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

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: 10 May 2013
Fund Project: 国家自然科学基金(21073132)资助项目 (21073132)

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.
1. [1]
  
  (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
3. [3]
  (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.
5. [5]
  (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
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
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
9. [9]
  (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
11. [11]
  (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.
13. [13]
  (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
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
16. [16]
  (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.
18. [18]
  (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
20. [20]
  (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
22. [22]
  (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+
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
25. [25]
  (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
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
1. [1]
  .
  南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积
  . CCS Chemistry, 2025, 7(0): -.
2. [2]
  Keweiyang Zhang , Zihan Fan , Liyuan Xiao , Haitao Long , Jing Jing . Unveiling Crystal Field Theory: Preparation, Characterization, and Performance Assessment of Nickel Macrocyclic Complexes. University Chemistry, 2024, 39(5): 163-171. doi: 10.3866/PKU.DXHX202310084
3. [3]
  Limin Shao , Na Li . A Unified Equation Derived from the Charge Balance Equation for Constructing Acid-Base Titration Curve and Calculating Endpoint Error. University Chemistry, 2024, 39(11): 365-373. doi: 10.3866/PKU.DXHX202401086
4. [4]
  Xiyuan Su , Zhenlin Hu , Ye Fan , Xianyuan Liu , Xianyong Lu . Change as You Want: Multi-Responsive Superhydrophobic Intelligent Actuation Material. University Chemistry, 2024, 39(5): 228-237. doi: 10.3866/PKU.DXHX202311059
5. [5]
  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, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
6. [6]
  Cunming Yu , Dongliang Tian , Jing Chen , Qinglin Yang , Kesong Liu , Lei Jiang . Chemistry “101 Program” Synthetic Chemistry Experiment Course Construction: Synthesis and Properties of Bioinspired Superhydrophobic Functional Materials. University Chemistry, 2024, 39(10): 101-106. doi: 10.12461/PKU.DXHX202408008
7. [7]
  Zhongxin YU , Wei SONG , Yang LIU , Yuxue DING , Fanhao MENG , Shuju WANG , Lixin YOU . Fluorescence sensing on chlortetracycline of a Zn-coordination polymer based on mixed ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2415-2421. doi: 10.11862/CJIC.20240304
8. [8]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
9. [9]
  Hong Zheng , Xin Peng , Chunwang Yi . The Tale of Caprolactam Cyclic Oligomers: The Ever-changing Life of “Princess Cyclo”. University Chemistry, 2024, 39(9): 40-47. doi: 10.12461/PKU.DXHX202403058
10. [10]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
11. [11]
  Xinyu ZENG , Guhua TANG , Jianming OUYANG . Inhibitory effect of Desmodium styracifolium polysaccharides with different content of carboxyl groups on the growth, aggregation and cell adhesion of calcium oxalate crystals. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1563-1576. doi: 10.11862/CJIC.20230374
12. [12]
  Qiuyang LUO , Xiaoning TANG , Shu XIA , Junnan LIU , Xingfu YANG , Jie LEI . Application of a densely hydrophobic copper metal layer in-situ prepared with organic solvents for protecting zinc anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1243-1253. doi: 10.11862/CJIC.20240110
13. [13]
  Yangrui Xu , Yewei Ren , Xinlin Liu , Hongping Li , Ziyang Lu . 具有高传质和亲和表面的NH₂-UIO-66基疏水多孔液体用于增强CO₂光还原. Acta Physico-Chimica Sinica, 2024, 40(11): 2403032-. doi: 10.3866/PKU.WHXB202403032
14. [14]
  Chunai Dai , Yongsheng Han , Luting Yan , Zhen Li , Yingze Cao . Preparation of Superhydrophobic Surfaces and Their Application in Oily Wastewater Treatment: Design of a Comprehensive Physical Chemistry Innovation Experiment. University Chemistry, 2024, 39(2): 34-40. doi: 10.3866/PKU.DXHX202307081
15. [15]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . 软模板法诱导Cu/Al₂O₃深孔道结构促进等离子催化CO₂加氢制二甲醚. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054
16. [16]
  Hui Shi , Shuangyan Huan , Yuzhi Wang . Ideological and Political Design of Potassium Permanganate Oxidation-Reduction Titration Experiment. University Chemistry, 2024, 39(2): 175-180. doi: 10.3866/PKU.DXHX202308042
17. [17]
  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, 2024, 39(11): 384-387. doi: 10.12461/PKU.DXHX202402039
18. [18]
  Changqing MIAO , Fengjiao CHEN , Wenyu LI , Shujie WEI , Yuqing YAO , Keyi WANG , Ni WANG , Xiaoyan XIN , Ming FANG . Crystal structures, DNA action, and antibacterial activities of three tetranuclear lanthanide-based complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2455-2465. doi: 10.11862/CJIC.20240192
19. [19]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
20. [20]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191

Get Citation

PDF

XML

Metrics

PDF Downloads(471)
Abstract views(861)
HTML views(14)

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

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

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

Metrics

通讯作者: 陈斌, bchen63@163.com