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应用小角X射线散射技术(SAXS)对两亲嵌段共聚物聚苯乙烯聚丙烯酸(PS-b-PAA)胶束形貌的温度影响进行了原位表征.SAXS结果表明:随着水含量的增加,粒子尺寸相应增加;对于水含量10%的PS3000-b-PAA5000胶束溶液,发现了明显的SAXS双峰现象;双峰的位置不随着温度的变化而改变,但是peak 1和peak 2的相对强度随着温度发生了减弱和增强的交错变化;相邻的SAXS双峰说明在PS3000-b-PAA5000胶束溶液中最初形成的粒子尺寸并不是均匀的,主要分为尺寸极其相近的两种球形粒子;随着温度的升高,粒径大小不同的两种粒子存在着一种消融和生长的过程,并且保持着一个相同的归一化动态平衡速率.Amphiphilic block copolymer has a character that it spontaneously self-assembles into various micellar morphologies when dissolved in selective solvents with different proportions. Amphiphilic block copolymer has wide potential applications in drug delivery such as the targeting delivery, controlled release, molecular recognition, etc. Poly (styrene)-block-poly (acrylic acid) (PS-b-PAA) is a representative amphiphilic block copolymer whose self-assembly in the selective solvents has been widely studied during the past years. Micellar morphology of PS-b-PAA sensitive to temperature, and temperature effect of PS-b-PAA are of great importance for the drug delivery. However, the micellar morphologies of PS-b-PAA have been investigated mainly at the room temperature so far. The understanding is still limited to micellar morphology of PS-b-PAA in the varying temperature processes. In the present work, an investigation of the relationship between micellar morphology of PS-b-PAA and the temperature is conducted by using in-situ small-angle X-ray scattering (in-situ SAXS). The SAXS experiments are performed on the BL19U2 beamline of Shanghai Synchrotron Radiation Facility. The energy is selected to be 10 keV and the wave length is 0.1033 nm. The two-dimensional (2D) SAXS patterns are recorded by Pilatus 1 M with a pixel size of 172 m172 m. A sample-to-detector distance of 5340 mm is chosen, giving access to a range of scattering vectors q of 0.11-0.89 nm-1. The temperatures of the specimens are monitored by using a Linkam thermal stage THMS600 (Linkam Scientific Instruments). One-dimensional (1D) integrated intensity curves are obtained from the 2D SAXS patterns by employing the Fit2D software. The PS-b-PAAs (PS:PAA=3000:5000) is purchased from Sigma-Aldrich Inc and used directly (without any treatment prior to experiment). The PS-b-PAA is dissolved in solvents of N, N-Dimethylformamide and H2O with various proportions. The concentration of solution of PS-b-PAA is 10 mg/mL. The experiments show that the sizes of micelle particles in PS3000-b-PAA5000 solution are grown with water content increasing, and double scattering peaks (qpeak1=0.418 nm-1, qpeak1=0.456 nm-1) appear for the solution with 10% water. A temperature-dependent change of SAXS intensity is demonstrated by in-situ SAXS. The intensities of peak 1 and peak 2 vary in a contrary waywith the sample's warming up, but the positions of the peaks are independent of temperature. The double peaks in SAXS profiles suggest that the size of micelle particles in the solution is not homogeneous but the micelles with two close sizes coexist. It is interesting that the number of two-sized particles changes at the same rate in the heating process although there is a significant difference between the initial number and the final number of micelles.
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Keywords:
- block copolymer /
- small angle X-ray scattering /
- temperature effect /
- synchrotron
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[1] Kataoka K, Harada A, Nagasaki Y 2001 Adv. Drug Deliv. Rev. 47 113
[2] Gaucher G, Dufresne M H, Sant V P, et al. 2005 J. Control. Release 109 169
[3] Allen C, Maysinger D, Eisenberg A 1999 Colloid. Surface. B 16 3
[4] Bates C M, Maher M J, Janes D W, et al. 2014 Macromolecules 47 2
[5] Park M, Harrison C, Chaikin P M, et al. 1997 Science 276 1401
[6] Peng Q, Tseng Y C, Darling S B, et al. 2010 Adv. Mater. 22 5129
[7] Phillip W A, O'neill B, Rodwogin M, et al. 2010 ACS Appl. Mater. Inter. 2 847
[8] Yang S Y, Park J, Yoon J, et al. 2008 Adv. Fun. Mater. 18 1371
[9] Cameron N S, Corbierre M K, Eisenberg A 1999 Can. J. Chem. 77 1311
[10] Lee A S, Gast A P, Btn V, et al. 1999 Macromolecules 32 4302
[11] Shim W S, Yoo J S, Bae Y H, et al. 2005 Biomacromolecules 6 2930
[12] Zhang L, Yu K, Eisenberg A 1996 Science 272 1777
[13] Alexandridis P, Olsson U, Lindman B 1998 Langmuir 14 2627
[14] Gao Z, Varshney S K, Wong S, et al. 1994 Macromolecules 27 7923
[15] Pang X, Zhao L, Akinc M, et al. 2011 Macromolecules 44 3746
[16] Choucair A, Eisenberg A 2003 Eur. Phys. J. E 10 37
[17] Zhang L, Eisenberg A 1996 J. Am. Chem. Soc. 118 3168
[18] Ivanova R, Lindman B, Alexandridis P 2000 Langmuir 16 9058
[19] Wang F, Bronich T K, Kabanov A V, et al. 2005 Bioconjugate Chem. 16 397
[20] He C, Kim S W, Lee D S 2008 J. Control. Release 127 189
[21] Shen H, Zhang L, Eisenberg A 1997 J. Phys. Chem. B 101 4697
[22] Shen H, Eisenberg A 2000 Macromolecules 33 2561
[23] Yue L, Zhang X H, Wu S K 2004 Acta Poly. Sin. 1 236 (in Chinese)[岳玲, 张晓宏, 吴世康 2004 高分子学报 1 236]
[24] Lu D Y, Wen H, Liu H Z, Xu Z H 2004 Acta Phys. Chim. Sin. 20 38 (in Chinese)[陆冬云, 温浩, 刘会洲, 许志宏 2004 物理化学学报 20 38]
[25] Li Y W, Bian F G, Hong C X, et al. 2015 Atom. Energ. Sci. Technol. 49 1914 (in Chinese)[李怡雯, 边风刚, 洪春霞, 等 2015 原子能科学技术 49 1914]
[26] Fedorova I S, Schmidt P W 1978 J. Appl. Crystallogr. 11 405
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