基于太赫兹时域谱技术的有机分子溶液检测与分析研究
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摘要
太赫兹(Terahertz, THz)电磁波谱与有机及生物分子的转动和振动能量对应,非常适于鉴别和研究这些分子的动力学行为,尤其是基于飞秒超快激光技术的太赫兹时域光谱技术(THz-TDS),可以测量太赫兹波电场的幅度和相位,直接得到材料太赫兹波段的折射率和吸收系数,以及反应物质内部结构及微观运动状态的复介电谱。不仅如此,THz波对生物分子中的水非常敏感,可直接探测其它技术很难探测的生物分子-水分子界面的水分子网络动力学变化。本文研究了基于THz-TDS技术的液态物质光学材料参数的提取方法；比较了可以用于定量分析有机分子溶液THz吸收谱的回归校正建模方法；研究了有机分子水溶液THz介电谱产生的介电响应机理；以及可以用于测量溶液浓度的THz波段人工电磁材料传感器的特性。本文的主要研究工作包括：
1)提出了一种基于THz脉冲时域波形重建技术的材料参数(如折射率和吸收系数)提取方法,该方法可以克服其它频域材料参数提取算法的固有缺陷,能够更为精确地测定材料的材料参数,特别是液体的材料参数。目前已有的材料参数频域提取算法在定义误差函数时必须把不同量纲的复数的幅度和相位一起考虑,而本文利用波形重建技术在时域定义的误差函数物理意义更为明确,结果更为准确可靠。该方法可以用于多层结构的透射测量以及反射测量方式,进一步提高了溶液材料参数的提取精度,并降低了测量难度,更适合现场测量。
2)利用支持向量机回归模型定量分析了常温下食用植物油(液态)的THz吸收谱。采用THz时域谱技术和波形重建技术测得了30个食用油样本的THz吸收谱,随机分为训练集和预测集,利用支持向量回归算法和标准方法测得的参考含量在训练集上建立了植物油主要油酸成分含量、酸价和过氧化值的预测模型,并应用这些模型对测试集样本进行预测。结果表明支持向量回归算法所建模型对油酸含量、酸价和过氧化值预测的精度高于传统的偏最小二乘法(Partial Least Square, PLS)方法。
3)利用基于动态Onsager有效电场的THz波段分子极化率模型估计了蔗糖和葡萄糖水溶液中结合水分子的数量、半径等重要参数。通过对蔗糖和葡萄糖水溶液的THz介电谱的研究,进一步印证了常温下水溶液中结合水分子的转动和平移等弛豫运动可从自由水的皮秒量级下降到纳秒和微秒量级,但相应的共振运动部分不变,并得到了结合水的宏观介电常数。结合水的这些性质可以用来估计生物有机分子水溶液中结合水分子的数量及大小等参数,并为将来动态监测生物分子的水合过程奠定基础。
4)利用有限元方法仿真分析了THz人工电磁介质作为溶液浓度传感器的可行性,设计了基于PCB柔版工艺的双层人工电磁介质溶液浓度传感器,用于测量酒精溶液的浓度,并用THz-TDS系统进行了实验验证。研究发现双层人工电磁材料对有机分子水溶液进行反射测量时可形成明显的谐振峰,并随溶液浓度变化发生显著偏移。使用THz波段人工电磁材料作为溶液浓度传感器是可行的,灵敏度与单元的结构和层数有密切关系,值得进一步研究。
Terahertz (THz) spectrum is corresponding to vibration and rotation of organic and biological molecules, which is suitable to identify and study those molecular dynamics. Especially, THz Time-domain spectroscopy(THz-TDS) can enable us to extract the material parameters or dielectric spectrum that show material micro-structure and dynamics by measuring amplitude and phase from coherent terahertz pulses. Furthermore, THz wave is very sensitive to water, through which we can directly detect the water dynamics in hydration layer between water and solute molecules. In this paper, material parameter extraction technology for THz-TDS is investigated. Different regressive calibration methods for THz spectrum quantitative analysis are compared. A THz metamaterial sensor is designed for the concentration measurement of the solution. Mechanism of dielectric response for glucose and sucrose in THz band is discussed. The details of the above research work are listed as follows:
1) An innovative optical material parameter extraction algorithm based on waveform rebuilding technology for Terahertz time-domain spectroscopy (THz-TDS) is proposed. Unlike previously reported extraction algorithms in frequency domain, which have to be compromised between amplitude and phase, or the real part and imaginary part of the transfer function, we calculate material parameters by minimizing the difference between the measured sample waveform and the rebuilt one in time domain. Our cost function is more meaningful than those extraction methods in frequency domain, and thus the results are more accurate. The new method can also be used effectively in multilayer transmission mode or in reflection mode.
2) THz Spectrum of edible oil is quantitatively analyzed by Support Vector Regression(SVR). The terahertz absorption spectrum of edible oil in 30 samples is measured by THz-TDS, and they are randomly divided into training set and testing set. Regression models for oil's oleic acid concentration, acid number and peroxide value are built by SVR algorithm and reference values from standard methods with training set, then the values of acid concentration, acid number and peroxide value in testing set are predicted by those regressive models. The results show that the models by SVR have significant advantage compared with traditional Partial Least Square(PLS) method.
3) Hydrated water parameters in glucose and sucrose solutions such as the number and the radius of the hydrated water molecule are estimated by Onsager's molecular polarization theory for the case of a time-varying field in THz band. By THz dielectric spectrum of glucose and sucrose solutions it is confirmed that the relaxation responses of hydrated water is slowed down to GHz or MHz with its resonant response unchangeable, which enable us to calculate the number of hydrated water in solutions. At the same time, the dielectric spectrum of hydrated water is calculated. This is very important for monitoring the hydration dynamically.
4) The feasibility of the solution's concentration sensor by THz metamaterial is evaluated by Finite Element Method, and a sensor with a double golden finger structure on a flexible PCB is designed and tested by THz-TDS. It is shown that there are sharp resonant peaks in reflection coefficient which are shifted with solution concentration changing. The sensitivity is relative with cell structure and the number of layers in THz metamaterial, which is worth further research.
1)提出了一种基于THz脉冲时域波形重建技术的材料参数(如折射率和吸收系数)提取方法,该方法可以克服其它频域材料参数提取算法的固有缺陷,能够更为精确地测定材料的材料参数,特别是液体的材料参数。目前已有的材料参数频域提取算法在定义误差函数时必须把不同量纲的复数的幅度和相位一起考虑,而本文利用波形重建技术在时域定义的误差函数物理意义更为明确,结果更为准确可靠。该方法可以用于多层结构的透射测量以及反射测量方式,进一步提高了溶液材料参数的提取精度,并降低了测量难度,更适合现场测量。
2)利用支持向量机回归模型定量分析了常温下食用植物油(液态)的THz吸收谱。采用THz时域谱技术和波形重建技术测得了30个食用油样本的THz吸收谱,随机分为训练集和预测集,利用支持向量回归算法和标准方法测得的参考含量在训练集上建立了植物油主要油酸成分含量、酸价和过氧化值的预测模型,并应用这些模型对测试集样本进行预测。结果表明支持向量回归算法所建模型对油酸含量、酸价和过氧化值预测的精度高于传统的偏最小二乘法(Partial Least Square, PLS)方法。
3)利用基于动态Onsager有效电场的THz波段分子极化率模型估计了蔗糖和葡萄糖水溶液中结合水分子的数量、半径等重要参数。通过对蔗糖和葡萄糖水溶液的THz介电谱的研究,进一步印证了常温下水溶液中结合水分子的转动和平移等弛豫运动可从自由水的皮秒量级下降到纳秒和微秒量级,但相应的共振运动部分不变,并得到了结合水的宏观介电常数。结合水的这些性质可以用来估计生物有机分子水溶液中结合水分子的数量及大小等参数,并为将来动态监测生物分子的水合过程奠定基础。
4)利用有限元方法仿真分析了THz人工电磁介质作为溶液浓度传感器的可行性,设计了基于PCB柔版工艺的双层人工电磁介质溶液浓度传感器,用于测量酒精溶液的浓度,并用THz-TDS系统进行了实验验证。研究发现双层人工电磁材料对有机分子水溶液进行反射测量时可形成明显的谐振峰,并随溶液浓度变化发生显著偏移。使用THz波段人工电磁材料作为溶液浓度传感器是可行的,灵敏度与单元的结构和层数有密切关系,值得进一步研究。
Terahertz (THz) spectrum is corresponding to vibration and rotation of organic and biological molecules, which is suitable to identify and study those molecular dynamics. Especially, THz Time-domain spectroscopy(THz-TDS) can enable us to extract the material parameters or dielectric spectrum that show material micro-structure and dynamics by measuring amplitude and phase from coherent terahertz pulses. Furthermore, THz wave is very sensitive to water, through which we can directly detect the water dynamics in hydration layer between water and solute molecules. In this paper, material parameter extraction technology for THz-TDS is investigated. Different regressive calibration methods for THz spectrum quantitative analysis are compared. A THz metamaterial sensor is designed for the concentration measurement of the solution. Mechanism of dielectric response for glucose and sucrose in THz band is discussed. The details of the above research work are listed as follows:
1) An innovative optical material parameter extraction algorithm based on waveform rebuilding technology for Terahertz time-domain spectroscopy (THz-TDS) is proposed. Unlike previously reported extraction algorithms in frequency domain, which have to be compromised between amplitude and phase, or the real part and imaginary part of the transfer function, we calculate material parameters by minimizing the difference between the measured sample waveform and the rebuilt one in time domain. Our cost function is more meaningful than those extraction methods in frequency domain, and thus the results are more accurate. The new method can also be used effectively in multilayer transmission mode or in reflection mode.
