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CHEMICAL ENGINEERING JOURNAL · 2016 · IF 5.31

Novel fluorescent pH/reduction dual stimuli-responsive polymeric nanoparticles for intracellular triggered anticancer drug release

Xu Jia,Xubo Zhao,Kun Tian,Tingting Zhou,Jiagen Li,Ruinian Zhang,Peng Liu

Fluorescent poly(methacrylic acid- co -poly(ethylene glycol) methyl ether methacrylate- co -N′-rhodamine B-acrylhydrazine) (P(MAA- co -PEGMA- co -RhBAh), PMPR) nanoparticles were designed as pH/reduction dual stimuli-responsive drug delivery system (DDS) for anti-cancer drug via facile distillation-precipitation copolymerization with bio-reducible disulfide-containing crosslinker. As a carrier for doxorubicin (DOX), high drug-loading capacity (DLC) and drug-loading efficiency (DLE) of 53.1% and 97.3% were achieved respectively, via the strong electrostatic interaction between the carboxyl groups of PMAA segments and the amino group of DOX. Due to the disulfide crosslinking structure and their drug-loading mode, the DOX-loaded PMPR nanoparticles were relatively stable under extracellular conditions with low drug leakage , while a rapid intracellular drug release took place in acidic and reductive environment of tumor cells. The fluorescence microscope analysis showed that the DOX-loaded PMPR nanoparticles could be successfully endocytosed by HepG2 cells and the released DOX was mainly accumulated in cell nuclei. These features make them potential DDS for tumor-environment-responsive controlled release. Furthermore, the PMPR nanoparticles showed strong fluorescence only at low pH media, which might be used for the real-time fluorescent imaging in cancer diagnosis as a potential theranostic nanoplatform for imaging-guided therapy of cancer.

CAS / MDL: 79-41-4 26915-72-0
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Materials · 2016 ·Vol. 9 ·期 3 ·129 · IF 2.728

Microstructure and Characteristic of BiVO4 Prepared under Different pH Values: Photocatalytic Efficiency and Antibacterial Activity

Zhengyao Qu,Peng Liu,Xiaoyu Yang,Fazhou Wang,Wenqin Zhang,Chenggang Fei

In the present study, BiVO4sample was prepared under different pH 0.5–13 without capping agent. Different morphology characteristics were observed, such as sheet crystal structure, cross crystal structure and branching crystal structure. The mechanism of the formation of BiVO4nanostructure was discussed. Under acid condition, sheet crystal structure was obtained. The phenomenon could be attributed to polymerization of vanadate in the presence of H+. In the weak alkaline solution, across structure and branching type morphology was obtained. The photocatalytic efficiency for the samples ranked as pH 5 > pH 3 > pH 7 > pH 9 > pH 1 > pH 11 > pH 13 > blank, which is in good agreement with X-ray diffraction (XRD) result.E. colienvelop was damaged in the presence of BiVO4under visible light. The protrusion on envelop was diminished by BiVO4. Attenuated Total Reflection Fourier transformed Infrared Spectroscopy (ATR-FTIR) results suggested the intensity was weakened for the amide, phosphoric, –COO−group and C-H bond in lipopolysaccharides (LPS), peptidoglycan and periplasm molecules.Keywords:BiVO4;monoclinic scheelite structure;photocatalytic efficiency;E. coli;envelop

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Polymer Chemistry · 2016 ·Vol. 8 ·期 6 ·1028-1038 · IF 5.687

Ultra-pH-sensitive polypeptide micelles with large fluorescence off/on ratio in near infrared range

Liyi Fu,Pan Yuan,Zheng Ruan,Le Liu,Tuanwei Li,Lifeng Yan

An amphiphilic copolymer of poly(oligo(ethylene glycol) methacrylate) (POEGMA) and poly(benzyl-L-aspartic acid) (PBLA) has been prepared by means of reversible addition–fragmentation chain transfer (RAFT) polymerization, ring-opening polymerization, and click reaction. After the PBLA segment was aminolyzed by the primary amine, N,N-diisopropylethylenediamine (DIEDA) and N,N-dibutylethylenediamine (DBEDA) with different ratios, amphiphilic block copolymers with various ionizable tertiary amines have been prepared, which can form stable micelles in neutral pH by self-assembly and disassembly under weak acidic conditions. After conjugation of Cy5.5/quencher to the copolymer, the as-formed micelles exhibit low fluorescence due to the Fluorescence Resonance Energy Transfer (FRET) between Cy5.5 and the quencher. However, an ultra-pH-sensitive fluorescence can be switched-on when it was in weak acidic conditions. The as-prepared nanoparticles have potential application in highly sensitive detection of the pH of tissues and cells, and can also work as a theranostic for cancer with drug delivery and imaging ability.

