Citation: GUO Zheng, HU Xin-Gen, LIANG Hong-Yu, JIA Zhao-Peng, CHENG Wei-Na, LIU Jia-Min. Enthalpic Pairwise Interactions of α-Aminobutyric Acid Enantiomers in DMF+Water Mixtures[J]. Acta Physico-Chimica Sinica doi: 10.3866/PKU.WHXB201206261 shu

Enthalpic Pairwise Interactions of α-Aminobutyric Acid Enantiomers in DMF+Water Mixtures

1.
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang Province, P. R. China

Received Date: 17 March 2012
Available Online: 26 June 2012
Fund Project: 国家自然科学基金(21073132)资助项目 (21073132)

Dilution enthalpies of two α-aminobutyric acid enantiomers, L-α-aminobutyric acid and D-α-aminobutyric acid, in dimethylformide (DMF)+water mixtures of various compositions are determined by isothermal titration microcalorimetry (ITC) at 298.15 K. Homotactic enthalpic pairwise interaction coefficients for each solvent composition are calculated according to the McMillan-Mayer theory of statistical thermodynamics. From the point of view of solute-solute and solute-solvent interactions, competition equilibria among hydrophobic-hydrophobic, hydrophobic-hydrophilic, and hydrophilichydrophilic interactions in ternary solutions are explored. It is found that all values of h_xx are positive across the entire studied composition range of mixed solvents (mass fraction of DMF, w_DMF=0-0.3), gradually reducing with the increasing w_DMF. It is of interest that the h_xx values for the L-enantiomer are universally larger than those of the D-enantiomer (h_LL>h_DD), which indicates that ITC is useful to discriminate homochiral enthalpic pairwise interaction of enantiomers. Our results show that hydrophobic-hydrophobic and hydrophobic-hydrophilic interactions are predominant in pairwise molecular interaction processes in ternary solutions containing α-aminobutyric acid, water, and DMF, and that the configuration of L-L molecular pair is more advantageous for the approach of hydrophobic side-chains (CH₃CH₂－) on α-carbon than a D-D pair, where part of the structured water molecules relax to less structured bulky water due to the overlap and partial breaking of hydrophobic hydration cospheres around nonpolar groups. This confirms that the process is spontaneous and is accompanied with positive enthalpy change and obvious increase in entropy (ΔG<0, ΔH>0, and ΔS=(ΔH-ΔG)/T>0), consequently releasing more heat upon dilution of the solutions and leading to larger values of h_xx.
- α-Aminobutyric acid,
- Enantiomer,
- DMF+water mixture,
- Isothermal ditration microcalorimetry,
- Dilution enthalpy,
- Enthalpic pairwise interaction,
- Chirality discrimination effect
1. [1]
  
