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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Fluorescence-color-changing biomimetic tough films with simultaneous shape-deformation triggered by pH

Junyi Tang,Yuanyuan Ren,Jiachun Feng

Stimuli-responsive materials with complex practical functions that could imitate certain behaviors of living organisms have wide potential applications in frontier fields. However, the fabrication of stimuli-responsive films with simultaneous change in fluorescence color and shape in response to a single stimulus, especially by a simple fabrication strategy, remains a challenge. Herein, a simple hydrogel-film-post crosslinking strategy is proposed to prepare films that exhibit fluorescence change accompanying with shape deformation under pH stimulus. The synchronous changes are realized by the combination of dynamic boron chemistry and pH-sensitive lanthanide complexes. Under different pH conditions, the protonation/deprotonation of the ligands coordinated to Eu 3+ ions could generate switchable on/off fluorescence behavior, while the association/dissociation of borate ester bonds between 3-aminobenzeneboronic acid (SA-PBA) and polyvinyl alcohol (PVA) could lead to macroscopic deformation. The existence of borate ester bonds is beneficial to the mechanical properties of composite films. Under pH stimulus, the film-based artificial flower could simulate the flowering of natural flowers accompanying with color changes and the film-based gripper could grasp object with a visual signal, which demonstrates that the SA-PBA/PVA/EuL films have great potential for wide application.

研究领域: 材料科学 · 仿生学
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DYES AND PIGMENTS · 2019 · IF 4.018

Dynamic coordination of natural amino acids-lanthanides to control reversible luminescent switching of hybrid hydrogels and anti-counterfeiting

Jingfang Li,Weizuo Li,Diandong Xia,Chuan Xiang,Yanjie Chen,Guangming Li

A new design of two environment-friendly hydrogels containing lanthanide ions emitting green and red luminescence have been fabricated by the coordinative self-assembly of natural phenylalanine (Phe) and lanthanide ions (Tb 3+ or Eu 3+ ). The coordination bond formation was confirmed by Fourier-transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis. Luminescent spectra indicated that such hydrogels exhibit reversible gel-sol transition along with the reversible luminescent ON/OFF properties through the reversible association and dissociation of coordinative bonds between Phe and lanthanides upon pH stimuli. Luminescent decay curves revealed that the lifetimes of both hydrogels (Phe-Tb and Phe-Eu) in their gel state were remarkably increased almost double in contrast to that in sol state. Shear rate sweep data indicated that the hydrogels possess shear thinning properties. Remarkably, such environment-friendly hydrogels with long luminescent lifetimes, good stability, colorless under daylight, together with shear thinning properties, could be applied directly as luminescent inks for anti-counterfeiting. This provides an alternative strategy to prepare environment-friendly luminescent inks based on lanthanides for anti-counterfeiting.

研究领域: 材料科学 · 化学 · 环境科学
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Supramolecular Assembly of Shape Memory and Actuating Hydrogels for Programmable Shape Transformation

Jie Zhuo,Baoyi Wu,Jiawei Zhang,Yu Peng,Huanhuan Lu,Xiaoxia Le,Shuxin Wei,Tao Chen

The deformable diversity of organisms in nature has inspired the development of bionic hydrogel actuators. However, the anisotropic structures of hydrogel actuators cannot be altered after the fabrication process, which restricts hydrogel actuators to provide complex and diverse shape deformations. Herein, we propose a dual programming method to generate numerous anisotropic structures from initial isotropic gelatin-containing hydrogels; the isotropic hydrogel blocks could be first assembled into anisotropic structures based on the coil-triple helix transition of gelatin, and then, the assembled hydrogels could further be fixed into various temporary anisotropies, so that they can produce complex and diverse deformations under the stimulation of pH. In addition, the shape programming and deformation behaviors are reversible. This dual programming method provides more potential for the application of hydrogel actuators in soft robots and bionics.

