金属卟啉-Sn网络可控非共价功能化碳纳米管的制备及蛋白吸附应用

doi:10.6023/A21100475

摘要/Abstract

本工作通过简便的一锅溶剂热法, 发展一种卟啉一步金属化且与Sn桥连形成的配合物网络非共价功能化的多壁碳纳米管复合材料(MMPT), 以增强对蛋白质的吸附. 在溶剂热条件下, Sn进入中位-四(4-羧基苯基)卟吩(TCPP)大环使卟啉金属化形成SnTCPP, 同时Sn作为交联剂桥连多壁碳纳米管(MWCNTs)表面的SnTCPP分子, 通过配位自组装形成均匀连续的SnTCPP-Sn网络壳层, 而无需对TCPP和/或MWCNTs进行任何的修饰. 在这种合成策略下, 通过调整MWCNTs/TCPP的比例, 实现了卟啉层厚和位点密度的可控. 并通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)及其能量色散X射线能谱(EDS)、紫外-可见分光光度计(UV-Vis spectrophotometer)、傅里叶变换红外分光光度计(FT-IR spectrophotometer)、zeta电位等对所得MMPT的结构和性能进行了全面的表征. 在最佳的碳纳米管比例和吸附条件下, MMPT对牛血清白蛋白(BSA)表现出较好的吸附性能, 此外, MMPT对其他蛋白质如牛血红蛋白(BHb)和溶菌酶(Lyz)也表现出良好的吸附亲和力, 使得其在蛋白吸附、药物递送、传感等方面具有广泛的应用前景.

关键词: 卟啉, 碳纳米管, 金属化, 非共价, 一锅法, 蛋白吸附

In order to enhance the adsorption of protein, a one-step metallization of porphyrin and a novel metalloporphyrin-Sn network non-covalently functionalized multi-walled carbon nanotube composite (MMPT), were developed only by a simple one-pot solvothermal method. Under solvothermal conditions, Sn entered the meso-tetrakis(4-carboxyphenyl)porphine (TCPP) macrocycle to metalize the porphyrins and formed SnTCPP. Meanwhile, Sn, as a crosslinker, bridged the SnTCPP molecules around the surface of multi-walled carbon nanotubes (MWCNTs) to form a uniform and continuous SnTCPP-Sn network layer through self-assembly without any pre-modification for TCPP and MWCNTs. Then, through π-π stacking, multilayers of SnTCPP-Sn network can be formed via layer-by-layer self-assembly, as well as MMPT with controllable layer thickness. With this synthetic strategy, the sites of porphyrin on the MWCNTs surfaces were found continuous and evenly distributed, which enabled the controllability of layer thickness as well as the site density by adjusting the MWCNTs/TCPP ratio. The morphology, structure and properties of MMPT were characterized comprehensively by scanning electron microscope (SEM), transmission electron microscope (TEM) and its energy-dispersive X-ray spectroscopy (EDS), ultraviolet- visible (UV-Vis) spectroscopy, Fourier transform infrared spectrophotometer (FT-IR), and zeta potential. In addition, the effects of various factors on its adsorption properties and the interaction between MMPT and bovine serum albumin (BSA) were investigated. When the mass ratio of MWCNTs was 1.0 and the concentration of BSA was 1.5 mg•g^-1, the effective adsorption sites per unit mass of MMPT reached the maximum, resulting in the maximum adsorption capacity of MMPT to BSA (651.4 mg•g^-1), and the adsorption equilibrium can be reached in only 5 min. Compared with other adsorbents, MMPT showed high adsorption capacity for BSA under the optimal carbon nanotube ratio and adsorption conditions. In addition, MMPT also exhibited a good adsorption affinity for other proteins like bovine hemoglobin (BHb) and lysozyme (Lyz), which has a wide application prospect in protein adsorption, drug delivery, sensing and so on.

Key words: porphyrin, carbon nanotubes, metallization, noncovalent, one pot method, protein adsorption

引用此文

王超峰, 郑国栋, 王悦, 宋慧佳, 陈小艺, 高瑞霞. 金属卟啉-Sn网络可控非共价功能化碳纳米管的制备及蛋白吸附应用[J]. 化学学报, 2022, 80(2): 126-132.

Chaofeng Wang, Guodong Zheng, Yue Wang, Huijia Song, Xiaoyi Chen, Ruixia Gao. Preparation of Controllable Non-covalent Functionalized Carbon Nanotubes with Metalloporphyrin-Sn Network and Application to Protein Adsorption[J]. Acta Chimica Sinica, 2022, 80(2): 126-132.

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图/表 6

图1. MWCNTs (A, B, C)和MMPT (D, E, F)的SEM (A, D), TEM (B, E)及高分辨TEM (C, F)图

Figure 1. SEM (A, D) and (high-resolution) TEM (B, C, E, F) of MWCNTs (A, B, C) and MMPT (D, E, F)

图2. MMPT的TEM-EDS图

Figure 2. TEM-EDS of MMPT

图3. MMPT的UV-Vis吸收光谱(A), FT-IR (B)图和Zeta电位(C)

Figure 3. UV-Vis absorption spectra (A), FT-IR spectra (B), and Zeta potential (C) of MMPT

图4. MWCNTs的比例(A), BSA浓度(B), MMPT浓度(C)和吸附时间(D)对MMPT吸附量的影响

Figure 4. Effect of MWCNTs ratio (A), BSA concentration (B), concentration of MMPT (C), and adsorption time (D) on the adsorption capacity of MMPT toward BSA

图5. 溶液pH (A)和KCl溶液浓度(B)对MMPT吸附量的影响

Figure 5. Effect of pH (A) and KCl concentration (B) on the adsorption capacity of MMPT toward BSA

序号	吸附剂	吸附量/ (mg•g^-1)	参考文献
1	CM-CNTs^a	91.51	[35]
2	MWNT^b	139.5	[36]
3	PMIM/MWNT^c	5.53	[37]
4	Nano-porous silica	≈70	[38]
5	Hybrid adsorbent	≈150	[39]
6	TiO₂	42.6	[40]
7	PMMIPs^d	258	[41]
8	Fe₃O₄@BSA-MIPs^e	39.26	[42]
9	Clay	≈250	[43]
10	γ-Fe₂O₃@CHO^f	≈69	[44]
11	SiV^g	≈40	[45]
12	MMPT	651.4	This work

表1. 不同材料对BSA吸附性能的比较

Table 1. Comparison of adsorption capacity towards BSA on different materials

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