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COLLOID AND POLYMER SCIENCE · 2015 ·Vol. 293 ·期 5 ·1505-1513 · IF 1.865

pH-responsible Pickering emulsion and its catalytic application for reaction at water–oil interface

Fang Zhihui,Yang Duanguang,Gao Yong,Li Huaming

In this work, pH-responsible Pickering emulsion stabilized by polymer-metal hybrid micelles and its catalytic application for reaction at oil–water interface were presented. Employing Au@poly(ethylene oxide)-b-poly(4-vinylpyridine) polymer-metal hybrid micelles as emulsifier, n -decanol in water Pickering emulsion was first generated. The produced Pickering emulsion displayed reversible emulsification/demulsification with pH variation of the water phase, and this pH-induced emulsification/demulsification could undergo multiple cycles with only a slight reduction in emulsion performance. Dynamic light scattering, zeta potential measurement, and interfacial tension measurement, as well as transmission electron microscopy characterization, all showed that this reversible emulsification/demulsification cycle was the result of the tunable wettabilities of the core cross-linked hybrid emulsifier micelles with pH variation. Benefited from the excellent catalytic performances of the implanted Au nanoparticles at the oil–water interface and the large interfacial area of the emulsion droplets together with the pH-responsible reversible emulsification/demulsification cycle, the generated Pickering emulsion could readily applied as a catalytic microreactor for a broad of organic reactions occurred in water medium. As a proof of the concept, Au catalyzed reduction reaction of p -nitroanisole by NaBH 4 was investigated. The catalyst showed both a highly catalytic activity  with a good recyclability.

研究领域: 胶体与界面化学 · 纳米催化 · 功能材料 · 绿色化学 · 微反应器
✓ 已验证 DOI 高影响因子
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RSC Advances · 2014 ·Vol. 4 ·期 39 ·20208-20215 · IF 3.708

Boronate ester bond-based core–shell nanocarriers with pH response for anticancer drug delivery

Lei Sun,Xinge Zhang,Jinxia An,Cui Su,Qianqain Guo,Chaoxing Li

Currently, the major challenge for cancer treatment is to develop simple and smart nanocarriers that can efficiently retain the encapsulated drug during blood circulation, recognize tumor cells and quickly release the drug under stimulation. In this paper, such a pH-sensitive core–shell composite nanoparticles is prepared based on a 3-aminophenylboronic acid modified mesoporous silica nanoparticles (MSN–APBA) core coated with a lactobionic acid grafted chitosan (CS–LA) shell via boronate ester bonds. The MSN core increases drug loading capacity and stability, and lactobionic acid offers abundant diols which can form pH sensitive boronate ester bonds with APBA on MSN. Meanwhile, the lactobionic acid-conjugated shell could also efficiently target the asialoglycoprotein receptor over expressing hepatoma cells. The successful synthesis of CS–LA and MSN–APBA is confirmed by the results of TGA, TEM, DLS, FT-IR, 1H-NMR and N2 adsorption–desorption. Doxorubicin hydrochloride (DOX) is applied as a model drug and the behaviors of drug loading/release are investigated. The drug loading behavior is pH-dependent, and its drug encapsulation efficiency is near 80% and loading capacity is 13.05%. The results of cumulative in vitro release indicate that at neutral pH, the pores of the MSN are effectively capped with a polymer shell and the drug release is strongly inhibited, almost zero release. While at acidic pH, the hydrolysis of the boroester bond takes place and thus results in a rapid release of the entrapped drug. The cytotoxicity assay indicates high cell biocompatibility of this material and it is suitable as a drug carrier. When loaded with DOX, it presents distinctly cytotoxic behavior to HepG2 cells, due to the sustained release of drug. These results imply that the core–shell nanoparticles are promising platforms to construct simple and effective pH-responsive controlled drug delivery systems for cancer therapy.

