Foams of Supramolecular Network Constructed by Poly(calixarene-piperazine) Amide and 2,2'-Bipyridine†

doi:10.7503/cjcu20180131

Abstract

Abstract:

Calixarene derivative, 5,11,17,23-tetra-tert-butyl-25,27-di(chloroacetyloxy)-26,28-dihydroxycalix[4]arene(DC), was used as organic phase monomer to prepare poly(calixarene-piperazine)amide(D) through interfacial polymerization with piperazine aqueous solution. Compound D showed induced self-assembly actions under different factors. It could self-associate into double distribution vesicles of average diameter of 28 and 164 nm, respectively. 2,2'-bipyridine(bpy) crosslinked D into supermolecular network. H₂O turned network into foams at the interface of water-ethyl acetate. Foams are large-scale structure constructed by D and bpy and H₂O droven by weak intermolecular interaction including π-π staking, hydrophobic-hydrophobic interaction and interfacial effect. This work provide a new material for large scale supermolecular building and stimuli-responsive function.

Key words: Induced self-assembly, Poly(calixarene-piperazine)amide, 2,2'-Bipyridine, Supermolecular network

CLC Number:

O631.4

TrendMD:

MIAO Ruixiang,LIU Dongqing,REN Shun,ZHU Zexian,CHEN Yingbo,ZHANG Yufeng. Foams of Supramolecular Network Constructed by Poly(calixarene-piperazine) Amide and 2,2'-Bipyridine^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2327.

Figures/Tables 9

Table 1 GPC data of compound D

Sample	M_n	M_w	M_z	M_w/M_n
D_NS	11994	14708	17770	1.226
D_S	136762	5.60×e³⁴	—	—

Fig.1 FTIR(A), 1H NMR(B) spectra and TG(C) and DSC(D) curves of DNS

Fig.2 Tyndall effect(A), PDI-concentration curve(B), DLS curve(C), Abs-λ curves(D) and Abs-concentration curve(E) of self-assembly of compound D in ethyl acetateConcentration of DNS/(μmol·L-1): a. 2.21; b. 11; c. 55.4; d. 110.8; e. 227; f. 554; g. 831; h. 1108; i. 1385; j. 1663; k. 2210; l. 2480.

Fig.3 TEM image(A) and different magnification high resolution TEM images[(B) and (C)] of 2210 μmol/L DNS in ethyl acetate solution

Scheme 1 Self-assembly of compound D of different configuaration of calix[4]arene(A) D with calix[4]arene unit as cone conformation; (B) as partial cone conformation; (C) stereoscopic model of D in solution; (D) crossection of D with calix[4]arene unit as cone conformation; (E) crossection of D with calix[4]arene unit as of partial cone conformation; (F) aggregates crossection of D of cone calix[4]arene; (G) aggregates crossection of D of partial cone calix[4]arene.

Fig.4 Fluorescence curves of different n(bpy)/n[(D+bpy](A), JOB’s plot in fluorescence curve(B), Abs-λ curves of different amount of bpy(C) and absorbance at 295 nm in Abs-λ curve(D)(A)n(bpy)/n[(D+bpy)]: a. 0; b. 0.05; c. 0.1; d. 0.15; e. 0.2; f. 0.25; g. 0.275; h. 0.3; i. 0.325; j. 0.35; k. 0.375; l. 0.4; m. 0.425; n. 0.45; o. 0.475; p. 0.5; q. 0.55; r. 0.6; s. 0.65; t. 0.7; u. 0.75; v. 0.8; w. 0.85; x. 0.9; y. 0.95; z. 1.

Fig.5 TEM images of 1.1 mmol/L D EtOAc sotution with different amount of bpy(A—D), photo(E) and TEM image(F) of foams at intersurface between D EtOAc solution and bpy aqueous solutionn(bpy)/n(D): (A) 0; (B) 0.1; (C) 0.67; (D) 1.

Scheme 2 Crosslink of compound D of different configuaration of calix[4] arene by bpy(A) D with calix[4]arene unit as cone conformation; (B) D with calix[4]arene unitas partial cone conformation.

