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MACROMOLECULES · 2018 · IF 5.914

Tetraphenylethene Cross-Linked Thermosensitive Microgels via Acylhydrazone Bonds: Aggregation-Induced Emission in Nanoconfined Environments and the Cononsolvency Effect

Jinqiao Xue,Wei Bai,Hanyi Duan,Jingjing Nie,Binyang Du,Jing Zhi Sun,Ben Zhong Tang

We studied the aggregation-induced emission (AIE) phenomenon in a nanoconfined environment, where the AIE-active molecule, namely, 1,1,2,2-tetrakis(4-methanoylphenyl)ethane (TPE-4ALD), was held in space via four acylhydrazone bonds within the thermosensitive microgel networks. The thermosensitive microgels, namely N-AH-TPE, were synthesized via the copolymerization of N-isopropylacrylamide (NIPAM) and 4-acylhydrazine-(2-hydroxy-3-(methacryloxypropyl)pyridine hydrochloride (AH monomer) with TPE-4ALD as cross-linker via surfactant free emulsion polymerization (SFEP) in aqueous solution at 70 °C. Acylhydrazone-bonded tetraphenylethene (TPE-4AH) moieties were thus constructed and worked as the fluorophore in N-AH-TPE microgels. The aqueous suspensions of N-AH-TPE microgels exhibit strongly bluish-green fluorescence under ultraviolet excitation because the four arms of TPE-4AH moieties were held and their intramolecular motions are strongly restricted. It is estimated that there is one TPE-4AH moiety per about 394 nm3 for the swollen N-AH-TPE microgels. The fluorescent properties of N-AH-TPE microgels can be modulated via the change of hydrophilic and hydrophobic environments of TPE-4AH moieties exerted by external stimuli, like addition of various good solvents for TPE-based structures, i.e., N,N-dimethylformamide (DMF), methanol, ethanol, tetrahydrofuran (THF), and N,N-dimethyl sulfoxide (DMSO), varying the solution temperature as well as the counteranions of the microgels. An unusual enhancement in the fluorescent intensity is observed when specific amounts of organic solvent are added into the aqueous suspensions of N-AH-TPE microgels, which can be attributed to the cononsolvency of the polyNIPAM network chains. The shrinkage of N-AH-TPE microgels caused by the cononsolvency effect further strengthens the confinement of TPE-4AH moieties and hence enhances the fluorescent emission of the microgels even though the organic solvents added are good solvents for TPE-4AH. Increasing the solution temperature of N-AH-TPE microgels or introducing hydrophobic counteranions into the microgels also significantly enhances the fluorescent emission of the microgels.

CAS / MDL: 7440-66-6 7550-45-0
研究领域: 材料科学 · 化学 · 高分子科学 · 纳米技术 · 光学
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ANALYST · 2020 ·Vol. 145 ·期 10 ·3528-3534 · IF 3.978

Synergy of CO2-response and aggregation induced emission in a small molecule: renewable liquid and solid CO2 chemosensors with high sensitivity and visibility

Zhijian Mai,Hao Li,Yixun Gao,Yue Niu,Yongrui Li,Nicolaas Frans de Rooij,Ahmad Umar,M. S. Al-Assiri,Yao Wang,Guofu Zhou

A tetraphenylethylene (TPE) derivative (N,N-dimethyl-N′-(4-(1,2,2-triphenylvinyl)phenyl)acetimidamide, TPE-amidine) was designed and synthesized, and used to prepare visible CO2 chemosensors, TPE-amidine-L (liquid) and TPE-amidine-S (solid). The hydrophilicity of TPE-amidine thoroughly changed because of the unique reversible reaction between the amidine group and CO2, which controlled the molecular aggregation extent in water by CO2. Combining with the well-known aggregate-induced emission effect, the highly selective CO2 chemosensor TPE-amidine-L was developed, which has the lowest CO2 detection limit of 24.6 ppm compared with other reported CO2 chemosensors, and can be regenerated within 10 s by adding triethylamine. With the aim of being safer and more convenient to use, a polyacrylamide hydrogel containing TPE-amidine was prepared as a renewable CO2 sensing “tape” (TPE-amidine-S). The flexibility, adhesivity, CO2 sensitivity and reversibility of the “tape” is systematically investigated, showing great potential for “on-site” and “real-time” CO2 detection in practical applications.

