电子诱导金属多肽的超分子组装、化学响应释放及其催化应用

doi:10.1016/S1872-2067(20)63655-5

催化学报 ›› 2021, Vol. 42 ›› Issue (3): 376-387.DOI: 10.1016/S1872-2067(20)63655-5

电子诱导金属多肽的超分子组装、化学响应释放及其催化应用

王宗元^a^,^b, 王嘉骏^a, 孙泽宇^a, 项文龙^a, 沈辰阳^a, 芮宁^a, 丁明珠^a, 元英进^a, 崔宏刚^b^,^c^,^d^,^#(), 刘昌俊^a^,^*()

^a天津大学化工学院化工科学与工程协同创新中心,天津300072,中国
^b约翰霍普金斯大学化学与生物分子工程系和纳米生物技术研究所,马里兰州21218,美国
^c约翰霍普金斯大学药学院威尔默眼科研究所纳米医学中心,马里兰州21218,美国
^d约翰霍普金斯大学药学院肿瘤科和西德尼·坎摩尔综合癌症中心,马里兰州21218,美国;

收稿日期:2020-05-17 接受日期:2020-06-21 出版日期:2021-03-18 发布日期:2021-01-23
通讯作者: 崔宏刚,刘昌俊
作者简介:^*电话/传真:(022)27406490;电子信箱: coronacj@tju.edu.cn;
基金资助:
国家自然科学基金(21621004);国家自然科学基金(21536008);国家留学基金委(201706250085)

Electron-induced rapid crosslinking in supramolecular metal-peptide assembly and chemically responsive disaggregation for catalytic application

Zongyuan Wang^a^,^b, Jiajun Wang^a, Zeyu Sun^a, Wenlong Xiang^a, Chenyang Shen^a, Ning Rui^a, Mingzhu Ding^a, Yingjin Yuan^a, Honggang Cui^b^,^c^,^d^,^#(), Chang-jun Liu^a^,^*()

^aCollaborative Innovation Center of Chemical Science and Engineering,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China
^bDepartment of Chemical and Biomolecular Engineering,and Institute for NanoBioTechnology,The Johns Hopkins University,3400 North Charles Street,Baltimore,Maryland 21218,United States
^cCenter for Nanomedicine,The Wilmer Eye Institute,Johns Hopkins University School of Medicine,400 North Broadway,Baltimore,Maryland 21231,United States
^dDepartment of Oncology and Sidney Kimmel Comprehensive

Received:2020-05-17 Accepted:2020-06-21 Online:2021-03-18 Published:2021-01-23
Contact: Honggang Cui,Chang-jun Liu
About author:^*E-mail:coronacj@tju.edu.cn;
Supported by:
National Natural Science Foundation of China(21621004);National Natural Science Foundation of China(21536008);China Scholarship Council(201706250085)

摘要/Abstract

摘要：

近年来,超分子组装在催化、制药、传感器、提纯、组织工程等领域获得广泛应用. 为了实现超分子结构功能化,经常会将金属纳米颗粒或者金属活性位引入或共组装至有机超分子骨架中,由此获得金属化的纳米材料. 例如,金属纳米颗粒修饰的多肽纤维、金属聚合物、金属负载的水凝胶和气凝胶. 常见的金属化策略包括自组织、金属有机配位络合、聚合和电子诱导组装等. 其中,由本课题组发展的电子诱导组装法已经被用于制备高效金属多肽催化剂、能源转化材料和非均相催化剂模板等. 室温电子诱导组装利用了辉光等离子体富含的电子,是室温电子还原制备纳米金属颗粒及相关催化剂的进一步发展. 该方法操作过程简单,仅需一步即可同时实现金属还原和有机物组装; 且绿色环保、不需要添加还原剂、操作条件温和、反应时间短(在室温条件下几分钟内即可反应完全). 所获得的二维多肽纳米薄膜含有高度分散的金属纳米颗粒. 研究表明,电子诱导组装法是构建超分子催化剂强有力的工具. 然而,电子诱导超分子组装的反应机理仍然不清楚. 为了进一步开发应用新的超分子材料,开展电子诱导组装机理研究十分必要.
本文选择β淀粉肽的五肽片段作为电子诱导组装的单体和贵金属(Pd,Pt和Au)离子通过电子还原得到金属多肽纳米膜. 通过调控原料配比和浓度,获得了包覆有超细贵金属纳米颗粒(1-2 nm)的金属多肽纳米薄膜. 通过扫描电子显微镜、透射电子显微镜、X射线衍射光谱、X射线光电能谱等表征手段,对金属多肽纳米薄膜的结构和成分进行了分析. 通过原子力显微镜对金属多肽纳米薄膜的多级结构进行分析发现,电子诱导组装的组装单元为碟状组合体,与常规自组装有显著区别,通过傅里叶变换红外光谱、X射线光电能谱等表征方法,结合密度泛函(DFT)计算,对组装过程多肽分子的表面性质和变化进行了分析. 发现多肽在电子诱导组装过程中会发生部分氧化. DFT研究给出两种可能的羟基自由基活化碳氢键过程,说明形成的羟基提供了额外的氢键相互作用,促进了组装的快速发生. 多肽中含有苯环的侧链对多肽组装后二维结构的形成起到重要作用.本文还首次发现金属多肽薄膜能够在化学试剂刺激下响应释放金属纳米颗粒. 如在硼氢化钠作用下可以快速释放金属纳米颗粒、在谷胱甘肽作用下可以缓慢释放金属纳米颗粒.硼氢化钠作用下释放后的金属颗粒对4-氨基苯酚还原反应具有良好的催化活性. 金属多肽薄膜的快速响应释放可以为稳定纳米金属颗粒提供一个新方法,替代那些以往采用的稳定剂难于脱除的纳米金属稳定方法. 而慢速响应释放则有潜力应用于药物缓释、光热治疗生物传感和成像等医学领域.

