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Journal of Materials Chemistry B · 2013 ·Vol. 1 ·期 46 ·6418-6426 · IF 0

Redox-triggered intracellular dePEGylation based on diselenide-linked polycations for DNA delivery

Wenyu Li,Peng Zhang,Kun Zheng,Qiaoling Hu,Youxiang Wang

Extracellular stability to protect DNA against nucleases and stimulus-triggered intracellular DNA release are key factors in designing non-viral gene vectors. In this study, the diselenide-linked polycation mPEG–SeSe–PEI was developed as a new type of PEG-detachable gene vector for redox-responsive gene delivery. The corresponding stable analog mPEG–PEI and the disulfide-linked polycation mPEG–SS–PEI were synthesized as controls. The results showed that all the PEGylated polycations could condense DNA into tightly packed spherical nanoparticles about 80 nm in size, which showed excellent stability under physiological conditions. The results of zeta-potential measurements, stability tests and DNA release ability assay indicated that at a GSH concentration of 0.3 mM, the diselenide bonds were more easily cleaved than disulfide bonds, which facilitated dePEGylation and DNA release. Meanwhile, it was interestingly found that mPEG–SeSe–PEI/DNA polyplexes showed higher gene expression than mPEG–SS–PEI/DNA polyplexes in both HEK293T and HepG2 cells. Confocal laser scanning microscope (CLSM) images revealed that mPEG–SeSe–PEI/DNA polyplexes showed more efficient endosomal escape ability than mPEG–SS–PEI/DNA polyplexes. Based on these results, the diselenide bonds as a novel strategy are more suitable to address the challenging problem of extracellular stability and intracellular DNA release.

研究领域: 基因递送 · 聚合物化学 · 分子生物学 · 生物医学工程
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Nature Communications · 2024 ·Vol. 15 ·期 1 ·1-9 · IF 14.7

Diurnal humidity cycle driven selective ion transport across clustered polycation membrane

Zhao Yuanyuan,Liu Ju,Lu Gang,Zhang Jinliang,Wan Liyang,Peng Shan,Li Chao,Wang Yanlei,Wang Mingzhan,He Hongyan,Xin John H.,Ding Yulong,Zheng Shuang

The ability to manipulate the flux of ions across membranes is a key aspect of diverse sectors including water desalination, blood ion monitoring, purification, electrochemical energy conversion and storage. Here we illustrate the potential of using daily changes in environmental humidity as a continuous driving force for generating selective ion flux. Specifically, self-assembled membranes featuring channels composed of polycation clusters are sandwiched between two layers of ionic liquids. One ionic liquid layer is kept isolated from the ambient air, whereas the other is exposed directly to the environment. When in contact with ambient air, the device showcases its capacity to spontaneously produce ion current, with promising power density. This result stems from the moisture content difference of ionic liquid layers across the membrane caused by the ongoing process of moisture absorption/desorption, which instigates selective transmembrane ion flux. Cation flux across the polycation clusters is greatly inhibited because of intensified charge repulsion. However, anions transport across polycation clusters is amplified. Our research underscores the potential of daily cycling humidity as a reliable energy source to trigger ion current and convert it into electrical current.

研究领域: 材料科学 · 环境科学 · 能源工程
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CHEMICAL ENGINEERING & TECHNOLOGY · 2015 ·Vol. 38 ·期 5 ·859-866 · IF 2.442

Polycation-Grafted Poly(vinylidene fluoride) Membrane with Biofouling Resistance

Xiang Shen,Yiping Zhao,Li Chen

Covalent immobilization of polycations onto a membrane surface has been shown to significantly improve the resistance to biofouling. The poly(vinylidene fluoride)-graft-poly( N , N -dimethylamino-2-ethylmethacrylate) (PVDF-g-PDMAEMA) copolymer was synthesized via radical grafting copolymerization and fabricated into a flat membrane. The polycation membrane surface was constructed by quaternization of PDMAEMA side chains with 1,5- dibromopentane and diquaternization of 4,4′-bipyridine. As revealed by membrane surface morphology, pore size, and porosity measurement, the polycations are distributed on the membrane surface and internal pore channel surface. Water contact angles confirm that the incorporation of polycations remarkably promotes the surface hydrophilicity of a membrane. The polycation membrane surface provides an excellent bactericidal efficiency against Escherichia coli.