2) THz Spectrum of edible oil is quantitatively analyzed by Support Vector Regression(SVR). The terahertz absorption spectrum of edible oil in 30 samples is measured by THz-TDS, and they are randomly divided into training set and testing set. Regression models for oil's oleic acid concentration, acid number and peroxide value are built by SVR algorithm and reference values from standard methods with training set, then the values of acid concentration, acid number and peroxide value in testing set are predicted by those regressive models. The results show that the models by SVR have significant advantage compared with traditional Partial Least Square(PLS) method.
3) Hydrated water parameters in glucose and sucrose solutions such as the number and the radius of the hydrated water molecule are estimated by Onsager's molecular polarization theory for the case of a time-varying field in THz band. By THz dielectric spectrum of glucose and sucrose solutions it is confirmed that the relaxation responses of hydrated water is slowed down to GHz or MHz with its resonant response unchangeable, which enable us to calculate the number of hydrated water in solutions. At the same time, the dielectric spectrum of hydrated water is calculated. This is very important for monitoring the hydration dynamically.
4) The feasibility of the solution's concentration sensor by THz metamaterial is evaluated by Finite Element Method, and a sensor with a double golden finger structure on a flexible PCB is designed and tested by THz-TDS. It is shown that there are sharp resonant peaks in reflection coefficient which are shifted with solution concentration changing. The sensitivity is relative with cell structure and the number of layers in THz metamaterial, which is worth further research.
引文
[1]G. Davies, E. Linfield, "Bridging the terahertz gap" Physics world,2004,17,37-41.
[2]B. Ferguson and X. C. Zhang, "Materials for terahertz science and technology" Nature Materials,2002,1,26-33.
[3]R. Woodward, B. E. Cole, V. P. Wallace, R. J. Pye, D. D. Arnone, E. H. Linfield and M. "Pepper Terahertz pulse imaging in reflection geometry of human skin cancer and skin tissue" Phys. Med. Biol.,2002,47,3853-63.
[4]J. T. Kindt and C. A. Schmuttenmaer, "Far-Infrared Dielectric Properties of Polar Liquids Probed by Femtosecond Terahertz Pulse Spectroscopy", Phys. Chem.1996,100, 10373-10379.
[5]J Xu, C Zhang, X Zhang, "Recent progress in terahertz science and technology" Progress in Nature Science,2002,12,729-736.
[6]Wallace V. P., Fitzgerald A. J., Shankar S., Flanagan N., Pye R., Cluff J., and Arnone D. D., "Terahertz pulsed imaging of basal cell carcinoma ex vivo and in vivo," J. Invest. Dermatol. 2004,151,424-432.
[7]Fitzgerald A. J., Wallace V. P., Jimenez-Linan M., Bobrow L., Pye R. J., Purushotham A. D., and Arnone D. D., "Terahertz pulsed imaging of human breast tumors," Radiology 2006, 239,533-540.
[8]Taylor Z. D., Singh R. S., Culjat M. O., Suen J. Y., Grundfest W. S., Lee H., and Brown E. R., "Reflective terahertz imaging of porcine skin burns," Opt. Lett.2008,33,1258-1260.
[9]Hoshina H., Hayashi A., Miyoshi N., Miyamaru F., and Otani C., "Terahertz pulsed imaging of frozen biological tissues," Appl. Phys. Lett.,2009,94,123901.
[10]Kawase K., Ogawa Y., Minamide H., and Ito H., "Terahertz parametric sources and imaging applications," Semicond. Sci. Technol.2005,20, S258-265.
[11]Darmo J., Tamosiunas V., Fasching G., Kroll J., Unterrainer K., Beck M., Giovannini M., Faist J., Kremser C., and Debbage P., "Imaging with a Terahertz quantum cascade laser," Opt. Express 2004,12,1879-1884
[12]Dobroiu A., Yamashita M., Ohshima Y. N., Morita Y, Otani C., and Kawase K., "Terahertz imaging system based on a backward-wave oscillator," Appl. Opt.2004,43,5637-5646.
[13]Woodward R M, Cole B E, Wallace V P, Pye R J, Arnone D D, Linfield E H and Pepper M 'Terahertz pulse imaging in reflection geometry of human skin cancer and skin tissue." Phys. Med. Biol.2002,47,3853-63.
[14]Ashworth P C, Pickwell-Mac Pherson E, Provenzano E, Pinder S E, Purushotham A D, Pepper M, and Wallace V P "Terahertz pulsed spectroscopy of freshly excised human breast cancer" Opt. Express,2009,17,12444-12454.
[15]D A Crawley, C Longbottom, V P Wallace, "Three dimensional terahertz pulse imaging of dental tissue". SPIE 2002,4633,84-89.
[16]J.A. Zeitler, P.F. Taday, D.A. Newnham, M. Pepper, K.C. Gordon, T. Rades, "Terahertz pulsed spectroscopy and imaging in the pharmaceutical setting - a review ",J. Pharm. Pharmacol.2007,59,209-223.
[17]H. Wu, E. J. Heilweil, A. S. Hussain, M. A. Khan, "Process analytical technology (PAT): Quantification approaches in terahertz spectroscopy for pharmaceutical application", Int. J. Pharm.2007,343,148-158.
[18]N. Laman, S. S. Harsha, D. Grischkowsky, "Narrow-line waveguide terahertz time-domain spectroscopy of aspirin and aspirin precursors", Appl. Spectrosc.2008,62,319-326.
[19]Walther M, Plochocka P, Fischer B, et al. "Collective vibrational modes in biological molecules investigated by terahertz time-domain spectroscopy", Biopolymers,2002,67, 310-313.
[20]Walther M, Fischer B, Uhd Jepsen P "Noncovalent intermolecular forces in polycrystalline and amorphous saccharides in the far infrared" P. Chem. Phys.,2003,288,261-268.
[21]Markelz A G, Roitberg A, Heilweil E J. "Pulsed terahertz spectroscopy of DNA, bovine serum albumin and collagen between 0.1 and 2.0 THz" Chem. Phys. Lett.,2000,32, 42-48.
[22]Walt her M, Fischer B, Schall M, et al. "Far-infrared vibrational spectra of all-trans,9-cis and 13-cis retinal measured by THz time-domain spectroscopy", Chem. Phys. Lett.,2000, 332,389-395.
[23]Fischer B M, Walther M, Uhd Jepsen P. "Far-infrared vibrational modes of DNA components studied by terahertz time-domain spectroscopy" Phys. Med. Biol.,2002,47, 3807-3814.
[24]Upadhya P C, Shen Y C, Davies A G, et al. "Terahertz Time-Domain Spectroscopy of Glucose and Uric Acid" J. Biol. Phys.,2003,29,117-121.
[25]Bigourd D, Cuisset A, Hindle F, Matton S, Bocquet R, Mourct G, et al. "Multiple component analysis of cigarette smoke using THz spectroscopy, comparison with standard chemical analytical methods". Appl. Phys. B 2007,86,579-86.
[26]M R Leahy-Hoppa, M J Fitch, X Zheng. "Wideband terahertz spectroscopy of explosives". Chemical Physics Letters,2007.434,227-230.
[27]A A Stark, J Bally, S P Balm. "The Antarctic Submillimeter Telescope and Remote Observatory (AST/RO)". Publications of the Astronomical Society of the Pacific, 2001.113(783),567-585.
[28]. H M Araujo, R J Walker, S A Rinehart. "Assessment of the 200-mum atmosphericwindow for ground-based astronomy." International Journal of Infrared and Millimeter Waves,2001, 22,965-982.