关键词: 金属, 多肽, 组装, 响应释放, 还原, 催化剂

Abstract:

The applications of supramolecular metal-peptide assemblies as catalyst or catalyst precursor have recent attracted increasing attentions. In this work,a fragment of the amyloid β-peptide,NH2-KLVFF-COOH,was assembled into nanofilms with encapsulated Pd,Pt and Au nanoparticles (NPs) via a one-step room temperature electron induction method. The effects of building block,intermolecular interaction,driving force and side-chain on the assembly were investigated. The assembly mechanism was thereby proposed. The crosslinking of peptide monomers results in mainly random and unordered structures. The obtained metal-peptide assemblies are extremely stable in water at neutral pH for long term. However,the metal NPs are able to be responsively released under basic and reductive conditions. The released NPs show a high activity to catalyze the reduction of 4-nitrophenol. The present studies on assembly mechanism and responsive release will be helpful for the design of organic skeletons and also for the future development of peptide stabilized metallic NPs with applications beyond catalysts.

Key words: Metal, Peptide, Assembly, Responsive release, Reduction, Catalyst

王宗元, 王嘉骏, 孙泽宇, 项文龙, 沈辰阳, 芮宁, 丁明珠, 元英进, 崔宏刚, 刘昌俊. 电子诱导金属多肽的超分子组装、化学响应释放及其催化应用[J]. 催化学报, 2021, 42(3): 376-387.

Zongyuan Wang, Jiajun Wang, Zeyu Sun, Wenlong Xiang, Chenyang Shen, Ning Rui, Mingzhu Ding, Yingjin Yuan, Honggang Cui, Chang-jun Liu. Electron-induced rapid crosslinking in supramolecular metal-peptide assembly and chemically responsive disaggregation for catalytic application[J]. Chinese Journal of Catalysis, 2021, 42(3): 376-387.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63655-5

https://www.cjcatal.com/CN/Y2021/V42/I3/376

图/表 8

Fig.1. Schematic synthesis and SEM images of the metal-peptide nanofilms. (a) The digital photos of Pd0.5-P0.5 nanofilm product; (b-d) the SEM images and digital photos (insets of b-d) of Pd0.5-P0.5 (b),Pt0.5-P0.5 (c) and Au0.01-P0.2 (d) nanofilms.

Fig.2. TEM images and metal distributions of metal-peptide nanofilms: Pd0.5-P0.5 (a-c),Pt0.5-P0.5 (d-f) and Au0.01-P0.2 (g-i); the insets in (b,e,h) show the distances of crystal facets; (c),(f) and (i) are the statistical result of particle size.

Fig.3. (a) The XRD patterns of pure KLVFF,Pd0.5-P0.5,Pt0.5-P0.5,Au0.01-P0.2 and Au0.1-P0.5 samples; (b-d) the XPS spectra of Pd 3d,Pt 4f and Au 4f.

Fig.4. The AFM images of Pd0.5-P0.5 nanofilms. AFM height (a,b) and phase (c) scanning images; (d,e) the height of the red-line and blue-line section in a and b,respectively; (f) schematic illustration of peptide nanofilms encapsulating metal NPs; (g) approximate geometric length of KLVFF estimated by Materials Studio.

