
有价值的模型。
关键词光合作用，化学诱导动态核极化，电子自旋共振，叶嘟苯配劲珠哇
氢转移，二次电子转移，氢键作用，囊泡
Photosynthesis is the most important chemical reaction on the earth For years, significant emphasis has been put on developing an understanding of photoinduced electron transfer. In this paper, electron transfer in mimic of photosynthesis and the kinetics of trans-vesicle electron transfer were studied by using the Chemical Induced Dynamic Nuclear Polarization(CIDNP) and Electron Spin Resonance(ESR) technique. The reaction mechanism and the dynamic were investigated Some results were obtained as the following:1. Investigation on the photo-induced reaction mechanism of porphyrin/benzoquinonePoiphyrin/benzoquinone/CK3OD and benzoquinone/CDsOD were studied by CIDNP and ESR technique. The results supported a new mechanism that excited benzoquinone can abstract hydrogen H from proton donor under photo-irradiation.2. Investigation on the photo-induced reaction mechanism of porphyrin/benzoquinone/imidazolePomhyrin/benzoquinone/irnidazole was studied in the various solvent and under the various light source by CIDNP technique, which indicated that the second-electron transfer process has been proceeded3. NMR study on static interaction in imidazole/quinone
Imidazole/benzoquinone and imidazole/tetrachlorobenzoquinone were researched by using the NMR technique. The results show that an intermolecular hydrogen bonding interaction between imidazole and quinone. 4. Research on the kinetics of trans-vesicle electron transfer process across small unimolecular vesiclesTrans-vesicle photoinduced electron transfer reaction was explored in the photosynthesis mimic of TPP/DODAC and HA/DODAC small unimolecular vesicle aqueous solution. Long life charge separated state was achieved, which illustrated that vesicle system can used as valuable photosynthesis model.
1．卟啉苯醌模型体系的光诱导反应机理探索
通过对比研究卟啉／苯醌／CD_3OD、苯醌／CD_3OD体系的CIDNP和ESR波谱，提出一个激发态苯醌与质子给体间的光诱导氢转移自由基反应新机理。
2．卟啉／苯醌／咪唑模型体系的光诱导反应机理探索
利用不同波长的光源(汞灯、镝灯)，在不同的溶剂(非质子溶剂C_6D_6、质子溶剂CDCl_3／CD_3OD)中对卟啉／苯醌／咪唑及其相关体系进行了光—CIDNP研究，发现卟啉／苯醌／咪唑体系均出现了强的发射极化信号，认为该体系发生了二次电子转移反应。
3．咪唑／醌模型体系的基态分子间相互作用的初探
分别进行了咪唑／苯醌、咪唑／四氯苯醌、咪唑／泛醌等体系基态NMR实验，发现加入醌后咪唑中—NH基团上H原子的化学位移和峰形都有较大的
北京化工大学硕士学位论文
改变，我f门认为咪哇和酿之间可能存在着分子间氢键作用。
4.跨膜电子传递反应动力学的探索
用ESR方法初步探讨了TPP汇心DAC与I称灯DODAC两种单层囊泡间
的光诱导电子转移反应，获得了长寿命的电荷分离态，为光合作用模拟提供
有价值的模型。
关键词光合作用，化学诱导动态核极化，电子自旋共振，叶嘟苯配劲珠哇
氢转移，二次电子转移，氢键作用，囊泡
Photosynthesis is the most important chemical reaction on the earth For years, significant emphasis has been put on developing an understanding of photoinduced electron transfer. In this paper, electron transfer in mimic of photosynthesis and the kinetics of trans-vesicle electron transfer were studied by using the Chemical Induced Dynamic Nuclear Polarization(CIDNP) and Electron Spin Resonance(ESR) technique. The reaction mechanism and the dynamic were investigated Some results were obtained as the following:1. Investigation on the photo-induced reaction mechanism of porphyrin/benzoquinonePoiphyrin/benzoquinone/CK3OD and benzoquinone/CDsOD were studied by CIDNP and ESR technique. The results supported a new mechanism that excited benzoquinone can abstract hydrogen H from proton donor under photo-irradiation.2. Investigation on the photo-induced reaction mechanism of porphyrin/benzoquinone/imidazolePomhyrin/benzoquinone/irnidazole was studied in the various solvent and under the various light source by CIDNP technique, which indicated that the second-electron transfer process has been proceeded3. NMR study on static interaction in imidazole/quinone
Imidazole/benzoquinone and imidazole/tetrachlorobenzoquinone were researched by using the NMR technique. The results show that an intermolecular hydrogen bonding interaction between imidazole and quinone. 4. Research on the kinetics of trans-vesicle electron transfer process across small unimolecular vesiclesTrans-vesicle photoinduced electron transfer reaction was explored in the photosynthesis mimic of TPP/DODAC and HA/DODAC small unimolecular vesicle aqueous solution. Long life charge separated state was achieved, which illustrated that vesicle system can used as valuable photosynthesis model.
