Estimation of Nematic Order Parameters via Haller Analysis of 1H NMR Spectra of Liquid Crystals

doi:10.11938/cjmr20182685

Abstract

Abstract: The Haller relationship was applied to estimate the nematic order parameter S from ¹H NMR spectra of fully protonated liquid crystals aligned in the magnetic field. The NMR line shapes were approximated as doublets of very broad peaks. Both the temperature-dependent doublet Splitting and the full width at half maximum of the whole spectra were used for Haller extrapolation. The order parameters obtained with the proposed approach for 4-cyano-4'-pentylbiphenyl (5CB) and the nematic mixture E7 were found to be in good agreement with previously reports.

Key words: nematic liquid crystal, order parameter, Haller analysis, ¹H NMR

CLC Number:

O482.53

TANG Ming-xue, SCHMIDT Claudia. Estimation of Nematic Order Parameters via Haller Analysis of ¹H NMR Spectra of Liquid Crystals[J]. Chinese Journal of Magnetic Resonance, 2019, 36(2): 138-147.

References

[1] TSVETKOV V N. Über die molekülanordnung in der anisotrop-flüssigen phase[On molecular order in the anisotropic liquid phase] [J]. Acta Physicochim URSS, 1942, 16:132-147.
[2] MAIER W, SAUPE A. Eine einfache molekular-statistische theorie der nematischen kristallinflüssigen phase[A simple molecular-statistical theory of the nematic crystalline-liquid phase] [J]. Z Naturforsch A, 1959, 14:882-889.
[3] ZANNONI C. On the description of ordering in liquid crystals[M]//LUCKHURST G R, VERACINI C A. The molecular dynamics of liquid crystals. Dordrecht:Kluwer, 1994:11-41.
[4] SAUPE A. Kernresonanzen in kristallinen flüssigkeiten[Nuclear magnetic resonances in crystalline liquids] [J]. Z Naturforsch A, 1964, 19:161-171.
[5] SAUPE A. Recent results in the field of liquid crystals[J]. Angew Chem Internat Edit, 1968, 7(2):97-112.
[6] MARČELJA S. Chain ordering in liquid crystals. I. Even-odd effect[J]. J Chem Phys, 1974, 60(9):3599-3604.
[7] EMSLEY J W, LUCKHURST G R, STOCKLEY C P. A theory of orientational ordering in uniaxial liquid crystals composed of molecules with alkyl chains[J]. Proc R Soc London A, 1982, 381:117-138.
[8] VAN DER EST A J, KOK M Y, BURNELL E E. Size and shape effects on the orientation of rigid molecules in nematic liquid crystals[J]. Mol Phys, 1987, 60(2):397-413.
[9] JANIK B, SAMULSKI E T, TORIUMI H. Flexible solutes in a uniaxial field:a 2H NMR study of n-alkanes in a nematic solvent[J]. J Phys Chem, 1987, 18(31):1842-1850.
[10] PHOTINOS D J, SAMULSKI E T, TORIUMI H. Alkyl chains in a nematic field. 1. A treatment of conformer shape[J]. J Phys Chem, 1990, 94(11):4688-4694.
[11] GOCHIN M, PINES A, ROSEN M E, et al. Two-dimensional N.M.R. studies of flexible molecules in liquid crystals:orientational order and conformational probabilities of n-hexane[J]. Mol Phys, 1990, 69(4):671-695.
[12] ROSEN M E, RUCKER S P, SCHMIDT C, et al. Two-dimensional proton NMR studies of the conformations and orientations of n-alkanes in a liquid crystal solvent[J]. J Phys Chem, 1993, 97(15):3858-3866.
[13] DONG R Y. Nuclear magnetic resonance of liquid crystals[M]. New Jersey:World Scientific, 2010.
[14] COURTIEU J, BAYLE J P, FUNG B M. Variable angle sample spinning NMR in liquid crystals[J]. Prog Nucl Magn Reson Spectrosc, 1994, 26:141-169.
