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EUROPEAN POLYMER JOURNAL · 2025 · IF 6.3

Polymerization-induced self-assembly of N-substituted glycine N-carboxyanhydrides in selected solvents

Qing Gao,Hailin Fu,Hui Liu,Pengfei Li,Jin Shi,Yao Lin,Ziyuan Song

Poly(sarcosine) (PSar)-based diblock copolypeptoid nanoparticles are promising alternatives to PEGylated polymeric nanocarriers. However, their preparation was limited by the slow polymerization kinetics and low assembly concentrations. Herein, we report the facile preparation of copolypeptoid nanoparticles through polymerization-induced self-assembly of N -substituted glycine N -carboxyanhydrides (NNCAs) in solvents with low polarity and weak hydrogen-bonding ability like dichloromethane (DCM). In contrast to the conventional polymerization in N , N -dimethylformamide (DMF), NNCAs were polymerized at an accelerated rate in DCM that minimized side reactions from water and other impurities. With isopentylamine-initiated PSar as the first stabilizing block, the polymerization of N -benzyl glycine N -carboxyanhydrides resulted in the formation of spherical or rod-like nano-assemblies at high solid contents (up to 15%) within several hours. We believe this work not only improves our basic understanding on NNCA polymerization behaviours, but also offers an efficient strategy to prepare drug nanocarriers with PSar corona, facilitating the downstream application studies.

研究领域: 材料科学 · 生物医学工程
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DYES AND PIGMENTS · 2016 · IF 4.055

Polymorphism-dependent aggregation-induced emission of pyrrolopyrrole-based derivative and its multi-stimuli response behaviors

Yingchun Ji,Zhe Peng,Bin Tong,Jianbing Shi,Junge Zhi,Yuping Dong

Bis(4-cyanophenyl)-4,4′-(2,5-diphenylpyrrolo[3,2-b] pyrrole-1,-4-diyl) dibenzoate (DPPCN) was synthesized and exhibited aggregation-induced emission properties. DPPCN was cultivated in different solvents getting three kinds of crystals, A, B and C. Crystals of A and B were respectively blue and cyan-blue emissive, while C was yellow-green emissive. They all displayed crystalline-induced emission behaviors. According to X-ray single crystal diffraction analysis, the intermolecular interactions account for restricted internal rotations , leading to fluorescence enhancement. The different kinds of co-effects of the solvent, intermolecular forces, molecular conformations and molecular packing modes endow DPPCN polymorphisms with multi-color emissions (from blue to yellow and up to 60 nm) and different fluorescence efficiencies. The fluorescence of A can be reversibly tuned by grinding and exposing to chloroform vapor with a 46 nm wavelength change. The crystal of C can blue shifted the fluorescence that matches with B upon fumed by chloroform for about 12 h and further blue shifted the fluorescence emission that matches with A when fumed by chloroform for about 24 h. Multi-color fluorescence tuning and switching is attributed to the nature of polymorphs, that is, a change of molecular conformation and intermolecular packing modes. The crystal of A also exhibited thermo-stimulus fluorescence switching behavior due to the co-crystallization with solvent chloroform. The properties of A show promising applications in temperature monitoring and volatile organic compound detecting devices.

研究领域: 材料科学 · 化学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2016 ·Vol. 34 ·期 3 ·367-377 · IF 1.811

Single emulsion microfluidic production of Janus and core-shell particles via off-chip polymerization

Zhu Ai-di,Guo Ming-yu

In this work, we describe a straightforward approach to produce monodisperse Janus and core-shell particles by using organic solvent free single emulsion droplet-based microfluidic device combining with off-chip polymerization. To accomplish this, methyl methacrylate (MMA) was used as both the oil phase and solvent to dissolve a polymerizable PEGbased macromolecular surfactant, instead of traditional surfactant, and the photo-initiator. Janus particles can be easily obtained by off-chip UV polymerization due to polymerization induced phase separation between PEG and the formed poly(methyl methacrylate). At the same time, core-shell particles can also be easily attained by inverting the original collecting tube several times and then exposing to UV light. These results may extend the scope of microfluidic technology and the studies on polymerization induced self-assembly/phase-separation into easy fabrication of various new functional materials.