研究领域: 肿瘤学 · 药剂学 · 纳米医学 · 生物材料 · 分子药理学 · 靶向治疗
✓ 已验证 DOI 高影响因子
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2015 · IF 2.752

pH-switchable wormlike micelle formation by N-alkyl-N-methylpyrrolidinium bromide-based cationic surfactant

Zhihu Yan,Caili Dai,Mingwei Zhao,Guang Zhao,Yuyang Li,Xuepeng Wu,Mingyong Du,Yifei Liu

A non-covalent bonding method is utilized for forming pH-switchable wormlike micelles system by mixing N -hexadecyl- N -methylpyrrolidinium bromide-based cationic surfactant and pyrocatechol. The peculiarity of this system is that it has high viscoelasticity at acidic conditions and alkaline conditions, while it shows water-like behaviors at neutral conditions. Rheology, dynamic light scattering, and cryogenic-transmission electron microscopy results revealed that the microstructure transition between spherical micelles and wormlike micelles was the fundamental cause of the pH-switchable rheological properties. The unusual rheological and micellar responses of this system to pH are caused by different binding capacity of hydrotrope to C 16 MPBr as pH varies. Fluorescence analysis and nuclear magnetic resonance result support this hypothesis.

研究领域: 胶体化学 · 物理化学
✓ 已验证 DOI 高影响因子
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ACS Applied Materials & Interfaces · 2020 · IF 8.758

Preparation of pH-Responsive Dual-Compartmental Microcapsules via Pickering Emulsion and Their Application in Multifunctional Textiles

Kunlin Chen,Jianlin Zhou,Jing Hu,Junhao Zhang,Tianzuo Heng,Changyue Xu,Xuemei Wang,Jingyan Liu,Kejing Yu

Currently, smart and functional textiles have attracted increasing attention for the research on their application in various fields. In this paper, perfluorooctyltriethoxysilane (FAS13)-loaded silica nanocapsules taken as the Pickering emulsifier was applied to stabilize O/W emulsion for obtaining pH-responsive dual-compartmental microcapsules which show a strawberry-like structure with jasmine essence as the core and pH-responsive polymers and silica nanocapsules as the shell. These microcapsules could endow it with multifunctions by functionalizing the fabric, while the preparation and functionalization process is effortless and environmental friendly. Not only does the treated fabric demonstrate the self-healing superhydrophobicity and ultraviolet (UV) resistance because of the hydrophobic FAS13 getting loaded into silica nanocapsules and the surface modification of UV absorbent, it is also capable of the pH control jasmine essence-releasing performance, which allows over 40% of the fragrance to be preserved for three months through the controlled release of jasmine essence from the microcapsules.

研究领域: 材料科学 · 纺织工程 · 化学工程
✓ 已验证 DOI 高影响因子
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Polymer Chemistry · 2017 ·Vol. 8 ·期 19 ·2997-3005 · IF 5.375

A pH, glucose, and dopamine triple-responsive, self-healable adhesive hydrogel formed by phenylborate–catechol complexation

Meng Shan,Chu Gong,Bingqiang Li,Guolin Wu

An injectable polyethylene glycol (PEG) hydrogel was successfully prepared via borate–catechol complexation using dopamine functionalized 4-armed PEG (4-arm-PEG-DA) and phenylboronic acid modified 4-armed PEG (4-arm-PEG-PBA). The hydrogel was formed within 10 s by mixing 15 wt% 4-arm-PEG-DA with 15 wt% 4-arm-PEG-PBA buffer solutions at pH 9.0. The hydrogel was characterized by Fourier transform infrared (FT-IR) spectroscopy, rheological measurements, scanning electron microscopy (SEM) and lap shear strength tests. Furthermore, pH, glucose and dopamine responsiveness of the hydrogel based on phenylborate–catechol complexation was demonstrated by degradation experiments and drug release tests. The lap shear strength tests indicated that the hydrogel possessed the ability of self-healing which was bestowed by the phenylborate–catechol dynamic covalent bond. Moreover, the hydrogel could serve as a decent bio-adhesive due to its adhesion properties on different substrates especially the porcine skin. In vitro cytotoxicity tests demonstrated the excellent cytocompatibility of the hydrogel. The results of all the experiments indicate that our newly developed multi-functionalized hydrogel can have potential applications in biomedical fields such as drug delivery, tissue engineering, and bio-adhesives.