  (1) McMillan,W. G.; Mayer, J. E. J. Chem. Phys. 1945, 13, 276.doi: 10.1063/1.1724036
2. [2]
  (2) Kozak, J. J.; Knight,W. S.; Kauzmann,W. J. Chem. Phys. 1968,48, 675. doi: 10.1063/1.1668700
3. [3]
  (3) Piekarski, H. Pure Appl. Chem. 1999, 71 (7), 1275. doi: 10.1351/pac199971071275
4. [4]
  (4) Castronuovo, G.; Elia, V.; Perez-Casas, S.; Velleca, F. J. Mol. Liq. 2000, 88 (2), 163. doi: 10.1016/S0167-7322(00)00151-3
5. [5]
  (5) Zhu, Y.; Yu, L.; Pang, X. J. Chem. Eng. Data 2009, 54 (6),1910. doi: 10.1021/je900086b
6. [6]
  (6) Palecz, B.; Dunal, J.;Waliszewski, D. J. Chem. Eng. Data 2010,55 (11), 5216. doi: 10.1021/je100756z
7. [7]
  (7) Alston, J. R.; Overson, D.; Poler, J. C. Langmuir 2012, 28 (1),264. doi: 10.1021/la203765j
8. [8]
  (8) Castronuovo, G.; Elia, V.; Moniello, V.; Velleca, F.; Perez-Casas, S. Phys. Chem. Chem. Phys. 1999, 1 (8), 1887.
9. [9]
  (9) Palecz, B. J. Am. Chem. Soc. 2002, 124 (21), 6003. doi: 10.1021/ja011937i
10. [10]
  (10) Palecz, B. J. Am. Chem. Soc. 2005, 127 (50), 17768.doi: 10.1021/ja054407l
11. [11]
  (11) Zhang, H.; Hu, X.; Shao, S. J. Chem. Eng. Data 2010, 55 (2),941. doi: 10.1021/je9005322
12. [12]
  (12) Guo, A.; Hu, X.; Fang, G.; Shao, S.; Zhang, H. J. Chem. Eng. Data 2011, 56 (5), 2489. doi: 10.1021/je101353r
13. [13]
  (13) Guo, Z.; Hu, X.; Fang, G.; Shao, S.; Guo, A.; Liang, H.Thermochim Acta 2012, 534, 51. doi: 10.1016/j.tca.2012.02.004
14. [14]
  (14) Fini, P.; Castagnolo, M. J. Therm. Anal. Calorim. 2001, 66 (1),91. doi: 10.1023/A:1012435631222
15. [15]
  (15) Borghesani, G.; Pulidori, F. Can. J. Chem. 1984, 62, 2898. doi: 10.1139/v84-490
16. [16]
  (16) Thompson, P. T.; Davis, C. B.;Wood, R. H. J. Phys. Chem.1988, 92 (22), 6386. doi: 10.1021/j100333a041
17. [17]
  (17) Gaffney, S. H.; Haslam, E.; Lilley, T. H. Thermochim. Acta1985, 86, 175. doi: 10.1016/0040-6031(85)87046-5
18. [18]
  (18) Piekarski, H. J. Chem. Soc. Faraday Trans. I 1988, 84, 591.doi: 10.1039/f19888400591
19. [19]
  (19) Bloemendal, M.; Sijpkes, A. H.; Somsen, G. J. Solut. Chem.1986, 11 (1), 81.
20. [20]
  (20) Bloemendal, M.; Somsen, G. J. Am. Chem. Soc. 1985, 107 (12),3426. doi: 10.1021/ja00298a005
21. [21]
  (21) Lei, Y.; Li, H.; Pan, H.; Han, S. J. Phys. Chem. A 2003, 107,1574.
22. [22]
  (22) Xu, Z.; Li, H.;Wang, C.; Pan, H.; Han, S. J. Chem. Phys. 2006,124, 244502. doi: 10.1063/1.2206177
23. [23]
  (23) Park, S. K.; Min, K. C.; Lee, C.; Hong, S. K.; Kim, Y.; Lee, N.S. Bull. Korean Chem. Soc. 2009, 30 (11), 2595. doi: 10.5012/bkcs.2009.30.11.2595
24. [24]
  (24) Gilli, P.; Bertolasi, V.; Ferretti, V.; Gilli, G. J. Am. Chem. Soc.1994, 116 (3), 909. doi: 10.1021/ja00082a011
25. [25]
  (25) Gallardo, M. A.; Lilley, T. H.; Linsdell, H.; Otin, S. Thermochim. Acta 1993, 223, 41. doi: 10.1016/0040-6031(93)80118-T
26. [26]
  (26) Lin, R.; Hu, X.; Ren, X. Thermochim. Acta 2000, 352-353, 31.
27. [27]
  (27) Lu, Y.; Xie,W.; Lu, J. Thermochim. Acta 2002, 385, 1.doi: 10.1016/S0040-6031(01)00700-6
28. [28]
  (28) Barone, G.; Castronuovo, G.; Vecchio, P.; Elia, V.; Puzziello, S.J. Solut. Chem. 1989, 18 (12), 1105. doi: 10.1007/BF00647267
29. [29]
  (29) Castronuovo, G.; Elia, V.; Velleca, F. J. Solut. Chem. 1995, 24 (12), 1209. doi: 10.1007/BF00972829
30. [30]
  (30) Andini, S.; Castronuovo, G.; Elia, V.; Velleca, F. J. Solut. Chem. 1995, 24 (5), 485.