研究领域: 材料科学 · 化学工程
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SENSORS AND ACTUATORS B-CHEMICAL · 2021 · IF 7.46

Multiparametric miRNAs profiling by polymerization induced fluorescence-off amplification for acute myocardial infarction diagnosis

Xingjie Wu,Hong Yang,Wei Li,Ling Tao,Qingteng Wang,Yingzu Jin,Xuecheng Sun,Xiangchun Shen

The prompt diagnosis of acute myocardial infarction (AMI) for patients with acute ischemic-type chest pain is critical for timely AMI treatment and lowering its casualty rate. In this article, we developed a multiparametric detection technique for AMI related microRNAs (miRNAs), which is based on the polymerization induced fluorescence-off (PIFO) signal amplification technique. PIFO can be implemented on a specially designed microfluidic chip equipping a fluorescence sensor, which is able to profile 3 miRNAs simultaneously in 45 min with a detection limit of 6100 miRNAs copies. Comparing with other polymerization-based signal amplification techniques, PIFO is rapid, oxygen-independent, multiparametric, and can be performed in ambient environment. The miniaturized PIFO device can be further applied to analyze AMI related miRNAs in clinical serum samples, and displays excellent performance in distinguishing AMI patients from patients with other cardiovascular diseases. Moreover, PIFO shows a high accuracy for AMI diagnosis among patients with low hypersensitivity troponin I level (< 0.1 ng mL −1 ) as a result of the early and fast respond to AMI onset by miRNAs.

研究领域: 医学诊断 · 分子生物学 · 生物传感器
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POLYMER · 2024 · IF 4.1

Polymerization-induced emission of borinic acid towards stimuli-responsive luminescent polymers

Xing-Ying Zheng,Tao Li,Hua-Wen Cai,Xin-Hui Wang,Xiao-Li Sun,Wen-Ming Wan

Stimuli-responsive luminescent polymer is generally prepared by incorporation of both stimuli-responsive and luminescent moieties into polymer chain, which cause difficulties in molecular design and synthesis. The preparation of stimuli-responsive luminescent polymer from one moiety represents a time-saving approach and is highly desirable. Here, we demonstrate a simple approach to achieve stimuli-responsive luminescent polymers through polymerization-induced emission of nonemissive borinic acid moiety. Attributed to versatile borinic acid moiety, the prepared borinic acid polymer (PBA) exhibits upper critical solution temperature (UCST) type thermo-responsive behavior and chemical sensitivities. Interestingly, PBA is not only stimuli-responsive but also luminescent, while the repeating borinic acid moiety is nonemissive, indicating borinic acid is a novel PIE luminogen (PIEgen). This work therefore opens a new avenue to molecularly design stimuli-responsive luminescent polymer from nonemissive borinic acid moiety, which might cause inspirations to the fields of boron chemistry, stimuli-responsive polymer and luminescent polymer.

研究领域: 高分子化学 · 发光材料 · 刺激响应性材料
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Polymer Chemistry · 2024 ·Vol. 15 ·期 45 ·4637-4649 · IF 4.1

Functionalization of nano-objects in living anionic polymerization-induced self-assembly and their use for improving thermal properties of epoxy resins

Guicun Guo,Jiali Wu,Jingwei Zhang,Peng Zhou,Ding Shen,Penghan Li,Guowei Wang

Nano-objects generated via a scalable polymerization-induced self-assembly (PISA) process can serve as organic nanofillers, replacing the widely used inorganic nanofillers in composites. In this contribution, polyisoprene (PI)-b-polystyrene (PS) (PI-b-PS) or PI-b-PS/PS nano-objects were prepared via a living anionic polymerization-induced self-assembly (LAPISA) process or a derived process of living anionic polymerization-induced cooperative assembly (LAPICA) using nonpolar n-heptane as a solvent, which facilitated the control over morphologies and sizes. After the living species in the core region were in situ crosslinked by divinylbenzene (DVB) monomers, stabilized PDVB@(PI-b-PS) or PDVB@(PI-b-PS/PS) nano-objects were generated. After hydroxylated or epoxidized nano-objects were obtained through thiol–ene or epoxidation reactions on the double bonds of the PI stabilizer, the miscibility between the nano-objects and epoxy resin was improved, and the functionalized nano-objects could be introduced into epoxy resin. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and thermomechanical analysis (TMA) results affirmed that the organic nano-objects could improve the thermal properties of the composites, which were obviously superior to commercial inorganic silica nano-objects. In particular, the composites with smaller spherical nano-objects had a higher glass transition temperature (Tg) than those with larger spherical ones or worm-like ones. Transmission electron microscopy (TEM) measurements verified the uniform distribution of organic nano-objects and the formation of sufficiently integrated interfaces between the epoxy resin and nano-objects, thereby improving the thermal properties of the composites.