研究领域: 生物材料 · 药物递送 · 组织工程
✓ 已验证 DOI 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2015 · IF 4.321

Polymeric micelle-coated mesoporous silica nanoparticle for enhanced fluorescent imaging and pH-responsive drug delivery

Xiubin Xu,Shaoyu Lü,Chunmei Gao,Xinggang Wang,Xiao Bai,Haogang Duan,Nannan Gao,Chen Feng,Mingzhu Liu

Can micelles be served as gating agents and fluorescent labels? Can a drug delivery system be constructed by combining two kinds of drug carriers, such as mesoporous silica nanoparticles and micelles? Will the combination be better or worse? To settle these questions, we designed and constructed a nanocarrier by cooperating two kinds of drug carriers (mesoporous silica nanoparticles and F127 micelles), providing a suitable method for the design of multifunctional stimuli-responsive drug delivery and self-fluorescent imaging systems. The system is fabricated using anticancer drug (curcumin) loaded micelles (CF127) as gating agents and fluorescent labels of mesoporous silica nanoparticles via Schiff base. Because of the pH-sensitive Schiff base, the gating micelles can achieve drug release under acidic condition, while preventing the drug release under natural condition. Moreover, due to the aggregation of CF127 micelles on the surface of mesoporous silica nanoparticles, the fluorescent intensity of CF127 micelles is significantly enhanced. Furthermore, CF127 micelles exhibit good anti-photobleaching property, indicating that the system here is promising for noninvasive in vivo tracking the delivery of therapeutic agents. The cooperation of two kinds of drugs in anti-cancer application and the easily further modification ability of the system is also be confirmed. These results indicate that this study paves the way for a generation of drug delivery systems and could provide a general route to prepare multifunctional biocompatible platforms for biomedical imaging diagnosis and simultaneous therapy for lesion sites such as cancers.

研究领域: 生物医学工程 · 纳米医学 · 药剂学
✓ 已验证 DOI 高影响因子
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Journal of Environmental Sciences · 2019 · IF 3.556

Understanding the electrode reaction process of dechlorination of 2,4-dichlorophenol over Ni/Fe nanoparticles: Effect of pH and 2,4-dichlorophenol concentration

Kaiyuan Zheng,Yuqiao Song,Xu Wang,Xin Li,Xuhui Mao,Dihua Wang

Herein, with the exploitation of iron and nickel electrodes, the 2,4-dichlorophenol (2,4-DCP) dechlorinating processes at the anode and cathode, respectively, were separately studied via various electrochemical techniques (e.g., Tafel polarization, linear polarization , electrochemical impedance spectroscopy). With this in mind, Ni/Fe nanoparticles were prepared by chemical solution deposition, and utilized to test the dechlorination activities of 2,4-DCP over a bimetallic system. For the iron anode, the results showed that higher 2,4-DCP concentration and solution acidity aggravated the corrosion within the electrode. The charge transfer resistance ( R ct ) values of the iron electrode were 703, 473, 444, and 437 Ω   ∙   cm 2 for the initial 2,4-DCP concentrations of 0, 20, 50, and 80 mg/L, respectively. When the bulk pH of the 2,4-DCP solution varied from 3.0, 5.0 to 7.0, the corresponding R ct values were 315, 376, and 444 Ω   ∙   cm 2 , respectively. For the nickel cathode, the reduction current densities on the electrode at −   0.75 V (vs. saturated calomel electrode) were 80, 106, and 111 μA/cm 2 , for initial 2,4-DCP concentrations of 40, 80, and 125 mg/L. The dechlorination experiments demonstrated that when the initial pH of the solution was 7.0, 5.0, and 3.0, the dechlorination percentage of 2,4-DCP by Ni/Fe nanoparticles was 62%, 69%, and 74%, respectively, which was in line with the electrochemical experiments. 10 wt.% Ni loading into Ni/Fe bimetal was affordable and gave a good dechlorination efficiency of 2,4-DCP, and fortunately the Ni/Fe nanoparticles remained comparatively stable in the dechlorination processes at pH 3.0.

研究领域: 环境科学 · 电化学工程
✓ 已验证 DOI 高影响因子
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2016 · IF 2.76

Core cross-linked and pH-responsive particulate emulsifiers from direct chemical preparation of divinylbenzene with P(AA-r-St) macro-CTA