[29]. N Krumbholz, K Gerlach, F Rutz. "Omnidirectional terahertz mirrors:A keyelement for future terahertz communication systems". Applied Physics Letters,2006,88,112-116.
[30]Al-Douseri F M, Chen Y Q, Zhang X C. THz wave sensing for petroleum industrial applications. Int J Infrared Millim Waves,2006,27,481-503.
[31]田璐,周庆莉,金彬等.“润滑油的太赫兹波段光学与光谱特性研究.”中国科学G辑：物理学力学天文学,2009,39,1589-1593.
[32]宝日玛,赵昆,田璐等.“汽油的太赫兹时域光谱特性研究.”中国科学G辑：物理学力学天文学,2010,40,950-954.
[33]Jin Y S, Kim G J, Shon C H, et al. "Analysis of petroleum products and their mixtures by using terahertz time domain spectroscopy." J Korean Phys Soc,2008,53,1879-1885.
[34]胡颖,王晓红,郭澜涛等,“植物油和动物脂肪在THz波段的吸收和色散”物理学报2005,54,4124-4128.
[35]M. Havenith, "Solute-induced retardation of water dynamics probed directly by terahertz spectroscopy" Proc. Natl. Acad. Sci. USA 2006,103,12301-12306.
[36]Xu J, Plaxco K W, Allen S J."Probing the collective vibrational dynamics of a protein in liquid water by terahertz absorption spectroscopy." Protein Science,2006,15,1175-1181.
[37]Born B, Kim S J, Ebbinghaus S, et al. "The terahertz dance of water with the proteins:the effect of protein flexibility on the dynamical hydration shell of ubiquitin." Faraday Discuss, 2009,141,161-173.
[38]Born B, Weingartner H, Brundermann E, et al. "Solvation Dynamics of Model Peptides Probed by Terahertz Spectroscopy. Observation of the Onset of Collective Network Motions." Journal of the American Chemical Society,2009,131,3752-3755.
[39]Havenith M, "An extended dynamical hydration shell around proteins" Proc. Natl. Acad. Sci. USA 2007,104,20749-20752.
[40]S. E. Ralph, S. Perkowitz, N. Katzenellenbogen, and D. Grischkowski, "Terahertz spectroscopy of optically thick multilayerd semiconductor structures," J. Opt. Soc. Amer. B, 1994,11,2528-2532.
[41]C B Reid, E Pickwell-MacPherson, J G Laufer, A P Gibson, J C Hebden and V P Wallace "Accuracy and resolution of THz reflection spectroscopy for medical imaging"Phys. Med. Biol.2010,55,4825-4838.
[42]J. Xu, K. W. Plaxco, S. J. Allen, Probing the Collective Vibrational Dyamics of a Protein in Liquid Water by Terahertz Absorption Spectroscopy, Protein Sci.,2006,15,1175-1181.
[43]B. B. Hu and M. C. Nuss, "Imaging with terahertz waves," Opt. Lett.,1995,20,1716-1718.
[44]李向军,陈裕泉,李九生,“利用THz时域谱技术和支持向量机回归法快速测定食用油的过氧化值和酸价”中国粮油学报2010,25(2),131-135.
[45]L. Thrane, R. H. Jacobsen, P. Uhd Jepsen, and S. R. Keiding, "THz reflection spectroscopy of liquid water," Chem. Phys. Lett.1995,240,330-333.
[46]P. Uhd Jepsen, U. Moller, and H. Merbold, "Investigation of aqueous alcohol and sugar solutions with reflection terahertz time-domain spectroscopy," Opt. Express 2007,15, 717-737.
[47]M. Nagai, H. Yada, T. Arikawa, and K. Tanaka, "Terahertz time-domain attenuated total reflection spectroscopy in water and biological solution," Int. J. Infrared Millim. Waves 2006, 27,505-515.
[48]U. Moller, D.G. Cooke, K. Tanaka, P. Uhd Jepsen, "Terahertz reflection spectroscopy of Debye relaxation in polar liquids", J. Opt. Soc. Am.B,2009,26,113-125.
[49]L. Duvillaret, F. Garet, and J.-L. Coutaz, "A reliable method for extraction of material parameters in Terahertz Time-Domain Spectroscopy," IEEE J. Sel. Top. Quantum Electron. 1996,2,739-746.
[50]T. Dorney, R. Baraniuk, and D. Mittleman, "Material parameter estimation with Terahertz Time-Domain Spectroscopy," J. Opt. Soc. Am. A,2001,18,1562-1571.
[51]I. Pupeza, R. Wilk, and M. Koch, "Highly accurate optical material parameter determination with THz time-domain spectroscopy," Opt. Exp.,2007,15,4335-4350.
[52]W. Withayachumnankul, B. Ferguson, T. Rainsford, S. P. Mickan, and D. Abbott, "Simple material parameter estimation via terahertz time-domain spectroscopy," IEE Electronics Letters 2005,41,800-801.
[53]Li Xangjun, Hong Zhi, He Jinlong, and Chen Yuquan, "Precisely optical material parameter determination by time domain waveform rebuilding with THz time-domain spectroscopy", Opt. Commun.2010,283,4701-4706.
[54]N. Nandi, K. Bhattacharyya, B. Bagchi, " Eelectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems", Chem. Rev.2000,100,2013-2045.
[55]B. L. Yu, F. Zeng, Q. Xing, and R. R. Alfano, "Probing dielectric relaxation properties of liquid CS2 with terahertz time-domain spectroscopy". Appl. Phys. Lett.2003,82, 4633-4635.
[56]M. Naftaly, R.E. Miles, "Terahertz time-domain spectroscopy:A new tool for the study of glasses in the far infrared", Journal of Non-Crystalline Solids.2005,351,3341-3346.
[57]Mattijs Koeberg, Chien-Ching Wu, Doseok Kim, Mischa Bonn, "THz dielectric relaxation of ionic liquid:water mixtures", Chemical Physics Letters 2007,439,60-64.
[58]Jing Xu, Kevin W. Plaxco, S. James Allen,"Absorption spectra of liquid water and aqueous buffers between 0.3 and 3.72 THz " J. Chem. Phys.2006,124,036101.
[59]R.Wilk, I. Pupeza, and M. Koch, "Highly accurate THz time-domain spectroscopy of Multilayer structures," IEEE J. of Selected Topics in Quantum Electronics.2007,14, 393-397.
[60]闫战科,张宏建,应义斌,“THz技术在农产品/食品品质检测中的应用”,光谱学与光谱分析,2007,27,2228-2234.
[61]陈敏伯,“计算化学-从理论化学到分子模拟”,科学出版社,2009。
[62]梁逸曾,俞汝勤,“化学计量学”,高等教育出版社,2003。
[63]Dief A S.4 "Advanced matrix theory for scientists and engineers." Tunbridge Wells and LondonrAbacus Press,1982.
[64]Stewart G W. "Introduction to matrix computations." New York:Academic Press,1973.
[65]Wold S, Martens H, Wold H. "The multivariate calibration method in chemistry solved by the PLS method. Ruhe A, Kagstrom B(eds). Proceedings on the Conference on Matrix Pencils, Lecture Notes in Mathematics. " Heidelberg:Springer-Verlag,1983,286-293.
[66]Hoskuldsson A. "PLS regression methods." Journal of Chemometrics,1988,2,211-228.
[67]Rumelhart D E, Hinton G E, Williams R J., "Learning internal representations by error propagation. In Parallel Distributing Processing, Explorations in the Microstructure of Cognition,Vol.1:Foundations." Cambridge, MA:MIT Press,1986,318-362.
[68]Werbos P, "Beyond regression:new tools for prediction and analysis the behavioral sciences." [PHD dissertation], Cambridge, MA:Harvard,1974.
[69]Simits J R M, Melssen W J. Buydens L M C et. al., "Using artificial neural networks for solving chemical problems." Chemom and Intell Lab Sys,1994,23,267
[70]Vapnik V N., "The nature of statistical learning theory."New York:Springer-Verlag,1995.
[71]Vapnik V N. "Statistical learning theory." New York:John Wiley and Sons,1998.
[72]Ying Dou, Hong Mi, Jiying Zou, Yulin Ren. "Support vector regression for determination of component of compound oxytetracycline powder on near-infrared spectroscopy. " Analytical Biochemistry,2006,355,1-7.
[73]王乐,胡健华,“食用油掺伪餐饮业废油脂鉴别检测方法研究进展”中国油脂2007,32,75-78.
[74]于燕波,藏鹏,付元华等.“近红外光谱法快速测定植物油中脂肪酸含量”,光谱学与光谱分析,2008,28(7),1554-1558.