研究领域: 化学 · 材料科学 · 环境科学
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FOOD CHEMISTRY · 2023 · IF 8.8

Development of a fluorescent sensor based on TPE-Fc and GSH-AuNCs for the detection of organophosphorus pesticide residues in vegetables

Xiaoyang Wang,Huajie Yu,Qiuhong Li,Yuhang Tian,Xiaolin Gao,Wanqi Zhang,Zhicong Sun,Yaoting Mou,Xia Sun,Yemin Guo,Falan Li

A novel dual-signal fluorescent sensor was developed for detecting organophosphorus pesticides (OPs). It relies on the catalytic activities of acetylcholinesterase (AChE) and choline oxidase (ChOx) to generate hydrogen peroxide (H 2 O 2 ) through the conversion of acetylcholine (ACh) to choline·H 2 O 2 then oxidizes ferrocene-modified tetraphenylethylene (TPE-Fc) to its oxidized state (TPE-Fc + ), resulting in enhanced cyan fluorescence due to aggregation. Simultaneously, ferrocene oxidation generates hydroxyl radicals (•OH), causing a decrease in orange fluorescence of glutathione-synthesized gold nanoclusters (GSH-AuNCs). The presence of OPs restricts AChE activity, reducing H 2 O 2 production. Increasing OPs concentration leads to decreased cyan fluorescence and increased orange fluorescence, enabling visual OPs detection. The sensor has a linear dynamic range of 10–2000 ng/mL with a detection limit of 2.05 ng/mL. Smartphone-based color identification and a WeChat mini program were utilized for rapid OPs analysis with successful outcomes.

研究领域: 分析化学 · 环境科学 · 食品安全
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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

AIE-based cyclodextrin metal–organic frame material for fluorescence detection of nitrofuran and tetracycline antibiotics in aqueous solution

Xuezhi Sun,Yunfan Qiao,Min Zhang,Yongzhe Cheng,Fanghong Ning,Hongyang Zhang,Ping Hu

The problem of antibiotic residues is very serious and is harmful to the ecological environment and the human body. We have developed a method for the rapid detection of antibiotics in water samples. Firstly, we prepared a fluorescent material (TPE@CLMOF) with cyclodextrin cross-linked MOF (CLMOF) and tetraphenylethylene (TPE) using a simple way. Due to diphenyl carbonate cross-linking, the fluorescent MOF can glow stably in water. Compared with TPE (40.1%), the absolute quantum yield of TPE@CLMOF increases to 63.2%. The fluorescence of TPE@CLMOF can be selectively quenched by Nitrofurans (NFs) and Tetracyclines (TCs) antibiotics in water. The detection limits of nitrofurazone, nitrofurantoin and chlortetracycline are 0.11, 0.13 and 0.16 μM, respectively. We have studied the adsorption of nitrofurazone, nitrofurantoin and chlortetracycline in TPE@CLMOF and the Langmuir adsorption model and pseudo-second-order kinetic model were established. The maximum adsorption capacity is 223, 209 and 185 mg g −1 , respectively. We also proposed a dual quenching mechanism of electron transfer and internal filtration effect, which is verified by quantum chemical calculations and experiments. Finally, the TPE@CLMOF was successfully used as a fluorescent sensor for the determination of antibiotic spiked honey samples.

研究领域: 环境科学 · 分析化学 · 材料科学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2023 · IF 4.3

pH Induced Self-assembly of AIE Fluorescent Probe for Tumor Imaging

Xiang Jing-Yuan,Zhang Wen-Long,Li He-Ting,He Ya-Ning

This work reported an AIE fluorescent probe for tumor imaging based on the pH induced self-assembly strategy. The fluorescent probe was composed of an acid-responsive soluble copolymer PEG- b -PAMA-DMMA with a maleic acid amide group and an anionic soluble aggregation-induced emission fluorogen (AIEgen) TPE-2SO 3 − . The polymer could be transformed into a protonated amine-containing polymer after the hydrolysis of maleic acid amide in acidic tumor microenvironment, which would be further self-assembled with TPE-2SO 3 − to form aggregated nanoparticles. The transition of TPE-2SO 3 − from dispersed state to aggregated state led to an obvious increase in fluorescence intensity due to its AIE characteristics.