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COLLOIDS AND SURFACES B-BIOINTERFACES · 2016 · IF 3.902

A pH and redox dual stimuli-responsive poly(amino acid) derivative for controlled drug release

Chu Gong,Meng Shan,Bingqiang Li,Guolin Wu

A pH and redox dual stimuli-responsive poly(aspartic acid) derivative for controlled drug release was successfully developed through progressive ring-opening reactions of polysuccinimide (PSI). Polyethylene glycol (PEG) chains were grafted onto the polyaspartamide backbone via redox-responsive disulfide linkages, providing a sheddable shell for the polymeric micelles in a reductive environment. Phenyl groups were introduced into the polyaspartamide backbone via the aminolysis reaction of PSI to serve as the hydrophobic segment of micelles. The polyaspartamide scaffold was also functionalized with N -(3-aminopropyl)-imidazole to obtain the pH-responsiveness manifesting as a swelling of the core of micelles at a low pH. The polymeric micelles with a core-shell nanostructure forming in neutral media exhibited both pH and redox responsive characteristics. Doxorubicin (DOX) as a model drug was encapsulated into the core of micelles through both hydrophobic and Ͽ-Ͽ interactions between aromatic rings and the DOX-loaded polymeric micelles exhibited accelerated drug release behaviors in an acidic and reductive environment due to the swelling of hydrophobic cores and the shedding of PEG shells. Furthermore, the cytocompability of the polymer and the cytotoxicity of DOX-loaded micelles towards Hela cells under corresponding conditions were evaluated, and the endocytosis of DOX-loaded polymeric micelles and the intracellular drug release from micelles were observed. All obtained data indicated that the micelle was a promising candidate for controlled drug release.

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Analytical Methods · 2016 ·Vol. 8 ·期 28 ·5684-5689 · IF 1.915

A sensitive detection of Cr(VI) in wide pH range using polyethyleneimine protected silver nanoclusters

Na Xu,Quan Zhu,Xiang-Yue Kong,Lei Meng

Polyethyleneimine protected silver nanoclusters (AgNCs@PEI) were prepared and used as high sensitive fluorescence probes for detecting Cr(VI). The mechanism worked by combining Cr(VI) with a primary amine of AgNCs@PEI causing electrostatic interaction, which led to the aggregation of AgNCs, as well as fluorescence quenching. Compared with other fluorescence sensors of Cr(VI) detection, this probe shows excellent performances: (i) The fluorescence probe responds immediately after adding Cr(VI). (ii) The fluorescence quenching efficiency of AgNCs@PEI was linearly related to the concentration of Cr(VI) over the range from 0.5 nM to 25 μM. (iii) The limit of detection is as low as 0.05 nM. (iv) High selectivity for Cr(VI) in 14 types of normal metal ions were obtained and especially the probe can be applied in both acidic and alkaline conditions (pH 2.0–11.0). (v) The probe can be used for the determination of Cr(VI) in real samples with satisfactory results. Therefore, the fluorescence probe is of practical significance and application prospects.

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CARBOHYDRATE POLYMERS · 2016 · IF 4.219

pH responsive polyurethane (core) and cellulose acetate phthalate (shell) electrospun fibers for intravaginal drug delivery

Dawei Hua,Zhongche Liu,Fang Wang,Buhong Gao,Fei Chen,Qilu Zhang,Ranhua Xiong,Jingquan Han,Sangram Keshari Samal,Stefaan C. De Smedt,Chaobo Huang

In this study we present the use of co-axial electrospinning to produce core-shell composite micro-/nano- fibers of polyurethane (PU) and cellulose acetate phthalate (CAP). The designed fibers possess enhanced mechanical properties with a tensile strength of 13.27   ±   2.32   MPa, which is a clear improvement over the existing CAP fibers that suffer from a poor mechanical strength (0.2   ±   0.03   MPa). The CAP imparts pH responsiveness to the core-shell structure giving the fibers potential for “semen sensitive” (intravaginal) drug delivery.