[75]CarmenM, Dobarganes. Joaquin Velasco. "Analysis of lipid hydroperoxides ". Eur. J. Lipid Sci-Technol.,2002,104,420-428.
[76]王淑艳,“氢化物发生原子荧光法在卫生检验中的应用”职业与健康,2005,21(2),217-219.
[77]崔晓君,袁昌明,徐立恒,“花生油中过氧化物的近红外光谱分析”,应用化学,2008,25(3),375-377.
[78]L. Young, V. V. Prabhu, and E. W. Prohofsky, "Calculation of far-infrared absorption in polymer DNA," Phys. Rev. A,1989,39,3173-3180.
[79]B. F. Putnam, L. L. Van Zandt, E. W. Prohofsky, and W. N. Mei, "Resonant and localized breathing modes in terminal regions of the DNA double helix," Biophys. J.,1981,35, 271-287.
[80]W. N. Mei, M. Kohli, E. W. Prohofsky, and L. L. Van Zandt, "Acoustic modes and nonbonded interactions of the double helix," Biopolymers,1981,20,833-852.
[81]B. Brooks andM. Karplus, "Normalmodes for specificmotions of macromolecules: Application to the hinge bending mode of lysozyme," Proc. Natl. Acad. Sci. USA,1985,82, 4995-4999.
[82]D. Lin, A. Matsumoto, and N. Go, "Normal mode analysis of a double stranded DNA dodecamer d(CGCGAATTCGCG)," J. Chem. Phys.,1997,107,3684-3690.
[83]A. Roitberg, R. B. Gerber, R. Elber, and M. A. Ratner, "Anharmonic wave functions of proteins:Quantum self-consistent field calculations of BPTI," Science,1995,268, 1319-1322.
[84]R. H. Austin, K. W. Beeson, L. Eisenstein, H. Frauenfelder, and I. C. Gunsalus, "Dynamics of ligand binding to myoglobin," Biochemistry,1975,14,5355-5373.
[85]W. Zheng, B. R. Brooks, and D. Thirumalai, "Low-frequency normal modes that describe allosteric transitions in biological nanomachines are robust to sequence variations," Proc. Natl. Acad. Sci. USA,2006,103,7664-7669.
[86]N. Nanddi, K. Bhattacharyya, B. Bagchi, "Dielectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems", Chem. Rev.2000,100,2012-2045.
[87]J. Xu, K.W. Plaxco, and S. J. Allen, "Collective dynamics of lysozyme in water:Terahertz absorption spectroscopy and comparison with theory," J. Phys. Chem. B,2006,110, 24255-24259.
[88]J. Xu, K. W. Plaxco, and S. J. Allen, "Probing the collective vibrational dynamics of a protein in liquid water by terahertz absorption spectroscopy," Protein Sci.,2006,15, 1175-1181.
[89]K. N. Woods, S. A. Lee, H.-Y. N. Holman, and H. Wiedemann, "The effect of solvent dynamics on the lowfrequency collective motions of DNA in solution and unoriented films," J. Chem. Phys.2006,124,224706-224708.
[90]Q.Wu and X.-C. Zhang, "Free-space electro-optic sampling of terahertz beams," Appl. Phys. Lett.1995,67,3523-3525.
[91]Y. C. Shen, P. C. Upadhya, E. H. Linfield, H. E. Beere, and A. G. Davies, "Ultrabroadband terahertz radiation from low-temperature-grown GaAs photoconductive emitters," Appl. Phys. Lett.2003,83,3117-3119.
[92]A. G. Markelz, "Terahertz dielectric sensitivity to biomolecular structure and function," IEEE J. Sel. Top. Quantum Electron.2008,4,180-190.
[93]R. B. Best, J. Clarke, and M. Karplus, "What contributions to protein side-chain dynamics are probed by NMR experiments? A molecular dynamics simulation analysis" J. Mol. Biol., 2005,349,185-203.
[94]R. Balu, H. Zhang, E. Zukowski, J.-Y. Chen, A. G. Markelz, and S. K. Gregurick, "Terahertz spectroscopy of bacteriorhodopsin and rhodopsin:Similarities and differences,"Biophys J.2008,94,3217-3226.
[95]I. Roy and M. N. Gupta, "Freeze-drying of proteins:Some emerging concerns," Biotechnol. Appl. Biochem.,2004,39,165-177.
[96]H. Chen, Y.-G. Qu, W.-X. Peng, T.-Y. Kuang, L.-B. Li, and L. Wang, "Investigation of chlorophyll protein 43 and 47 denaturation by terahertz time domain spectroscopy," Chin. Phys. Lett.,2007,24,2131-34.
[97]C. F. Zhang, E. Tarhan, A. K. Ramdas, A. M. Weiner, and S. M. Durbin,"Broadened far-infrared absorption spectra for hydrated and dehydrated myoglobin," J. Phys. Chem. B, 2004,108,10077-10082.
[98]J. A. Rupley and G. Careri, "Protein hydration and function," Adv. Protein Chem.,1991,41, 137-172.
[99]C. Kistner, A. Andr'e, T. Fischer, A. Thoma, C. Janke, A. Bartels,T.Gisler, G. Maret, and T. Dekorsy, "Hydration dynamics of oriented DNA films investigated by time-domain terahertz spectroscopy," Appl. Phys. Lett.,2007,90,233902
[100]B. M. Fischer, M. Hoffmann, H. Helm, R. Wilk, F. Rutz, T. Kleine-Ostmann, M. Koch, and P. U. Jepsen, "Terahertz time-domain spectroscopy and imaging of artificial RNA," Opt. Exp.2005,13,5206-5215.
[101]S. Whitmire, A. G. Markelz, J. R. Hillebrecht, and R. Birge, "Terahertz time domain spectroscopy of biomolecular conformational modes," Phys. Med. Biol.2002,21, 3797-3805.
[102]A. G. Markelz, J. R. Knab, J. Y. Chen, and Y. He, "Protein dynamical transition in terahertz dielectric response," Chem. Phys. Lett.2007,442,413-417.
[103]J.-Y. Chen, J. R. Knab, S. Ye, Y. He, and A. G. Markelz, "Terahertz dielectric assay of solution phase protein binding," Appl. Phys. Lett.2007,90,243901.
[104]Y. Marcus, Introduction to Liquid State Chemistry, John Wiley & Sons,1977.
[105]H. Kawai, Y. Sakurai, Y. Inoue, R. Chujo and S. Kobayashi, "Hydration of oligosaccharides:anomalous hydration ability of trehalose, " Cryobiology.1992,29, 599-606.
[106]C. Branca, S. Magazu, G. Maisano, F. Migliardo and G. Romeo, "a,a-Trehalose/water solutions.5. Hydration and viscosity in dilute and semidilute disaccharide solutions, " J. Phys. Chem. B 2001,105,10140-10145.
[107]Pal, J. Peon and A.H. Zewail, "Biological water at the protein surface:dynamical solvation probed directly with femtosecond resolution," Proc. Natl. Acad. Sci. USA,2002, 99,1763-1768.
[108]T. Kamei, M. Oobatake and M. Suzuki, "Hydration of apomyoglobin in native, molten globule, and unfolded states by using microwave dielectric spectroscopy, " Biophys. J.2002, 82,418-425
[109]D. Walther, F.E. Cohen and S. Doniach, "Reconstruction of low-resolution three-dimensional density maps from one-dimensional small-angle X-ray solution scattering data for biomolecules", J. Appl. Crystallogr.1999,33,350-363.
[110]T. Arikawa, M. Nagai, and K. Tanaka, "Characterizing hydration state in solution using terahertz time-domain attenuated total reflection spectroscopy," Chem. Phys. Lett.2008,457, 12-17.
[111]赵孔双,介电谱方法及用,化学工业出版社,2008.
[112]张良莹等,电介质物理,西安交通大学出版社,1991.
[113]Maxwell J C. Treatise on dielectricity and magnetism. Oxford:Clarendon Press,1891.
[114]Wagner K W. "Erklarung der dielektrischen Nachwirkungsvorgange auf Grund Maxwellscher Vorstellungen", Arch Eelectrotichinik(Berl),1914,2,371-387.
[115]Takashima S. Electrical properties of biopolymers and membranes. Bristol:Adam Hilger, 1989.
[116]Hanai T., "Theory of the dielectric dispersion due to the interfacial polarization and its application to emulsion", Kolloid-Z,1960,171,23-31.
[117]N. E. Hill, W. E. Vaughan, A. H. Price and M. Davies, Dielectric Properties and Molecular Behaviour, Van Nostrand Reinhold, Company, London (1969).
