BSA在不同形貌氧化锌材料上的吸附热力学

doi:10.7503/cjcu20140370

摘要/Abstract

摘要：

采用高分子模板法合成了4种不同形貌的ZnO, 分别为球状颗粒(ZnO NPs)、针状(ZnO NRs)、片状(ZnO NSs)和棒状(ZnO NBs). 利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)对产物进行了表征. 通过傅里叶变换红外光谱仪(FTIR)和圆二色光谱仪(CD)研究了小牛血清白蛋白(BSA)在不同形貌ZnO上的等温吸附规律、吸附热力学和吸附作用机理. 结果表明, 4种不同形貌的ZnO对BSA的吸附均较好地符合Langmuir等温吸附模型; 吸附量随温度的升高略有增加; 从热力学参数(ΔG, ΔH, ΔS)可知, 吸附反应为自发进行的吸热反应, 作用机理主要为氢键和静电作用. 从热力学角度, 针状的ZnO更有利于BSA的吸附.

关键词: 氧化锌, 小牛血清白蛋白, 形貌, 吸附热力学

Abstract:

Zinc oxide(ZnO) materials with four different morphologies of were synthesized by polymer template method, which were ZnO nanoparticles(ZnO NPs), ZnO nanorods(ZnO NRs), ZnO nanosheets(ZnO NSs) and ZnO nanobeams(ZnO NBs), respectively. They were characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), energy dispersive spectroscopy(EDS). Fourier transform infrared spectra(FTIR) and circular dichroism spectra(CD) were used to analyse the adsorption of bovine serum albumin(BSA) layer onto ZnO. Adsorption of BSA onto ZnO was investigated under different temperatures, and the adsorption thermodynamics and interaction mechanisms were discussed. The results indicate that the isothermal adsorption of BSA can be described by the Langmuir and modified Langmuir adsorption models. With the increase of adsorption temperature, the quantity of BSA absorbed onto ZnO increased. Thermodynamic parameters(ΔG, ΔH, ΔS) show that adsorption processes of BSA onto ZnO were endothermic(ΔH>0) and sponta-neous(ΔG<0) in nature. The adsorption behavior was controlled by electrostatic interaction and hydrogen bonding. The analysis shows that the ZnO NRs is better for BSA adsorption.

Key words: Zinc oxide(ZnO), Bovine serum albumin(BSA), Morphology, Adsorption thermodynamics

中图分类号:

O642

TrendMD:

刘小霞, 邓浩, 王妍媖, 鲁志伟, 曾宪垠, 王显祥, 邹平, 饶含兵. BSA在不同形貌氧化锌材料上的吸附热力学. 高等学校化学学报, 2014, 35(10): 2156.

LIU Xiaoxia, DENG Hao, WANG Yanying, LU Zhiwei, ZENG Xianyin, WANG Xianxiang, ZOU Ping, RAO Hanbing. Thermodynamics Studies on the BSA Adsorption onto Zinc Oxide Surfaces with Different Morphologies^†. Chem. J. Chinese Universities, 2014, 35(10): 2156.

图/表 13

Fig.1 Preparation processes for ZnO NPs, ZnO NRs, ZnO NSs and ZnO NBs

Fig.2 XRD patterns of ZnO NPs(a), ZnO NRs(b), ZnO NSs(c) and ZnO NBs(d)

Fig.3 Energy dispersive spectrum of ZnO NRs

Fig.4 SEM images of ZnO NPs(A), ZnO NRs(B), ZnO NSs(C) and ZnO NBs(D)

Fig.5 FTIR spectra of ZnO NPs(a), ZnO NRs(b), ZnO NSs(c) and ZnO NBs(d) immersed in BSA solution

Fig.6 Far-UV circular dichroism spectra(CD) of BSA in absence and in presence of ZnO a. BSA; b. BSA+ZnO NBs; c. BSA+ZnO NRs; d. BSA+ZnO NSs; e. BSA+ZnO NPs.

Fig.7 Effect of time on adsorption a. ZnO NPs; b. ZnO NBs; c. ZnO NSs; d. ZnO NRs.

Fig.8 Adsorption isotherms of BSA onto ZnO at 303 K(A) and 310 K(B) t=360 min. a. ZnO NPs; b. ZnO NBs; c. ZnO NSs; d. ZnO NRs.

Fig.9 Fitting results of Langmuir adsorption models of BSA onto ZnO at 303 K(A) and 310 K(B) and Freundlich adsorption models at 303 K(C) and 310 K(D)

Table 1 BSA adsorption isotherm equations and parameters of Langmuir and Freundlich models of ZnO

T/K	Material	Langmuir adsorption isotherm			Freundlich adsorption isotherm
T/K	Material	q_max/(μg·mg^-1)	k_a/(mL·μg^-1)	R²	1/n_F	K_F	R²
303	ZnO NRs	97.0874	0.0109	0.9733	1.6276	0.3390	0.9698
	ZnO NSs	39.3701	0.0272	0.9349	2.1993	3.5059	0.8336
	ZnO NBs	67.1741	0.0056	0.9431	1.3379	0.7571	0.9619
	ZnO NPs	41.8410	0.0083	0.9508	1.4507	0.7819	0.9619
310	ZnO NRs	94.1620	0.0177	0.9827	0.5147	5.4438	0.9511
	ZnO NSs	59.5238	0.0139	0.9545	0.5887	2.2631	0.9366
	ZnO NBs	47.2114	0.0167	0.9852	0.5313	2.5044	0.9504
	ZnO NPs	31.3479	0.0141	0.9528	0.5686	1.3143	0.9227

Fig.10 RL of different concentrations of BSA

Table 2 Thermodynamic parameters of adsorption of BSA onto ZnO at 310 K

Nano-material	ΔH/ (kJ·mol^-1)	ΔS/ (J·mol^-1·K^-1)	ΔG/ (kJ·mol^-1)
ZnO NRs	13.41	95.96	-16.34
ZnO NSs	13.83	93.83	-15.25
ZnO NBs	12.40	86.84	-14.52
ZnO NPs	9.47	74.64	-13.67

Fig.11 Thermdynamic curves of adsorption of BSA onto ZnO a. ZnO NRs, InK0=-1612.56/T+11.54; b. ZnO NSs, InK0=-1663.89/T+11.29; c. ZnO NBs, InK0=-1491.76/T+10.44; d. ZnO NPs, InK0=-1139.50/T+8.98.

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