Ye Zhu,Qiong Hu,Wei Wei,Chenglin Yi,Xiaoya Liu

In this study a type of colloidal particles with a cross-linked poly(divinylbenzene) (poly(DVB)) core and a poly(acrylic acid- r -styrene) (PAS) shell were directly prepared by reversible addition-fragmentation chain transfer (RAFT)-mediated cross-linking copolymerization. The particle size, morphology, zeta potential and pH responsibility were studied. The emulsification study showed that PAS-Poly(DVB) colloidal particles were effective particulate emulsifiers when homogenized with various oils including toluene, white oil, isooctyl palmitate, dicaprylyl carbonate, silicone oil, and propylheptyl caprylate. Additionally, the emulsification performance of PAS-Poly(DVB) colloidal particles at different pH values were investigated. Gelled white oil- in -water high internal phase emulsions (HIPEs) were formed at a high oil volume fraction of 80% when the colloidal particles were flocculated at low pH value. The addition of base can trigger the demulsification of the HIPEs, exhibiting a pH-responsive behavior. The effects of oil phase volume fraction on emulsion rheological properties were investigated. Both the emulsion viscosity and storage modulus (G′) progressively increased with the increasing of oil phase volume fraction. These results suggest that our work provides a convenient and feasible way to prepare effective particulate emulsifiers via the direct chemical reaction, and the PAS-Poly(DVB) colloidal particles have promising potential application in the oil industry and preparation and exploitation of smart materials.

研究领域: 材料科学 · 化学工程
✓ 已验证 DOI 高影响因子
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Materials Science & Engineering C-Materials for Biological Applications · 2020 · IF 5.88

Fabrication of novel dual thermo- and pH-sensitive poly (N-isopropylacrylamide-N-methylolacrylamide-acrylic acid) electrospun ultrafine fibres for controlled drug release

Zhimei Wei,Qingyu Lin,Jie Yang,Shengru Long,Gang Zhang,Xiaojun Wang

Dual temperature- and pH-sensitive materials used as drug carriers have attracted a particularly high level of interest. However, it is limited by low sensitivity to changes in conditions because of large size and low specific surface area. In this work, novel dual temperature- and pH-sensitive poly( N -isopropylacrylamide- N -methylolacrylamide acrylic acid) (PNIPAm-NMA-AAc) ultrafine fibres were successfully prepared by radical copolymerisation, electrospinning and thermal chemical treatment. The PNIPAm-NMA-AAc ultrafine fibres were characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance ( 1 H NMR), spectroscopy UV–visible spectroscopy, scanning electron microscopy (SEM) and cell counting kit-8 (CCK-8) assay. The uniformity and small size of PNIPAm-NMA-AAc ultrafine fibres with LCST range from 31 °C to 43 °C were used to drug carrier because of good thermal stability, no cytotoxic. Curcumin as a model drug was well distributed in PNIPAm-NMA-AAc ultrafine fibres. In addition, analysis of curcumin release at different pH values and temperatures confirmed that the PNIPAm-NMA-AAc ultrafine fibres are responsive to both temperature and pH. The maximum amount of curcumin released was 98.47% ± 1.87%. In addition, the release mechanism of curcumin-based PNIPAm-NMA-AAc ultrafine fibres was shown to conform to Fickian diffusion (r 2  ≥ 0.95). These results indicated that dual-responsive PNIPAm-NMA-AAc ultrafine fibres are promising as drug carriers.

研究领域: 材料科学 · 生物医学工程
✓ 已验证 DOI PubMed 高影响因子
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Advanced Fiber Materials · 2020 ·Vol. 2 ·期 5 ·265-278 · IF 0

Facile and Low-Cost Fabrication of a Thread/Paper-Based Wearable System for Simultaneous Detection of Lactate and pH in Human Sweat

Xiao Gang,He Jing,Qiao Yan,Wang Feng,Xia Qingyou,Wang Xin,Yu Ling,Lu Zhisong,Li Chang-Ming

Wearable devices have received tremendous interests in human sweat analysis in the past few years. However, the widely used polymeric substrates and the layer-by-layer stacking structures greatly influence the cost-efficiency, conformability and breathability of the devices, further hindering their practical applications. Herein, we report a facile and low-cost strategy for the fabrication of a skin-friendly thread/paper-based wearable system consisting of a sweat reservoir and a multi-sensing component for simultaneous in situ analysis of sweat pH and lactate. In the system, hydrophilic silk thread serves as the micro-channel to guide the liquid flow. Filter papers were functionalized to prepare colorimetric sensors for lactate and pH. The smartphone-based quantitative analysis shows that the sensors are sensitive and reliable. Although pH may interfere the lactate detection, the pH detected simultaneously could be employed to correct the measured data for the achievement of a precise lactate level. After being integrated with a hydrophobic arm guard, the system was successfully used for the on-body measurement of pH and lactate in the sweats secreted from the volunteers. This low-cost, easy-to-fabricate, light-weight and flexible thread/paper-based microfluidic sensing device may hold great potentials as a wearable system in human sweat analysis and point-of-care diagnostics.

