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Nature Communications · 2025 ·Vol. 16 ·期 1 ·1-7 · IF 15.7

Guest-induced structural transformation of single-crystal 3D covalent organic framework at room and high temperatures

Yao Aiping,Xu Hongliang,Shao Kuizhan,Sun Chunyi,Qin Chao,Wang Xinlong,Su Zhongmin

Soft porous crystals, recognized as the third generation of smart porous materials, can undergo structural deformations in response to external stimuli, such as temperature, pressure, and guest molecules. Currently, the dynamic phase transformations of soft porous crystals are predominantly determined through quantitative modeling based on gas adsorption and powder X-ray diffraction. Herein, we investigate the single-crystal-to-single-crystal structural transformation of covalent organic soft porous crystal modeled on COF-300 and identified nine distinct conformational isomers induced by different guest molecules at room and high temperatures. Notably, COF-300 can maintain its single-crystal structure even at 280 °C and efficiently absorbs polycyclic aromatic hydrocarbons in their molten state. The kinetics of structural transformations among conformational isomers are investigated by combining PXRD and theoretical calculations. The structural transformation from a high-energy state to a low-energy state is a rapid, energetically favorable process, while the reverse transformation is a slow process driven by concentration gradients.

研究领域: 材料科学 · 化学
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Polymer Chemistry · 2014 ·Vol. 5 ·期 14 ·4348-4357 · IF 5.368

Light-responsive fluorescent cross-linked polymeric micelles based on a salicylidene Schiff base pendant-functionalized block copolymer

Qiangfang He,Jianbing Huang,Hui Liang,Jiang Lu

A well-defined block copolymer polystyrene-block-poly(2-hydroxy-5-vinylbenzaldehyde) (PS-b-PHVB) was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization of HVB using a trithiocarbonate terminated polystyrene macro-chain transfer agent. Sequential grafting of monoamine-terminated PEG (PEG–NH2) and 2-(2-aminoethoxy)ethanol (AME) onto the HVB blocks of PS-b-PHVB via aldehyde–amine condensation afforded an amphiphilic block copolymer PS-b-(PHVB-g-PEG-and-AME) bearing a pendant salicylidene Schiff base with a precise structure. PS-b-(PHVB-g-PEG-and-AME) could self-assemble in ethanol into micelles with salicylidene Schiff base groups at the core–shell interface. Addition of Zn2+ ions into the resulting micellar solution not only endowed the micelles with fluorescent features but also enabled the resulting luminescent micelles to be stabilized through ionic cross-linking in consequence of the salicylaldimine–Zn2+ complexation. The obtained fluorescent cross-linked micelle was “light-controllable” in terms of its fluorescence emission and cross-linking structure due to the reversibility of the salicylaldimine–Zn2+ coordinative bond in response to light stimuli. The reversible fluorescence decrease and recovery could be achieved periodically upon alternative 254 nm UV irradiation and maintaining in the dark, and the micelles could be de-stabilized by UV irradiation-induced de-cross-linking. The capture of guest molecules and the light-triggered release of the guests for this Zn2+ coordinated micelle were also demonstrated using the coumarin-153 dye as a model guest molecule.

研究领域: 高分子化学 · 材料科学 · 光化学
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Polymers · 2018 ·Vol. 10 ·期 1 ·58 · IF 2.935

Preparation and Characterization of Antibacterial Polypropylene Meshes with Covalently Incorporated β-Cyclodextrins and Captured Antimicrobial Agent for Hernia Repair