Fig.5. The FTIR and XPS analysis of the electron‐induced assembly process. The FTIR spectra of KLVFF powders (a) and Pd‐P films (b,c) under different conditions; (b) change the Pd ion concentration from 0 to 0.5 mM; (c) change the reaction time from 0 to 10 min; (d-g) The XPS spectra of KLVFF before and after assembly.

Fig.6. The DFT calculatation of the C-H hydroxylation process and 1H-NMR results of KLVFF peptide before and after the electron-induced assembly. (a) The classify of C-H bonds in KLVFF molecule; Potential energy surface of C-H hydroxylation to C-OH through single OH radical S route (b) and double OH radical D route (c). IC,initial complex; TS1,transition state for H-abstraction; TS2-S,transition state for HOH-rebound in S route; INT,intermediate; INT-D,intermediate in D route; FC-S and FC-D,final complex. (d) The 1H-NMR results of KLVFF peptide and M0-P0.5 nanofilms tested in DMSO-d6 with and without D2O.

Fig.7. Schematic illustration of the electron-induced assembly,long-term storage of metal-peptide nanofilms and their responsive release under NaBH4 and glutathione (GSH) conditions.

Fig.8. Catalytic performance of noble-metal-peptide nanofilms. UV-vis absorption spectra and the plot of C/C0 (a,c,e) and ln(C/C0) (b,d,f) versus reaction time during the catalytic reduction of 4-NP over NaBH4 treated Pd0.5-P0.5 (a,d),Pt0.5-P0.5 (b,e) and Au0.01-P0.2 (c,f) samples. Initial curves at 0 s were obtained by adding NaBH4 into 4-NP solution.