研究领域: 材料科学 · 环境工程 · 生物学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Polycations inclusion to simultaneously boost permeation and selectivity of two-dimensional TaS2 membranes for acid recovery

Shichao Zhang,Yong Li,Xinxin Li,Jingjing Gu,Hongwei Shao,Qiang Huang,Peng Cui,Yahua Liu,Jin Ran,Cen-Feng Fu

Two dimensional (2D) TaS 2 laminates have highly regular and ordered transfer mass channels, thus being promising acid recovery membrane candidates for diffusion dialysis (DD) applications to discern H + and metallic ions. However, it remains a daunting task to get access to high-performance 2D acid recycling membranes made from single TaS 2 nanosheets . Here, we report manipulation of the chemical environments of TaS 2 channels to develop excellent acid recycling 2D membranes. As demonstration projects, positively charged poly(diallyldimethylammonium chloride) (PDDA) and poly(4-vinylpyridine) (P4VP) in acid solution were chosen as polycation intercalators to modify the TaS 2 2D channels. Under the DD mode, the TaS 2 membrane exhibits a H + dialysis coefficient (U H + ) of 3.72 × 10 −3 m h −1 and separation factor (S) of 9 towards the simulated acid pickle. In contrast, the U H + and S value of the PDDA@TaS 2 membrane improve to 12.7 × 10 −3 m h −1 and 34.4 respectively. Those of the P4VP@TaS 2 membrane increase to 12.5 × 10 −3 m h −1 and 29.1 respectively. The reported acid recovery properties of PDDA@TaS 2 and P4VP@TaS 2 membranes exceed the commercial DF-120 acid recovery membranes. The experiment and simulation results reveal that the synergistical enhancements of U H + and S originate from the incorporating polycations in PDDA@TaS 2 and P4VP@TaS 2 composite channels.

研究领域: 材料科学 · 化学工程
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Polymer Chemistry · 2015 ·Vol. 7 ·期 1 ·89-100 · IF 5.52

Rheological behavior and molecular relaxation of polycations with macrocounterions in aqueous solutions

Yilan Ye,Shangguan Yonggang,Qiang Zheng

Counterions play significant roles in the characteristics of polyelectrolytes, whereas many problems still remain unsolved. Among most previous research studies, counterions were too small to be “seen” by light scattering. In this article, we prepare macrocounterions which are single/double carboxylate ion-terminated polyethylene glycols (Mn ≈ 5000 g mol−1). The solution properties of polycations with macrocounterions are investigated through rheological, conductivity and dynamic light scattering measurement. On the basis of the scaling theory, the static and dynamic parameters of polyelectrolytes are analyzed over wide concentration ranges. In rheological measurement, a critical concentration () has been observed. When the concentration is below , the role of macrocounterions can be ignored; while above , macrocounterions determine the longest relaxation and prevent entanglement of polycations. Moreover, the same turning point exists in the dependence of conductivity and viscosity on the molar fraction of macrocounterions, which indicates that macrocounterions can't serve as brushes condensed on the polycation until their molar fraction is above the effective charge density of polyelectrolytes. In dynamic light scattering, we investigate the relaxation of polycations with macrocounterions on the length scale of electrostatic blobs, where the size of macrocounterions becomes significant. In comparison with ordinary polyelectrolytes, it is observed that both fast and slow diffusive relaxations of polycations with macrocounterions are significantly slowed down, and the fast mode relaxation becomes dominant. Since no independent relaxation of macrocounterions has been observed, it is supposed that the fast mode relaxation is the coupled relaxation of polycations and macrocounterions.

研究领域: 高分子化学 · 物理化学
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International Journal of Electrochemical Science · 2023 · IF 1.5

Amperometric Sensor Based on Carbon Nanotubes and Polycations for the Determination of Vitamin C

Bingcheng Su,Yan Chen,Xiangli Yang,Juan Han,Hongyu Jia,Pei Jing,Yu Wang

Detection of vitamin C (VC) is necessary because of its wide use in chemical, biological, and pharmaceutical engineering. Here, we describe a sensing system for the determination of VC. Instead of a bare glassy carbon electrode (GCE), a prepared multi-walled carbon nanotube-polycation-GCE was used to detect VC in samples with higher sensitivity, better repeatability, and with a lower detection limit. Under the optimal conditions, the obtained sensor presented a linear response to VC in the range of 1–100 μM with a detection limit of 500 nM. The proposed electrode also successfully detected VC concentrations in real samples.

