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一种非共价的“点击化学”策略,可有效地在高度多孔的 MOF 纳米粒子表面涂覆稳定的聚合物壳。

A non-covalent "click chemistry" strategy to efficiently coat highly porous MOF nanoparticles with a stable polymeric shell.

机构信息

Departamento de Química y Física, Universidad de Almería, 04120 Almería, Spain.

Faculté de Pharmacie, UMR 8612 CNRS Université Paris-Sud, Châtenay-Malabry, France.

出版信息

Biochim Biophys Acta Gen Subj. 2017 Jun;1861(6):1606-1616. doi: 10.1016/j.bbagen.2017.01.016. Epub 2017 Jan 28.

Abstract

BACKGROUND

Metal-organic framework nanoparticles (nanoMOFs) are biodegradable highly porous materials with a remarkable ability to load therapeutic agents with a wide range of physico-chemical properties. Engineering the nanoMOFs surface may provide nanoparticles with higher stability, controlled release, and targeting abilities. Designing postsynthetic, non-covalent self-assembling shells for nanoMOFs is especially appealing due to their simplicity, versatility, absence of toxic byproducts and minimum impact on the original host-guest ability.

METHODS

In this study, several β-cyclodextrin-based monomers and polymers appended with mannose or rhodamine were randomly phosphorylated, and tested as self-assembling coating building blocks for iron trimesate MIL-100(Fe) nanoMOFs. The shell formation and stability were studied by isothermal titration calorimetry (ITC), spectrofluorometry and confocal imaging. The effect of the coating on tritium-labeled AZT-PT drug release was estimated by scintillation counting.

RESULTS

Shell formation was conveniently achieved by soaking the nanoparticles in self-assembling agent aqueous solutions. The grafted phosphate moieties enabled a firm anchorage of the coating to the nanoMOFs. Coating stability was directly related to the density of grafted phosphate groups, and did not alter nanoMOFs morphology or drug release kinetics.

CONCLUSION

An easy, fast and reproducible non-covalent functionalization of MIL-100(Fe) nanoMOFs surface based on the interaction between phosphate groups appended to β-cyclodextrin derivatives and iron(III) atoms is presented.

GENERAL SIGNIFICANCE

This study proved that discrete and polymeric phosphate β-cyclodextrin derivatives can conform non-covalent shells on iron(III)-based nanoMOFs. The flexibility of the β-cyclodextrin to be decorated with different motifs open the way towards nanoMOFs modifications for drug delivery, catalysis, separation, imaging and sensing. This article is part of a Special Issue entitled "Recent Advances in Bionanomaterials" Guest Editors: Dr. Marie-Louise Saboungi and Dr. Samuel D. Bader.

摘要

背景

金属有机骨架纳米粒子(nanoMOFs)是可生物降解的高多孔材料,具有负载具有广泛物理化学性质的治疗剂的卓越能力。对纳米 MOFs 表面进行工程改造可以提供更高的稳定性、控制释放和靶向能力。设计用于 nanoMOFs 的后合成、非共价自组装壳特别有吸引力,因为它们简单、多功能、没有有毒副产品,并且对原始主客体能力的影响最小。

方法

在这项研究中,几种带有甘露糖或罗丹明的 β-环糊精基单体和聚合物被随机磷酸化,并作为铁三嗪 MIL-100(Fe)纳米 MOFs 的自组装涂层构建块进行测试。通过等温滴定量热法(ITC)、荧光光谱法和共聚焦成像研究了壳的形成和稳定性。通过闪烁计数法估计了涂层对氚标记 AZT-PT 药物释放的影响。

结果

通过将纳米粒子浸泡在自组装剂水溶液中,方便地实现了壳的形成。接枝的磷酸基团使涂层牢固地锚定在纳米 MOFs 上。涂层稳定性与接枝磷酸基团的密度直接相关,并且不会改变纳米 MOFs 的形态或药物释放动力学。

结论

提出了一种基于接枝到 β-环糊精衍生物上的磷酸基团与铁(III)原子之间相互作用的简便、快速且可重复的 MIL-100(Fe)纳米 MOFs 表面的非共价功能化方法。

一般意义

本研究证明离散的和聚合的磷酸 β-环糊精衍生物可以在基于铁(III)的纳米 MOFs 上形成非共价壳。β-环糊精具有用不同基序进行修饰的灵活性,为药物输送、催化、分离、成像和传感的纳米 MOFs 修饰开辟了道路。本文是题为“生物纳米材料的最新进展”的特刊的一部分,客座编辑为 Marie-Louise Saboungi 博士和 Samuel D. Bader 博士。

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