研究领域: 生物医学工程 · 分析化学
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International Journal of Nanomedicine · 2018 · IF 4.37

pH-responsive hybrid nanoparticle with enhanced dissociation characteristic for siRNA delivery

Menghao Shi,Xiufeng Zhao,Jiulong Zhang,Shuang Pan,Chunrong Yang,Ying Wei,Haiyang Hu,Mingxi Qiao,Dawei Chen,Xiuli Zhao

Introduction Specific polo-like kinase (PLK1) silencing with small interface RNA (siRNA) may be an effective approach for PLK1-overexpressed lung cancer. However, low siRNA concentration into cytoplasm of tumor tissue severely limits its application. Materials and methods In this study, a novel triblock copolymer methoxy poly(ethylene glycol)-poly(histidine)-poly(sulfadimethoxine) (mPEG-PHis-PSD, shorten as PHD) was synthesized and used to construct novel nonviral gene vector with cationic liposomes. Results The resulting hybrid nanoparticles (PHD/LR) loaded with siPLK1 possessed excellent physiochemical properties. In vitro study indicated that PHD/LR could be efficiently internalized into human lung adenocarcinoma A549 cells and downregulated PLK1 protein expression to induce cell apoptosis, which was attributed to pH-induced instantaneous dissociation, efficient endo/lysosomal escape arose from PHD copolymer. Furthermore, in vivo antitumor activity demonstrated that PHD/LR could efficiently accumulated into tumor tissue and silenced PLK1 expression to possess antitumor activity. Conclusion Taken all these together, PHD/LR was expected to be a suitable carrier for specific delivering siRNA for lung cancer therapy.

研究领域: 癌症研究 · 纳米技术 · 药学 · 分子生物学
✓ 已验证 DOI PubMed 高影响因子
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RSC Advances · 2016 ·Vol. 6 ·期 112 ·111217-111225 · IF 3.289

pH-sensitive drug release of star-shaped micelles with OEG brush corona

Sijie Zhao,Huiru Yang,Cai Zuo,Lu Sun,Liwei Ma,Hua Wei

Star-shaped polymers are attractive as drug carriers due to the integration of relatively easy synthesis compared to the preparation of hyper-branched dendrimers and their potential ability to form unimolecular nanoparticles with enhanced stability to survive the high dilution-associated deformation and subsequently premature drug release in the body fluids and blood during circulation. Clearly, the star structure exerts a significant effect on their bioproperties and potential applications. In this study, three star-shaped amphiphilic copolymers with the same polymer compositions but different star structures were synthesized to investigate the effect of star architecture on their properties as well as potential applications as drug carriers. Three different branched alcohols, 2-(hydroxymethyl) propane-1,3-diol, pentaerythritol and dipentaerythritol with 3, 4, and 6 respective hydroxyl groups were chosen as the starting core to generate the target star-shaped amphiphilic block copolymers composed of hydrophobic poly(ε-caprolactone) (PCL) and hydrophilic poly(oligoethyleneglycol methacrylate) (POEGMA) with 3, 4, and 6 corresponding star arms by a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Dynamic light scattering (DLS) measurements and pyrene fluorescence probe technique confirmed the capability of the resultant star-shaped amphiphilic copolymers to form unimolecular micelles with average diameters smaller than 50 nm in an aqueous phase. A comparison of the drug loading capacity revealed that the micelles of 4-star-PCL–POEGMA (4s-PCL–POEGMA) exhibited the highest drug loading content (DLC) of all the three formulations. More importantly, in vitro doxorubicin (DOX) release study showed unique pH-mediated drug release behaviors, i.e., dramatically accelerated release at pH 6.0 but a much slower profile at pH 7.4, from these generally recognized “pH-insensitive” 4-arm star-shaped micelles. An acid-triggered degradation and an acid–base titration were performed to further reveal that such interesting pH-responsive drug release behaviors were attributed primarily to the hydrophilic corona of OEG brushes. This study is believed to provide a new insight into the structure–bioproperties relationship of star-shaped polymers, thus should be useful for the future design and development of novel star-shaped polymers for controlled drug delivery.

研究领域: 高分子药剂学 · 纳米医学 · 药物控释 · 生物材料 · 药剂学 · 肿瘤治疗 · 纳米载体
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