氨基酸的太赫兹光谱及其振动模式研究
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摘要
太赫兹(THz )辐射是指频率位于微波和红外光之间的电磁辐射,属于远红外波段。近十几年来,超快激光技术的迅速发展,为THz脉冲的产生提供了稳定、可靠的激发光源,使THz辐射的产生和应用研究得到了蓬勃发展。太赫兹时域光谱(THz-TDS)技术作为一种崭新的THz探测技术,近年来在光谱和成像方面得到了广泛应用,由于生物分子的振动-转动能级落在THz波段,而且THz本身具有低能性,不会对生物组织造成破坏等特点,使得THz对生物材料的无损检测成为研究的热点之一。目前THz-TDS技术在若干生物分子的研究中取得了很好的实验结果,但相应的光谱分析研究还不成熟,寻找合适的理论模拟软件和方法对于合理和完善的解释THz光谱的形成机制具有重要的意义。
本论文主要是采用理论模拟与实验相结合的方法研究蛋氨酸、苏氨酸等五种蛋白质氨基酸的THz光谱并对其在0.2-2.8THz波段的吸收进行了详细的归属和讨论。采用THz-TDS技术,获取它们可靠的THz吸收光谱。选取剑桥数据库分子模型,应用Gaussian03软件,选取DFT理论等不同的理论模型和基组进行单分子与晶胞多分子模拟,获得它们的THz理论吸收光谱。对比理论与实验光谱,借助GaussView3.09软件的视频功能,对它们的振动模式进行探讨,发现THz吸收峰主要是由分子内的集体振动模式造成的。随着频率升高,分子的刚性振转模式减弱,而分子内部基团振转模式加强。
本论文的另一部分工作是选取菠菜的提取物三种植物光合膜蛋白,利用THz-TDS技术测量微量样品的THz光谱响应,设计适合该微量样品的THz测量方法,利用THz技术测试生物大分子的光谱响应,进一步探究分子内部的结构差异。
本研究不仅为氨基酸及蛋白质分子的应用研究提供借鉴,而且为以后生物大分子的微量测试研究提供了参考。
Terahertz (THz) wave,which lies between infrared and microwave in electromagnetic spectrum,belongs to far-infrared band. In the last decade, rapid progress in ultra-fast laser technology provides a steady and reliable optical source for the THz pulses generation,which greatly promotes the research in the THz waveband that is difficult to access before.THz time-domain spectroscopy (THz-TDS), as a newly technique of THz technology, has been widely used in the sensing and imaging field. THz radiation has low photon energies and will not cause harmful photo-ionization in biological tissues. Owing to these advantages, THz-TDS technology is a hot topic for nondestructive sensing in the bio-related fields. Until now this technique has made many significant experimental results in some bio-molecules; the spectrum analysis study in THz range, however, develops incomplete relative to the experiment. Researching adaptive simulation software and methods will help to understand logically the origin of THz spectrum.
The main work of this paper is that,we obtained the THz spectra of five amino acids,such as L-methionine and L- threonine ,ascribed and discussed their absorption spectra with experiment and theory simulation.We Obtained their reliable spectra in 0.2-2.8THz by THz-TDS technology. the moleculer structures were download from cambridge structural database ,choose different theories and basis sets such as DFTof Gaussian03,using single and polymolecular conformation to simulate,compare the calculated results and experiment,then with the help of Gaussian View 3.09,we discuss their far-infrared collective vibrational modes. It was found that the absorption peaks are mainly caused by different intramolecular collective vibrational mode,as the frequency higher,the rigidity collective vibrational mode weaker,the group moveing in molecules strengthen.
The other work is we select three chlorophyll protein extract from spinach,measure spectrum respond of minim sample with THz-TDS technology. And explore the difference in molecules.
This study not only offer references to the application of amino acids and protein,but also useful for mini sample measurement.