CAS / MDL: 50-81-7 62-31-7 69-93-2
研究领域: 分析化学 · 生物工程 · 制药工程
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CARBOHYDRATE POLYMERS · 2015 · IF 4.074

Polymeric nanoparticles based on chitooligosaccharide as drug carriers for co-delivery of all-trans-retinoic acid and paclitaxel

Jing Zhang,Jian Han,Xiuli Zhang,Jing Jiang,Maolei Xu,Daolai Zhang,Jingtian Han

An amphiphilic all- trans -retinoic acid (ATRA)–chitooligosaccharide (RCOS) conjugate was synthesized to form self-assembled polymeric nanoparticles to facilitate the co-delivery of ATRA and paclitaxel (PTX). The blank RCOS nanoparticles possessed low hemolytic activity and cytotoxicity, and could efficiently load PTX with a drug loading of 22.2% and a high encapsulation efficiency of 71.3%. PTX-loaded RCOS nanoparticles displayed a higher cytotoxicity to HepG2 cells compared to PTX plus ATRA solution when corrected by the accumulated drug release. Cellular uptake profiles of RCOS nanoparticles were evaluated via confocal laser scanning microscope and flow cytometry with FITC as a fluorescent mark. The RCOS nanoparticles could be rapidly and continuously taken up by HepG2 cells via endocytosis and transported into the nucleus, and the uptake rates increased with particle concentration. These results revealed the promising potential of RCOS nanoparticles as drug carriers for co-delivery of ATRA and PTX or other hydrophobic therapeutic agents.

研究领域: 药剂学 · 生物材料学 · 肿瘤学
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Journal of Materials Chemistry B · 2014 ·Vol. 3 ·期 5 ·911-918 · IF 0

Polycations with excellent gene transfection ability based on PVP-g-PDMAEMA with random coil and micelle structures as non-viral gene vectors

Yuhua Song,Tingbin Zhang,Xiaoyan Song,Ling Zhang,Chunqiu Zhang,Jinfeng Xing,Xing-Jie Liang

The low transfection efficiency of polycations is still a major problem for successful gene therapy. To address this issue, in this study, hydrophilic poly(vinyl pyrrolidone)-graft-poly[2-(N,N-dimethylamino)ethyl methacrylate] (PVP-g-PDMAEMA) and amphiphilic poly(vinyl pyrrolidone)-graft-poly[2-(N,N-dimethylamino)ethyl methacrylate]-block-poly(methylmethacrylate) (PVP-g-PDMAEMA-b-PMMA) were synthesized via the atom transfer radical polymerization (ATRP) method, and their properties as gene vectors were investigated subsequently. PVP-g-PDMAEMA formed random coils in water and PVP-g-PDMAEMA-b-PMMA self-assembled into spherical core–shell micelles with a very low critical micelle concentration of only 6.3 × 10−3 mg mL−1. PVP-g-PDMAEMA-b-PMMA/pDNA polyplexes demonstrated an excellent gene transfection efficiency, which showed not only much higher gene transfection efficiency than PVP-g-PDMAEMA/pDNA polyplexes, but obviously surpassed 25k PEI at low N/P ratio around 3 on 293T cell lines. Hence, the results suggested that PVP-g-PDMAEMA-b-PMMA could be a highly efficient gene vector.

研究领域: 生物化学 · 基因治疗 · 材料科学
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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Thermally regulated flocculation-coalescence process by temperature-responsive cationic polymeric surfactant for enhanced crude oil-water separation

Xianwu Zhang,Yijun Cao,Dan Yang,Wenshuai Yang,Bin Yan,Ling Zhang

Polymeric surfactants play a crucial role in the flocculation-assisted coalescence process due to their unique bridging effect. However, the steric hindrance induced by their large molecules severely impedes the coalescence of oil droplets. Herein, temperature-responsive polymeric surfactants (quaternary ammonium chitosan-g-PNIPAM, Q-g-PN) with thermally-modulated structure were designed by integrating thermal responsive moieties onto cationic chitosan. The as-prepared Q-g-PN exhibited enhanced oil-water separation efficiency through a thermally regulated flocculation-coalescence process. At low temperatures, the thermal-responsive Q-g-PN remains in a flexible hydrophilic extended state, facilitating the flocculation of dispersed oil droplets through bridging via electrostatic interaction. At high temperatures, the Q-g-PN structure collapses into a hydrophobic coil state, reducing steric hindrance and enhancing hydrogen bonding to asphaltenes, thus effectively promoting oil droplet coalescence. Bottle tests demonstrated that the demulsification performance of Q-g-PN could reach up to 94 % with the Q-g-PN concentration only of 0.001 wt% via the proposed temperature-regulated flocculation-coalescence process, which was further confirmed by investigating oil droplet behavior and phase transition of Q-g-PN during through molecular dynamic (MD) simulation of the reaction process. This work presents new insights into enhancing oil-water separation efficiency by regulating the flocculation-coalescence process through precise modulation of the molecular interactions between polymeric surfactants and emulsion droplets.

