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
References
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]
  
  (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
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沈阳化工大学材料科学与工程学院沈阳 110142

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

References

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通讯作者: 陈斌, bchen63@163.com