[118]M. Walther, B. M. Fischer, and P. U. Jepsen, "Non covalent intermolecular forces in polycrystalline and amorphous saccharides in the far infrared", Chem. Phys.,2003,288, 261-268.
[119]V. G. Veselago, "The electrodynamics of substances with simultaneously negative values of ε and μ ", Sov. Phys. Uspekhi,1968,10,509.
[120]Pendry J B et. al., "Magnetism from conductors and enhanced nonlinear phenomena, IEEE Trans. Microwave Theory and Technology, " 1999,47,2075.
[121]Pendry J B, Holden A J, Stewart W J et al. "Extremely Low Frequency Plasmons in Metallic Mesostructures", Phys. Rev.Lett.,1996,76,4773.
[122]Pendry J B, Holden A J, Robbins D J et al. "Low frequency plasmons in thin-wire structures", J.Phys.:Condens. Matt.,1998,10,4785.
[123]Sigalas M, Chan C T, Ho K, "Metallic photonic band-gap materials", Phys. Rev. B,1995, 52,11744.
[124]Smith D R, Padilla W, Vier D et al., "Composite Medium with Simultaneously Negative Permeability and Permittivity", Phys. Rev. Lett.,2000,84,4184.
[125]Smith D R, Schultz S, Markos P, et al. "Determination of effective permittivity and permeability of metamaterials from reflection and transmission coefficients". Phys Rev. B, 2002,65,195104.
[126]C. Luo, S. G. Johnson, J. D. Joannopoulos, and J. B. Pendry."All-angle negative refraction without negative effective index", Phys. Rev. B,2002,65,201104.
[127]X. Zhang et al. "Optical Negative Refractive in Bulk Metamaterials of Nanowires", Science 2008,321,930.
[128]Wynne K, Carey J J, Zawadzka J and Jaroszynski D A. "Tunneling of single_cycle terahertz pulses through waveguides". Optics Communications 2000,176,429-435.
[129]Wu Dongmin, Nicholas Fang, et al. "Terahertz plasmonic high pass filter". Appl Phys Lett, 2003,83,201-203.
[130]Yen T J, Padilla W J, Fang N. "Terahertz Magnetic Response from Artificial Materials". SCIENCE,2004,303:1494-1496.
[131]W. Withayachumnankul and D. Abbott, "Metamaterials in the terahertz regime", IEEE Photonics J.2009,1,99-118.
[132]H. Tao, N. I. Landy, C. M. Bingham, X. Zhang, R. D. Averitt, and W. J. Padilla, "A metamaterial absorber for the terahertz regime:Design, fabrication and characterization", Opt. Express,2008,16,7181-7188.
[133]A. C. Strikwerda, K. Fan, H. Tao, D. V. Pilon, X. Zhang, and R. D. Averitt, "Comparison of birefringent electric split-ring resonator and meanderline structures as quarter-wave plates at terahertz frequencies", Opt. Express,2009,17,136-149.
[134]W. J. Padilla, A. J. Taylor, C. Highstrete, M. Lee, and R. D. Averitt, "Dynamical electric and magnetic metamaterial response at terahertz frequencies", Phys. Rev. Lett.,2006,96, 107401.
[135]T. Driscoll, G. O. Andreev, D. N. Basov, S. Palit, S. Y. Cho, N. M. Jokerst, and D. R. Smith, "Tuned permeability in terahertz split-ring resonators for devices and sensors", Appl. Phys. Lett.,2007,91,062511.
[136]I. A. I. Al-Naib, C. Jansen, and M. Koch, "Thin-film sensing with planar asymmetric metamaterial resonators", Appl. Phys. Lett.,2008,93,083507.
[137]J. F. O'Hara, R. Singh, I. Brener, E. Smirnova, J. Han, A. J. Taylor, and W. Zhang, 'Thin-film sensing with planar terahertz metamaterials:sensitivity and limitations," Opt. Express 2008,16,1786-1795.
[138]Y. Sun, X. Xia, H. Feng, H. Yang, C. Gu, and L. Wang, "Modulated terahertz responses of split ring resonators by nanometer thick liquid layers," Appl. Phys. Lett.2008,92,221101.
[139]C. Debus and P. H. Bolivar, "Frequency selective surfaces for high sensitivity terahertz sensing," Appl. Phys. Lett.2007,91,184102.
[140]H. Yoshida, Y. Ogawa, Y. Kawai, S. Hayashi, A. Hayashi, C. Otani, E. Kato, F. Miyamaru, and K. Kawase, "Terahertz sensing method for protein detection using a thin metallic mesh, " Appl. Phys. Lett.,2007,91,253901.
[141]Z. Tian, J Han c, X Lu, J Gu, Q Xing, W Zhang. "Surface plasmon enhanced terahertz spectroscopic distinguishing between isotopes". Chem. Phys. Lett.,2009,475,132-134.
[142]王长清,现代计算电磁学基础,北京大学出版社,2005.
[143]陈抗生,微波与光导波技术教程,浙江大学出版社,2001.
[144]R. W. Clough, "The Finite Element in Plane Stress Analysis", in Proceedings of the 2nd ASCE Conference on Electronic Computation, Pittsburgh, PA,1960,345-378.
[145]D. R. Smith, D. C. Vier, T. Koschny, and C. M. Soukoulis. "Electromagnetic parameter retrieval from inhomogeneous metamaterials". Phys. Rev. E 2005,71,036617.
[146]X. Chen, T. M. Grzegorczyk, B. I. Wu, et al. "Robust method to retrieve the constitutive effective parameters of metamaterials". Phys. Rev. E 2004,70,016608.
[2]B. Ferguson and X. C. Zhang, "Materials for terahertz science and technology" Nature Materials,2002,1,26-33.
[3]R. Woodward, B. E. Cole, V. P. Wallace, R. J. Pye, D. D. Arnone, E. H. Linfield and M. "Pepper Terahertz pulse imaging in reflection geometry of human skin cancer and skin tissue" Phys. Med. Biol.,2002,47,3853-63.
[4]J. T. Kindt and C. A. Schmuttenmaer, "Far-Infrared Dielectric Properties of Polar Liquids Probed by Femtosecond Terahertz Pulse Spectroscopy", Phys. Chem.1996,100, 10373-10379.
[5]J Xu, C Zhang, X Zhang, "Recent progress in terahertz science and technology" Progress in Nature Science,2002,12,729-736.
[6]Wallace V. P., Fitzgerald A. J., Shankar S., Flanagan N., Pye R., Cluff J., and Arnone D. D., "Terahertz pulsed imaging of basal cell carcinoma ex vivo and in vivo," J. Invest. Dermatol. 2004,151,424-432.
[7]Fitzgerald A. J., Wallace V. P., Jimenez-Linan M., Bobrow L., Pye R. J., Purushotham A. D., and Arnone D. D., "Terahertz pulsed imaging of human breast tumors," Radiology 2006, 239,533-540.
[8]Taylor Z. D., Singh R. S., Culjat M. O., Suen J. Y., Grundfest W. S., Lee H., and Brown E. R., "Reflective terahertz imaging of porcine skin burns," Opt. Lett.2008,33,1258-1260.
[9]Hoshina H., Hayashi A., Miyoshi N., Miyamaru F., and Otani C., "Terahertz pulsed imaging of frozen biological tissues," Appl. Phys. Lett.,2009,94,123901.
[10]Kawase K., Ogawa Y., Minamide H., and Ito H., "Terahertz parametric sources and imaging applications," Semicond. Sci. Technol.2005,20, S258-265.
[11]Darmo J., Tamosiunas V., Fasching G., Kroll J., Unterrainer K., Beck M., Giovannini M., Faist J., Kremser C., and Debbage P., "Imaging with a Terahertz quantum cascade laser," Opt. Express 2004,12,1879-1884
[12]Dobroiu A., Yamashita M., Ohshima Y. N., Morita Y, Otani C., and Kawase K., "Terahertz imaging system based on a backward-wave oscillator," Appl. Opt.2004,43,5637-5646.
[13]Woodward R M, Cole B E, Wallace V P, Pye R J, Arnone D D, Linfield E H and Pepper M 'Terahertz pulse imaging in reflection geometry of human skin cancer and skin tissue." Phys. Med. Biol.2002,47,3853-63.
[14]Ashworth P C, Pickwell-Mac Pherson E, Provenzano E, Pinder S E, Purushotham A D, Pepper M, and Wallace V P "Terahertz pulsed spectroscopy of freshly excised human breast cancer" Opt. Express,2009,17,12444-12454.
