Abstract
The terahertz regime has particular value for liquid and biomolecular spectroscopy. In the case of liquids, terahertz is sensitive to relaxational and collective motions in liquids [1–13]. Applications include determination of sugar, alcohol, and water content. While there are no narrow band identification features for liquids in the terahertz range, the ability of THz to transmit through packaging materials and high sensitivity of relative water content is considered highly appealing for its use as a method to rapidly verify labeled contents. The determination of the water, sucrose, alcohol, liquid fuel, and petroleum content using terahertz have been demonstrated [1, 10]. The fundamental findings from terahertz measurements of liquids include the hydration number associated with solutes [14, 15], the extent of the perturbation of the liquid structure by the solute [16, 17], and the role of interactions in binary liquids [13, 18] . New collective mode vibrations have been identified for alcohols [19, 20], and the changes in the relaxational dynamics due to mixing, and the role of collective vibrations in ionic liquids [21–24]. In order to achieve these many findings, sensitive measurement techniques and data analysis have been developed. In parallel, great strides in modeling have been made to effectively model the picosecond dielectric response for these highly complex systems.
Biological applications of terahertz have been explored from spectroscopy of biologically relevant molecules as small as sucrose up to organisms such as bacterial spores. Significant progress has been made in fundamental characterization of small biomolecules with accurate modeling of both intramolecular modes, and the intermolecular modes for crystalline material. Initial measurements of small proteins have been explored; however, theoretical understanding is not as well developed. While a variety of groups have demonstrated sensitivity in the THz dielectric response to protein and nucleic acid functional state, the origin of this sensitivity is still somewhat controversial.
In this chapter, we will discuss measurement methods, modeling of the terahertz response for these systems, and major results. We will conclude with a discussion on future directions for the applications of terahertz for liquid and biomolecular characterization.
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P.U. Jepsen, U. Moller, H. Merbold, Investigation of aqueous alcohol and sugar solutions with reflection terahertz time-domain spectroscopy. Opt. Express 15(22), 14717–14737 (2007)
U. Moller, D.G. Cooke, K. Tanaka, P.U. Jepsen, Terahertz reflection spectroscopy of Debye relaxation in polar liquids [Invited]. J. Opt. Soc. Am. B Opt. Phys. 26(9), A113–A125 (2009)
Y. Yomogida, Y. Sato, R. Nozaki, T. Mishina, J. Nakahara, Comparative dielectric study of monohydric alcohols with terahertz time-domain spectroscopy. J. Mol. Struct. 981(1–3), 173–178 (2010)
Y. Yomogida, Y. Sato, R. Nozaki, T. Mishina, J. Nakahara, Comparative study of boson peak in normal and secondary alcohols with terahertz time-domain spectroscopy. Phys. B Condens. Matter 405(9), 2208–2212 (2010)
Y. Danten, M. Besnard, J.C. Delagnes, P. Mounaix, Far infrared absorption and terahertz time domain spectroscopy of liquid CS2: experiments and molecular dynamics simulation. Appl. Phys. Lett. 92(21), 214102 (2008)
J.T. Kindt, C.A. Schmuttenmaer, Far-infrared dielectric properties of polar liquids probed by femtosecond terahertz pulse spectroscopy. J. Phys. Chem. 100(24), 10373–10379 (1996)
