光谱学与光谱分析 |
|
|
|
|
|
Experimental and Theoretical Study on Terahertz Spectra for Regenerated Cellulose |
DAI Ze-lin, XU Xiang-dong*, GU Yu, ZOU Rui-jiao, HAN Shou-sheng, PENG Yong, LIAN Yu-xiang, WANG Fu, LI Xin-rong, CHEN Zhe-geng, SUN Ming-hui, JIANG Ya-dong |
State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China, Chengdu 610054, China |
|
|
Abstract In this work, regenerated cellulose films were prepared with an iced dissolution method, while the physical morphologies and crystal types of the products were systematically characterized with scanning electron microscope (SEM), Fourier transform infrared(FTIR), while X-Ray Diffraction (XRD). The results demonstrate that the as-prepared continuous and uniform films are indeed cellulose Ⅱ, whose morphology and crystal type are significantly different from those of the degreased cotton. Moreover, Terahertz time domain system (THz-TDS) and FTIR were employed to measure the THz spectra of the regenerated cellulose films. Accordingly, the THz characteristic peaks for the regenerated cellulose films are experimentally identified for the first time. In addition, the increase of the THz transmittance with the decrease of the wavenumber is attributed to the existence of amorphous components in the regenerated cellulose films. Although the shapes of Far-IR spectra in the range of 100~700 cm-1 are similar, the absorption peaks of the regenerated cellulose films move to lower wavenumbers (blue shift) compared with those of the degreased cotton. Based on this, we developed a new approach to distinguish the allomorphism of cellulose Ⅱ and cellulose Iβ by Far-IR. Particularly, geometry optimization and IR calculation for the crystal structure of cellulose Ⅱ have been successfully processed by Density Functional Theory (DFT) using periodic boundary condition via CASTEP package. The calculated absorption peak positions are in good agreement with those experimentally measured. Consequently, the THz characteristic peaks of the regenerated cellulose films have been systematically and successfully assigned. Theoretical calculations reveal that the peaks at 42 and 54 cm-1 are assigned to the lattice vibration modes coupled with translational mode and rotational mode, respectively. Moreover, the absorption peaks in the range of 68~238 cm-1 are related with the torsion vibration of —CH2OH group and deformation vibration of C—H bond and O—H bond, while those in the range of 351~583 cm-1 are assigned to the skeletal vibration of C—O—C bond and pyranoid ring, and those at 611 and 670 cm-1 are originated from the out-of-plane bending vibration of O—H bond. Each absorption peak is involved in more than single vibration mode. The THz spectra presented in this work, together with the theoretical simulations, indicate that the THz responses of regenerated cellulose are closely associated with both its chemical constituents and molecular structure. These results will be helpful not only for better understanding the relations between the molecular structure of the regenerated cellulose and its THz spectrum, but also for providing valuable information for future studies on the physical mechanisms of THz responses of other partially-crystalline polymers and organic biological macromolecules.
|
Received: 2016-02-26
Accepted: 2016-06-21
|
|
Corresponding Authors:
XU Xiang-dong
E-mail: xdxu@uestc.edu.cn
|
|
[1] Ishikawa A, Okano T, Sugiyama J. Polymer, 1997, 38(2): 463. [2] Chung C, Lee M, Choe E K. Carbohydrate Polymers, 2004, 58(4): 417. [3] Nelson M L, O’Connor R T. Journal of Applied Polymer Science, 1964, 8(3): 1325. [4] Guo H, He M, Huang R, et al. RSC Advances, 2014, 4(101): 57945. [5] Vieira F S, Pasquini C. Analytical Chemistry, 2014, 86(8): 3780. [6] Yan C, Yang B, Yu Z. Analytical Letters, 2013, 46(6): 946. [7] Husan S K, Hasted J B, Rosen D, et al. Infrared Physics, 1984, 24(2-3): 209. [8] Cai J, Zhang L. Macromolecular Bioscience, 2005, 5(6): 539. [9] Zhang L, Ruan D, Zhou J. Industrial & Engineering Chemistry Research, 2001, 40(25): 5923. [10] Colom X, Carrillo F. European Polymer Journal, 2002, 38(11): 2225. [11] Atalla R H, Vanderhart D L. Science, 1984, 223(4633): 283. [12] Isogai A, Usuda M, Kato T, et al. Macromolecules, 1989, 22(7): 3168. [13] Liu H B, Plopper G, Earley S, et al. Biosensors and Bioelectronics, 2007, 22(6): 1075. [14] Strom U, Taylor P C. Physical Review B, 1977, 16(12): 5512. [15] Walther M, Fischer B M, Jepsen P U. Chemical Physics, 2003, 288(2): 261. [16] LIU Yi-ke, LIU Yu-tong, XU Xiang-dong, et al(刘一客, 刘禹彤, 许向东, 等). Acta Physica Sinica(物理学报), 2014, 64(6): 68701. [17] Kolpak F J, Blackwell J. Macromolecules, 1976, 9(2): 273. [18] Nishiyama Y, Langan P, Chanzy H. Journal of the American Chemical Society, 2002, 124(31): 9074. [19] WANG Guo, WANG Wei-ning(王 果, 王卫宁). Acta Physico-Chemica Sinica(物理化学学报), 2012, 28(7): 1579. [20] Jepsen P U, Clark S J. Chemical Physics Letters, 2007, 442(4): 275. [21] Szymańska-Chargot M, Cybulska J, Zdunek A. Sensors, 2011, 11(6): 5543. |
