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RSC Advances · 2014 ·Vol. 4 ·期 63 ·33391-33398 · IF 3.708

pH-responsive drug release from porous zinc sulfide nanospheres based on coordination bonding

Dong Zhu,Hong-Mei Wen,Wei Li,Xiao-Bing Cui,Li Ma,An Kang

pH-responsive systems have attracted special research interest in drug delivery. Herein, we report a pH-responsive system based on the “COOH–Zn2+–drug” architecture via coordination bonding in ZnS nanospheres' mesopores. PAA-functionalized porous ZnS nanospheres were employed as cargo carriers for hosting metal ion (Zn2+) binders and drug molecules to form the “COOH–Zn2+–drug” architecture. The cleavage of either the “COOH–Zn2+” or the “Zn2+–drug” coordination bond, in response to pH variation, gives rise to a significant release of drug molecules under weakly acidic conditions (pH 5–6.5). We anticipate that the porous ZnS nanospheres and subsequently prepared pH-responsive system may prove to be a significant step toward the development of a finely pH-sensitive drug delivery system that minimizes drug toxicity.

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RSC Advances · 2014 ·Vol. 4 ·期 31 ·15856-15862 · IF 3.708

Magnetic and pH sensitive drug delivery system through NCA chemistry for tumor targeting

Jingjing Wang,Chu Gong,Yinong Wang,Guolin Wu

For the purpose of tumor-specific drug delivery applications, a magnetic and pH dually responsive nano-carrier with a multilayer core–shell architecture was prepared from amine-functionalized Fe3O4@SiO2 through the surface-initiated ring opening polymerization of benzyl-L-aspartate N-carboxyanhydride, and then coated with α-methoxy poly(ethylene glycol) (mPEG) via a pH-sensitive benzoic–imine bond. In order to control the layer thickness of poly(benzyl-L-aspartate) (PBLA), a surface passivation agent was applied to modulate the amino density of the functionalized Fe3O4@SiO2 initiator. In this system, the Fe3O4@SiO2 nanoparticles function as a superparamagnetic core used to target the drug loaded nanocarriers to the pathological site. Meanwhile, the mPEG and PBLA segments serve as a pH-sheddable hydrophilic corona and a hydrophobic middle layer used to load the drug via hydrophobic interactions. The obtained materials were characterized by FT-IR, 1H NMR, DLS, zeta-potential, TEM, TGA and hysteresis loop analysis. Furthermore, the loading and release behavior of doxorubicin on the nanocarrier was investigated and it was shown that the drug loaded nanoparticle was relatively stable under physiological conditions and quickly released in response to acidity due to the shedding of mPEG shells through the pH-cleavage of intermediate benzoic–imine bonds. This pH and magnetic responsive nanoparticle has appeared highly promising for the targeted intracellular delivery of hydrophobic chemotherapeutics in cancer therapy.

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Polymer Chemistry · 2013 ·Vol. 5 ·期 3 ·854-861 · IF 5.231

A biomimic pH-sensitive polymeric prodrug based on polycarbonate for intracellular drug delivery

Haibo Wang,Yin Wang,Yangjun Chen,Qiao Jin,Jian Ji

A biodegradable and endosomal pH-sensitive polymeric prodrug poly(5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one)-graft-12-acryloyloxy dodecyl phosphorylcholine-co-6-maleimidocaproyl-doxorubicin (PMAC-graft-(ADPC-co-Mal-DOX) was synthesized by ring-opening polymerization (ROP) and “click” reaction. DOX was conjugated to the polymer by hydrazone bonds which would result in a pH-sensitive controlled release of drug. The polymeric prodrug can form a self-assembled micellar structure which was confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Flow cytometry and fluorescence microscopy results demonstrated that prodrug micelles could be internalized by cancer cells remarkably. In vitro drug release studies showed that the release of DOX was faster at endosomal pH (pH = 5.0) than at normal physiological environment (pH = 7.4). Moreover, this prodrug exhibited high cytotoxicity against HepG2 cells and HeLa cells, indicating its great potential for cancer therapy.

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LANGMUIR · 2013 · IF 4.187

A Mesoporous Silica Nanocomposite Shuttle: pH-Triggered Phase Transfer between Oil and Water

Haixia Wang,Hengquan Yang,Huanrong Liu,Yuhong Yu,Hongchuan Xin

With a simple protocol, we synthesize a novel mesoporous silica nanocomposite shuttle that can reversibly transfer between an organic phase and water in response to the pH, due to the switchable surface hydrophobicity/hydrophilicity. Our synthesis protocol allows the phase transfer ability to be tuned in a controllable fashion. This nanocomposite shuttle exhibits a good ability to load various cargoes such as Pd(OAc)2, Pd nanoparticles, and organic molecules. The built-in properties of the nanocomposite shuttle lay the foundations for many innovative applications. As a proof of concept, we successfully demonstrate its application in separating and recycling Pd nanoparticle catalysts. The composite shuttle can take Pd nanoparticles to an organic phase for catalyzing hydrogenation of olefins and come back to an aqueous phase at the end of reaction, making in situ separation and recycling of nanocatalysts possible. This pH-driven round trip for catalysis can be repeated several times. Our investigations not only supply a novel nanocomposite shuttle with controllable properties but also open an innovative avenue to in situ separation and recycling of nanocatalysts, which can address the obstacles of the conventional methods such as centrifugation and filtration.