引文
[1] [美] 葛培根，光合作用，安徽教育出版社出版发行
[2] L．Stryer，Biochemistry，第22章—光合作用，第三版，WH．Freeman and Co．，1988
[3] KI. Zamaraev VN. Parmon, Potential Methods and Perspectives of Solar Energy Conversion, via Photocatalytic Processes, Catalvsis Rev., 1980, 22, 261-324
[4] R. Govindjee, The Absorption of Light in photosynthesis, Svi. Am., 1974, 231, 68-82
[5] BR. Velthays, The Photosysem Ⅱ Reaction Center, Tropics in Photosynthesis, vol. 8 The light Reaction(J. Barber) 341-377
[6] 张宏，人工模拟光合作用的若干方面，1996，博士论文
[7] Ibers. J. A. Holm, R. H. Science, 1980, 209-223
[8] J. H. Fendler, J. Phys. Chem., 1985, 89, 2730
[9] Wasielewski, M. R. Photohem. Photobiol., 1988, 47, 923
[10] D. Gust, T. A. Moore, Science, 1989, 244, 533
[11] D. Gust, T. A. Moore, A. L. Moore, S. J. Lee, E. Bittersmann, D. K. Luttrull, A. A. Rehms, J. M. De Graziano, X. C. Ma, F. Gao, R. E. Belford, T. T. Trier, 1990, Science, 248, 199
[12] M. R. Wasielewski, GL. Ⅲ Gaines, M. P. O. eil, W. A. Svec, M. ENiemezyk, J. Am. Chem. Soc., 1990, 112, 4559
[13] M. R. Wasielewski, M. P. Niemczyk, W. A. Svec, J. Am. Chem. Soc., 1985, 107, 5562
[14] 裘祖文 裴奉奎，核磁共振波谱，科学出版社
[15] 赵瑶兴，光谱解析与有机结构鉴定，中国科学技术大学出版社
[16] 严宝珍，核磁共振在分析化学中的应用，化学工业出版社
[17] J. Bargon H. Fischerand U. Johnsen, Z. Natarforsch, 1967, 22a, 1551
[18] H.R.Ward, J.Amer.Chem.Soc, 1967, 89, 5517
[19] 高汉宾，郑耀华，简明核磁共振手册， 1989, 111
[20] R.Kaptein,J.L.Oosterhoff, Chem.Phys.Letters, 4, 1969, 195, 214
[21]G.L.Closs, J.Am.Chem.Soc, 1969, 91, 4452
[22] F.J.Adrain, J.Chem.Phys., 1970, 53, 3374 1971, 54, 3912
[23] (a) R.Kaptein, Doctoral Dissertation, University of Leiden, 1971, chap III (b) R.Kaptein, J.Am.Chem.Soc, 1972, 94(18), 6251
[24] 唐有褀，徐广智，活泼中间体结构的研究方法，云南科技出版社，1990
[25] R.Kaptein, J.Am.Chem.Soc, 1972, 94(18), 6251
[26] R.Kaptein, J.Chem.Foc.D., 1971, 732
[27] R.R.Ernst, Pure and Appliedchem Chem., 1974, 37, 74
[28] M.Tomkiwicz,M.P. Klein, Rev.Sei.Inst., 1972, 43, 1206
[29] S.Caplain,G.Vermeersch, Org.Magn.Reson., 1976, 8, 277
[30] R.GLawter, in Chemically Induced Dynamic Magnetic Polarization, D.Reidel publishing Company, 1977, 275
[31] R.GLawter, J.Am.Chem.Soc, 1972, 94, 6300
[32] Yu.P.Tsentalovich,A.A.Obynochny and R.Z.Sagdeev, Chem.Phys., 1989, 139,301-306
[33] P. J.Hore,Ee.R.p.Zuiderweg,R.Kaptein and K.Dijkstra., Chem.Phy.Lett., 1981, 83, 376
[34] N.J.Turro,M.B.Zimmt and I.R.Gold, JAm.Chem.Soc., 1983, 105, 6347
[35]M.Lauferand M.Dreeskamp, J.Magn.Reson., 1984, 60, 357