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Journal of Materials Chemistry B · 2017 ·Vol. 5 ·期 16 ·2964-2978 · IF 4.543

Redox/pH dual-sensitive hybrid micelles for targeting delivery and overcoming multidrug resistance of cancer

Mingxing Yin,Yuling Bao,Xueqin Gao,Yupei Wu,Yu Sun,Xinyuan Zhao,Hongzhe Xu,Zhiping Zhang,Songwei Tan

A redox/pH dual-sensitive graft copolymer, poly(β-amino ester)-g-D-α-tocopherol polyethylene glycol succinate (PBAE-g-TPGS), was synthesized through a Michael-type step polymerization using disulfide linkage-containing TPGS macromonomers. Pluronic F127 (F127) and folate-F127 conjugation were introduced to prepare paclitaxel (PTX)-loaded hybrid micelles to improve their biocompatibility and serum stability and also to achieve targeted delivery. The hybrid micelles exhibited in vitro redox/pH-sensitive PTX release, enhanced cellular uptake through receptor-mediated endocytosis, and strengthened anticancer activities in both the drug-sensitive human breast cancer MCF-7 and drug-resistant MCF-7/ADR cells. P-Glycoprotein inhibition by TPGS and folate-mediated targeted delivery helped overcome multidrug resistance (MDR) and increase the therapeutic efficiency of the drug, leading to good anticancer effects in the MCF-7/ADR xenograft model. Overall, the folate-modified redox/pH-sensitive hybrid micelles provided a three-step approach to enhance anticancer activities via targeted delivery, controlled release, and depressed drug efflux; thus, these micelles may be a powerful weapon against MDR cancers in the future.

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ACS Applied Materials & Interfaces · 2016 · IF 7.145

pH-Responsive Core–Shell Structured Nanoparticles for Triple-Stage Targeted Delivery of Doxorubicin to Tumors

Lu Han,Cui Tang,Chunhua Yin

The application of cytotoxic chemotherapeutics in cancer therapy has been largely restricted by their lack of selectivity. Despite the existence of numerous targeted delivery systems, it is practically challenging to develop one single system to simultaneously cover tumor-targeted delivery of chemotherapeutics at the tissue, cellular, and subcellular levels. To solve this problem, pH-responsive core–shell structured nanoparticles (CSNPs) were self-assembled in this study to provide triple-stage targeted delivery of doxorubicin (DOX) from the injection site to the nuclei of cancer cells. Amino-functionalized mesoporous silica nanoparticles (MSN) were doubly modified with TAT peptide and acid-cleavable polyethylene glycol (PEG) as the DOX-loaded cationic core. The anionic shell was constituted by galactose-modified poly(allylamine hydrochloride)-citraconic anhydride, a hepato-carcinoma-targeting polymer with charge-reversible property. In vitro results showed that PEG effectively reduced protein adsorption and phagocytic capture of CSNPs in the circulating blood (pH 7.4), thus facilitating passive accumulation in tumors (tissue level). Following PEG detachment via acidic hydrolysis in tumor microenvironment (pH 6.5), the exposed galactose ligands endowed CSNPs with active internalization into hepato-carcinoma cells (cellular level). Afterward, the acidity in endosomes and lysosomes (pH 5.0) triggered the conversion of anionic shell into positive charges, leading to core–shell disassembly and subsequent TAT-mediated delivery of DOX to the nuclei (subcellular level). Importantly, the efficiencies of each targeting moiety were nicely preserved when combining together in CSNPs. As a result, improved tumorous distribution and potent therapeutic efficacy of CSNPs were noted in tumor-bearing mice at a relatively low dose. CSNPs therefore provide an efficient and nontoxic platform for the targeted delivery of antitumor drugs.