31. [31]
  (31) Andini, S.; Castronuovo, G.; Elia, V.; Pignone, A.; Velleca, F.J. Solut. Chem. 1996, 25 (9), 837.
32. [32]
  (32) Smirnov, V. I.; Badelin, V. G. J. Solut. Chem. 2008, 37 (10),1419. doi: 10.1007/s10953-008-9313-z
1. [1]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, doi: 10.3866/PKU.DXHX202311034
2. [2]
  Xiaolei Jiang , Fangdong Hu . Exploring the Mirror World in Organic Chemistry: the Teaching Design of “Enantiomers” from the Perspective of Curriculum and Ideological Education. University Chemistry, doi: 10.3866/PKU.DXHX202402052
3. [3]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, doi: 10.12461/PKU.DXHX202403106
4. [4]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, doi: 10.3866/PKU.DXHX202309053
5. [5]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240379
6. [6]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, doi: 10.3866/PKU.DXHX202308113
7. [7]
  Qiuting Zhang , Fan Wu , Jin Liu , Zian Lin . Chromatographic Stationary Phase and Chiral Separation Using Frame Materials. University Chemistry, doi: 10.12461/PKU.DXHX202405174
8. [8]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB202309027
9. [9]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, doi: 10.3866/PKU.DXHX202311024
10. [10]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, doi: 10.3866/PKU.DXHX202309004
11. [11]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, doi: 10.12461/PKU.DXHX202310091
12. [12]
  Renqing Lü , Shutao Wang , Fang Wang , Guoping Shen . Computational Chemistry Aided Organic Chemistry Teaching: A Case of Comparison of Basicity and Stability of Diazine Isomers. University Chemistry, doi: 10.12461/PKU.DXHX202404119
13. [13]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240265
14. [14]
  Jiahao Lu , Xin Ming , Yingjun Liu , Yuanyuan Hao , Peijuan Zhang , Songhan Shi , Yi Mao , Yue Yu , Shengying Cai , Zhen Xu , Chao Gao . 基于稳态电热法的石墨烯膜导热系数的精确可靠测量. Acta Physico-Chimica Sinica, doi: 10.1016/j.actphy.2025.100045
15. [15]
  Yongqing Kuang , Jie Liu , Jianjun Feng , Wen Yang , Shuanglian Cai , Ling Shi . Experimental Design for the Two-Step Synthesis of Paracetamol from 4-Hydroxyacetophenone. University Chemistry, doi: 10.12461/PKU.DXHX202403012
16. [16]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, doi: 10.3866/PKU.DXHX202311011
17. [17]
  Hui Shi , Shuangyan Huan , Yuzhi Wang . Ideological and Political Design of Potassium Permanganate Oxidation-Reduction Titration Experiment. University Chemistry, doi: 10.3866/PKU.DXHX202308042
18. [18]
  Tiejun Su . The Construction and Application of the Calculation Formula for Endpoint Error in Precipitation Titration: A Case Study of the Mohr Method. University Chemistry, doi: 10.12461/PKU.DXHX202402039
19. [19]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20230431
20. [20]
  Hong CAI , Jiewen WU , Jingyun LI , Lixian CHEN , Siqi XIAO , Dan LI . Synthesis of a zinc-cobalt bimetallic adenine metal-organic framework for the recognition of sulfur-containing amino acids. Chinese Journal of Inorganic Chemistry, doi: 10.11862/CJIC.20240382

Get Citation

PDF

XML

Metrics

PDF Downloads(871)
Abstract views(2028)
HTML views(11)

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