本论文主要是采用理论模拟与实验相结合的方法研究蛋氨酸、苏氨酸等五种蛋白质氨基酸的THz光谱并对其在0.2-2.8THz波段的吸收进行了详细的归属和讨论。采用THz-TDS技术,获取它们可靠的THz吸收光谱。选取剑桥数据库分子模型,应用Gaussian03软件,选取DFT理论等不同的理论模型和基组进行单分子与晶胞多分子模拟,获得它们的THz理论吸收光谱。对比理论与实验光谱,借助GaussView3.09软件的视频功能,对它们的振动模式进行探讨,发现THz吸收峰主要是由分子内的集体振动模式造成的。随着频率升高,分子的刚性振转模式减弱,而分子内部基团振转模式加强。
本论文的另一部分工作是选取菠菜的提取物三种植物光合膜蛋白,利用THz-TDS技术测量微量样品的THz光谱响应,设计适合该微量样品的THz测量方法,利用THz技术测试生物大分子的光谱响应,进一步探究分子内部的结构差异。
本研究不仅为氨基酸及蛋白质分子的应用研究提供借鉴,而且为以后生物大分子的微量测试研究提供了参考。
Terahertz (THz) wave,which lies between infrared and microwave in electromagnetic spectrum,belongs to far-infrared band. In the last decade, rapid progress in ultra-fast laser technology provides a steady and reliable optical source for the THz pulses generation,which greatly promotes the research in the THz waveband that is difficult to access before.THz time-domain spectroscopy (THz-TDS), as a newly technique of THz technology, has been widely used in the sensing and imaging field. THz radiation has low photon energies and will not cause harmful photo-ionization in biological tissues. Owing to these advantages, THz-TDS technology is a hot topic for nondestructive sensing in the bio-related fields. Until now this technique has made many significant experimental results in some bio-molecules; the spectrum analysis study in THz range, however, develops incomplete relative to the experiment. Researching adaptive simulation software and methods will help to understand logically the origin of THz spectrum.
The main work of this paper is that,we obtained the THz spectra of five amino acids,such as L-methionine and L- threonine ,ascribed and discussed their absorption spectra with experiment and theory simulation.We Obtained their reliable spectra in 0.2-2.8THz by THz-TDS technology. the moleculer structures were download from cambridge structural database ,choose different theories and basis sets such as DFTof Gaussian03,using single and polymolecular conformation to simulate,compare the calculated results and experiment,then with the help of Gaussian View 3.09,we discuss their far-infrared collective vibrational modes. It was found that the absorption peaks are mainly caused by different intramolecular collective vibrational mode,as the frequency higher,the rigidity collective vibrational mode weaker,the group moveing in molecules strengthen.
The other work is we select three chlorophyll protein extract from spinach,measure spectrum respond of minim sample with THz-TDS technology. And explore the difference in molecules.
This study not only offer references to the application of amino acids and protein,but also useful for mini sample measurement.
引文
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[2] D. H. Auston and K. P. Cheung. J. Opt. Soc. Am. B. 45, 284, 1984
[3] Ch. Fattinger and D. Grischkowsky. Appl. Phys. Lett. 54, 490, 1989
[4] F. Zernike, Jr. and P. R. Berman. Phys. Rev. Lett. 15(26), 999, 1965
[5] F. Zernike. Phys. Rev. Lett. 22(18), 931, 1969
[6] Y. -R. Shen. Prog. Quant. Electro. 4(3), 207, 1976
[7] J. R. Morris and Y. R. Shen. Phys. Rev. A. 15(3), 1143, 1977
[8] L. Wu, X. -C. Zhang and D. H. Auston. Appl. Phys. Lett. 61, 1784, 1992
[9] B. B. Hu, X. -C. Zhang and D. H. Auston et al. Appl. Phys. Lett. 56, 506, 1990
[10] D. M. Mittleman, R. H. Jacobse and M. C. Nuss. IEEEJ. Sel. Top. Quantum Electron. 2, 689, 1996,
[11]周同军,博士学位论文,浙江,浙江大学博士学位论文。
[12] C.Zhang. PhysiealReviewB.2002.65(15),1012一1015
[13] Y. C. Shen, P. C. Upadhya, E. H. Linfield et al. Appl. Phys. Lett. 83(15), 13, 2003
[14]王宏飞,改变世界的十大技术之一,全球科技经济瞭望,4,60-64,2005
[15] A. G. Markelz, A. Roitberg, E. J. Heilweil. Chem. Phys. Lett. 320, 42, 2000
[16] B M Fischer, M Walther and P Uhd Jepsen, Phys. Med. Biol., 47, 3807, 2002
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[18] M.Walther,B.M.Fiseher,P.U.JePsen.2003.288(2-3),261-268.
