大环疏水效应: 冠醚在DMF+H<sub>2</sub>O混合物中的焓对作用

引用本文: 程维娜, 胡新根, 邵爽. 大环疏水效应: 冠醚在DMF+H₂O混合物中的焓对作用[J]. 物理化学学报, 2013, 29(10): 2114-2122. doi: 10.3866/PKU.WHXB201305103 shu

Citation: CHENG Wei-Na, HU Xin-Gen, SHAO Shuang. Macrocyclic Hydrophobic Effect：Enthalpic Pairwise Interactions of Crown Ethers in Mixtures of DMF and Water[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2114-2122. doi: 10.3866/PKU.WHXB201305103 shu

大环疏水效应: 冠醚在DMF+H₂O混合物中的焓对作用

基金项目:
国家自然科学基金(21073132)资助项目 (21073132)

摘要:

利用等温滴定微量热法测定了298.15 K时12-冠-4、15-冠-5、18-冠-6和4,13-二氮杂-18-冠-6四种冠醚在纯水及不同质量分数(w=0-0.3)的N,N-二甲基甲酰胺(DMF)+H₂O混合物中的稀释焓, 根据McMillan-Mayer理论计算得到相应的焓对作用系数(h_xx). 实验发现, h_xx均为较大的正值, 表明在冠醚-冠醚自相互作用中疏水性成分占绝对优势, 主要表现为两种机制: (1) 当疏水-疏水作用发生时, 共球交盖使得水结构形成减少, 对h_xx有正的贡献; (2) 当疏水-亲水作用发生时, 共球交盖使得水结构破坏增加, 对h_xx有正的贡献. 此外, 四种冠醚h_xx的大小关系为: h_xx(18-冠-6)>h_xx(4,13-二氮杂-18-冠-6)≈h_xx(15-冠-5)>h_xx(12-冠-4), 表明冠醚环越大, 疏水-疏水作用越强, 存在显著的大环疏水效应.

关键词:

English

Macrocyclic Hydrophobic Effect：Enthalpic Pairwise Interactions of Crown Ethers in Mixtures of DMF and Water

1.
1 College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, Zhejiang Province, P. R. China;
2 Department of Chemistry, Zhejiang International Studies University, Hangzhou 310012, P. R. China
Received Date: 26 March 2013
Available Online: 26 September 2013
Fund Project:
国家自然科学基金(21073132)资助项目

Abstract:

The dilution enthalpies of four crown ethers, namely 12-crown-4, 15-crown-5, 18-crown-6, and 4,13-diaza-18-crown-6, in pure water and mixtures of N,N-dimethylformamide (DMF) and water of various mass fraction (w=0-0.3) were determined at 298.15 K by isothermal titration microcalorimetry. The corresponding enthalpic pairwise interaction coefficients (h_xx) were evaluated according to the McMillan-Mayer theory. Values of h_xx were all positive and large, which indicates that hydrophobic components predominate in crown-crown self-interactions. There are two main kinds of mechanisms: (1) When hydrophobic-hydrophobic interactions occur, cosphere overlapping reduces the formation of water structure, which makes a positive contribution to h_xx. (2) Hydrophobic-hydrophilic interactions increasingly destroy the water structure because of cosphere overlapping, which also makes a positive contribution to h_xx. In addition, h_xx values of the four crown ethers follow the order: h_xx(18-crown-6)>h_xx(4,13-diaza-18-crown-6)≈ h_xx(15-crown-5) >h_xx(12-crown-4), which indicates that the larger the size of the crown ether ring, the stronger the hydrophobic-hydrophobic interaction; namely, that crown ethers are subject to macrocyclic hydrophobic effects.

Key words:

1. [1]
  