[15] DOMENICI V, GEPPI M, VERACINI C A. NMR in chiral and achiral smectic phases:structure, orientational order and dynamics[J]. Prog Nucl Magn Reson Spectrosc, 2007, 50(1):1-50.
[16] FUNG B M. ¹³C NMR studies of liquid crystals[J]. Prog Nucl Magn Reson Spectrosc, 2002, 41(3/4):171-186.
[17] DOMENICI V. Nuclear magnetic resonance:a powerful tool to study liquid crystals[J]. Liquid Crystals Today, 2017, 26(1):2-10.
[18] SAUPE A. Ultraviolet, infrared and magnetic resonance spectroscopy on liquid crystals[J]. Mol Cryst Liq Cryst, 1972, 16(1/2):87-104.
[19] EMSLEY J W, LUCKHURST G R, STOCKLEY C P. The deuterium and proton-{deuterium} N.M.R. spectra of the partially deuteriated nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl[J]. Mol Phys, 1981, 44(3):565-580.
[20] HEEKS S K, LUCKHURST G R. Deuterium nuclear magnetic resonance study of the orientational order in the nematic phase of 4-n-pentyloxy-4'-cyanobiphenyl[J]. J Chem Soc Faraday Trans, 1993, 89(20):3783-3790.
[21] MAGNUSON M L, FUNG B M, BAYLE J P. On the temperature dependence of the order parameter of liquid crystals over a wide nematic range[J]. Liq Cryst, 1995, 19(6):823-832.
[22] SIEBERT H. Untersuchung des Fließverhaltens von flüssigkristallinen polymeren unter Scherung mit ²H-NMR-spektroskopie, Röntgenbeugung, neutronenstreuung und polarisationsmikroskopie[Investigation of the flow properties of liquid -crystalline polymers under shear by ²H NMR spectroscopy, x-ray scattering, neutron scattering and polarizing microscopy] [D]. Freiburg:University of Freiburg, 1999.
[23] NAGARAJA C S, RAMANATHAN K V. Determination of order parameters of liquid crystals:use of dipolar oscillations enhanced by Lee-Goldburg decoupling[J]. Liq Cryst, 1999, 26(1):17-21.
[24] CINACCHI G, DOMENICI V. Orientational odering of a banana-shaped solute molecule in a nematic calamitic solvent by ²H-NMR-spectroscopy:an indication of glasslike behavior[J]. Phys Rev E, 2006, 74(3 Pt 1):030701.
[25] CATALANO D, GEPPI M, MARINI A, et al. Orientational order properties in fluorinated liquid crystals from an optical, dielectric, and ¹³C NMR combined approach[J]. J Phys Chem C, 2007, 111(14):5286-5299.
[26] GEPPI M, MARINI A, VERACINI C A, et al. Orientational order of difluorinated liquid crystals:a comparative ¹³C-NMR, optical, and dielectric study in nematic and smectic B phases[J]. J Phys Chem B, 2008, 112(32):9663-9676.
[27] GEPPI M, MARINI A, MENNUCCI B, et al. Determination of order parameters in laterally fluorosubstituted terphenyls by ¹⁹F-NMR, optical and dielectric anisotropies[C]//Proceedings of the 23rd international liquid crystal conference (ILCC 2010) Part Ⅱ of VⅢ. 2011, 541(1):104-117.
[28] TANG Y Y, SUN P C, LIN H, et al. Dynamics of liquid crystalline phases in block copolymers studied by ²H-NMR spectroscopy[J]. Chinese J Magn Reson, 2005, 22(3):253-259. 谭玉英, 孙平川, 林海, 等. 嵌段共聚物溶致液晶相中水的²H-NMR动力学分析[J]. 波谱学杂志, 2005, 22(3):253-259.
[29] MA J H, GUO C, TANG Y L, et al. NMR studies on PEO-PPO-PEO block copolymers:A review[J]. Chinese J Magn Reson, 2008, 25(3):421-434. 马俊鹤, 郭晨, 唐亚林, 等. PEO-PPO-PEO嵌段共聚物的NMR研究进展[J]. 波谱学杂志, 2008, 25(3):421-434.