J.P. Laib, D.V. Nickel, D.M. Mittleman, Terahertz vibrational modes induced by heterogeneous nucleation in n-alkanes. Chem. Phys. Lett. 493(4–6), 279–282 (2010)
J.S. Li, X.J. Li, Determination principal component content of seed oils by THz-TDS. Chem. Phys. Lett. 476(1–3), 92–96 (2009)
S.R. Keiding, Dipole correlation functions in liquid benzenes measured with terahertz time domain spectroscopy. J. Phys. Chem. A 101(29), 5250–5254 (1997)
Y.S. Jin, G.J. Kim, C.H. Shon, S.G. Jeon, J.I. Kim, Analysis of petroleum products and their mixtures by using terahertz time domain spectroscopy. J. Korean Phys. Soc. 53(4), 1879–1885 (2008)
J.P. Laib, D.M. Mittleman, Temperature-dependent terahertz spectroscopy of liquid n-alkanes. J. Infrared Millim. Terahertz Waves 31(9), 1015–1021 (2010)
P. Dutta, K. Tominaga, Dependence of low frequency spectra on solute and solvent in solutions studied by terahertz time-domain spectroscopy. Mol. Phys. 107(18), 1845–1854 (2009)
A. Oka, K. Tominaga, Terahertz spectroscopy of polar solute molecules in non-polar solvents. J. NonCryst. Solids 352(42–49), 4606–4609 (2006)
T. Arikawa, M. Nagai, K. Tanaka, Characterizing hydration state in solution using terahertz time-domain attenuated total reflection spectroscopy. Chem. Phys. Lett. 457(1–3), 12–17 (2008)
K.J. Tielrooij, N. Garcia-Araez, M. Bonn, H.J. Bakker, Cooperativity in ion hydration. Science 328(5981), 1006–1009 (2010)
U. Heugen, G. Schwaab, E. Brundermann, M. Heyden, X. Yu, D.M. Leitner, M. Havenith, Solute-induced retardation of water dynamics probed directly by terahertz spectroscopy. Proc. Natl. Acad Sci. U. S. A. 103, 12301–12306 (2006)
J. Xu, K.W. Plaxco, S.J. Allen, J.E. Bjarnason, E.R. Brown, 0.15–3.72 THz absorption of aqueous salts and saline solutions. Appl. Phys. Lett. 90(3), 031908 (2007)
B.N. Flanders, R.A. Cheville, D. Grischkowsky, N.F. Scherer, Pulsed terahertz transmission spectroscopy of liquid CHCl3, CCl4, and their mixtures. J. Phys. Chem. 100(29), 11824–11835 (1996)
Y. Yomogida, Y. Sato, R. Nozaki, T. Mishina, J. Nakahara, Comparative dielectric study of monohydric alcohols with terahertz time-domain spectroscopy. J. Mol. Struct. 981(1–3), 173–178 (2010)
Y. Yomogida, Y. Sato, R. Nozaki, T. Mishina, J. Nakahara, Comparative study of boson peak in normal and secondary alcohols with terahertz time-domain spectroscopy. Phys. B Condens. Matter 405(9), 2208–2212 (2010)
K. Yamamoto, M. Tani, M. Hangyo, Terahertz time-domain spectroscopy of imidazolium ionic liquids. J. Phys. Chem. B 111(18), 4854–4859 (2007)
Y. Shim, H.J. Kim, Dielectric relaxation, ion conductivity, solvent rotation, and solvation dynamics in a room-temperature ionic liquid. J. Phys. Chem. B 112(35), 11028–11038 (2008)
J. Sangoro, C. Iacob, A. Serghei, S. Naumov, P. Galvosas, J. Karger, C. Wespe, F. Bordusa, A. Stoppa, J. Hunger, R. Buchner, F. Kremer, Electrical conductivity and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid. J. Chem. Phys. 128(21), 214509 (2008)
M. Koeberg, C.C. Wu, D. Kim, M. Bonn, THz dielectric relaxation of ionic liquid: water mixtures. Chem. Phys. Lett. 439(1–3), 60–64 (2007)
J.T. Kindt, C.A. Schmuttenmaer, Far-infrared dielectric properties of polar liquids probed by femtosecond terahertz pulse spectroscopy. J. Chem. Phys. 100(24), 10373 (1996)
J. Xu, K.W. Plaxco, S.J. Allen, Probing the collective vibrational dynamics of a protein in liquid water by terahertz absorption spectroscopy. Protein Sci. 15(5), 1175–1181 (2006)
J. Xu, K.W. Plaxco, S.J. Allen, Collective dynamics of lysozyme in water: terahertz absorption spectroscopy and comparison with theory. J. Phys. Chem. B 110(47), 24255–24259 (2006)