  (1) Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 2495. doi: 10.1021/ja00986a052
  (1) Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 2495. doi: 10.1021/ja00986a052
2. [2]
  (2) Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 7017. doi: 10.1021/ja01002a035(2) Pedersen, C. J. J. Am. Chem. Soc. 1967, 89, 7017. doi: 10.1021/ja01002a035
3. [3]
  (3) kel, G. W.; Leevy, W. M.; Weber, M. E. Chem. Rev. 2004,104, 2723. doi: 10.1021/cr020080k(3) kel, G. W.; Leevy, W. M.; Weber, M. E. Chem. Rev. 2004,104, 2723. doi: 10.1021/cr020080k
4. [4]
  (4) Mathias, L. J. J. Macromol. Sci.-Chem. 1981, A15, 853.(4) Mathias, L. J. J. Macromol. Sci.-Chem. 1981, A15, 853.
5. [5]
  (5) Chen, H. C.; Chen, S. H. J. Phys. Chem. 1984, 88, 5118. doi: 10.1021/j150665a063(5) Chen, H. C.; Chen, S. H. J. Phys. Chem. 1984, 88, 5118. doi: 10.1021/j150665a063
6. [6]
  (6) Hu, X. L.; Bausch, C. C.; Johnson, J. S. J. Am. Chem. Soc.2005, 127, 1833. doi: 10.1021/ja044086y(6) Hu, X. L.; Bausch, C. C.; Johnson, J. S. J. Am. Chem. Soc.2005, 127, 1833. doi: 10.1021/ja044086y
7. [7]
  (7) Liu, Y. K.; Li, R.; Yue, L.; Li, B. J.; Chen, Y. C.; Wu, Y.; Ding,L. S. Org. Lett. 2006, 8, 1521. doi: 10.1021/ol0529905(7) Liu, Y. K.; Li, R.; Yue, L.; Li, B. J.; Chen, Y. C.; Wu, Y.; Ding,L. S. Org. Lett. 2006, 8, 1521. doi: 10.1021/ol0529905
8. [8]
  (8) France, S.; Wack, H.; Taggi, A. E.; Hafez, A. M.; Wagerle, T. R.;Shah, M. H.; Dusich, C. L.; Lectka, T. J. Am. Chem. Soc. 2004,126, 4245. doi: 10.1021/ja039046t(8) France, S.; Wack, H.; Taggi, A. E.; Hafez, A. M.; Wagerle, T. R.;Shah, M. H.; Dusich, C. L.; Lectka, T. J. Am. Chem. Soc. 2004,126, 4245. doi: 10.1021/ja039046t
9. [9]
  (9) Naumowicz, M.; Petelska, A. D.; Figaszewski, Z. A. Cell Mol. Biol. Lett. 2003, 8, 383.(9) Naumowicz, M.; Petelska, A. D.; Figaszewski, Z. A. Cell Mol. Biol. Lett. 2003, 8, 383.
10. [10]
  (10) Thompson, R. A.; Ge, Z.; Grinberg, N.; Ellison, D.; Tway, P.Anal. Chem. 1995, 67, 1580. doi: 10.1021/ac00105a017(10) Thompson, R. A.; Ge, Z.; Grinberg, N.; Ellison, D.; Tway, P.Anal. Chem. 1995, 67, 1580. doi: 10.1021/ac00105a017
11. [11]
  (11) Schneider, H. J.; Yatsimirsky, A. K. Chem. Soc. Rev. 2008, 37,263. doi: 10.1039/b612543n(11) Schneider, H. J.; Yatsimirsky, A. K. Chem. Soc. Rev. 2008, 37,263. doi: 10.1039/b612543n
12. [12]
  (12) Kulikov, O. V.; Zielenkiewicz, W.; Krestov, G. A. Thermochim. Acta 1994, 241 (1-2), 1.(12) Kulikov, O. V.; Zielenkiewicz, W.; Krestov, G. A. Thermochim. Acta 1994, 241 (1-2), 1.
13. [13]
  (13) Kulikov, O. V.; Krestov, G. A.; Zielenkiewicz, W. E. J. Solut. Chem. 1995, 24, 1155. doi: 10.1007/BF00972962(13) Kulikov, O. V.; Krestov, G. A.; Zielenkiewicz, W. E. J. Solut. Chem. 1995, 24, 1155. doi: 10.1007/BF00972962
14. [14]
  (14) Jó?wiak, M.; Kosiorowska, M. A.; Wasiak, M. J. Chem. Eng. Data 2010, 55, 5138. doi: 10.1021/je100700z(14) Jó?wiak, M.; Kosiorowska, M. A.; Wasiak, M. J. Chem. Eng. Data 2010, 55, 5138. doi: 10.1021/je100700z
15. [15]
  (15) Guo, Z.; Hu, X. G.; Liang, H. Y.; Jia, Z. P.; Cheng, W. N.; Liu, J.M. Acta Phys. -Chim. Sin. 2012, 28, 2015. [郭政,胡新根,梁红玉, 贾召鹏, 程维娜,刘嘉敏. 物理化学学报, 2012, 28,2015.] doi: 10.3866/PKU.WHXB201206261(15) Guo, Z.; Hu, X. G.; Liang, H. Y.; Jia, Z. P.; Cheng, W. N.; Liu, J.M. Acta Phys. -Chim. Sin. 2012, 28, 2015. [郭政,胡新根,梁红玉, 贾召鹏, 程维娜,刘嘉敏. 物理化学学报, 2012, 28,2015.] doi: 10.3866/PKU.WHXB201206261