Noor Sanbhal,Ying Mao,Gang Sun,Yan Li,Mazhar Peerzada,Lu Wang

Polypropylene (PP) light weight meshes are commonly used as hernioplasty implants. Nevertheless, the growth of bacteria within textile knitted mesh intersections can occur after surgical mesh implantation, causing infections. Thus, bacterial reproduction has to be stopped in the very early stage of mesh implantation. Herein, novel antimicrobial PP meshes grafted with β-CD and complexes with triclosan were prepared for mesh infection prevention. Initially, PP mesh surfaces were functionalized with suitable cold oxygen plasma. Then, hexamethylene diisocyanate (HDI) was successfully grafted on the plasma-activated PP surfaces. Afterwards, β-CD was connected with the already HDI reacted PP meshes and triclosan, serving as a model antimicrobial agent, was loaded into the cyclodextrin (CD) cavity for desired antibacterial functions. The hydrophobic interior and hydrophilic exterior of β-CD are well suited to form complexes with hydrophobic host guest molecules. Thus, the prepared PP mesh samples, CD-TCL-2 and CD-TCL-6 demonstrated excellent antibacterial properties againstStaphylococcus aureusandEscherichia colithat were sustained up to 11 and 13 days, respectively. The surfaces of chemically modified PP meshes showed dramatically reduced water contact angles. Moreover, X-ray diffractometer (XRD), differential scanning calorimeter (DSC), and Thermogravimetric (TGA) evidenced that there was no significant effect of grafted hexamethylene diisocyanate (HDI) and CD on the structural and thermal properties of the PP meshes.Keywords:antibacterial meshes;guest molecule;cyclodextrin grafting;polypropylene;oxygen plasma

CAS / MDL: 3380-34-5
研究领域: 生物医学工程 · 材料科学
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ADVANCED FUNCTIONAL MATERIALS · 2023 · IF 19

Cascade Bioreactors Based on Host–Guest Molecular Inclusion Complexes for Triple-Negative Breast Cancer Therapy via Inducing Ferroptosis

Zengguang Jia,Jun Zhang,Yawen Wei,Xiuhua Pan,Zongwei Hu,Ruixin Kang,Xiawei Zhou,Qi Shen

Triple-negative breast cancer (TNBC) poses significant challenges in tumor treatment. Ferroptosis, as a novel cell death mechanism, holds promise as a potential therapeutic strategy for TNBC. In this study, cascade bioreactors based on host–guest molecular inclusion complexes (PCFP@PL/p53) are constructed for TNBC therapy via inducing ferroptosis. The bioreactors are composed of hydrophobic hemirotaxane (mPEG-β-CD/α-CD) and hydrophilic multi-branched polyethyleneimine-ferrocene (PEI-Fc). They are linked by the reactive oxygen species (ROS)-responsive molecular switch β-CD@Fc, which can be activated by high levels of ROS. This activation leads to the rapid disassembly of PCFP@PL/p53 and the subsequent release of the loaded piperlongumine (PL) and p53 plasmids. In addition to acting as a “switch,” Fc can react with hydrogen peroxide (H 2 O 2 ) in a Fenton reaction to produce hydroxyl radicals. PL decreases intracellular reduced glutathione and induces H 2 O 2 accumulation, which corporates with Fc to launch ferroptosis and activated p53. The activated p53 disrupts the SLC7A11-GSH-GPX4 pathway, further increasing the intracellular ROS levels, resulting in a cascade amplification of ROS that ultimately induces massive ferroptosis. Meanwhile, the PCFP@PL/p53-induced ferroptosis also activates the immune system in vivo, restricting the growth and metastasis of TNBC, thus providing a novel approach for TNBC therapy based on ferroptosis.

研究领域: 肿瘤学 · 分子生物学 · 药理学
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JOURNAL OF COORDINATION CHEMISTRY · 2023 · IF 1.9

Guest molecular guided syntheses of 2-dimensional uranyl complexes with rigid benzenedicarboxylate ligands

Hong-Yan Wu,Ju-Xiang Luo,Hao-Hong Li,Jian-Han Zhang

Two new heterometallic uranyl-organic frameworks (UOFs), [Cd(phen)2(H2O)2][(UO2)2(BDC)3]·2H2O (1) and [Ni(phen)3][(UO2)2(BDC)3]·2H2O (2), were obtained under hydrothermal conditions. Both crystal structures were characterized by single-crystal X-ray diffraction analyses and the results indicate that both complexes feature a similar 2D honeycomb framework that is connected by rigid benzenedicarboxylate (BDC) ligands and uranyl units. BDC works as a linker to bridge neighboring UO22+ units, where UO22+ is tris-chelated. Different guest molecules guided the stacking of 2D layers and lead into their 3D supramolecular crystal structures with different space groups. As a result, 1 crystallized in a polar space group Cc, whereas 2 belongs to a chiral space group P6122. Thermogravimetric measurements were performed to study their thermal stability. UV-visible diffuse reflectance spectroscopy measurements indicate an experimental optical bandgap of 3.87 eV and 3.63 eV, respectively, for 1 and 2. Luminescent studies of both samples show strong green light emissions.