[15]D A Crawley, C Longbottom, V P Wallace, "Three dimensional terahertz pulse imaging of dental tissue". SPIE 2002,4633,84-89.
[16]J.A. Zeitler, P.F. Taday, D.A. Newnham, M. Pepper, K.C. Gordon, T. Rades, "Terahertz pulsed spectroscopy and imaging in the pharmaceutical setting - a review ",J. Pharm. Pharmacol.2007,59,209-223.
[17]H. Wu, E. J. Heilweil, A. S. Hussain, M. A. Khan, "Process analytical technology (PAT): Quantification approaches in terahertz spectroscopy for pharmaceutical application", Int. J. Pharm.2007,343,148-158.
[18]N. Laman, S. S. Harsha, D. Grischkowsky, "Narrow-line waveguide terahertz time-domain spectroscopy of aspirin and aspirin precursors", Appl. Spectrosc.2008,62,319-326.
[19]Walther M, Plochocka P, Fischer B, et al. "Collective vibrational modes in biological molecules investigated by terahertz time-domain spectroscopy", Biopolymers,2002,67, 310-313.
[20]Walther M, Fischer B, Uhd Jepsen P "Noncovalent intermolecular forces in polycrystalline and amorphous saccharides in the far infrared" P. Chem. Phys.,2003,288,261-268.
[21]Markelz A G, Roitberg A, Heilweil E J. "Pulsed terahertz spectroscopy of DNA, bovine serum albumin and collagen between 0.1 and 2.0 THz" Chem. Phys. Lett.,2000,32, 42-48.
[22]Walt her M, Fischer B, Schall M, et al. "Far-infrared vibrational spectra of all-trans,9-cis and 13-cis retinal measured by THz time-domain spectroscopy", Chem. Phys. Lett.,2000, 332,389-395.
[23]Fischer B M, Walther M, Uhd Jepsen P. "Far-infrared vibrational modes of DNA components studied by terahertz time-domain spectroscopy" Phys. Med. Biol.,2002,47, 3807-3814.
[24]Upadhya P C, Shen Y C, Davies A G, et al. "Terahertz Time-Domain Spectroscopy of Glucose and Uric Acid" J. Biol. Phys.,2003,29,117-121.
[25]Bigourd D, Cuisset A, Hindle F, Matton S, Bocquet R, Mourct G, et al. "Multiple component analysis of cigarette smoke using THz spectroscopy, comparison with standard chemical analytical methods". Appl. Phys. B 2007,86,579-86.
[26]M R Leahy-Hoppa, M J Fitch, X Zheng. "Wideband terahertz spectroscopy of explosives". Chemical Physics Letters,2007.434,227-230.
[27]A A Stark, J Bally, S P Balm. "The Antarctic Submillimeter Telescope and Remote Observatory (AST/RO)". Publications of the Astronomical Society of the Pacific, 2001.113(783),567-585.
[28]. H M Araujo, R J Walker, S A Rinehart. "Assessment of the 200-mum atmosphericwindow for ground-based astronomy." International Journal of Infrared and Millimeter Waves,2001, 22,965-982.
[29]. N Krumbholz, K Gerlach, F Rutz. "Omnidirectional terahertz mirrors:A keyelement for future terahertz communication systems". Applied Physics Letters,2006,88,112-116.
[30]Al-Douseri F M, Chen Y Q, Zhang X C. THz wave sensing for petroleum industrial applications. Int J Infrared Millim Waves,2006,27,481-503.
[31]田璐,周庆莉,金彬等.“润滑油的太赫兹波段光学与光谱特性研究.”中国科学G辑：物理学力学天文学,2009,39,1589-1593.
[32]宝日玛,赵昆,田璐等.“汽油的太赫兹时域光谱特性研究.”中国科学G辑：物理学力学天文学,2010,40,950-954.
[33]Jin Y S, Kim G J, Shon C H, et al. "Analysis of petroleum products and their mixtures by using terahertz time domain spectroscopy." J Korean Phys Soc,2008,53,1879-1885.
[34]胡颖,王晓红,郭澜涛等,“植物油和动物脂肪在THz波段的吸收和色散”物理学报2005,54,4124-4128.
[35]M. Havenith, "Solute-induced retardation of water dynamics probed directly by terahertz spectroscopy" Proc. Natl. Acad. Sci. USA 2006,103,12301-12306.
[36]Xu J, Plaxco K W, Allen S J."Probing the collective vibrational dynamics of a protein in liquid water by terahertz absorption spectroscopy." Protein Science,2006,15,1175-1181.
[37]Born B, Kim S J, Ebbinghaus S, et al. "The terahertz dance of water with the proteins:the effect of protein flexibility on the dynamical hydration shell of ubiquitin." Faraday Discuss, 2009,141,161-173.
[38]Born B, Weingartner H, Brundermann E, et al. "Solvation Dynamics of Model Peptides Probed by Terahertz Spectroscopy. Observation of the Onset of Collective Network Motions." Journal of the American Chemical Society,2009,131,3752-3755.
[39]Havenith M, "An extended dynamical hydration shell around proteins" Proc. Natl. Acad. Sci. USA 2007,104,20749-20752.
[40]S. E. Ralph, S. Perkowitz, N. Katzenellenbogen, and D. Grischkowski, "Terahertz spectroscopy of optically thick multilayerd semiconductor structures," J. Opt. Soc. Amer. B, 1994,11,2528-2532.
[41]C B Reid, E Pickwell-MacPherson, J G Laufer, A P Gibson, J C Hebden and V P Wallace "Accuracy and resolution of THz reflection spectroscopy for medical imaging"Phys. Med. Biol.2010,55,4825-4838.
[42]J. Xu, K. W. Plaxco, S. J. Allen, Probing the Collective Vibrational Dyamics of a Protein in Liquid Water by Terahertz Absorption Spectroscopy, Protein Sci.,2006,15,1175-1181.
[43]B. B. Hu and M. C. Nuss, "Imaging with terahertz waves," Opt. Lett.,1995,20,1716-1718.
[44]李向军,陈裕泉,李九生,“利用THz时域谱技术和支持向量机回归法快速测定食用油的过氧化值和酸价”中国粮油学报2010,25(2),131-135.
[45]L. Thrane, R. H. Jacobsen, P. Uhd Jepsen, and S. R. Keiding, "THz reflection spectroscopy of liquid water," Chem. Phys. Lett.1995,240,330-333.
[46]P. Uhd Jepsen, U. Moller, and H. Merbold, "Investigation of aqueous alcohol and sugar solutions with reflection terahertz time-domain spectroscopy," Opt. Express 2007,15, 717-737.
[47]M. Nagai, H. Yada, T. Arikawa, and K. Tanaka, "Terahertz time-domain attenuated total reflection spectroscopy in water and biological solution," Int. J. Infrared Millim. Waves 2006, 27,505-515.
[48]U. Moller, D.G. Cooke, K. Tanaka, P. Uhd Jepsen, "Terahertz reflection spectroscopy of Debye relaxation in polar liquids", J. Opt. Soc. Am.B,2009,26,113-125.
[49]L. Duvillaret, F. Garet, and J.-L. Coutaz, "A reliable method for extraction of material parameters in Terahertz Time-Domain Spectroscopy," IEEE J. Sel. Top. Quantum Electron. 1996,2,739-746.
[50]T. Dorney, R. Baraniuk, and D. Mittleman, "Material parameter estimation with Terahertz Time-Domain Spectroscopy," J. Opt. Soc. Am. A,2001,18,1562-1571.
[51]I. Pupeza, R. Wilk, and M. Koch, "Highly accurate optical material parameter determination with THz time-domain spectroscopy," Opt. Exp.,2007,15,4335-4350.
[52]W. Withayachumnankul, B. Ferguson, T. Rainsford, S. P. Mickan, and D. Abbott, "Simple material parameter estimation via terahertz time-domain spectroscopy," IEE Electronics Letters 2005,41,800-801.
[53]Li Xangjun, Hong Zhi, He Jinlong, and Chen Yuquan, "Precisely optical material parameter determination by time domain waveform rebuilding with THz time-domain spectroscopy", Opt. Commun.2010,283,4701-4706.
[54]N. Nandi, K. Bhattacharyya, B. Bagchi, " Eelectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems", Chem. Rev.2000,100,2013-2045.
[55]B. L. Yu, F. Zeng, Q. Xing, and R. R. Alfano, "Probing dielectric relaxation properties of liquid CS2 with terahertz time-domain spectroscopy". Appl. Phys. Lett.2003,82, 4633-4635.
[56]M. Naftaly, R.E. Miles, "Terahertz time-domain spectroscopy:A new tool for the study of glasses in the far infrared", Journal of Non-Crystalline Solids.2005,351,3341-3346.