16. [16]
  (16) Wasada, H.; Tsutsui, Y.; Yamabe, S. J. Phys. Chem. 1996, 100,7367. doi: 10.1021/jp951840g(16) Wasada, H.; Tsutsui, Y.; Yamabe, S. J. Phys. Chem. 1996, 100,7367. doi: 10.1021/jp951840g
17. [17]
  (17) Kleinpeter, E.; Gäbler, M.; Schroth, W. Magn. Reson. Chem.1988, 26, 380.(17) Kleinpeter, E.; Gäbler, M.; Schroth, W. Magn. Reson. Chem.1988, 26, 380.
18. [18]
  (18) Desnoyers, J. E.; Arel, M.; Perron, G.; Jolicoeur, C. J. Phys. Chem. 1969, 73, 3346. doi: 10.1021/j100844a032(18) Desnoyers, J. E.; Arel, M.; Perron, G.; Jolicoeur, C. J. Phys. Chem. 1969, 73, 3346. doi: 10.1021/j100844a032
19. [19]
  (19) Visser, C. D.; Perron, G.; Desnoyers, J. E. J. Am. Chem. Soc.1977, 99, 5894. doi: 10.1021/ja00460a009(19) Visser, C. D.; Perron, G.; Desnoyers, J. E. J. Am. Chem. Soc.1977, 99, 5894. doi: 10.1021/ja00460a009
20. [20]
  (20) Friedman, H. L.; Krishnan, C. V. J. Solut. Chem. 1973, 2, 119.doi: 10.1007/BF00651969(20) Friedman, H. L.; Krishnan, C. V. J. Solut. Chem. 1973, 2, 119.doi: 10.1007/BF00651969
21. [21]
  (21) Buschmann, H. J.; Mutihac, R. C.; Schollmeyer, E. J. Solut. Chem. 2010, 39, 291. doi: 10.1007/s10953-010-9499-8(21) Buschmann, H. J.; Mutihac, R. C.; Schollmeyer, E. J. Solut. Chem. 2010, 39, 291. doi: 10.1007/s10953-010-9499-8
22. [22]
  (22) Mishustin, A. I.; Kessler, Y. M. J. Struct. Chem. 1974, 15, 191.doi: 10.1007/BF00746555(22) Mishustin, A. I.; Kessler, Y. M. J. Struct. Chem. 1974, 15, 191.doi: 10.1007/BF00746555
23. [23]
  (23) Lei, Y.; Li, H.; Pan, H.; Han, S. J. Phys. Chem. A 2003, 107,1574. doi: 10.1021/jp026638+(23) Lei, Y.; Li, H.; Pan, H.; Han, S. J. Phys. Chem. A 2003, 107,1574. doi: 10.1021/jp026638+
24. [24]
  (24) Jia, G. Z.; Huang, K. M.; Yang, L. J.; Yang, X. Q. Int. J. Mol. Sci. 2009, 10, 1590. doi: 10.3390/ijms10041590(24) Jia, G. Z.; Huang, K. M.; Yang, L. J.; Yang, X. Q. Int. J. Mol. Sci. 2009, 10, 1590. doi: 10.3390/ijms10041590
25. [25]
  (25) Takamuku, T.; Shimomura, T.; Tachikawa, M.; Kanzaki, R.Phys. Chem. Chem. Phys. 2011, 13, 11222. doi: 10.1039/c0cp00338g(25) Takamuku, T.; Shimomura, T.; Tachikawa, M.; Kanzaki, R.Phys. Chem. Chem. Phys. 2011, 13, 11222. doi: 10.1039/c0cp00338g
26. [26]
  (26) Yang, J.; Tang, Z. H.; Wu, D. Y.; Li, Z. R.; Tian, A. M.; Yan, G.S. Acta Phys. -Chim. Sin. 1995, 11, 1008. [杨捷,唐作华,吴德印,李泽荣, 田安民, 鄢国森. 物理化学学报, 1995, 11,1008.] doi: 10.3866/PKU.WHXB19951110(26) Yang, J.; Tang, Z. H.; Wu, D. Y.; Li, Z. R.; Tian, A. M.; Yan, G.S. Acta Phys. -Chim. Sin. 1995, 11, 1008. [杨捷,唐作华,吴德印,李泽荣, 田安民, 鄢国森. 物理化学学报, 1995, 11,1008.] doi: 10.3866/PKU.WHXB19951110
27. [27]
  (27) Vedernikov, A. I.; Dmitrieva, S. N.; Kuz'mina, L. G.;Kurchavov, N. A.; Strelenko, Y. A.; Howard, J. A. K.; Gromov,S. P. Russ. Chem. Bull. 2009, 58, 978. doi: 10.1007/s11172-009-0127-y
  (27) Vedernikov, A. I.; Dmitrieva, S. N.; Kuz'mina, L. G.;Kurchavov, N. A.; Strelenko, Y. A.; Howard, J. A. K.; Gromov,S. P. Russ. Chem. Bull. 2009, 58, 978. doi: 10.1007/s11172-009-0127-y

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大环疏水效应: 冠醚在DMF+H₂O混合物中的焓对作用

English

Macrocyclic Hydrophobic Effect：Enthalpic Pairwise Interactions of Crown Ethers in Mixtures of DMF and Water

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