Citation: WANG Wen-Qing, SHEN Xin-Chun, WU Ji-Lan, NG Yan, SHEN Guo-Hua, ZHAO Hong-Kai. Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N⁺H…O^- Bond in Chiral Alanine Crystal[J]. Acta Physico-Chimica Sinica, ;2012, 28(04): 773-780. doi: 10.3866/PKU.WHXB201202132 shu

Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N⁺H…O^- Bond in Chiral Alanine Crystal

1.
1. Beijing National Laboratory for Molecular Sciences, Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China;
2. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250061, P. R. China

Received Date: 31 October 2011
Available Online: 13 February 2012
Fund Project: 国家自然科学基金(21002006, 20452002) (21002006, 20452002)国家科技部基础研究重大项目(2004-973-36)资助 (2004-973-36)

With a view to understanding the argument of phase-transition mechanisms of D- and L-alanine at around 270 K, the temperature dependence of heat capacity measurements was investigated, for single crystals, ground powders, and polycrystalline products, using differential scanning calorimetry (DSC). The C_p (heat capacity under constant pressure) values of D- and L-alanine were calibrated with standard sapphire by the triple-curve method; these values coincide with the standard C_p values in the literature. Endothermic transition peaks were observed at T_c=272.02 K, ΔH=1.87 J·mol^-1 and T_c=271.85 K, ΔH=1.46 J·mol^-1 for D- and L- alanine, respectively, and T_c=273.59 K, ΔH=1.75 J·mol^-1 and T_c=273.76 K, ΔH=1.57 J·mol^-1 for the reference crystals D- and L-valine, respectively. The energy differences of 0.41 J· mol^-1 for D-and L-alanine and 0.18 J·mol^-1 for D- and L-valine, which were observed from pre-aligned molecules in the single crystals and vanished in the ground powders and polycrystalline products, show that the phase transition is related to the crystal lattice. Neutron diffraction results exclude the possibility of a D→L configuration change, and show that the hydrogen bonds run antiparallel to the c-axis in the D- and Lcrystals. Polarized Raman vibrational spectroscopy shows that the transition mechanism may be related to the electronic orbital angular momentum and magnetic dipole moments of N⁺H…O^- in the crystals. External magnetic fields, H=+1, -1 T, were applied parallel to the c(z)-axis of the D- and L-alanine crystalline lattices, respectively. The DC-magnetic susceptibilities show electron spin-flip transitions at around 270 K in D- and L-alanine. The spin is“up”or“down”relative to the direction of N⁺H…O^- bond along the c(z)-axis. Based on spin rigidity and magnetic anisotropy, the results help to explain the discrepancies among heat capacity and magnetic susceptibility data for single crystals and polycrystalline powders of D- and L-alanine.
- Heat capacity,
- DC-magnetic susceptibility,
- N⁺H…O^- bonding,
- Electron spin-flip,
- Asymmetry transition,
- D- and L-alanine crystals
1. [1]
  (1) MacDermott, A. J. Enantiomer 2000, 5, 153.
2. [2]
  (2) MacDermott, A. J.; Hegstrom, R. A. Chemical Physics 2004, 305, 55.
3. [3]
  (3) Simpson, H. J.; Marsh, R. E. Acta Cryst. 1966, 20, 550.
4. [4]
  (4) Destro, R.; Marsh, R. E. J. Phys. Chem. 1988, 92, 966.
5. [5]
  (5) Crowell, R. A.; Chronister, E. L. Phys. Rev. B 1993, 48, 172.
6. [6]
  (6) Kosic T. J.; Raymond, E. C., Jr. Chem. Phys. Lett. 1983, 103, 109.