CAS / MDL: 3033-77-0 110-18-9
研究领域: 化学工程 · 材料科学 · 环境科学
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ADVANCED FUNCTIONAL MATERIALS · 2024 · IF 18.5

Gradient p-Polyanion/n-Polycation Heterojunction Endows Ionic Diodes with Vastly Boosted Output Voltage, Power Density and Sensitivity

Hongkun Wang,Mingyu Du,Hao Jiang,Ruixuan Zhou,Yan Wang,Kunyan Sui,Wenxin Fan

Ionic diode-based generators show great superiority in harvesting low-frequency mechanical energy from human motions for various wearable applications. The major challenge is to improve their extremely limited output voltage for the miniaturization/simplicity of ionic diode-based self-powered devices as well as further improvement of mechanoelectric conversion performance. Herein, the construction of gradient polycation/polyanion heterojunction is demonstrated to vastly boost the output voltage, energy-harvesting efficiency, and sensing performance of ionic diode. Besides an inherent potential at the polyanion/polycation heterojunction interface, the additional transmembrane potentials can be generated across gradient polyanion and polycation conductors of ionic diodes due to their gradient charge distribution. Consequently, the gradient ionic diode-based generators produce much higher output voltage (306.53 mV) than previously reported homogeneous ones (4.1–135 mV). Meanwhile, the high output voltage imparts gradient ionic diode-based generator with ultrahigh power density (50.16 µW cm − 2 or 250.8 µW cm −3 ) and pressure-perception sensitivity (43582 mV/MPa), which are dramatically increased by 162.76% and 128.71%, respectively, compare to those of homogeneous one. Impressively, the resulting diode-based generators can generate ultralarge current density (≈0.52 mA cm −2 ) with ultralong discharge time (>400 s), thus enabling the continuous power generation under the low-frequency pressure for various wearable and implantable applications.

CAS / MDL: 110-18-9 5165-97-9
研究领域: 材料科学 · 能源技术 · 生物医学工程
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MACROMOLECULAR MATERIALS AND ENGINEERING · 2021 ·Vol. 307 ·期 1 ·2100593 · IF 4.367

Rational Design of Polycationic Hydrogel with Excellent Combination Functions for Flexible Wearable Electronic Devices

Xiaoqing Liu,Peng Huang,Jinqing Wang,Xiangyuan Wang,Yufeng He,Pengfei Song,Rongmin Wang

With the popularization of intelligent terminals and the improvement of medical level, the development of flexible wearable electronic devices (FWEDs) with high sensitivity and excellent mechanical properties plays a vital role in human motion and health monitoring. But most of FWEDs still stuck in a difficult choice of mechanical, functional, and sensory properties. In this work, it is found a strategy for extricating such plight. Using zwitterionic and quaternary ammonium salt, a novel polycationic hydrogel [P(ImSL-AmC)] with excellent performance is synthesized by copolymerization under photoinitiation. After optimizing conditions of synthesis, its structure and properties are characterized. It is found that the electrostatic interaction enhances the mechanical applicability of P(ImSL-AmC), which combines high stretchability (≈500% strain) with perfect strength (≈900 kPa) successfully. It is exciting that P(ImSL-AmC) not only exhibits excellent antibacterial activities against both E. coli and S. aureus , but also maintains transparency and flexibility at −10 °C. This polycationic hydrogel also has superior conductivity as a stretchable pressure-strain sensor, which can accurately monitor human motion. In summary, the obtained polycationic hydrogel possesses excellent combination functions, including intelligent conductivity, mechanical adaptability, antibacterial, frost resistance, and transparency. Furthermore, the practical strategy can be applied in preparation of intelligent wearable devices and human–computer interaction.

研究领域: 材料科学 · 生物医学工程 · 智能材料
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Journal of Materials Chemistry A · 2023 ·Vol. 11 ·期 27 ·14646-14654 · IF 11.9

A chloric polycation binder enables rapid ionic transport in thick electrodes of high-energy aluminum-ion batteries

Jingwen Li,Chengyun Ma,Xinle Geng,Yongxiao Tuo,Ruoxuan Sun,Huiping Du,Meng-Chang Lin,Mian Cai

The design of binder materials is vital for achieving an active impact on charge or mass transport in battery electrodes. Nevertheless, design rules are still lacking for aluminum-ion batteries. For high-loading graphite cathodes, we report the application of chloric polycation binders, which facilitate ionic transport through the in situ polycation-AlCl4− networks. We find that conjugated unit doping is an effective method to enhance adhesive properties. These attributes endow cells with improved electrochemical properties in terms of area-specific capacity, energy efficiency, rate capability, and long-term cycling stability.

CAS / MDL: 26062-79-3
研究领域: 材料科学 · 电化学 · 能源存储
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