[30] ZHOU P, HU B W. Temperature-induced phase transitions in the silk gland of Bombyx mori silkworm lumen:A high-resolution solid-state ¹³C NMR study[J]. Chinese J Magn Reson, 2009, 26(1):17-26. 周平, 胡炳文. 低温诱导桑蚕体内腺体相行为的高分辨¹³C固体核磁共振研究(英文)[J]. 波谱学杂志, 2009, 26(1):17-26.
[31] MULDER F A, FILATOV M. NMR chemical shift data and ab initio shielding calculations:emerging tools for protein structure determination[J]. Chem Soc Rev, 2010, 39(2):578-590.
[32] HALLER I. Thermodynamic and static properties of liquid crystals[J]. Prog Solid State Chem, 1975, 10(2):103-118.
[33] CHIRTOC I, CHIRTOC M, GLORIEUX C, et al. Determination of the order parameter and its crytical exponent for nCB (n=5-8) liquid crystals from refractive index data[J]. Liq Cryst, 2004, 31(2):229-240.
[34] JADZYN J. On the molecular interpretation of the static dielectric properties of nematic liquid crystals[J]. Liq Cryst, 1999, 26(3):437-442.
[35] DUNMUR D A. The determination of molecular parameters from dielectric measurements on nematic liquid crystals[J]. Liq Cryst, 2005, 32(11/12):1379-1387.
[36] URBAN S, WÜRFLINGER A, GESTBLOM B. On the derivation of the nematic order parameter from the dielectric relaxation times[J]. Phys Chem Chem Phys, 1999, 1:2787-2791.
[37] WU S T. Infrared markers for determining the order parameters of uniaxial liquid crystals[J]. Appl Opt, 1987, 26(16):3434-3440.
[38] PENCHEV I I, DOZOV I N. Anisotropic correction factors in the evaluation of nematic order parameters from polarized fluorescence measurements[J]. Mol Cryst Liq Cryst, 1981, 73(3/4):267-271.
[39] JONES W J, THOMAS D K, THOMAS D W, et al. On the determination of order parameters for homogeneous and twisted nematic liquid crystals from Raman spectroscopy[J]. J Mol Struct, 2004, 708(1/2/3):145-163.
[40] DE GENNES P G. Short range order effects in the isotropic phase of nematics and cholesterics[J]. Mol Cryst Liq Cryst, 1971, 12(3):193-214.
[41] BUKA A, DE JEU W H. Diamagnetism and orientational order of nematic liquid crystals[J]. J Phys France, 1982, 43(2):361-367.
[42] DRIES T, FUHRMANN K, FISCHER E W, et al. Magnetic susceptibility and order parameter of nematic liquid crystals as determined by a high-temperature SQUID magnetometer[J]. J Appl Phys, 1991, 69(11):7539-7546.
[43] WEISS S M, OUYANG H M, ZHANG J D, et al. Electrical and thermal modulation of silicon photonic bandgap microcavities containi ng liquid crystals[J]. Opt Express, 2005, 13(4):1090-1097.
[44] KIM N, KYU T. Phase equilibria and photopolymerisation-induced phase transitions of mesogenic diacrylate monomer and low molecular mass liquid crystal mixture[J]. Liq Cryst, 2012, 39(6):745-754.
[45] SIEBERT H, BECKER P, QUIJADA-GARRIDO I, et al. In situ deuteron NMR investigations of sheared liquid crystalline polymers[J]. Solid State Nucl Magn Reason, 2002, 22(2/3):311-326.
[46] ZHOU W J, KORNFIELD J A, UGAZ V M, et al. Dynamics and shear orientation behavior of a main-chain thermotropic liquid crystalline polymer[J]. Macromolecules, 1999, 32(17):5581-5593.
[47] PELÁEZ J, WILSON M. Molecular orientational and dipolar correlation in the liquid crystal mixture E7:a molecular dynamics si mulation study at a fully atomistic level[J]. Phys Chem Chem Phys, 2007, 9(23):2968-2975.