Fig.6 XPS sprctra of dried foams D(A), N1s of D(B), D+bpy(C) and N1s of D+bpy(D)

References 25

[1]	Wang H.C., Grolman J. M., Rizvi A., Hisao G. S., Rienstra C. M., Zimmerman S. C., ACS Macro. Lett., 2017, 6, 321—325
[2]	Tevis I.D., Palmer L. C., Herman D. J., Murray I. P., Stone D. A., Stupp S. I., J. Am. Chem. Soc., 2011, 133, 16486—16494
[3]	Saravanan V., Kannan A., Rajakumar P., Sensor Actuator B-Chem., 2017, 242, 904—911
[4]	Shetty D., Skorjanc T., Raya J., Sharma S.K., Jahovic I., Polychronopoulou K., Asfari Z., Han D. S., Dewage S., Olsen J. C., Jagannathan R., Kirmizialtin S., Trabolsi A., ACS Appl. Mater. Inter., 2018, 10(20), 17359—17365
[5]	Castellano R.K., Rudkevich D. M., Rebek J., Proc. Natl. Acad. Sci.USA, 1997, 94(14), 7132—7137
[6]	Castellano R.K., Nuckolls C., Eichhorn S. H., Wood M. R., Lovinger A. J., Rebek J., Angew. Chem. Int. Ed., 1999, 38(17), 2603—2606
[7]	Bai Y.P., Huang L., Huang T., Long J., Zhou Y. F., Polymer, 2013, 54(16), 4171—4176
[8]	Huang L., Yu C.Y., Huang T., Xu S., Bai Y., Zhou Y. F., Nanoscale, 2016, 8(9), 4922—4926
[9]	Huang L., Huang T., Bai Y.P., Zhou Y. F., Acta Chim.Sinica, 2016, 74(12), 990—994
	(黄磊, 黄通, 白永平, 周永丰. 化学学报, 2016, 74(12), 990—994)
[10]	Stempfle F., Ortmann P., Mecking S., Chem. Rev., 2016, 116(7), 4597—4641
[11]	Wang X.X., Zeng F. Y., Jin C., Jiang Y. L., Han Q. R., Wang B. X., Ma Z. Y., Polym. Chem., 2015, 6(7), 1044—1051
[12]	Li Y.F., Niu Y. L., Hu D., Song Y. W., He J. W., Liu X. Y., Xia X. N., Lu Y. B., Xu W. J., Macromol. Chem. Phys., 2014, 216(1), 77—84
[13]	Hao W., Shao Z.Z., Acta. Chim.Sinica, 2014, 72(9), 1023—1028
	(郝威, 邵正中. 化学学报, 2014, 72(9), 1023—1028)
[14]	Yang Y.A., Feng W., Hu J. C., Zou S. L., Gao R. Z., Yamato K., Kline M., Cai Z. H., Gao Y., Wang Y. B., Li Y. B., Yang Y. L., Yuan L. H., Zeng X. C., Gong B., J. Am. Chem. Soc., 2011, 133, 18590—18593
[15]	Hu J.C., Chen L., Ren Y., Deng P. C., Li X. W., Wang Y. J., Jia Y. M., Luo J., Yang X. S., Feng W., Yuan L. H., Org. Lett., 2013, 15(18), 4670—4673
[16]	Eom G.H, Park H. M., Hyun Y. H., Jang S. P., Kim C., Li J. H., Li S. J., Kim S. J., Kim Y., Polyhedron, 2011, 30(9), 1555—1564
[17]	Burrows A.D., Frost C. G., Kandiah M., Keenan L. L., Mahon M. F., Savarese T. L., Warren J. E., Inorg. Chim.Acta, 2011, 366(1), 303—309
[18]	Peng Z.H., Cai P., Fang C. J., Guo W. Y., Deng K. J., Zhou Y. H., Chem. J. Chinese Universities, 2003, 24(5), 765—771
	(彭正合, 蔡苹, 房晨婕, 郭文勇, 邓克俭, 周运鸿. 高等学校化学学报, 2003, 24(5), 765—771)
[19]	Hogberg A.G. S., J. Am. Chem. Soc., 1980, 102(19), 6046—6050
[20]	King A.M., Moore C. P., Sandanayake K. R. A. S., Sutherland I. O., J. Chem. Soc. Chem. Commun., 1992, 7(7), 582—584
[21]	Gutsche C.D., Lin L. G., Tetrahedron, 1986, 42(6), 1633—1640
[22]	Tu C.L., Zheng C., Chen Y., Shu M. H., Chem. J. Chinese Universities, 2007, 28(10), 1917—1919
	(屠春来, 郑超, 陈燕, 舒谋海. 高等学校化学学报, 2007, 28(10), 1917—1919)
[23]	He X.D., Ge X. W., Liu H. R., Wang A. M., Zhang Z. C., Chem. Mater., 2005, 17(24), 5891—5892
[24]	Li C.M., Tan J. J., Liu Y. L., Zhang B. L., Fan X. L., Zhang Q. Y., Colloid Polym. Sci., 2015, 293(3), 993—1001
[25]	Yu S., Ahmadi S., Palmgren P., Hennies F., Zuleta M., Gothelid M., J. Phys. Chem. C, 2009, 113(31), 13765—13771