7. [7]
  (7) Gledhill, M. Analyst 2001, 126, 1359.
8. [8]
  (8) Cronin J. R.; Pizzarello, S. Science 1997, 275, 951.
9. [9]
  (9) Wang,W. Q.; ng, Y.; Liang, Z.; Sun, F. L.; Shi, D. X.; Gao, H. J.;Wang, Z. M. Surface Science 2002, 512, L379.
10. [10]
  (10) Perkin-Elmer Corporation, Thermal Analysis Instrument Division, Shanghai, 2008
11. [11]
  (11) Mraw, S. C. Rev. Sci. Instrum. 1982, 53, 228.
12. [12]
  (12) Pak, J.; Qiu,W.; Pyda, M.; Nowak-Pyda, E.;Wunderlic, B. J. Therm. Anal. Cal. 2005, 82, 565.
13. [13]
  (13) Morad, N. A.; Idrees, M.; Hasan, A. A. J. Therm. Anal. 1995, 44, 823.
14. [14]
  (14) (a) Hutchens, J. O.; Cole, A. G.; Stout, J.W. J. Am. Chem. Soc. 1960, 82, 4813. (b) Handbook of Biochemistry and Molecular Biology V.4; Physical and Chemical data, CRC Press: Cleveland, 1976.
15. [15]
  (15) Huffman, H. M.; Borsook, H. J. Am. Chem. Soc. 1932, 54, 4297. Handbook of Biochemistry and Molecular Biology V. 4; Physical and Chemical data, CRC Press: Cleveland, 1976.
16. [16]
  (16) Wilson, C. C.; Myles, D.; Ghosh, M.; Johnson, L. N.;Wang,W. Q. New J. Chem. 2005, 29, 1318.
17. [17]
  (17) Wang,W. Q.; Liu, Y. N.; ng, Y. Acta Phys. -Chim. Sin. 2004, 20, 1345. [王文清, 刘轶男, 龚. 物理化学学报, 2004, 20, 1345.]
18. [18]
  (18) Wang,W. Q.; ng, Y.; Yao, N. Acta Phys. -Chim. Sin. 2005, 21, 774. [王文清, 龚, 姚楠. 物理化学学报, 2005, 21, 774.]
19. [19]
  (19) Forss, S. A. J. Raman Spec. 1982, 12, 266.
20. [20]
  (20) Sullivan, R.; Pyda, M.; Pak, J.;Wunderlich, B.; Thompson, J. R.; Pagni, R.; Pan, H. J.; Barnes, C.; Schwerdtfeger, P.; Compton, R. J. Phys. Chem. 2003, 107, 6674.
21. [21]
  (21) Hutchens, J. O.; Cole, A. G.; Stout, J.W. J. Phys. Chem. 1963, 67, 1128. Handbook of Biochemistry and Molecular Biology V. 4; Physical and Chemical data, CRC Press: Cleveland, 1976.
22. [22]
  (22) Eisberg, R.; Resnick, R. Quantum Physics of Atoms, Molecules, Solids, Nuclei, and Particlesm, 2nd ed. JohnWiley & Sons: 1985; p 432.
23. [23]
  (23) Barron, L. D.; Buckingham, A. D. Accounts Chem. Res. 2001, 34, 785.
24. [24]
  (24) Ray, K.; Ananthavel, S. P.;Waldeck, D. H.; Naaman, R. Science 1999, 283, 814.
25. [25]
  (25) ng, Y. Ph. D. Dissertation, Peking University, Beijing, 2006.
26. [26]
  (26) Compton, R. N.; Pagni, R. M. Adv. At. Mol. Opt. Phy. 2002, 48, 219.
27. [27]
  (27) Barron, L. D. Space Sci. Rev. 2008, 135, 187.
28. [28]
  (28) Lorenzo, J. E.; Boullier, C.; Regnault, L. P.; Ammerahl, U.; Revcolevschi, A. Phys. Rev. B 2007, 75, 054418.
1. [1]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
2. [2]
  Hong Wu , Yuxi Wang , Hongyan Feng , Xiaokui Wang , Bangkun Jin , Xuan Lei , Qianghua Wu , Hongchun Li . Application of Computational Chemistry in the Determination of Magnetic Susceptibility of Metal Complexes. University Chemistry, 2025, 40(3): 116-123. doi: 10.12461/PKU.DXHX202405141
3. [3]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
4. [4]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
5. [5]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
6. [6]
  Hualin Jiang , Wenxi Ye , Huitao Zhen , Xubiao Luo , Vyacheslav Fominski , Long Ye , Pinghua Chen . Novel 3D-on-2D g-C₃N₄/AgI._x._y heterojunction photocatalyst for simultaneous and stoichiometric production of H₂ and H₂O₂ from water splitting under visible light. Chinese Chemical Letters, 2025, 36(2): 109984-. doi: 10.1016/j.cclet.2024.109984