CAS / MDL: 2002-24-6
研究领域: 材料科学 · 生物医学工程 · 癌症研究 · 纳米技术
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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

A dual-template molecularly imprinted sensor with TPE-XGBoost model for simultaneous specific detection of chloramphenicol and metronidazole in animal-derived foods

Shenghui Chen,Luming Xu,Wei Yu,Xiaobin Zhang,Shijuan Cao,Bo Liang,Ying Xu

A MIP/AuNPs/GCE electrode was constructed for simultaneous detection of CAP and MNZ. • The sensor shows a wide linear range (50–1500 μM) and low LODs of 1.70 and 2.09 μM. • Wavelet transform expands the feature dimensions of the DPV signals to enhance model prediction accuracy. • TPE-optimized XGBoost realizes accurate and robust dual-analyte concentration prediction. • The method achieves satisfactory recoveries in milk, fish, and egg real samples. Food safety concerns have increased the demand for reliable simultaneous detection of chloramphenicol (CAP) and metronidazole (MNZ), as these antibiotics are strictly regulated due to their potential health risks. However, the presence of aromatic nitro groups in both compounds poses a challenge for their simultaneous detection. In this study, an electrochemical sensor integrating electrodeposited gold nanoparticles (AuNPs) with a dual-template molecularly imprinted polymer (MIP) film was developed to achieve selective recognition and signal enhancement for both analytes. However, competitive adsorption at active sites in multi-component systems leads to nonlinear signal responses, rendering traditional linear calibration ineffective. To overcome this limitation, differential pulse voltammetry (DPV) signals were transformed into two-dimensional wavelet spectrograms, from which quantitative image features were extracted, and the necessity and robustness of these features were verified using SHAP analysis. An XGBoost regression model optimized via a Tree-structured Parzen Estimator (TPE) was subsequently constructed, yielding significantly improved predictive performance. The sensor exhibited a wide linear range for both CAP and MNZ (50–1500 μM) and low detection limits (1.70 μM and 2.09 μM, respectively). Satisfactory recoveries (89.37–107.31%) were obtained in spiked milk and fish samples. The proposed TPE-XGBoost-assisted dual-template molecular sensor provides a robust and generalizable strategy for rapid and accurate multi-residue detection in complex food matrices. Download: Download high-res image (218KB) Download: Download full-size image

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Materials Science & Engineering C-Materials for Biological Applications · 2020 · IF 5.88

Fabrication of claviform fluorescent polymeric nanomaterials containing disulfide bond through an efficient and facile four-component Ugi reaction

Hongye Huang,Ruming Jiang,Haijun Ma,Yongsan Li,Yuan Zeng,Naigen Zhou,Liangji Liu,Xiaoyong Zhang,Yen Wei

Multicomponent reactions (MCRs) have attracted broad interest for preparation of functional nanomaterials especially for the synthesis of functional polymers. Herein, we utilized an “old” MCR, the four-component Ugi reaction, to synthesize disulfide bond containing poly(PEG-TPE-DTDPA) amphiphilic copolymers with aggregation-induced emission (AIE) feature. This four-component Ugi reaction was carried out under rather mild reaction conditions, such as room temperature, no gas protection and absent of catalysts. The amphiphilic poly(PEG-TPE-DTDPA) copolymers with high number-average molecular weight (up to 86,440 Da) can self-assemble into claviform fluorescent polymeric nanoparticles (FPNs) in aqueous solution, and these water-dispersed nanoparticles exhibited strong emission, large Stokes shift (142 nm), low toxicity and remarkable ability in cellular imaging. Moreover, owing to the introduction of 3,3′-dithiodipropionic acid with disulfide bond, the resultant AIE-active poly(PEG-TPE-DTDPA) could display reduction-responsiveness and be utilized for synthesis of photothermal agents in-situ. Therefore, the AIE-active poly(PEG-TPE-DTDPA) could be promising for controlled intracellular delivery of biological activity molecules and fabrication of multifunctional AIE-active materials. Therefore, these novel AIE-active polymeric nanoparticles could be of great potential for various biomedical applications, such as biological imaging, stimuli-responsive drug delivery and theranostic applications.