研究领域: 材料科学 · 仿生学 · 生物医学工程
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ACS Agricultural Science & Technology · 2022 · IF 0

Pillar[6]arene@quantum-Dot Membrane for Controlled Release Pesticides Based on Host–Guest Chemistry

Guang Li,Siyun Zhang,Lei Yang,Weiwei Xu,Haonan Qu,Demei Tian,Jia Li,Haibing Li,Xiaobing Zhang

Controlled release of pesticides is highly desirable for improving efficacy and reducing side effects in agricultural applications. Herein, in this work, based on the optical property and host–guest chemistry of quantum dot and pillararene, we develop a new type of fluorescent, current-responsive, pH stimuli-responsive pillar[6]arene@quantum dots mixed-matrix membranes (PQDs-MMMs) for pesticide delivery, which achieves highly selective detection and controlled release for methyl viologen (MV2+). In the experiments of fluorescence spectrum and I–V current, PQDs-MMMs could realize the visual fluorescence detection and current selection for MV2+. Moreover, the controlled release experiments indicated that the PQDs-MMMs could effectively immobilize and stimuli-release the MV2+ depending on the pH regulation, which achieved the pH-stimuli-responsive release of MV2+. Additionally, the herbicidal activity of MV2+-loaded PQDs-MMMs (MV2+@PQDs-MMMs) was tested, and results showed the weed control effects were identified to free MV2+ under pH control. This work provides the great potential of PQDs-MMMs used in agricultural membranes with environmentally friendly and stimuli-responsive release.

研究领域: 农业科学 · 材料科学 · 化学
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CHEMISTRY-A EUROPEAN JOURNAL · 2012 ·Vol. 18 ·期 51 ·16517-16524 · IF 5.925

Hollow-Core Magnetic Colloidal Nanocrystal Clusters with Ligand-Exchanged Surface Modification as Delivery Vehicles for Targeted and Stimuli-Responsive Drug Release

Dian Li,Jing Tang,Jia Guo,Shilong Wang,Deeptangshu Chaudhary,Changchun Wang

Graphical A hollow victory : Hollow-core magnetic colloidal nanocrystal clusters (HMCNCs) with controllable chambers and tunable porous shells are endowed with pH-stimulated drug-release and targeting capability through a ligand-exchange method (see scheme, PAA= poly(acrylic acid)). Folate-HMCNCs with doxorubicin in the core showed higher cytotoxicity towards HeLa cells than free doxorubicin. The fabrication of hierarchical magnetic nanomaterials with well-defined structure, high magnetic response, excellent colloidal stability, and biocompatibility is highly sought after for drug-delivery systems. Herein, a new kind of hollow-core magnetic colloidal nanocrystal cluster (HMCNC) with porous shell and tunable hollow chamber is synthesized by a one-pot solvothermal process. Its novelty lies in the “tunability” of the hollow chamber and of the pore structure within the shell through controlled feeding of sodium citrate and water, respectively. Furthermore, by using the ligand-exchange method, folate-modified poly(acrylic acid) was immobilized on the surface of HMCNCs to create folate-targeted HMCNCs (folate-HMCNCs), which endowed them with excellent colloidal stability, pH sensitivity, and, more importantly, folate receptor-targeting ability. These assemblages exhibited excellent colloidal stability in plasma solution. Doxorubicin (DOX), as a model anticancer agent, was loaded within the hollow core of these folate-HMCNCs (folate-HMCNCs-DOX), and drug-release experiments proved that the folate-HMCNCs-DOX demonstrated pH-dependent release behavior. The folate-HMCNCs-DOX assemblages also exhibited higher potent cytotoxicity to HeLa cells than free doxorubicin. Moreover, folate-HMCNCs-DOX showed rapid cell uptake apart from the enhanced cytotoxicity to HeLa cells. Experimental results confirmed that the synthesized folate-HMCNCs are smart nanovehicles as a result of their improved folate receptor-targeting abilities and also because of their combined pH- and magnetic-stimuli response for applications in drug delivery.

研究领域: 纳米医学 · 生物材料 · 肿瘤学
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Biomaterials Science · 2015 ·Vol. 4 ·期 1 ·104-114 · IF 3.831

Dual acid-responsive supramolecular nanoparticles as new anticancer drug delivery systems

Chunran Wang,Xiaofei Chen,Xuemei Yao,Li Chen,Xuesi Chen

Considering the specific pH gradients of tumour microenvironments, a dual acid-responsive drug delivery system, which can respond to the tumor extracellular and intercellular pH stimuli, has been fabricated via simple host–guest recognition. Firstly, we synthesise 2,4,6-trimethoxybenzaldehyde modified dextran (Dex-TMBA) and mPEG-imine-β-cyclodextrin (PIC), respectively. And then, through the host–guest recognition between the cyclodextrin (CD) of PIC and the benzene ring of Dex-TMBA, a kind of dual acid-responsive supramolecular drug delivery system can be fabricated. Under neutral pH conditions, anticancer drugs can be loaded by forming supramolecular nanoparticles via the host–guest recognition. While, at tumor extracellular pH (∼6.8), the acid-labile benzoic–imine of PIC cleaves and the nanoparticles are amino positively charged to facilitate cell internalization. Subsequently, due to the hydrolysis of acetal bonds in Dex-TMBA under significantly increased acidity in subcellular compartments such as the endosomes (∼5.3), the loaded doxorubicin releases from the endocytosed drug delivery. This dual acid-responsive nanoparticles can efficiently load and release drugs, acting as drug delivery systems for enhancing anticancer efficiency.