[36] RXeuschner and H.Fischer, Chem.Phys.Lett., 1985, 121, 554
[37] M.Laufer, Chem.Phys.Lett., 1986, 127, 136
[38]Closs.GL.,Miller.R.J., J.Am.Chem.Soc, 1979, 101, 1639
[39]Closs.GL.,Miller.R.J., J.Am.Chem.Soc, 1981, 103, 3586
[40] Gerhard l.Closs,Robert J.Miller and O.David Redwine, Acc.Chem.Res., 1985, 18, 196-202
[4
[41] K. Maruyama and H. Furuta, Chem. Lett., 1986, 473-474
[42] K. Maruyama H. Furuta and T. Otsuki, Chem. Lett., 1981, 1509-1510
[43] K. Maruyama and H. Furuta, Chem. Lett., 1986, 645-648
[44] K. Maruyama H. Furuta and A. Osuka, Tetra., 1986, 42(22), 6149-6155
[45] K. Maruyama H. Furuta and A. Osuka, Chem. Lett., 1989, 833-836
[46] K. Maruyama and A. Osuka, Chem. Lett., 1986, 1853-1856
[47] Kurreck H, Huber M., Angew Chem Int Ed Engl, 1995, 34, 846-866
[48] Michael R W., Chem Rev, 1992, 92, 435-461
[49] Macpherson A N, Liddell P A, Lin S, Noss L, Seely G R, DeGraziano J M, Moore A L, Moore T A, Gust D., J Am Chem Soc, 1995. 117, 7207-7212
[50] Sun J, Liu Y, Chen D W, Zhang Q Y., J Phys Chem Solid, 2000, 61(7), 1149-1152
[51] 孙健，刘扬，陈德文，张启元，李凤英，李玉良，朱道本，甘良兵，黄春辉，化学学报，2000，58(7)，786-78
[52] 孙健，刘扬，陈德文，张启元，物理化学学报，1999，15(12)，1088
[53] 刘海锋，刘扬，张启元，高等化学学报，2001，21(8)，刊印中
[54] Goez M., J Inf Rec, 1998, 24(1-2), 9-22
[55] 田秋，陈次平，何光龙，简华华，徐广智，波谱学杂志，1998，15(3)，205
[56] Michael R. W., Chem. Rev., 1992, 92, 435-461
[57] Kurreck H., Huber M., Angew. Chem. Int. Ed. Engl., 1995, 34, 846-866
[58] Sessler J. L., Wang B., Harriman A., J. Am. Chem. Soc., 1995, 117, 704-714
[59] Macpherson A. N., Liddell P. A., Lin S., J. Am. Chem. Soc., 1995, 117(7), 202-212
[60] Magnuson A., Berglund H., Korall P., J. Am. Chem. Soc., 1997, 119(10), 720-725
[61] Kodera Y., Takura K. Kawamori A., Biochim. biophys. Acta, 1992, 1101, 23-32
[62] Svensson B.,Etchebest C.Juffery P., Biocchemistry, 1996, 35(14), 486-502
[63] GJ.Kavarnos, Top.Curr.Chem., 1990, 156, 21-58
[64] H.Tributsch,L.Pohlmann, Science, 1998, 279, 1891-1895
[65]R.C.Jennings,G.Zucchelli,R.Bassi, Top.Curr.Chem., 1996, 177, 147-182
[66]M.D.Esposti,A.Ghelli, Biochim.Biophy.Acta, 1994, 1187
[67] H.Nohl,W.Jordan,R.J.Youngman, Free Radical Biol. And Med., 1986, 2, 211-279
[68] J.F.Turren,AAlexandre,A.L.Lehninger, Arch.Biochem.Biophy., 1985, 237(2),408-414
[69] P.C.Hinkle, Federation Proc., 1973, 1988, 1992 [70]S.VLymar,V.N.Parmon,K.IZamarev, Top.Curr.Chem., 1990, 159, 1-66 [71]M.A.Fox, Top.Curr.Chem., 1990, 159, 67-102 [72]J.K.Hurst,L.Y.C.Lee,M.Gratzel, J.Am.Chem.Soc., 1983, 105, 7048-7056
