Amino Acid Functionalized Crystalline Porous Polymers

Abstract

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) are representative crystalline porous polymers. Due to their high surface area, high porosity, open channels, abundant functional groups and easy functionalization, they show great applications in gas storage and separation, catalysis, energy storage, photovoltaic devices, etc. Amino acids are the basic structural units that constitute peptides and proteins, which not only have important biological functions, but also play an important role in industrial applications such as pharmaceutical production, biodegradable plastics, and chiral catalysts. The introduction of amino acids into MOFs and COFs could endow them with diverse and flexible frameworks, special pore environment, and chiral sites, improving their biocompatibility and degradability to some extent and enriching their functions and applications. This review focuses on the progress of the amino acid functionalized MOFs and COFs, including their synthetic strategies, such as employing amino acids and their derivatives as building unit, covalent modification of amino acids onto the framework, and utilizing amino acids as modulators. The advantages and disadvantages of these strategies are compared and their challenges are discussed. In addition, we also introduce their applications in chiral separation, catalysis, adsorption and proton conduction. Finally, we summarize the current challenges in the preparation of amino acid functionalized crystalline porous polymers and outlook the future research direction in this field. Keywords crystalline porous polymer; metal-organic frameworks; covalent organic frameworks; amino acid; functionalization 1 引言 晶态多孔聚合物是一类具有丰富结构和官能团、高 结晶度、 高比表面积、 发达孔道结构的功能多孔材料, 展 现出良好的应用前景, 近年来该领域取得了长足的发 展 [1]. 其中, 金属有机框架(metal-organic frameworks, MOFs)或称多孔配位聚合物(porous coordination polymers, PCPs), 是由金属离子/团簇和有机配体组装形成 的无机有机杂化多孔材料 [2] ; 共价有机框架(covalent organic frameworks, COFs)是由有机构筑单元通过共价 键组装而成的晶态多孔材料 [3]. 与传统的多孔材料相比, 晶态多孔聚合物具有以下特点: (1)丰富可设计的组成和 结构, 在网状化学的设计理念下可通过调控构筑单元及 其连接方式构筑具有不同结构特征的框架结构; (2)规整 有序的孔道结构, 且可对其孔径、形状、化学环境进行 调控; (3)易于官能化, 可通过官能化的构筑单元或合成 后修饰的策略实现骨架的功能化 [1a]. 因此, 此类材料在

Investigating the Increased CO2 Capture Performance of Amino Acid Functionalized Nanoporous Materials from First-Principles and Grand Canonical Monte Carlo Simulations

“…In contrast to MOF-808, the surface amine groups in DBCOF and NH 2 –UiO-66 serve as the anchoring points for functionalized AAs via the formation of peptide bonds. This process has been established as an effective means of postsynthetic amino acid functionalization in MIL-68-NH 2 by Canivet et al, and similar such examples in the literature exist of grafting AAs or amino rich functional groups to the host nanoporous framework. − Here, we report our investigations of adsorptive performance, CO 2 /N 2 selectivity, accessible surface area (ASA), and thermodynamics of CO 2 capture in MOF-808, NH 2 –UiO-66, and DBCOF frameworks under the functionalization of six AAs: asparagine, cysteine, serine, tryptophan, lysine, and glycine (Figure ). We also carried out periodic DFT calculations on the functionalized MOFs/COF to assess the energetics and optimal binding sites of CO 2 within the host framework.…”

A review on chiral metal–organic frameworks: synthesis and asymmetric applications

“…The sensor recognition of chiral molecules, such as chiral drug molecules and their precursors, chiral amino acids and so on, are of great significance in life sciences and other fields. 106 Cinchonine and cinchonidine are a pair of epimers, they can be used as an antimalarial drug, and can also be used in asymmetric catalytic reactions. In 2019, Chen et al 107 introduced chirality into the pores of Zn-based MOF through the chiral post-modification of the channel method, and obtained chiral Zn-MOF-C; then they used Tb 3+ ion as the second luminescence center and introduced it into the pores of Zn-MOF-C, eventually, they prepared Zn-MOF-C-Tb (Fig.…”

Characteristic Synthesis of a Covalent Organic Framework and Its Application in Multifunctional Tumor Therapy

“…COFs are a class of crystalline porous organic polymers , that are formed by the covalent bonds of light elements (hydrogen, carbon, nitrogen, oxygen, boron, etc.). COFs are a potential tool in purification, catalysis, biosensors, and nanomedicine due to their regular pore structure, diverse functions, large specific surface area, and high porosity. − In 2005, two kinds of two-dimensional (2D) COFs, (C 3 H 2 BO) 6 (C 9 H 12 ) 1 (COF-1) and C 9 H 4 BO 2 (COF-5), were synthesized by condensation and were stable at 500 and 600 °C, and their specific surface area reached 711 and 1590 m 2 /g, respectively. In 2007, the research group synthesized two kinds of three-dimensional (3D) COFs, COF-102, and COF-103 for the first time, which were completely composed of Cmurc, Cmuro, and CmurB .…”