CAS / MDL: 619-66-9
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APPLIED SURFACE SCIENCE · 2016 · IF 3.15

A pH/glutathione double responsive drug delivery system using molecular imprint technique for drug loading

Kelin Zhang,Xiujuan Guan,Yanxin Qiu,Dongdong Wang,Xiaoyu Zhang,Haixia Zhang

A surface molecular imprinting polymer (SMIP) with doxorubicin (DOX) as the template was prepared on the surface of mesoporous silica nanoparticles (MSNs), which were further used as DOX carriers. The loading amount of DOX was calculated as 10.5   ±   0.2   wt% with loading efficiency of 70   ±   8%. The DOX release was controlled because the monomer molecule used in polymerization of SMIP containing sulfur-sulfur bonding, which could be decomposed with an acidic pH and glutathione (GSH). Under an acidic pH and high concentration of GSH, there was greater release of DOX than under normal physiological conditions, which induced less damage to normal cells than to cancer cells. Confocal laser scanning microscopy studies verified the invasion of the DOX within SMIP into TCA8113 cancer cells. These results indicate that the prepared SMIP was an effective nanocarrier.

CAS / MDL: 70-18-8
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2016 · IF 4.179

pH-sensitive drug controlled release core/shell fibers fabricated by combination of electrospinning and photopolymerization

Xiaolei Zhu,Hongwei Zhang,Jun Nie,Guiping Ma

pH-sensitive drug loaded core shell fibers were fabricated by a combination of electrospinning and UV photo-polymerization. Combretastatin A4 (CA4) was selected as the model drug loaded in PLA to test the pH-sensitivity property of the core shell fibers. The morphology of the fibers was studied by scanning electron microscopy (SEM), and the core shell structure of the fibers was confirmed by transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The drug release assay was tested via the UV–vis spectrophotometer, and the pH-sensitivity of core shell fibers was tested by drug release assay under pH 5.0 and 7.4.

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ACS Sustainable Chemistry & Engineering · 2017 · IF 5.951

pH-Triggered Charge-Reversal Silk Sericin-Based Nanoparticles for Enhanced Cellular Uptake and Doxorubicin Delivery

Doudou Hu,Zongpu Xu,Zeyun Hu,Binhui Hu,Mingying Yang,Liangjun Zhu

Silk-based nanoparticles have been exhibiting an increasing potential for use as drug delivery systems due to their great versatility. To extend applications of silk sericin in nanomedicine and improve the performance of silk-based nanoparticles in drug delivery, a facile two-step cross-linking is attempted, for the first time, to fabricate surface charge-reversal silk sericin-based nanoparticles (SSC@NPs) by introducing chitosan into silk sericin. The results suggest stable SSC@NPs are formed with a negative surface charge in a neutral environment. Under mildly acidic conditions, however, surface charge of SSC@NPs undergoes a negative-to-positive conversion. It proves that pH can regulate surface charge of SSC@NPs. It is the increased amino/carboxyl ratio in SSC@NPs that explains the underlying mechanism of the charge conversion property of SSC@NPs. Furthermore, the positively charged SSC@NPs triggered by tumor acidic microenvironment (pH 6.0) result in a 6.0-fold higher cellular uptake than the negatively charged counterparts at pH 7.4. In addition, an anticancer drug doxorubicin (DOX) is readily loaded into SSC@NPs and released in a pH-dependent manner. This work provides a simple method to fabricate smart pH-responsive nanoparticles for anticancer drug delivery.

CAS / MDL: 9012-76-4 25952-53-8
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Silicon · 2024 · IF 2.8

Effect of pH and Ratio of Alumina Sol on Properties of 3D Printed Silica Ceramics

Huang Yunzhi,Li He,Colombo Paolo

3D printed silica ceramics have the advantages of low thermal expansion coefficient, high thermal stability, easy removal, etc., and are widely used in ceramic core manufacturing. However, in the sintering stage, silica often cracks due to shrinkage and phase transformation, which seriously affects the mechanical properties of the material. The impregnation of alumina sol can promote the formation of cristobalite phase in ceramics, and the mechanical properties of ceramics can be improved with appropriate amount of cristobalite. In this study, 3D printed silica ceramics were impregnated with alumina sol, and the effects of pH value and the concentration of alumina in the sol on the properties of the samples were investigated. When pH was 2.5, the mechanical properties of alumina sol impregnated samples reached a flexural strength of 24.98 ± 0.93 MPa, with a bulk density of 1.70 ± 0.01 g/cm 3 , and an open porosity of 25.82 ± 0.33%. When the ratio of alumina sol to silica sol was 3:1, the mechanical properties of alumina sol impregnated ceramics reached the maximum, with a flexural strength of 33.85 ± 1.69 MPa, a bulk density of 1.73 ± 0.01 g/cm 3 , and an open porosity of 24.02 ± 0.72%.

CAS / MDL: 7647-01-0
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