[19] Y. C. Shen, P. C. Upadhya and E. H. Linfield., Appl. Phys. Lett. 82. 2350, 2003
[20] M.R. Kutteruf, C.M. Brown and L.K. Iwaki et al., Chem. Phys. lett., 375, 337, 2003
[21] M.R. Kutteruf, C.M. Brown and L.K. Iwaki et al., Chem. Phys. lett., 375, 337, 2003
[22] B. Yu, F. Zeng and Y. Yang et al., Biophysical Journal, 86, 1649, 2004
[23] Qunqing Chen, Haibo Liu and Yanqing Deng et al., Chem. Phys. lett., 400, 357, 2004
[24] S. C. Shen , L. Santo , L. Genzel,Int J Infrared Milli Waves (2007) 28:595–610
[25] Laman, N., Harsha, S. S., Grischkowsky, D., and Melinger, J. S. 2008.94, 1010-1020
[26] Jeffrey Barber, Daniel E. Hooks and David J. Funk et al., J. Phys. Chem. A, 109, 3501, 2005
[27] F.Huang,B.Schulkin,H.Altan et., Appl.Phys.Lett.85,5535-5537,2004
[28] Damian.G.Allis,Timothy.M.Korter,ChemPhysChem,7,2398-2408,2006
[29] P. F. Taday, I.V. Bradley , D.D. Arnone, Journal of Biological Physics, 29, 109, 2003
[30] F. Miyamaru, M. Yamaguchi, M. Tani, et al. CLEO’03, 3, 2003
[31] Y. C. Shen, P. C. Upadhya and E. H. Linfield., Appl. Phys. Lett. 82. 2350, 2003
[32] Mariko Yamaguchi, Fumiaki Miyamaru, Kohji Yamamoto, et al. Appl. Phys. Lett. 86, 053903, 2005
[33] Yulei.shi, Li Wang, J. Phys. D:Appl.Phys. 38, 3741, 2005.
[34] Naoto,N., Ryoichi,K., Ryoichi, F. Chem.Phys.lett. 413,495, 2005
[35] H. T. Yan, W. N. Wang., Chin. Phys. Lett. 22, 3179, 2005
[36] W. N. Wang, H. T. Yan and W. W. Yue et al., Science in China Ser.G Physics, Mechanics & Astronomy. 48 (5), 585, 2005
[37]王卫宁,闫海涛,岳伟伟等,还原型谷肤甘肤的THz光谱,中国科学G辑物理学力学天文学, 35 (5), 492, 2005
[38] W. N. Wang, W. W. Yue and Y. B. Li, PIBM'2005
[39]马士华,施宇雷,徐新龙等,物理学报, 55(08), 4091, 2006
[40] T. M. Korter, R. Balu, M. B. Campbell et. al., Chemical Physics Letters, 418, 65,2006
[41] Nishizawa, J., Sasaki, T., Suto, K., Tanabe, T., Yoshida, T., Kimura, T., Saito, K., International Journal of Infrared and Millimeter Waves. 27: 779-789. 2006.
[42] Yuanbo Li, Yingying Zheng ,Weining Wang, , Ultrafast Measurements, and Imaging(IRMMW-THz2006), 422, 2006.
[43]郑盈盈,李元波,王卫宁,化学学报, 65(1), 72, 2007
[44]王卫宁,李元波,岳伟伟,物理学报, 56(2), 781, 2007
[45] S. C. Shen,L. Santo, L. Genzel,Int J Infrared Milli Waves (2007) 28:595–610
[46] Laman, N., Harsha, S. S., Grischkowsky, D.,Melinger, Biophys. J. 2008.94, 1010-1020
[47] Yan, Z. G., Hou, D. B., Huang, P. J., Cao, B. H., Zhang, G. X., Zhou, Z. K., Meas. Sci. Technol. 19:015602. 2008.
[48]徐慧,余笑寒,张增燕等.中国科学院研究生院学报. 22 (1), 91, 2005
[49]郑盈盈,硕士学位论文,北京,首都师范大学物理系,2007
[50] Chen, H., Wang, L., Qu, Y., Kuang, T., Li, L., Peng, W. J. Appl. Phys. 102:074701. 2007.
[51]程兆华,祝大军,刘盛纲,电子测量与仪器学报,2005(4),l-5
[52] Bradley Ferguson,张希成,物理, 2003, 32(5):286~292
[53]马成举,陈延伟,向军,张显斌,太赫兹辐射产生技术进展,Laser & Optoelect ronics Progress,2007,Vol44,No.4
[54]张兴宁,陈稷,周泽魁.激光与光电子学进展, 2005,42(7):35-37
[55] X. C. Zhang, Y. Jin, X. F. Ma. Appl.Phys. Lett., 1992, 61(23):2764-2766
[56]王秀敏,徐新龙,李福利.首都师范大学学报(自然科学版), 2003, 24(3):17～21
[57]张显斌,碇智文,陈颍丽等.光学学报, 2006, 26(4):617-620
[58] Kodo Kawase,Takaaki Hatanaka, Hidenori Takahashi et al. Opt. Lett., 2000, 25(23), 1714-1716
[59] T. Tanabe, K. Suto, J. Nishizawa et al. Appl.Phys. Lett.,2003, 83(2):237-239
[60] Kodo Kawase, Jun- ichi Shikata, Hiromasa Ito, J . phys. D; Appl. Phys., 2001, 34(01)R1-R14
[61]张存林等著,太赫兹感测与成像,国防工业出版社,2008
[62]闫海涛,硕士学位论文,北京,首都师范大学物理系,2006
[63]李德华,周薇,徐士林,梁敏,2007,物理与工程,Vol . 17,No. 6
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