研究领域: 药剂学 · 生物医学工程 · 肿瘤学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2020 · IF 3.232

pH-stimulus response dye-cucurbituril sensor for amino acids in aqueous solution

Mei-Xiang Yang,Qing Tang,Mei Yang,Qin Wang,Zhu Tao,Xin Xiao,Ying Huang

The host–guest inclusion complexes that comprise an inverted cucurbit[7]uril ( i Q[7]) and a quinoline derivative, 4-(4-dimethylaminostyryl) quinoline (DSQ) at different pHs were exploited as multiple supramolecular sensors to sense l -α-amino acids. DSQ complexation inside i Q[7] at different pHs leads to increased fluorescence and formation of different-colored i Q[7]-DSQ complexes. The enhanced fluorescence of DSQ after i Q[7] encapsulation may be attributed to limited dimethylamine rotation and the formation of a twisted internal charge transfer (TICT) state. The DSQ@ i Q[7] sensors have different affinities for l -α-amino acids at different pHs. Therefore, we propose a pH-stimulus response supramolecular sensor for the discrimination of structurally similar l -α-amino acids in aqueous solution.

研究领域: 分析化学 · 超分子化学
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CHINESE CHEMICAL LETTERS · 2016 · IF 1.947

Synthesis and characterization of silsesquioxane-cored star-shaped hybrid polymer via “grafting from” RAFT polymerization

Zhi-Wei Yu,Shu-Xi Gao,Kai Xu,You-Xiong Zhang,Jun Peng,Ming-Cai Chen

Organic/inorganic hybrid polymers have been widely studied for their potential use in nanocontainers and nanocarriers. In this article, one star-shaped hybrid polymer, polyhedral oligomeric silsesquioxane (POSS) grafted poly( N , N -(dimethylamino)ethyl methacrylate) (POSS- g -PDMA), was synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT). The pH stimuli-responsive character of POSS- g -PDMA in aqueous solution were also studied.

CAS / MDL: 25154-86-3
研究领域: 材料科学 · 高分子化学 · 纳米技术
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LANGMUIR · 2019 · IF 3.683

Dual-Sensitive Graphene Oxide Loaded with Proapoptotic Peptides and Anticancer Drugs for Cancer Synergetic Therapy

Jing Zhang,Liqun Chen,Biao Shen,Lingdong Chen,Jiaying Mo,Jie Feng

A dual-sensitive drug delivery system (DDS) based on graphene oxide (GO) which is simultaneously loaded with proapoptotic peptides and anticancer drugs was rationally designed and fabricated for cancer synergetic therapy. Specifically, a kind of cell apoptosis peptide (KLAKLAK)2 (KLA) was anchored on the surface of GO via a disulfide bond to obtain GO-SS-KLA. Then, the aromatic anticancer drug doxorubicin (DOX) was loaded on GO through π–π conjugation and hydrogen bonding interactions. Finally, bovine serum albumin (BSA) was used to coat the GO carrier to obtain a biological medium-stable GO-based DDS, DOX@GO-SS-KLA/BSA. The results show that KLA and DOX can be released responding to the reductive and pH stimulus inside the cells, respectively, and achieve a synergetic therapy for cancer. Moreover, the results of stability studies show that DOX@GO-SS-KLA/BSA could be stably dispersed in water for more than 8 days and in 10% fetal bovine serum for at least 6 days. The constructed DOX@GO-SS-KLA/BSA exhibits great potential as a drug carrier for co-delivery of various therapeutic agents.