[57]Mattijs Koeberg, Chien-Ching Wu, Doseok Kim, Mischa Bonn, "THz dielectric relaxation of ionic liquid:water mixtures", Chemical Physics Letters 2007,439,60-64.
[58]Jing Xu, Kevin W. Plaxco, S. James Allen,"Absorption spectra of liquid water and aqueous buffers between 0.3 and 3.72 THz " J. Chem. Phys.2006,124,036101.
[59]R.Wilk, I. Pupeza, and M. Koch, "Highly accurate THz time-domain spectroscopy of Multilayer structures," IEEE J. of Selected Topics in Quantum Electronics.2007,14, 393-397.
[60]闫战科,张宏建,应义斌,“THz技术在农产品/食品品质检测中的应用”,光谱学与光谱分析,2007,27,2228-2234.
[61]陈敏伯,“计算化学-从理论化学到分子模拟”,科学出版社,2009。
[62]梁逸曾,俞汝勤,“化学计量学”,高等教育出版社,2003。
[63]Dief A S.4 "Advanced matrix theory for scientists and engineers." Tunbridge Wells and LondonrAbacus Press,1982.
[64]Stewart G W. "Introduction to matrix computations." New York:Academic Press,1973.
[65]Wold S, Martens H, Wold H. "The multivariate calibration method in chemistry solved by the PLS method. Ruhe A, Kagstrom B(eds). Proceedings on the Conference on Matrix Pencils, Lecture Notes in Mathematics. " Heidelberg:Springer-Verlag,1983,286-293.
[66]Hoskuldsson A. "PLS regression methods." Journal of Chemometrics,1988,2,211-228.
[67]Rumelhart D E, Hinton G E, Williams R J., "Learning internal representations by error propagation. In Parallel Distributing Processing, Explorations in the Microstructure of Cognition,Vol.1:Foundations." Cambridge, MA:MIT Press,1986,318-362.
[68]Werbos P, "Beyond regression:new tools for prediction and analysis the behavioral sciences." [PHD dissertation], Cambridge, MA:Harvard,1974.
[69]Simits J R M, Melssen W J. Buydens L M C et. al., "Using artificial neural networks for solving chemical problems." Chemom and Intell Lab Sys,1994,23,267
[70]Vapnik V N., "The nature of statistical learning theory."New York:Springer-Verlag,1995.
[71]Vapnik V N. "Statistical learning theory." New York:John Wiley and Sons,1998.
[72]Ying Dou, Hong Mi, Jiying Zou, Yulin Ren. "Support vector regression for determination of component of compound oxytetracycline powder on near-infrared spectroscopy. " Analytical Biochemistry,2006,355,1-7.
[73]王乐,胡健华,“食用油掺伪餐饮业废油脂鉴别检测方法研究进展”中国油脂2007,32,75-78.
[74]于燕波,藏鹏,付元华等.“近红外光谱法快速测定植物油中脂肪酸含量”,光谱学与光谱分析,2008,28(7),1554-1558.
[75]CarmenM, Dobarganes. Joaquin Velasco. "Analysis of lipid hydroperoxides ". Eur. J. Lipid Sci-Technol.,2002,104,420-428.
[76]王淑艳,“氢化物发生原子荧光法在卫生检验中的应用”职业与健康,2005,21(2),217-219.
[77]崔晓君,袁昌明,徐立恒,“花生油中过氧化物的近红外光谱分析”,应用化学,2008,25(3),375-377.
[78]L. Young, V. V. Prabhu, and E. W. Prohofsky, "Calculation of far-infrared absorption in polymer DNA," Phys. Rev. A,1989,39,3173-3180.
[79]B. F. Putnam, L. L. Van Zandt, E. W. Prohofsky, and W. N. Mei, "Resonant and localized breathing modes in terminal regions of the DNA double helix," Biophys. J.,1981,35, 271-287.
[80]W. N. Mei, M. Kohli, E. W. Prohofsky, and L. L. Van Zandt, "Acoustic modes and nonbonded interactions of the double helix," Biopolymers,1981,20,833-852.
[81]B. Brooks andM. Karplus, "Normalmodes for specificmotions of macromolecules: Application to the hinge bending mode of lysozyme," Proc. Natl. Acad. Sci. USA,1985,82, 4995-4999.
[82]D. Lin, A. Matsumoto, and N. Go, "Normal mode analysis of a double stranded DNA dodecamer d(CGCGAATTCGCG)," J. Chem. Phys.,1997,107,3684-3690.
[83]A. Roitberg, R. B. Gerber, R. Elber, and M. A. Ratner, "Anharmonic wave functions of proteins:Quantum self-consistent field calculations of BPTI," Science,1995,268, 1319-1322.
[84]R. H. Austin, K. W. Beeson, L. Eisenstein, H. Frauenfelder, and I. C. Gunsalus, "Dynamics of ligand binding to myoglobin," Biochemistry,1975,14,5355-5373.
[85]W. Zheng, B. R. Brooks, and D. Thirumalai, "Low-frequency normal modes that describe allosteric transitions in biological nanomachines are robust to sequence variations," Proc. Natl. Acad. Sci. USA,2006,103,7664-7669.
[86]N. Nanddi, K. Bhattacharyya, B. Bagchi, "Dielectric Relaxation and Solvation Dynamics of Water in Complex Chemical and Biological Systems", Chem. Rev.2000,100,2012-2045.
[87]J. Xu, K.W. Plaxco, and S. J. Allen, "Collective dynamics of lysozyme in water:Terahertz absorption spectroscopy and comparison with theory," J. Phys. Chem. B,2006,110, 24255-24259.
[88]J. Xu, K. W. Plaxco, and S. J. Allen, "Probing the collective vibrational dynamics of a protein in liquid water by terahertz absorption spectroscopy," Protein Sci.,2006,15, 1175-1181.
[89]K. N. Woods, S. A. Lee, H.-Y. N. Holman, and H. Wiedemann, "The effect of solvent dynamics on the lowfrequency collective motions of DNA in solution and unoriented films," J. Chem. Phys.2006,124,224706-224708.
[90]Q.Wu and X.-C. Zhang, "Free-space electro-optic sampling of terahertz beams," Appl. Phys. Lett.1995,67,3523-3525.
[91]Y. C. Shen, P. C. Upadhya, E. H. Linfield, H. E. Beere, and A. G. Davies, "Ultrabroadband terahertz radiation from low-temperature-grown GaAs photoconductive emitters," Appl. Phys. Lett.2003,83,3117-3119.
[92]A. G. Markelz, "Terahertz dielectric sensitivity to biomolecular structure and function," IEEE J. Sel. Top. Quantum Electron.2008,4,180-190.
[93]R. B. Best, J. Clarke, and M. Karplus, "What contributions to protein side-chain dynamics are probed by NMR experiments? A molecular dynamics simulation analysis" J. Mol. Biol., 2005,349,185-203.
[94]R. Balu, H. Zhang, E. Zukowski, J.-Y. Chen, A. G. Markelz, and S. K. Gregurick, "Terahertz spectroscopy of bacteriorhodopsin and rhodopsin:Similarities and differences,"Biophys J.2008,94,3217-3226.
[95]I. Roy and M. N. Gupta, "Freeze-drying of proteins:Some emerging concerns," Biotechnol. Appl. Biochem.,2004,39,165-177.
[96]H. Chen, Y.-G. Qu, W.-X. Peng, T.-Y. Kuang, L.-B. Li, and L. Wang, "Investigation of chlorophyll protein 43 and 47 denaturation by terahertz time domain spectroscopy," Chin. Phys. Lett.,2007,24,2131-34.
[97]C. F. Zhang, E. Tarhan, A. K. Ramdas, A. M. Weiner, and S. M. Durbin,"Broadened far-infrared absorption spectra for hydrated and dehydrated myoglobin," J. Phys. Chem. B, 2004,108,10077-10082.
[98]J. A. Rupley and G. Careri, "Protein hydration and function," Adv. Protein Chem.,1991,41, 137-172.
[99]C. Kistner, A. Andr'e, T. Fischer, A. Thoma, C. Janke, A. Bartels,T.Gisler, G. Maret, and T. Dekorsy, "Hydration dynamics of oriented DNA films investigated by time-domain terahertz spectroscopy," Appl. Phys. Lett.,2007,90,233902
[100]B. M. Fischer, M. Hoffmann, H. Helm, R. Wilk, F. Rutz, T. Kleine-Ostmann, M. Koch, and P. U. Jepsen, "Terahertz time-domain spectroscopy and imaging of artificial RNA," Opt. Exp.2005,13,5206-5215.