[2] L．Stryer，Biochemistry，第22章—光合作用，第三版，WH．Freeman and Co．，1988
[3] KI. Zamaraev VN. Parmon, Potential Methods and Perspectives of Solar Energy Conversion, via Photocatalytic Processes, Catalvsis Rev., 1980, 22, 261-324
[4] R. Govindjee, The Absorption of Light in photosynthesis, Svi. Am., 1974, 231, 68-82
[5] BR. Velthays, The Photosysem Ⅱ Reaction Center, Tropics in Photosynthesis, vol. 8 The light Reaction(J. Barber) 341-377
[6] 张宏，人工模拟光合作用的若干方面，1996，博士论文
[7] Ibers. J. A. Holm, R. H. Science, 1980, 209-223
[8] J. H. Fendler, J. Phys. Chem., 1985, 89, 2730
[9] Wasielewski, M. R. Photohem. Photobiol., 1988, 47, 923
[10] D. Gust, T. A. Moore, Science, 1989, 244, 533
[11] D. Gust, T. A. Moore, A. L. Moore, S. J. Lee, E. Bittersmann, D. K. Luttrull, A. A. Rehms, J. M. De Graziano, X. C. Ma, F. Gao, R. E. Belford, T. T. Trier, 1990, Science, 248, 199
[12] M. R. Wasielewski, GL. Ⅲ Gaines, M. P. O. eil, W. A. Svec, M. ENiemezyk, J. Am. Chem. Soc., 1990, 112, 4559
[13] M. R. Wasielewski, M. P. Niemczyk, W. A. Svec, J. Am. Chem. Soc., 1985, 107, 5562
[14] 裘祖文 裴奉奎，核磁共振波谱，科学出版社
[15] 赵瑶兴，光谱解析与有机结构鉴定，中国科学技术大学出版社
[16] 严宝珍，核磁共振在分析化学中的应用，化学工业出版社
[17] J. Bargon H. Fischerand U. Johnsen, Z. Natarforsch, 1967, 22a, 1551
[18] H.R.Ward, J.Amer.Chem.Soc, 1967, 89, 5517
[19] 高汉宾，郑耀华，简明核磁共振手册， 1989, 111
[20] R.Kaptein,J.L.Oosterhoff, Chem.Phys.Letters, 4, 1969, 195, 214
[21]G.L.Closs, J.Am.Chem.Soc, 1969, 91, 4452
[22] F.J.Adrain, J.Chem.Phys., 1970, 53, 3374 1971, 54, 3912
[23] (a) R.Kaptein, Doctoral Dissertation, University of Leiden, 1971, chap III (b) R.Kaptein, J.Am.Chem.Soc, 1972, 94(18), 6251
[24] 唐有褀，徐广智，活泼中间体结构的研究方法，云南科技出版社，1990
[25] R.Kaptein, J.Am.Chem.Soc, 1972, 94(18), 6251
[26] R.Kaptein, J.Chem.Foc.D., 1971, 732
[27] R.R.Ernst, Pure and Appliedchem Chem., 1974, 37, 74
[28] M.Tomkiwicz,M.P. Klein, Rev.Sei.Inst., 1972, 43, 1206
[29] S.Caplain,G.Vermeersch, Org.Magn.Reson., 1976, 8, 277
[30] R.GLawter, in Chemically Induced Dynamic Magnetic Polarization, D.Reidel publishing Company, 1977, 275
[31] R.GLawter, J.Am.Chem.Soc, 1972, 94, 6300
[32] Yu.P.Tsentalovich,A.A.Obynochny and R.Z.Sagdeev, Chem.Phys., 1989, 139,301-306
[33] P. J.Hore,Ee.R.p.Zuiderweg,R.Kaptein and K.Dijkstra., Chem.Phy.Lett., 1981, 83, 376
[34] N.J.Turro,M.B.Zimmt and I.R.Gold, JAm.Chem.Soc., 1983, 105, 6347
[35]M.Lauferand M.Dreeskamp, J.Magn.Reson., 1984, 60, 357
[36] RXeuschner and H.Fischer, Chem.Phys.Lett., 1985, 121, 554