研究领域: 材料科学 · 化学工程
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Materials Science & Engineering C-Materials for Biological Applications · 2018 · IF 5.08

Fabrication and biological imaging of hydrazine hydrate cross-linked AIE-active fluorescent polymeric nanoparticles

Yanzhu Liu,Liucheng Mao,Saijiao Yang,Meiying Liu,Hongye Huang,Yuanqing Wen,Fengjie Deng,Yongxiu Li,Xiaoyong Zhang,Yen Wei

Amphiphilic copolymers play a paramount role in the fabrication of fluorescent polymeric nanoparticles (FPNs) through the self-assembly procedure. In this work, novel hydrazine hydrate cross-linked amphiphilic poly(PEG‑ co ‑FHMA) copolymers were constructed via reversible addition-fragmentation chain transfer (RAFT) polymerization, containing an aggregation-induced emission (AIE) active hydrophobic moiety and a hydrophilic poly(ethylene glycol) (PEG) group. Different characterization techniques have been employed to confirm their successful synthesis. Due to their amphiphilic property, the resulting poly(PEG‑ co ‑FHMA) copolymers can self-assemble into FPNs in aqueous solution and form poly(PEG‑ co ‑FHMA) FPNs with size ranging from 100 to 200 nm. The investigation of photophysical properties demonstrated poly(PEG‑ co ‑FHMA) FPNs possess strong fluorescence, large Stokes shift, excellent AIE characteristic, low critical micelle concentration and remarkable photostability. Biological assay results suggested that these cross-linked AIE-active FPNs are of low toxicity and excellent cell dyeing performances. All of these features make them promising candidates for biomedical applications. As compared with typical AIE-active FPNs based on the synthetic AIE-active compounds, the novel cross-linked AIE-active FPNs based on the Schiff base is rather simple, good designable and universal. More importantly, this strategy could also be adopted for preparation of a large number of AIE-active FPNs because of the well designability of copolymers and salicylaldehyde derivatives. Thus this work will provide a novel route for preparation of multifunctional AIE-active FPNs in a rather facile manner.

研究领域: 材料科学 · 生物医学工程 · 高分子化学
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Materials Chemistry Frontiers · 2017 ·Vol. 1 ·期 6 ·1200-1206 · IF 0

The photo-controlled polymerization-induced self-assembly and reorganization process for fabrication of polymeric nanomaterials

Jiemei Zhou,Chunyan Hong,Caiyuan Pan

A visible light mediated reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) is conducted in ethanol using poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) as a macro-chain transfer agent (macro-CTA), affording polymeric nanomaterials with various morphologies. Unlike the polymerization-induced self-assembly and reorganization (PISR) process initiated by thermal stimuli, the photo-controlled PISR can be performed under more mild conditions, such as visible light and room temperature. Photoredox catalysis is employed to regulate the polymerization via a photoinduced electron transfer (PET) process. It is observed that the polymerization can be affected by catalyst concentration and light intensity, and “ON/OFF” control over polymerization is also demonstrated.

研究领域: 材料科学 · 高分子化学
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LANGMUIR · 2021 · IF 3.882

Pickering Emulsions Stabilized by Diblock Copolymer Worms Prepared via Reversible Addition–Fragmentation Chain Transfer Aqueous Dispersion Polymerization: How Does the Stimulus Sensitivity Affect the Rate of Demulsification?

Yong Gao,Zhe Xiang,Xi Zhao,Guoxiang Wang,Chenze Qi

Responsive Pickering emulsions exhibit promising application in industry owing to the integration of the high storage stability with on-demand demulsification. In this study, stimuli-responsive Pickering emulsions stabilized by poly[oligo(ethylene glycol) methyl ether methacrylate]15-b-poly(diacetone acrylamide)120 (E15D120) worms were indicated, in which E15D120 worms were prepared via reversible addition–fragmentation chain transfer-based aqueous dispersion polymerization using thermo-sensitive POEGMA15 as both the stabilizer block and macro-chain transfer agent. The factors influencing the morphologies of copolymers during polymerization-induced self assembly have been investigated. A series of different morphological polymer nanoparticles including spheres, worms, and vesicles could be produced through rational synthesis. E15D120 worms demonstrated excellent emulsifying performances and could be used as emulsifiers to form n-dodecane-in-water Pickering emulsions at a low content. The formed n-dodecane-in-water Pickering emulsions revealed a slow demulsification at pH 10 or 70 °C or pH 10/70 °C combinations, and several hours were needed for the demulsification of Pickering emulsions. However, n-dodecane-in-water Pickering emulsions displayed a rapid demulsification (∼10 min) at an elevated temperature, such as 90 °C. The different demulsification rates were attributed to different sensitivities of E15D120 worms to external stimuli. Pickering emulsions integrating a rapid responsive demulsification with a slow one would be well satisfactory on different occasions.