Estimation of Nematic Order Parameters via Haller Analysis of ¹H NMR Spectra of Liquid Crystals

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles 0

Metrics

Comments

[1]	XIAO Xiong-jie, HU Mary, ZHANG Xu, HU Jian-zhi. An NMR-Based Metabolomics Study of Kidneys from Mice Exposed to Ionizing Radiation [J]. Chinese Journal of Magnetic Resonance, 2019, 36(2): 172-181.
[2]	WANG Shuang-hong, ZENG Pei, PAN Si-na, WANG Jia, WANG Shu-mei, YANG Yong-xia. Effects of Gegen Qinlian Decoction on the Fecal Metabonome of High Fructose-Induced Insulin Resistance Rats Studied by ¹H NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2019, 36(2): 182-194.
[3]	WU Jin-ze, XIN Jia-xiang, FU Xiao-bin, YAO Ye-feng. A Wide-Line Solid-State ¹H NMR Study of Phase Structures of Semi-Crystalline Polymers [J]. Chinese Journal of Magnetic Resonance, 2019, 36(1): 23-33.
[4]	ZHAO Hong-bo, CHAI Xiao-fei, WANG Yue-hua, SHI Hui-bing, ZHANG Rui, DONG Zhao-ping, HAN Li-xia. Analysis of Styrene-Butadiene-Styrene (SBS) Content in Modified Asphalt with ¹H NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2017, 34(3): 323-328.
[5]	CAO Chao-tun, LUO Qing-qing, CAO Chen-zhong. Substituent Effects on the ¹H NMR Chemical Shifts of CH=N(O) Bridge Group in Diaryl Nitrone [J]. Chinese Journal of Magnetic Resonance, 2017, 34(1): 69-77.
[6]	GUO Qiang-sheng, LIU Ming-ke, YU Shan, SHEN Ting-ting, SONG Wei, XU Xu. A Quantitative NMR Method to Analyze Vitamin B1, Vitamin B2, Nicotinamide and Calcium Pantothenate Contents in Compound Vitamin B Tablets [J]. Chinese Journal of Magnetic Resonance, 2016, 33(3): 442-451.
[7]	ZHOU Qiu-ju, XIANG Jun-feng, TANG Ya-lin, CUI Jie, WU Ning-ning. Pure Shift Proton NMR Spectroscopy and Its Applications [J]. Chinese Journal of Magnetic Resonance, 2016, 33(3): 502-513.
[8]	WANG Qiang, LI Yu-jiang, TAO Le, GUO Xiao-he, DONG Li-hong, SONG Chuan-jun, CHANG Jun-biao. Positions of Protonation in Cytidine Hydrochloride Revealed by NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2016, 33(2): 281-287.
[9]	ZHENG Jin, XUE Hui-yun, LIN Cai-feng, LIN De-xun, LU Jia, YANG Hui, WANG Xiang-peng, ZOU You-si. Dating Oily Ballpoint Pen Hand-Writings by ¹H NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2016, 33(2): 198-207.
[10]	HAN Wei-jian, LIN Xiao-tong, GUO Na, CHEN Qiao, ZHANG Ting-ting, XU Nan. Changes of Chemical Constitution in Alismatis rhizoma after Saline Processing as Revealed by ¹H NMR Analysis [J]. Chinese Journal of Magnetic Resonance, 2016, 33(1): 117-124.
[11]	KUMAR Sriramoju M 1，LYU Ping-chiang1，HSU Shang-te Danny1,2,3*. Structural Perturbation of the Parkinson´s Disease-Associated I93M Mutation in Human UCH-L1 Revealed by Solution State NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2015, 32(2): 329-341.
[12]	. Differentiating Bupleurum bicaule from Bupleurum chinense Using ¹H NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2014, 31(2): 214-221.
[13]	FENG Ju, HU Jian-zhi*, BURTON Sarah D., HOYT David W.. High Resolution Magic Angle Spinning ¹H NMR Metabolic Profiling of Nanoliter Biological Tissues at High Magnetic Field [J]. Chinese Journal of Magnetic Resonance, 2013, 30(1): 1-11.
[14]	YANG Ying-wen, WANG Ya-li, SA Ri-na, PAN Xin-bo, XIAO Yu-qi, SUN Yu-jing, WANG Lan-xia. Chemical Fingerprinting of Angelica Sinensis* at Different Growth Stages by ¹H NMR [J]. Chinese Journal of Magnetic Resonance, 2013, 30(1): 69-79.
[15]	Yei-Chen LAI , Yun-Wei CHIANG. Asymmetric Partition of Spin Labeled Lipids in the Coexistence of DPPC-Rich Ordered and DLPC-Rich Fluid Phases [J]. Chinese Journal of Magnetic Resonance, 2010, 27(3): 470-484.