参考文献

[1]	K. Sato, M. P. Hendricks, L. C. Palmer, S. I. Stupp, Chem. Soc. Rev., 2018,47, 7539-7551.
[2]	L. L. Lock, Y. Li, X. Mao, H. Chen, V. Staedtke, R. Bai, W. Ma, R. Lin, Y. Li, G. Liu, H. Cui, ACS Nano, 2017,11, 797-805.
[3]	A. S. Weingarten, R. V. Kazantsev, L. C. Palmer, M. McClendon, A. R. Koltonow, A. P. S. Samuel, D. J. Kiebala, M. R. Wasielewski, S. I. Stupp, Nat. Chem., 2014,6, 964-970.
[4]	A. Z. Khan, M. Bilal, T. Rasheed, H. M. N. Chin. J. Catal., 2018,39, 1861-1868.
[5]	N. Wang, H. Zheng, W. Zhang, R. Cao, Chin. J. Catal., 2018,39, 228-244.
[6]	Y. Li, L. L. Lock, Y. Wang, S.-H. Ou, D. Stern, A. Schön, E. Freire, X. Xu, S. Ghose, Z. J. Li, H. Cui, Biomaterials, 2018,178, 448-457.
[7]	C. F. Anderson, R. W. Chakroun, H. Su, R. E. Mitrut, H. Cui, ACS Nano, 2019,13, 12957-12968.
[8]	E. Pazos, E. Sleep, C. M. Rubert Pérez S. S. Lee F. Tantakitti S. I. Stupp J. Am. Chem. Soc., 2016,138, 5507-5510.
[9]	A. Ghorbani-Choghamarani, Z. Taherinia, Chin. J. Catal., 2017,38, 469-474.
[10]	F. S. Han, M. Higuchi, D. G. Kurth, Adv. Mater., 2007,19, 3928-3931.
[11]	G. Nyström, M.P. Fernández-Ronco, S. Bolisetty, M. Mazzotti, R. Mezzenga, Adv. Mater., 2016,28, 472-478.
[12]	R. Xing, K. Liu, T. Jiao, N. Zhang, K. Ma, R. Zhang, Q. Zou, G. Ma, X. Yan, Adv. Mater., 2016,28, 3669-3676.
[13]	V. Kunz, D. Schmidt, M. I. S. Roehr, R. Mitric, F. Wuerthner, Adv. Energy Mater., 2017,7, 1602939.
[14]	B. Yang, X. Jiang, Q. Guo, T. Lei, L.-P. Zhang, B. Chen, C.-H. Tung, L.-Z. Wu, Angew. Chem. Int. Ed., 2016,55, 6229-6234.
[15]	J. Z. Zheng, Y. J. Wu, K. Deng, M. He, L. C. He, J. Cao, X. G. Zhang, Y. L. Liu, S. X. Li, Z. Y. Tang, ACS Nano, 2016,10, 8564-8570.
[16]	Z. Sun, F. Lv, L. Cao, L. Liu, Y. Zhang, Z. Lu, Angew. Chem. Int. Ed., 2015,54, 7944-7948.
[17]	B. Ma, Y. Wu, S. Zhang, S. Wang, J. Qiu, L. Zhao, D. Guo, J. Duan, Y. Sang, L. Li, ACS Nano, 2017,11, 1973-1981.
[18]	H. Hu, Q. Yan, R. Ge, Y. Gao, Chin. J. Catal., 2018,39, 1167-1179.
[19]	M. Cong, D. Sun, L. Zhang, X. Ding Chin. J. Catal., 2020,41, 242-248.
[20]	R. Misra, A. Saseendran, S. Dey, H. N. Gopi, Angew. Chem. Int. Ed., 2019,58, 2251-2255.
[21]	J. Navarro-Sánchez, A. I. Argente-García, Y. Moliner-Martínez, D. Roca-Sanjuán, D. Antypov, P. Campíns-Falcó, M. J. Rosseinsky, C. Martí-Gastaldo, J. Am. Chem. Soc., 2017,139, 4294-4297.
[22]	H. Su, W. Zhang, H. Wang, F. Wang, H. Cui, J. Am. Chem. Soc., 2019,141, 11997-12004.
[23]	W. Wang, Z. Wang, M. Yang C.-J. Zhong, C.-J. Liu, Nano Energy, 2016,25, 26-33.
[24]	W. Wang, C. F. Anderson, Z. Wang, W. Wu, H. Cui C.-J. Liu, Chem. Sci., 2017,8, 3310-3324.
[25]	J. Yan, Y. Pan, A. G. Cheetham Y.-A. Lin, W. Wang, H. Cui, C.-J. Liu, Langmuir, 2013,29, 16051-16057.
[26]	Y.-X. Pan, H.-P. Cong, Y.-L. Men, S. Xin, Z.-Q. Sun, C.-J. Liu, S.-H. Yu, ACS Nano, 2015,9, 11258-11265.
[27]	Y.-x. Pan, C.-j. Liu, S. Zhang, Y. Yu, M. Dong, Chem. Eur. J., 2012,18, 14614-14617.
[28]	N. Rui, Z. Wang, K. Sun, J. Ye, Q. Ge, C.-j. Liu Appl. Catal. B, 2017,218, 488-497.
[29]	B. Delley, J. Chem. Phys., 1990,92, 508-517.
[30]	B. Delley, J. Chem. Phys., 2000,113, 7756-7764.
[31]	B. Delley, J. Chem. Phys., 1991,94, 7245-7250.
[32]	W.-l. Chen, W.-X. Chen, G.-l. Zhuang, J. Zheng, L. Tan, X. Zhong, J.-g. Wang, CrystEngComm, 2013,15, 5545-5551.
[33]	X. Zhu, C. Jin, X.-S. Li, J.-L. Liu, Z.-G. Sun, C. Shi, X. Li, A.-M. Zhu, ACS Catal., 2017,7, 6514-6524.
[34]	B. Zhu, X.-S. Li, P. Sun, J.-L. Liu, X.-Y. Ma, X. Zhu, A.-M. Zhu, Chin. J. Catal., 2017,38, 1759-1769.
[35]	L. Di, D. Duan, Z. Zhan, X. Zhang, Adv. Mater. Interfaces, 2016, 3,1600760.1-1600760. 5.
[36]	L. Di, Z. Li, X. Zhang, H. Wang, Z. Fan, Catal.Today, 2019,337, 55-62.
[37]	Z.-G. Sun, X.-S. Li, J.-L. Liu, Y.-C. Li, B. Zhu, A.-M. Zhu, J. Catal., 2019,375, 380-388.
[38]	X. Zhu, J.-H. Liu, X.-S. Li, J.-L. Liu, X. Qu, A.-M. Zhu, J. Energy Chem., 2017,26, 488-493.
[39]	J. Zhang, H. Wang, Q. Zhao, L. Di, X. Zhang, Int. J. Hydrogen Energy, 2020,45, 9624-9634.
[40]	B. Qi, L. Di, W. Xu, X. Zhang, J. Mater. Chem. A, 2014,2, 11885-11890.
[41]	M. J. Krysmann, V. Castelletto, A. Kelarakis, I. W. Hamley, R. A. Hule, D. J. Pochan, Biochemistry, 2008,47, 4597-4605.
[42]	M. Jackson, H. H. Mantsch, Crit. Rev. Biochem. Mol. Biol., 1995,30, 95-120.
[43]	J. Seo, W. Hoffmann, S. Warnke, X. Huang, S. Gewinner, W. Schöllkopf, M. T. Bowers G. von Helden, K. Pagel, Nat. Chem., 2016,9, 39-44.
[44]	R. Gao, L. Pan, Z. Li, X. Zhang, L. Wang, J.-J. Zou, Chin. J. Catal., 2018,39, 664-672.
[45]	L. Q. Xu, W. J. Yang, K.-G. Neoh, E.-T. Kang, G. D. Fu, Macromolecules, 2010,43, 8336-8339.
[46]	K. Yoshizawa, Y. Shiota, J. Am. Chem. Soc., 2006,128, 9873-9881.
[47]	P. Verma, K. D. Vogiatzis, N. Planas, J. Borycz, D. J. Xiao, J. R. Long, L. Gagliardi, D. G. Truhlar, J. Am. Chem. Soc., 2015,137, 5770-5781.
[48]	A. Bassan, M. R. A. Blomberg,P. E. M. Siegbahn,L. Que Jr,Chem. Eur. J., 2005,11, 692-705.
[49]	D. Balcells, C. Raynaud, R. H. Crabtree, O. Eisenstein, Chem. Commun., 2008, 744-746.
[50]	Y. Hu, R. Lin, P. Zhang, J. Fern, A. G. Cheetham, K. Patel, R. Schulman, C. Kan, H. Cui, ACS Nano, 2016,10, 880-888.
[51]	E. Kan, L. Kuai, W. Wang, B. Geng, Chem.-Eur. J., 2015,21, 13291-13296.
[52]	C. Wang, R. Ciganda, L. Salmon, D. Gregurec, J. Irigoyen, S. Moya, J. Ruiz, D. Astruc, Angew. Chem. Int. Ed., 2016,55, 3091-3095.
[53]	Y. Tan, H. Liu, X.Y. Liu, A. Wang, C. Liu, T. Zhang, Chin. J. Catal., 2018,39, 929-936.