研究领域: 材料科学 · 生物医学工程 · 化学合成
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FOOD CHEMISTRY · 2023 · IF 8.8

Open roads and bridge: Preservation of fresh beef by a packaging film constructed from photosensitizing bacterial cellulose

Rui Chen,Yajie Zhang,Zuwang Zhang,Lenan Yao,Lizhi Liu,Jianlong Wang,Rong Wang

Food packaging is now widely used in everyday life to protect food from certain environmental factors. In this work, we have successfully prepared a bacterial cellulose/chitosan-TPE-COOH composite film (BC/CS-TPE), which can achieve broad-spectrum killing of bacteria through a variety of antibacterial mechanisms and ensure the freshness of the beef. In this complex film, CS acts as “advance team”, responsible for breaking through the cell wall or outer membrane of bacteria, while the reactive oxygen species produced by photosensitizer under irradiation attacks bacteria, further increasing the destructive effect on the bacterial cell membrane. This allows the film to have outstanding antibacterial properties that can kill 10 8 CFU/mL pathogens in 10 min. At the same time, cell experiments and hemolysis experiments proved that the film has good biocompatibility. Therefore, BC/CS-TPE film, as the efficient functional food packaging film, has a broad future application prospect.

CAS / MDL: 8004-87-3
研究领域: 材料科学 · 食品科学 · 生物技术
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FOOD CHEMISTRY · 2022 · IF 9.231

Preparation of magnetic hyper-crosslinked polymer for high efficient preconcentration of four aflatoxins in rice and sorghum samples

Jie Li,Bin Zhao,Lin Hao,Weihua Liu,Chun Wang,Zhi Wang,Qiuhua Wu

Aflatoxins have carcinogenic effect on human health, developing effective adsorbents for their enrichment and detection is particularly required. A magnetic hyper-crosslinked polymer (MHCP-TPE) was prepared and used as a magnetic sorbent to adsorb and isolate aflatoxins from rice and sorghum samples prior to high performance liquid chromatography-fluorescence detection. MHCP-TPE exhibited good magnetic separation ability and reusability, with fast adsorption kinetics and quite good adsorption efficiency for the aflatoxins. At optimized conditions, a sensitive and reliable method was established for the determination of four aflatoxins (B 1 , B 2 , G 1 and G 2 ) in rice and sorghum samples. The limits of detection were 0.003–0.075 ng g −1 and 0.01–0.25 ng g −1 for rice and sorghum, respectively. Good method recoveries ranging from 83.0 % to 117 % were obtained, with relative standard deviations less than 8.0 %. This method offered a superior alternative to determine trace level of aflatoxins in cereal foods. MHCP-TPE holds great potential in separation science.

CAS / MDL: 1667-10-3 632-51-9
研究领域: 食品科学 · 分析化学 · 材料科学
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Nanoscale · 2019 ·Vol. 11 ·期 38 ·17831-17840 · IF 6.97

Janus micromotors for motion-capture-lighting of bacteria

Long Zhao,Songzhi Xie,Yuan Liu,Qingjie Liu,Xiaojie Song,Xiaohong Li

The rapid and sensitive identification of bacteria has long been a major challenge in quality control, environmental monitoring and food safety. In the current study, the “motion-capture-lighting” strategy is proposed via integration of motion-enhanced capture of bacteria and capture-induced fluorescence turn-on of micromotors. Compared with the commonly used microtubes and microparticles, micromotors of flexible fiber rods could offer multiple interactions with the bacterial surface with less steric hindrance. Janus fiber rods (JFRs) are prepared by cryocutting of aligned fibers prepared by side-by-side electrospinning. Catalase is grafted on one side of JFRs to produce oxygen bubbles for propulsion of Janus micromotors (JMs), and mannose is conjugated on the other side for specific recognition of FimH proteins from fimbriae on the bacterial surface. The biphasic Janus structure of JFRs and the separate grafting of catalase and mannose on the opposite sides of JMs are confirmed after fluorescent labelling. JMs with aspect ratios of 0.5, 1, 2 and 4 are fabricated, and the aspect ratios of JMs show significant effects on the tracking trajectories and motion speed. JMs with the aspect ratio of 2 exhibit significantly higher magnitudes of mean square displacement (MSD) with a directional motion trajectory, leading to higher bacterial capture and larger fluorescence intensity changes. The bacteria capture leads to lighting up of JMs due to the aggregation-induced emission (AIE) effect of tetraphenylethene (TPE) derivatives. Under an ultraviolet lamp, the fluorescence color of JM suspensions turns from blue to bluish-green and to green after incubation with E. coli of 102 and 105 CFU mL−1, respectively. The fluorescence intensities of JM suspensions could be fitted to an equation versus bacterial concentrations, and the limit of detection (LOD) was around 45 CFU mL−1 within 1 min. Thus, this study demonstrates a motion-capture-lighting strategy for visual, rapid and real-time detection of bacteria without complicated sample pretreatment, expensive apparatus, and trained operators.