7. [7]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . 两步焙烧法制备大比表面积和结晶性增强超薄g-C₃N₄纳米片及其高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-. doi: 10.3866/PKU.WHXB202406019
8. [8]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
9. [9]
  Li'na ZHONG , Jingling CHEN , Qinghua ZHAO . Synthesis of multi-responsive carbon quantum dots from green carbon sources for detection of iron ions and L-ascorbic acid. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 709-718. doi: 10.11862/CJIC.20240280
10. [10]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-. doi: 10.3866/PKU.WHXB202406005
11. [11]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . 熔融中间体运输导向合成富氨基g-C₃N₄纳米片用于高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-. doi: 10.3866/PKU.WHXB202406021
12. [12]
  Cailiang Yue , Nan Sun , Yixing Qiu , Linlin Zhu , Zhiling Du , Fuqiang Liu . A direct Z-scheme 0D α-Fe₂O₃/TiO₂ heterojunction for enhanced photo-Fenton activity with low H₂O₂ consumption. Chinese Chemical Letters, 2024, 35(12): 109698-. doi: 10.1016/j.cclet.2024.109698
13. [13]
  Fei Xie , Shichong Yu , Ting Wang , Yongsheng Jin , Dazhi Zhang , Yumeng Hao . Practice and Exploration of O-PIRTAS Flipped Classroom in Organic Chemistry Course. University Chemistry, 2024, 39(4): 238-243. doi: 10.3866/PKU.DXHX202310055
14. [14]
  Yubang Li , Xixi Hu , Daiqian Xie . The microscopic formation mechanism of O + H2 products from photodissociation of H2O. Chinese Journal of Structural Chemistry, 2024, 43(5): 100274-100274. doi: 10.1016/j.cjsc.2024.100274
15. [15]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(VI) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-. doi: 10.3866/PKU.WHXB202309020
16. [16]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . ZnO/D-A共轭聚合物S型异质结高效光催化产H₂O₂及其电荷转移动力学研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-. doi: 10.3866/PKU.WHXB202406027
17. [17]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
18. [18]
  Qin ZHU , Jiao MA , Zhihui QIAN , Yuxu LUO , Yujiao GUO , Mingwu XIANG , Xiaofang LIU , Ping NING , Junming GUO . Morphological evolution and electrochemical properties of cathode material LiAl_0.08Mn_1.92O₄ single crystal particles. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1549-1562. doi: 10.11862/CJIC.20240022
19. [19]
  Xin Li , Wanting Fu , Ruiqing Guan , Yue Yuan , Qinmei Zhong , Gang Yao , Sheng-Tao Yang , Liandong Jing , Song Bai . Nucleophiles promotes the decomposition of electrophilic functional groups of tetracycline in ZVI/H₂O₂ system: Efficiency and mechanism. Chinese Chemical Letters, 2024, 35(10): 109625-. doi: 10.1016/j.cclet.2024.109625
20. [20]
  Yunkang Tong , Haiqiao Huang , Haolan Li , Mingle Li , Wen Sun , Jianjun Du , Jiangli Fan , Lei Wang , Bin Liu , Xiaoqiang Chen , Xiaojun Peng . Cooperative bond scission by HRP/H₂O₂ for targeted prodrug activation. Chinese Chemical Letters, 2024, 35(12): 109663-. doi: 10.1016/j.cclet.2024.109663

Get Citation

PDF

XML

Metrics

PDF Downloads(628)
Abstract views(1848)
HTML views(9)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N+H…O- Bond in Chiral Alanine Crystal

Metrics

通讯作者: 陈斌, bchen63@163.com

Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N⁺H…O^- Bond in Chiral Alanine Crystal