电子诱导金属多肽的超分子组装、化学响应释放及其催化应用

Electron-induced rapid crosslinking in supramolecular metal-peptide assembly and chemically responsive disaggregation for catalytic application

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 8

参考文献

相关文章 15

编辑推荐

Metrics

[1]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[2]	石靖, 郭煜华, 谢飞, 章名田, 张洪涛. 氧化还原活性配体的电子效应对钌催化水氧化反应的影响[J]. 催化学报, 2023, 52(9): 271-279.
[3]	张季, 俞爱民, 孙成华. 非金属掺杂石墨烯异核双原子催化剂氮还原特性研究[J]. 催化学报, 2023, 52(9): 263-270.
[4]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[5]	洪岩, 王琦, 阚子旺, 张禹烁, 郭晶, 李思琦, 刘松, 李斌. 电化学氮还原氨反应催化剂的最新研究进展[J]. 催化学报, 2023, 52(9): 50-78.
[6]	孙嘉辰, 陈赛, 付东龙, 王伟, 王显辉, 孙国栋, 裴春雷, 赵志坚, 巩金龙. 氧扩散与表面反应在VO_x-Ce_1‒_xZr_xO₂催化丙烷脱氢反应中的影响[J]. 催化学报, 2023, 52(9): 217-227.
[7]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[8]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[9]	高晖, 张恭, 程东方, 王永涛, 赵静, 李晓芝, 杜晓伟, 赵志坚, 王拓, 张鹏, 巩金龙. 构建Cu台阶位促进电催化CO₂还原制醇类化学品的研究[J]. 催化学报, 2023, 52(9): 187-195.
[10]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[11]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[12]	张雯, 宋彩彩, 王嘉蔚, 蔡舒婷, 高梦语, 冯有祥, 鲁统部. 双向主客体作用促进水溶液中选择性光催化CO₂还原与醇氧化[J]. 催化学报, 2023, 52(9): 176-186.
[13]	邹心仪, 顾均. 酸性条件下二氧化碳高效电还原策略[J]. 催化学报, 2023, 52(9): 14-31.
[14]	刘鑫, 王茂弟, 任亦起, 刘嘉立, 戴慧聪, 杨启华. 构建模块化催化体系用于氢转移反应: 氢键的促进作用[J]. 催化学报, 2023, 52(9): 207-216.
[15]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.