CAS / MDL: 38215-36-0 81-88-9
研究领域: 生物医学工程 · 微流控技术 · 分析化学 · 细菌学
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ANALYTICAL CHEMISTRY · 2018 · IF 6.042

DNA-Conjugated Amphiphilic Aggregation-Induced Emission Probe for Cancer Tissue Imaging and Prognosis Analysis

Xudong Wang,Jun Dai,Xuehong Min,Zhihua Yu,Yong Cheng,Kaixun Huang,Juliang Yang,Xiaoqing Yi,Xiaoding Lou,Fan Xia

Detection of an ultralow concentration of mRNA is important in the prognosis of gene-related diseases. In this study, a DNA-conjugated amphiphilic aggregation-induced emission probe (TPE-R-DNA) was synthesized for cancer tissue imaging and prognosis analysis based on an exonuclease III-aided target recycling technique. TPE-R-DNA comprise two components: a hydrophobic component that serves as the “turn-on” long wavelength fluorescence imaging agent (TPE-R-N3); and a hydrophilic single DNA strand (Alk-DNA) which acts as specific recognition part for target mRNA. In the absence of target mRNA, TPE-R-DNA had almost no fluorescence because of its high water solubility. Conversely, the TPE-R-DNA was digested by exonuclease III (Exo III) in the presence of MnSOD mRNA to release the hydrophobic fluorogens (TPE-R-AT). Subsequently, TPE-R-AT formed aggregates, and therefore, fluorescence signal was distinctly observed. For the first time, the structure of the hydrolysis product (TPE-R-AT), containing two bases A and T, was proved by the mass spectrum (MS) and high-performance liquid chromatography (HPLC). Moreover, the detection limit toward mRNA could be achieved in as low as 0.6 pM. Furthermore, the fluorescent signal can be used to confirm the MnSOD mRNA expression level in cancer tissue. The MnSOD mRNA expression in renal cancer was lower than in renal cancer adjacent tissue. In particular, the expression level was analyzed to predict prognosis of cancer patients. Our results demonstrate that a shorter survival time was evident among patients in lower MnSOD mRNA expression. Thereby, it indicates great potential for the development of an ultrasensitive biosensing platform for the application in disease prognosis.

研究领域: 癌症研究 · 分子生物学 · 生物医学工程 · 分析化学
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BIOCONJUGATE CHEMISTRY · 2017 · IF 4.818

Polyplex Micelle with pH-Responsive PEG Detachment and Functional Tetraphenylene Incorporation to Promote Systemic Gene Expression

Zhu Jiang,Qixian Chen,Xi Yang,Xiyi Chen,Zhen Li,De-E Liu,Wei Li,Yingjie Lei,Hui Gao

Tetraphenylene (TPE), characterized as a lipophilic and aggregation-induced-emissive fluorophore, was used to incorporate into an electrostatic self-assembled polyethylenimine-poly(ethylene glycol) (PEI–PEG)/plasmid DNA (pDNA) complexed micelle. The hydrophobic character of TPE appeared to drive a higher degree of condensation of the pDNA payload, which consequently resulted in not only strengthened colloidal stability of the constructed polyplex micelle but also improved biocompatibility by virtue of the elevated PEG crowdedness owing to the TPE-induced collapse of pDNA. These beneficial consequences potentially permitted a larger number of polyplex micelles to be internalized into the cells. PEG segments were designed to enable selective detachment from polyplex micelles in acidic milieu, e.g., the tumor microenvironment, and intracellular endosome compartment, based on the strategic arrangement of acid-responsive cleavable linkage between PEG and PEI. Upon PEG detachment, the exposure of cationic PEI/TPE polyplex was allowed to directly interact with the cell membrane, endosome membrane, and charged intracellular species, thus promoting cell internalization, endosome escape, and the release of the pDNA payload. Of note, this association of cationic PEI/TPE polyplex with the endosomal membrane could be further facilitated with the aid of lipophilic TPE, thereby eliciting pronounced destabilization potency to the endosome membrane and exerting an endosomal escape function. Eventually, the proposed system of these facile strategies, including responsive PEG detachment and functional TPE incorporation, was proven to provide efficient gene expression in the targeted tumors with an appreciable safety profile via systemic administration.

研究领域: 纳米医学 · 基因治疗 · 生物医学工程 · 材料科学
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