S. Ebbinghaus, S.J. Kim, M. Heyden, X. Yu, U. Heugen, M. Gruebele, D.M. Leitner, M. Havenith, An extended dynamical hydration shell around proteins. Proc. Natl. Acad Sci. U. S. A. 104(52), 20749–20752 (2007)
M. Nagai, H. Yada, T. Arikawa, K. Tanaka, Terahertz time-domain attenuated total reflection spectroscopy in water and biological solution. Int. J. Infrared Millim. Waves 27(4), 505–515 (2006)
H. Hirori, K. Yamashita, M. Nagai, K. Tanaka, Attenuated total reflection spectroscopy in time domain using terahertz coherent pulses. Jpn. J. Appl. Phys. Part 2 Lett. Express Lett. 43(10A), L1287–L1289 (2004)
B. You, T.A. Liu, J.L. Peng, C.L. Pan, J.Y. Lu, A terahertz plastic wire based evanescent field sensor for high sensitivity liquid detection. Opt. Express 17(23), 20675–20683 (2009)
L. Cheng, S. Hayashi, A. Dobroiu, C. Otani, K. Kawase, T. Miyazawa, and Y. Ogawa, Terahertz-wave absorption in liquids measured using the evanescent field of a silicon waveguide. Appl. Phys. Lett. 92(18), 181104 (2008)
J.P. Laib, D.V. Nickel, D.M. Mittleman, Terahertz vibrational modes induced by heterogeneous nucleation in n-alkanes. Chem. Phys. Lett. 493(4–6), 279–282 (2010)
M. Heyden, J. Sun, S. Funkner, G. Mathias, H. Forbert, M. Havenith, D. Marx, Dissecting the THz spectrum of liquid water from first principles via correlations in time and space. Proc. Natl. Acad. Sci. U. S. A. 107(27), 12068–12073 (2010)
D.A. Schmidt, O. Birer, S. Funkner, B.P. Born, R. Gnanasekaran, G.W. Schwaab, D.M. Leitner, M. Havenith, Rattling in the cage: ions as probes of sub-picosecond water network dynamics. J. Am. Chem. Soc. 131(51), 18512–18517 (2009)
S.J. Kim, B. Born, M. Havenith, M. Gruebele, Real-time detection of protein-water dynamics upon protein folding by terahertz absorption. Angewandte Chemie Int. Ed. 47(34), 6486–6489 (2008)
S. Ebbinghaus, S.J. Kim, M. Heyden, X. Yu, M. Gruebele, D.M. Leitner, M. Havenith, Protein sequence- and pH-dependent hydration probed by terahertz spectroscopy. J. Am. Chem. Soc. 130(8), 2374–2375 (2008)
M. Sajadi, Y. Ajaj, I. Ioffe, H. Weingartner, N.P. Ernsting, Terahertz absorption spectroscopy of a liquid using a polarity probe: a case study of trehalose/water mixtures. Angew. Chem. Int. Ed. 49, 454–457 (2010)
M.L.T. Asaki, A. Redondo, T.A. Zawodzinski, A.J. Taylor, Dielectric relaxation of electrolyte solutions using terahertz transmission spectroscopy. J. Chem. Phys. 116(19), 8469–8482 (2002)
M. Krüger, E. Bründermann, S. Funkner, H. Weingärtner, M. Havenith, Communications: polarity fluctuations of the protic ionic liquid ethylammonium nitrate in the terahertz regime. J. Chem. Phys. 132, 101101 (2010)
A. Chakraborty, T. Inagaki, M. Banno, T. Mochida, K. Tominaga, Low-frequency spectra of metallocenium ionic liquids studied by terahertz time-domain spectroscopy. J. Phys. Chem. A 115, 1313–1319 (2011)
M.C. Rheinstadter, K. Schmalzl, K. Wood, D. Strauch, Protein–protein interaction in purple membrane. Phys. Rev. Lett. 103(12), 128104 (2009)
K. Wood, C. Caronna, P. Fouquet, W. Haussler, F. Natali, J. Ollivier, A. Orecchini, M. Plazanet, G. Zaccai, A benchmark for protein dynamics: Ribonuclease A measured by neutron scattering in a large wavevector-energy transfer range. Chem. Phys. 345, 305–314 (2008)
D. Liu, X.-q. Chu, M. Lagi, Y. Zhang, E. Fratini, P. Baglioni, A. Alatas, A. Said, E. Alp, S.-H. Chen, Studies of phononlike low-energy excitations of protein molecules by inelastic X-ray scattering. Phys. Rev. Lett. 101, 135501 (2008)
W.B. Person, G. Zerbi, Vibrational Intensities in Infrared and Raman Spectroscopy. (Elsevier Scientific Publishing, Amsterdam, 1982)
B.S. Galabov, T. Dudev, Vibrational Intensities (Elsevier Science, Amsterdam, 1996)