研究领域: 材料科学 · 化学工程
✓ 已验证 DOI PubMed 高影响因子
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REACTIVE & FUNCTIONAL POLYMERS · 2024 · IF 4.5

HSA fibrillar networks assembled and stabilized in the condensed phase of thermoset polybenzoxazine

Huan Liu,Xiao-jie Zhang,Yu-xin Ding,Shao-hui Xiong,Zi-en Fu

12-hydroxystearic acid (HSA) was introduced into the thermoset benzoxazine, we expected that the stable ordered structures could be introduced into the thermoset three-dimensional network through the self-assembly of HSA and the polymerization-induced phase separation of benzoxazine monomers. To better understand the structural effects attributed to the introduction of HSA, some model compounds possessing the chemical structure-like HSA were also involved into the study. HSA and benzoxazine (Ba-bz) mixed with different weight ratios, an isotropic solution could be formed after the mixture melted, indicating that HSA molecules in Ba-bz monomers could assemble into ordered structures like in other organic solvents. The study found that the HSA molecules did not aggregate together in the form of individual molecule which completely distinguished from the model compounds. A conjunction of observation of macroscopic structure picture and characterization of microstructure of the samples, the results showed that HSA molecules spontaneously assembled into the fibrillar networks (SAFINs) in Ba-bz. Nanometric spherical micelles consist of HSA could be formed in the molten isotropic solution of HSA and Ba-bz and aggregate into tubes upon cooling. Due to the high concentration of HSA, the nanometric spherical micelles were easier to self-assembly into the large scale fibrillar tubes. During the polymerization, the fibrillar tubes could be stacked further under the action of the polymerization-induced and the rapid formation of the cross-linking network of polybenzoxazine stabilized the tubes. The tubular structure of HSA aggregation was filled with the polybenzoxazine, contributing to the formation of the interpenetrating structure.

研究领域: 材料科学 · 生物化学
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FOOD HYDROCOLLOIDS · 2024 · IF 11

An edible, photodynamic antimicrobial and fluorescent film containing aggregation-induced emission luminogens from berberine and citric acid for freshening cooked chicken

Yuping Ning,Shuaimin Liu,Zihao Ren,Dongmei Yang,Jian Li,Lijuan Wang

Some chemicals used as preservatives may be found to be harmful to human health as a result of clinical studies conducted over time, or their limits may be updated. Natural, safe and antibacterial food packaging can simultaneously maintain the food quality , reduce preservative usage and prevent foodborne diseases . In this work, an edible, green and fluorescent packaging film with photodynamic inhibition of Staphylococcus aureus and Escherichia coli was prepared through incorporating the salt of berberine and citric acid (CA) into a composite film of carboxylated cellulose nanofibrils (CCNF) and κ-carrageenan (κC). The berberine/citric acid salt (BCA) was successfully synthesized via simple metathesis reaction, which endowed the blended film with improved thermal stability , ultraviolet shielding, water vapor barrier and mechanical properties. Among the prepared films, the film prepared from 0.6 g of CCNF and 8% of BCA (κC–CCNF–BCA8) showed the strongest fluorescence, the highest ROS production capacity and antimicrobial rate of 100% against both E. coli and S. aureus under white light. The total number of bacterial colonies in cooked chicken packaged in κC–CCNF–BCA8 film was 2.36 Log CFU/mL, which was lower than that packaged in κC-CCNF film (3.00 Log CFU/mL). The sustainable and fluorescent film could kill microorganisms in cooked chicken with only adequate sunlight and has a promising application in antibacterial packaging.

CAS / MDL: 11114-20-8 50-70-4
研究领域: 食品科学 · 材料科学 · 微生物学
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BIOMACROMOLECULES · 2024 · IF 5.5

Copper Nanodrugs with Controlled Morphologies through Aqueous Atom Transfer Radical Polymerization

Ziyan Song,Peng Chen,Lisong Teng,Weibin Wang,Weipu Zhu

Copper (Cu) nanodrugs can be facilely prepared through atom transfer radical polymerization (ATRP) in an aqueous medium. However, it is difficult to control the morphology of Cu nanodrugs and thereby optimize their anticancer activity. In this work, aqueous ATRP was combined with polymerization-induced self-assembly (PISA) to prepare Cu nanodrugs with various morphologies. We mapped the relationship between polymerization condition and product morphology in which each morphology shows a wide preparation window. Decreasing the reaction temperature and feeding more Cu catalysts can improve the mobility of chains, facilitating the morphology evolution from sphere to other high-order morphologies. The resultant Cu nanodrugs with high monomer conversion and high Cu loading efficiency could be easily taken by cancer cells, showing excellent anticancer efficacy in vitro. This work proposed a potential strategy to prepare Cu nanodrugs with a specific morphology in batches, providing the method to optimize the anticancer efficacy through morphology control.

CAS / MDL: 7447-39-4 7732-18-5
研究领域: 材料科学 · 药学 · 肿瘤学
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