研究领域: 材料化学 · 配位化学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Reaction rate enhancement by reducing surface diffusion barriers of guest molecules over ZSM-5 zeolites: a structured illumination microscopy study

Shichao Peng,Hua Li,Wenjuan Liu,Junyi Yu,Zhaochao Xu,Mao Ye,Zhongmin Liu

Mass transfer of guest molecules is crucial for zeolite catalysis. Compared to intracrystalline diffusion, the surface barriers in zeolite catalysis have been less understood. Taking furfuryl alcohol oligomerization catalyzed by ZSM-5 zeolites as model reaction, here we present a single-crystal level study and gain insight into the surface barriers induced spatiotemporal evolution of oligomer products using structured illumination microscopy (SIM). It is shown that, as a result of the enhanced accessibility to zeolite crystals, promoting the surface permeability leads to the increase in catalytic reaction rate that is characterized as the generation rate of oligomer products.

研究领域: 催化化学 · 材料科学 · 物理化学 · 纳米催化 · 多相催化 · 分子筛催化 · 原位表征技术
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Nano Materials Science · 2022 · IF 0

Water-based synthesis of nanoscale hierarchical metal-organic frameworks: Boosting adsorption and catalytic performance

Yi Yu,Zewei Liu,Xiaofei Chen,Shujun Liu,Chongxiong Duan,Hongxia Xi

The combination of nano sizes, large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks (MOFs). Herein, a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs (NH-MOFs) with high crystallinity and excellent stability. This approach allows the morphology and porosity of MOFs to be fine tuned, thereby enabling the nanoscale crystal generation and a well-defined hierarchical system. The aqueous solution facilitates rapid nucleation kinetics, and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent (SDA) to guide the formation of hierarchical networks. The as-synthesized NH-MOFs (NH-ZIF-67) were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules, outperforming the parent microZIF-67. This study focuses on understanding the NH-MOF growth rules, which could allow tailor-designing NH-MOFs for various functions.

研究领域: 材料科学 · 化学工程 · 纳米技术 · 催化 · 环境科学
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RSC Advances · 2020 ·Vol. 10 ·期 32 ·18572-18580 · IF 3.119

Multiple-responsive supramolecular vesicle based on azobenzene–cyclodextrin host–guest interaction

Jiao Wang,Ting Wang,Xiaohui Liu,Yan Lu,Jingjing Geng

Multiple-responsive supramolecular vesicles have been successfully fabricated by the complexation between β-cyclodextrin (β-CD) and a pH/photo dual-responsive amphiphile 4-(4-(hexyloxy)phenylazo)benzoate sodium (HPB) with azobenzene and carboxylate groups. When mixing β-CD with HPB to reach a host/guest molar ratio of 1 : 1, the azobenzene group of HPB could be spontaneously included by β-CD molecules. Then, the formed inclusion complexes (HPB@β-CD) could self-assemble into vesicles, which was driven by the hydrophobic interaction of the alkyl chain of HPB and the hydrogen bonds between neighboring β-CDs. The reversible assembly/disassembly of the vesicles could be simply regulated under UV or visible light irradiation. The reversible phase transformation between vesicles and microbelts could also be realized by adjusting the pH values of the sample. Adding both competitive guest molecules (1-adamantane carboxylic acid sodium (ADA)) and α-amylase would result in the phase transformation from vesicles to micelles. Moreover, the vesicles would be destroyed when β-CD was continuously added until the ratio of host/guest reached 2 : 1. Such an interesting quintuple-responsive vesicle system reported here not only has potential applications in various fields such as controlled release or drug delivery, but also provides a reference for the design and construction of multiple responsive systems.

研究领域: 超分子化学 · 材料科学 · 纳米技术 · 药学
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