研究领域: 纳米医学 · 癌症研究 · 药物递送 · 生物材料科学
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MATERIALS & DESIGN · 2018 · IF 4.525

Design of Janus-like PMMA-PEG-FA grafted fluorescent carbon dots and their nanoassemblies for leakage-free tumor theranostic application

Mingliang Pei,Xu Jia,Peng Liu

Theranostic nanomedicines for imaging guided therapy, simultaneously monitoring the real-time response of therapy, have aroused great interest in cancer research. Here, the Janus-like poly(methyl methacrylate)- b -poly(ethylene glycol)-folic acid block -copolymer-grafted fluorescent carbon dots (CDs-PMMA-PEG-FA) were synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP) of methyl methacrylate (MMA) in ethanol with the modified carbon dots (CDs-Br) as initiator, followed by the PEGylation via click chemistry. Interestingly, they could self-assemble into blank nanoassemblies with hydrodynamic diameter of about 150 nm and Doxorubicin (DOX)-loaded nanoassemblies of about 270 nm with high DOX–loading capacity of 67.2%. The DOX-loaded nanoassemblies could release >80% of DOX at pH 5.0 within 36 h, while that at pH 7.4 was only 2%, demonstrating the excellent on-off behavior on pH stimuli. A possible mechanism was proposed to explore the drug release pathway in vitro. Enhanced anti-cancer efficacy of the CDs-PMMA-PEG-FA/DOX nanoassemblies with folate receptor (FR)-mediated targeting function than the free DOX was revealed by the MTT assays, while the bare CDs-PMMA-PEG-FA nanoassemblies possessed good cytocompatibility. The cellular uptake result showed that the proposed fluorescent theranostic nanomedicines could be effectively internalized into HepG2 cells and release DOX into the cell nuclei.

CAS / MDL: 6066-82-6 471-25-0
研究领域: 生物材料学 · 纳米医学 · 肿瘤学
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Chemical Science · 2017 ·Vol. 9 ·期 5 ·1184-1190 · IF 8.668

Imaging multiple microRNAs in living cells using ATP self-powered strand-displacement cascade amplification

Xiangdan Meng,Wenhao Dai,Kai Zhang,Haifeng Dong,Xueji Zhang

Herein, we design a smart autonomous ATP self-powered strand-displacement cascade amplification (SDCA) system for highly sensitive multiple intracellular miRNA detection. Rationally engineered Y-motif DNA structures are functionalized on mesoporous silica-coated copper sulfide nanoparticles loaded with numerous ATPs (CuS@mSiO2-Y/ATP) through pH stimulus-responsive disulfide bonds. The SDCA system is implemented by endogenous specific miRNA as a trigger and ATP as fuel released from the nanocarrier at acidic pH and photothermal stimuli-responsive CuS. The ATP self-powered SDCA process presents higher sensitivity compared to that without amplification for intracellular miRNA imaging. Two-color simultaneous and sensitive imaging of multiple cancer-related miRNAs in living cells is also confirmed. This enables facile and accurate differentiation between normal cells and different types of cancer cell using intracellular miRNA imaging, which improves the veracity and timeliness for early cancer diagnosis.

CAS / MDL: 67-68-5 57-09-0
研究领域: 纳米技术 · 生物医学工程 · 分子生物学 · 癌症研究
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EUROPEAN POLYMER JOURNAL · 2015 · IF 3.005

Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation

Zhongqian Song,Yuanhong Xu,Wenrong Yang,Liang Cui,Jizhen Zhang,Jingquan Liu

A novel tri-block copolymer poly(oxopentanoate ethyl methacrylate)-block-poly(pyridyl disulfide ethyl acrylate)-block-poly(ethylene glycol acrylate) [poly(OEMA-b-PDEA-b-PEGA)], retaining active keto groups and pyridyl disulfide (PDS) side functionalities, was synthesized as a drug delivery vehicle using reversible addition–fragmentation chain transfer (RAFT) polymerization method. One mimic drug pyridine-2-thione (PT) was introduced into the monomer, PDEA for copolymerization. The other mimic drug O-benzylhydroxylamine (BHA) was conjugated with tri-block copolymer via efficient oxime coupling chemistry, followed by the attachment onto graphene via π–π stacking interaction to obtain a graphene/tri-block copolymer composite. 1 H NMR, UV–vis absorption spectroscopy, fluorescence spectroscopy, gel permeation chromatography (GPC), atomic force microscope (AFM) and transmission electron microscope (TEM) were used to verify the successful step-wise preparation of the tri-block copolymer and drug loaded composite. In vitro release behaviors of BHA and PT from graphene/tri-block copolymer composite via dual drug release mechanisms were investigated. BHA can be released under acid environment, while PT will be released in the presence of reducing agents, such as dithiothreitol (DTT) or glutathione (GSH). It can be envisioned that this novel composite could be exploited as a novel intracellular drug delivery system via dual release mechanisms.

研究领域: 材料科学 · 聚合物化学 · 药物传递系统 · 纳米技术
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