[1] |
NIE Mei-tong1,2, XU De-gang1,2*, WANG Yu-ye1,2*, TANG Long-huang1,2, HE Yi-xin1,2, LIU Hong-xiang1,2, YAO Jian-quan1,2. Investigation on Characteristics of Edible Oil Spectra with Terahertz Time-Domain Attenuated Total Reflection Spectroscopy[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(07): 2016-2020. |
[2] |
XIAO Xue-feng1, SUN Yong-jun1, 2*, SHEN Hao1, SUN Wen-qaun1, ZHENG Huai-li3, XU Yan-hua2, ZHU Cheng-yu1. Spectral Characterizations of CSC-P(AM-AA) with Function of Trapping Heavy Metals and Its Removal Efficiency of Cu2+[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(06): 1809-1813. |
[3] |
JIANG Zhong-min1, KONG Ling-jun2, NIE Peng1, YU Hai-qi1. Study on the Spectral Characterization Model of Multi-Color Printer Based on LabPQR Dimension Reduction[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(06): 1975-1981. |
[4] |
LIU Chong1, HE Xiang1*, ZHANG Ya-chun2, CHEN Jian-ping3, CHEN Yu-dong3, ZENG Xiao-jun3, CHEN Bing-yan1, ZHU Wei-hua1. Spectroscopic Diagnostics on Discharge Characteristics of RF Capacitive Coupled Plasma[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(04): 1007-1013. |
[5] |
CHEN Xi-ai1,2,3, WU Xue1, ZHANG Song1, WANG Ling1. Study of Plant Growth Regulators Detection Technology Based on Terahertz Spectroscopy[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(03): 665-669. |
[6] |
YU Jiang-ping1, LI Chun2, YI Wen-ting1, JIN Biao-bing2, LIU Yun-fei1, JIANG Ling1*. Temperature Dependence of Terahertz Spectra of Amino Acid[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2018, 38(02): 386-393. |
[7] |
MA Pin1, YANG Yu-ping1*, ZHANG Zhen-wei2, ZHANG Cun-lin2. Study on the FTIR and THz Spectra of Azitromycin Drugs with Different Physical Forms[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(10): 3016-3020. |
[8] |
ZHANG Hong-hai1, 2, 3, GAO Yi-bo1, 2, 3, LI Chao1, 2, 3, MA Jin-ji1, 2, 3*, FANG Xue-jing4, XIONG Wei4. Simulation of Limb Measurements for Mesospheric Hydroxyl Radical Based on SHS Detector[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(09): 2685-2691. |
[9] |
HUANG Yu1, SUN Ping1*, ZHANG Zheng1, JIN Chen1, LIU Wei2, WANG Wen-ai2. Experimental Study on Terahertz Spectrum of Lacidipine
[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(08): 2356-2359. |
[10] |
倪家鹏1,沈 韬1, 2* ,朱 艳2,李灵杰1,毛存礼1,余正涛1. Terahertz Spectroscopic Identification with Diffusion Maps[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(08): 2360-2364. |
[11] |
LIANG Liang1, TONG Min-ming1*, WEI Ming-sheng1, 2, LI Meng1, DONG Hai-bo1. Research on Scattering in the THz Quantitative Analysis of Granulated Coal[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(08): 2365-2370. |
[12] |
ZHANG Zheng-an1, 2, ZHENG Huai-li1, 3*, HUANG Fei2, FU Mao-mei4, LI Xiang1, 3, ZHOU Yu-hao1, 3. Ultraviolet-Initiated Template Polymerization of Cationic Polyacrylamide and Its Sludge Dewatering Performance[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(08): 2480-2485. |
[13] |
SUN Yong-jun1, 2, ZHENG Huai-li3, ZHAO Chun3, XIAO Xue-feng1, XU Yan-hua2, WU Hui-fang1, SUN Wen-quan1, REN Meng-jiao1, ZHU Cheng-yu1. The Spectral Characterizations of Chitosan Based Flocculants Synthesized by Photopolymerization[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(08): 2527-2532. |
[14] |
ZHANG Liang-liang1, ZHANG Rui2, HUANG Su-xia1, ZHANG Cun-lin1 . Terahertz Spectroscopic Investigation of Substrate Materials for Biological Application in the Frequency Range of 1~15 THz [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(02): 346-349. |
[15] |
CHEN Tao, LI Zhi, HU Fang-rong, YIN Xian-hua, XU Chuan-pei* . Discrimination of GMOs Using Terahertz Spectroscopy and CS-SVM [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2017, 37(02): 618-623. |
|
|
|
|