[37] M.Laufer, Chem.Phys.Lett., 1986, 127, 136
[38]Closs.GL.,Miller.R.J., J.Am.Chem.Soc, 1979, 101, 1639
[39]Closs.GL.,Miller.R.J., J.Am.Chem.Soc, 1981, 103, 3586
[40] Gerhard l.Closs,Robert J.Miller and O.David Redwine, Acc.Chem.Res., 1985, 18, 196-202
[4
[41] K. Maruyama and H. Furuta, Chem. Lett., 1986, 473-474
[42] K. Maruyama H. Furuta and T. Otsuki, Chem. Lett., 1981, 1509-1510
[43] K. Maruyama and H. Furuta, Chem. Lett., 1986, 645-648
[44] K. Maruyama H. Furuta and A. Osuka, Tetra., 1986, 42(22), 6149-6155
[45] K. Maruyama H. Furuta and A. Osuka, Chem. Lett., 1989, 833-836
[46] K. Maruyama and A. Osuka, Chem. Lett., 1986, 1853-1856
[47] Kurreck H, Huber M., Angew Chem Int Ed Engl, 1995, 34, 846-866
[48] Michael R W., Chem Rev, 1992, 92, 435-461
[49] Macpherson A N, Liddell P A, Lin S, Noss L, Seely G R, DeGraziano J M, Moore A L, Moore T A, Gust D., J Am Chem Soc, 1995. 117, 7207-7212
[50] Sun J, Liu Y, Chen D W, Zhang Q Y., J Phys Chem Solid, 2000, 61(7), 1149-1152
[51] 孙健，刘扬，陈德文，张启元，李凤英，李玉良，朱道本，甘良兵，黄春辉，化学学报，2000，58(7)，786-78
[52] 孙健，刘扬，陈德文，张启元，物理化学学报，1999，15(12)，1088
[53] 刘海锋，刘扬，张启元，高等化学学报，2001，21(8)，刊印中
[54] Goez M., J Inf Rec, 1998, 24(1-2), 9-22
[55] 田秋，陈次平，何光龙，简华华，徐广智，波谱学杂志，1998，15(3)，205
[56] Michael R. W., Chem. Rev., 1992, 92, 435-461
[57] Kurreck H., Huber M., Angew. Chem. Int. Ed. Engl., 1995, 34, 846-866
[58] Sessler J. L., Wang B., Harriman A., J. Am. Chem. Soc., 1995, 117, 704-714
[59] Macpherson A. N., Liddell P. A., Lin S., J. Am. Chem. Soc., 1995, 117(7), 202-212
[60] Magnuson A., Berglund H., Korall P., J. Am. Chem. Soc., 1997, 119(10), 720-725
[61] Kodera Y., Takura K. Kawamori A., Biochim. biophys. Acta, 1992, 1101, 23-32
[62] Svensson B.,Etchebest C.Juffery P., Biocchemistry, 1996, 35(14), 486-502
[63] GJ.Kavarnos, Top.Curr.Chem., 1990, 156, 21-58
[64] H.Tributsch,L.Pohlmann, Science, 1998, 279, 1891-1895
[65]R.C.Jennings,G.Zucchelli,R.Bassi, Top.Curr.Chem., 1996, 177, 147-182
[66]M.D.Esposti,A.Ghelli, Biochim.Biophy.Acta, 1994, 1187
[67] H.Nohl,W.Jordan,R.J.Youngman, Free Radical Biol. And Med., 1986, 2, 211-279
[68] J.F.Turren,AAlexandre,A.L.Lehninger, Arch.Biochem.Biophy., 1985, 237(2),408-414
[69] P.C.Hinkle, Federation Proc., 1973, 1988, 1992 [70]S.VLymar,V.N.Parmon,K.IZamarev, Top.Curr.Chem., 1990, 159, 1-66 [71]M.A.Fox, Top.Curr.Chem., 1990, 159, 67-102 [72]J.K.Hurst,L.Y.C.Lee,M.Gratzel, J.Am.Chem.Soc., 1983, 105, 7048-7056