[101]S. Whitmire, A. G. Markelz, J. R. Hillebrecht, and R. Birge, "Terahertz time domain spectroscopy of biomolecular conformational modes," Phys. Med. Biol.2002,21, 3797-3805.
[102]A. G. Markelz, J. R. Knab, J. Y. Chen, and Y. He, "Protein dynamical transition in terahertz dielectric response," Chem. Phys. Lett.2007,442,413-417.
[103]J.-Y. Chen, J. R. Knab, S. Ye, Y. He, and A. G. Markelz, "Terahertz dielectric assay of solution phase protein binding," Appl. Phys. Lett.2007,90,243901.
[104]Y. Marcus, Introduction to Liquid State Chemistry, John Wiley & Sons,1977.
[105]H. Kawai, Y. Sakurai, Y. Inoue, R. Chujo and S. Kobayashi, "Hydration of oligosaccharides:anomalous hydration ability of trehalose, " Cryobiology.1992,29, 599-606.
[106]C. Branca, S. Magazu, G. Maisano, F. Migliardo and G. Romeo, "a,a-Trehalose/water solutions.5. Hydration and viscosity in dilute and semidilute disaccharide solutions, " J. Phys. Chem. B 2001,105,10140-10145.
[107]Pal, J. Peon and A.H. Zewail, "Biological water at the protein surface:dynamical solvation probed directly with femtosecond resolution," Proc. Natl. Acad. Sci. USA,2002, 99,1763-1768.
[108]T. Kamei, M. Oobatake and M. Suzuki, "Hydration of apomyoglobin in native, molten globule, and unfolded states by using microwave dielectric spectroscopy, " Biophys. J.2002, 82,418-425
[109]D. Walther, F.E. Cohen and S. Doniach, "Reconstruction of low-resolution three-dimensional density maps from one-dimensional small-angle X-ray solution scattering data for biomolecules", J. Appl. Crystallogr.1999,33,350-363.
[110]T. Arikawa, M. Nagai, and K. Tanaka, "Characterizing hydration state in solution using terahertz time-domain attenuated total reflection spectroscopy," Chem. Phys. Lett.2008,457, 12-17.
[111]赵孔双,介电谱方法及用,化学工业出版社,2008.
[112]张良莹等,电介质物理,西安交通大学出版社,1991.
[113]Maxwell J C. Treatise on dielectricity and magnetism. Oxford:Clarendon Press,1891.
[114]Wagner K W. "Erklarung der dielektrischen Nachwirkungsvorgange auf Grund Maxwellscher Vorstellungen", Arch Eelectrotichinik(Berl),1914,2,371-387.
[115]Takashima S. Electrical properties of biopolymers and membranes. Bristol:Adam Hilger, 1989.
[116]Hanai T., "Theory of the dielectric dispersion due to the interfacial polarization and its application to emulsion", Kolloid-Z,1960,171,23-31.
[117]N. E. Hill, W. E. Vaughan, A. H. Price and M. Davies, Dielectric Properties and Molecular Behaviour, Van Nostrand Reinhold, Company, London (1969).
[118]M. Walther, B. M. Fischer, and P. U. Jepsen, "Non covalent intermolecular forces in polycrystalline and amorphous saccharides in the far infrared", Chem. Phys.,2003,288, 261-268.
[119]V. G. Veselago, "The electrodynamics of substances with simultaneously negative values of ε and μ ", Sov. Phys. Uspekhi,1968,10,509.
[120]Pendry J B et. al., "Magnetism from conductors and enhanced nonlinear phenomena, IEEE Trans. Microwave Theory and Technology, " 1999,47,2075.
[121]Pendry J B, Holden A J, Stewart W J et al. "Extremely Low Frequency Plasmons in Metallic Mesostructures", Phys. Rev.Lett.,1996,76,4773.
[122]Pendry J B, Holden A J, Robbins D J et al. "Low frequency plasmons in thin-wire structures", J.Phys.:Condens. Matt.,1998,10,4785.
[123]Sigalas M, Chan C T, Ho K, "Metallic photonic band-gap materials", Phys. Rev. B,1995, 52,11744.
[124]Smith D R, Padilla W, Vier D et al., "Composite Medium with Simultaneously Negative Permeability and Permittivity", Phys. Rev. Lett.,2000,84,4184.
[125]Smith D R, Schultz S, Markos P, et al. "Determination of effective permittivity and permeability of metamaterials from reflection and transmission coefficients". Phys Rev. B, 2002,65,195104.
[126]C. Luo, S. G. Johnson, J. D. Joannopoulos, and J. B. Pendry."All-angle negative refraction without negative effective index", Phys. Rev. B,2002,65,201104.
[127]X. Zhang et al. "Optical Negative Refractive in Bulk Metamaterials of Nanowires", Science 2008,321,930.
[128]Wynne K, Carey J J, Zawadzka J and Jaroszynski D A. "Tunneling of single_cycle terahertz pulses through waveguides". Optics Communications 2000,176,429-435.
[129]Wu Dongmin, Nicholas Fang, et al. "Terahertz plasmonic high pass filter". Appl Phys Lett, 2003,83,201-203.
[130]Yen T J, Padilla W J, Fang N. "Terahertz Magnetic Response from Artificial Materials". SCIENCE,2004,303:1494-1496.
[131]W. Withayachumnankul and D. Abbott, "Metamaterials in the terahertz regime", IEEE Photonics J.2009,1,99-118.
[132]H. Tao, N. I. Landy, C. M. Bingham, X. Zhang, R. D. Averitt, and W. J. Padilla, "A metamaterial absorber for the terahertz regime:Design, fabrication and characterization", Opt. Express,2008,16,7181-7188.
[133]A. C. Strikwerda, K. Fan, H. Tao, D. V. Pilon, X. Zhang, and R. D. Averitt, "Comparison of birefringent electric split-ring resonator and meanderline structures as quarter-wave plates at terahertz frequencies", Opt. Express,2009,17,136-149.
[134]W. J. Padilla, A. J. Taylor, C. Highstrete, M. Lee, and R. D. Averitt, "Dynamical electric and magnetic metamaterial response at terahertz frequencies", Phys. Rev. Lett.,2006,96, 107401.
[135]T. Driscoll, G. O. Andreev, D. N. Basov, S. Palit, S. Y. Cho, N. M. Jokerst, and D. R. Smith, "Tuned permeability in terahertz split-ring resonators for devices and sensors", Appl. Phys. Lett.,2007,91,062511.
[136]I. A. I. Al-Naib, C. Jansen, and M. Koch, "Thin-film sensing with planar asymmetric metamaterial resonators", Appl. Phys. Lett.,2008,93,083507.
[137]J. F. O'Hara, R. Singh, I. Brener, E. Smirnova, J. Han, A. J. Taylor, and W. Zhang, 'Thin-film sensing with planar terahertz metamaterials:sensitivity and limitations," Opt. Express 2008,16,1786-1795.
[138]Y. Sun, X. Xia, H. Feng, H. Yang, C. Gu, and L. Wang, "Modulated terahertz responses of split ring resonators by nanometer thick liquid layers," Appl. Phys. Lett.2008,92,221101.
[139]C. Debus and P. H. Bolivar, "Frequency selective surfaces for high sensitivity terahertz sensing," Appl. Phys. Lett.2007,91,184102.
[140]H. Yoshida, Y. Ogawa, Y. Kawai, S. Hayashi, A. Hayashi, C. Otani, E. Kato, F. Miyamaru, and K. Kawase, "Terahertz sensing method for protein detection using a thin metallic mesh, " Appl. Phys. Lett.,2007,91,253901.
[141]Z. Tian, J Han c, X Lu, J Gu, Q Xing, W Zhang. "Surface plasmon enhanced terahertz spectroscopic distinguishing between isotopes". Chem. Phys. Lett.,2009,475,132-134.
[142]王长清,现代计算电磁学基础,北京大学出版社,2005.
[143]陈抗生,微波与光导波技术教程,浙江大学出版社,2001.
[144]R. W. Clough, "The Finite Element in Plane Stress Analysis", in Proceedings of the 2nd ASCE Conference on Electronic Computation, Pittsburgh, PA,1960,345-378.
[145]D. R. Smith, D. C. Vier, T. Koschny, and C. M. Soukoulis. "Electromagnetic parameter retrieval from inhomogeneous metamaterials". Phys. Rev. E 2005,71,036617.
[146]X. Chen, T. M. Grzegorczyk, B. I. Wu, et al. "Robust method to retrieve the constitutive effective parameters of metamaterials". Phys. Rev. E 2004,70,016608.