J.S. Melinger, N. Laman, S.S. Harsha, S. Cheng, D. Grischkowsky, High-resolution waveguide terahertz spectroscopy of partially oriented organic polycrystalline films. J. Phys. Chem. A 111, 10977–10987 (2007)
C.F. Zhang, S.M. Durbin, Hydration-induced far-infrared absorption increase in myoglobin. J. Phys. Chem. B 110(46), 23607–23613 (2006)
J. Knab, J.-Y. Chen, A. Markelz, Hydration dependence of conformational dielectric relaxation of lysozyme. Biophys. J. 90, 2576–2581 (2006)
Y.F. He, J.Y. Chen, J.R. Knab, W.J. Zheng, A.G. Markelz, Evidence of protein collective motions on the picosecond timescale. Biophys. J. 100(4), 1058–1065 (2011)
T. Ding, R.Y. Li, J.A. Zeitler, T.L. Huber, L.F. Gladden, A.P.J. Middelberg, R.J. Falconer, Terahertz and far infrared Spectroscopy of alanine-rich peptides having variable ellipticity. Opt. Express 18(26), 27431–27444 (2010)
J.Y. Chen, J.R. Knab, S.J. Ye, Y.F. He, A.G. Markelz, Terahertz dielectric assay of solution phase protein binding. Appl. Phys. Lett. 90(24), 243901 (2007)
K.M. Tych, A.D. Burnett, C.D. Wood, J.E. Cunningham, A.R. Pearson, A.G. Davies, E.H. Linfield, Applying broadband terahertz time-domain spectroscopy to the analysis of crystalline proteins: a dehydration study. J. Appl. Crystallogr. 44, 129–133 (2011)
E.R. Brown, E.A. Mendoza, D.Y. Xia, S.R.J. Brueck, Narrow THz spectral signatures through an RNA solution in nanofluidic channels. IEEE Sens. J. 10(3), 755–759 (2010)
Y.W. Sun, Y.T. Zhang, E. Pickwell-MacPherson, Investigating antibody interactions with a polar liquid using terahertz pulsed spectroscopy. Biophys. J. 100(1), 225–231 (2011)
G.M. Png, R.J. Falconer, B.M. Fischer, H.A. Zakaria, S.P. Mickan, A.P.J. Middelberg, D. Abbott, Terahertz spectroscopic differentiation of microstructures in protein gels. Opt. Express 17(15), 13102–13115 (2009)
H. Yoneyama, M. Yamashita, S. Kasai, K. Kawase, R. Ueno, H. Ito, T. Ouchi, Terahertz spectroscopy of native-conformation and thermally denatured bovine serum albumin (BSA). Phys. Med. Biol. 53(13), 3543–3549 (2008)
H. Chen, L. Wang, Y.G. Qu, T.Y. Kuang, L.B. Li, W.X. Peng, Investigation of guanidine hydrochloride induced chlorophyll protein 43 and 47 denaturation in the terahertz frequency range. J. Appl. Phys. 102(7) 74700 (2007)
Y. He, P.I. Ku, J.R. Knab, J.-Y. Chen, A.G. Markelz, Protein dynamical transition does not require protein structure. Phys. Rev. Lett. 101, 178103 (2008)
R. Liu, M.X. He, R.X. Su, Y.J. Yu, W. Qi, Z.M. He, Insulin amyloid fibrillation studied by terahertz spectroscopy and other biophysical methods. Biochem. Biophys. Res. Commun. 391(1), 862–867 (2010)
Y. Ogawa, S. Hayashi, M. Oikawa, C. Otani, K. Kawase, Interference terahertz label-free imaging for protein detection on a membrane. Opt. Express 16(26), 22083–22089 (2008)
A. Menikh, S.P. Mickan, H. Liu, R. MacColl, X.-C. Zhang, Label-free amplified bioaffinity detection using terahertz wave technology. Biosens. Bioelectron. 20(3), 658–662 (2004)
M. Brucherseifer, M. Nagel, P.H. Bolivar, H. Kurz, A. Bosserhoff, R. Buttner, Label-free probing of the binding state of DNA by time-domain terahertz sensing. Appl. Phys. Lett. 77(24), 4049–4051 (2000)
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George, D.K., Markelz, A.G. (2012). Terahertz Spectroscopy of Liquids and Biomolecules. In: Peiponen, KE., Zeitler, A., Kuwata-Gonokami, M. (eds) Terahertz Spectroscopy and Imaging. Springer Series in Optical Sciences, vol 171. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-29564-5_9
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DOI: https://doi.org/10.1007/978-3-642-29564-5_9
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