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ACS Applied Materials & Interfaces · 2015 · IF 6.723

A pH- and Temperature-Responsive Magnetic Composite Adsorbent for Targeted Removal of Nonylphenol

Yang Zhen,Zhuo Ning,Zhang Shaopeng,Dong Yayi,Zhang Xuntong,Shen Jiachun,Yang Weiben,Wang Yuping,Chen Jianqiang

A pH- and temperature-responsive magnetic adsorbent [poly(N-isopropylacrylamide) grafted chitosan/Fe3O4 composite particles, CN-MCP], was synthesized for the removal of the endocrine-disrupting chemical nonylphenol. According to the structural characteristics (changeable surface-charge and hydrophilic/hydrophobic properties) of the targeted contaminant, CN-MCP was designed owning special structure (pH- and temperature-responsiveness for the changeable surface-charge and adjustable hydrophilic/hydrophobic properties, respectively). Compared to chitosan magnetic composite particles without grafting modification (CS-MCP) and several other reported adsorbents, CN-MCP exhibited relatively high adsorption capacity for nonylphenol under corresponding optimal conditions (123 mg/g at pH 9 and 20 °C; 116 mg/g at pH 5 and 40 °C). Meanwhile, high selectivity of the novel adsorbent in selective adsorption of nonylphenol from bisolute solution of nonylphenol and phenol was found. Effects of grafting ratio of the grafted polymer branches and coexisting inorganic salts on the adsorption were systematically investigated. Moreover, CN-MCP demonstrated desired reusability during 20 times of adsorption–desorption recycling. The high adsorption capacity, high selectivity, and desired reusability aforementioned revealed the significant application potential of CN-MCP in the removal of NP. On the basis of the adsorption behaviors, isotherms equilibrium, thermodynamics and kinetics studies, and instrumental analyses including X-ray photoelectron spectroscopy, BET specific surface area, zeta potential, and static water contact angle measurements, distinct adsorption mechanisms were found under various conditions: charge attraction between CN-MCP and the contaminant, as well as binding between polymeric branches of CN-MCP and nonyls, contributed to the adsorption at pH 9 and 20 °C; whereas hydrophobic interaction between CN-MCP and nonylphenol played a dominant role at pH 5 and 40 °C. The current study provided a strategy for the structural design of adsorbents according to the features of targeted emerging contaminants, and the continuity of the work was discussed and proposed.

CAS / MDL: 84852-15-3 104-40-5
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NEW CARBON MATERIALS · 2015 · IF 0.979

Self-assembled graphene monoliths: properties, structures and their pH-dependent self-assembly behavior

Gang Wang,Li-tao Jia,Bo Hou,De-bao Li,Jun-gang Wang,Yu-han Sun

Fabricating self-supporting, three dimensional graphene macroscopic structures from two dimensional graphene sheets by self-assembly has been an intriguing subject in exploring the performance of graphene structures for practical advanced applications. Monolithic graphene hydrogels (GHs) with quite good mechanical properties and excellent resilience were self-assembled from graphene oxide (GO) dispersions under hydrothermal conditions by changing the pH value. The structure-property relationships and the self-assembly behavior of GHs were investigated. It was found that the formation of GHs was pH-dependent. The charge state of carboxyl groups on the graphene was the key factor that influenced the balance of attraction and repulsion interactions of the GO and consequently determined the self-assembly behavior. Both the graphene molecular structure and colloidal interactions were correlated with the unique self-assembly behavior, which can be used to design graphene arrangements with various structures, functions and mechanical properties. This method is superior to the conventional method that adjusts the concentration and reduction time of the GO dispersion.

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2016 · IF 3.138

pH-Sensitive drug delivery system based on modified dextrin coated mesoporous silica nanoparticles

Hongyu Chen,Diwei Zheng,Jia Liu,Ying Kuang,Qilin Li,Min Zhang,Haifeng Ye,Hongyang Qin,Yanglin Xu,Cao Li,Bingbing Jiang

In this work, a novel pH-sensitive drug delivery system based on modified dextrin coated mesoporous silica nanoparticles (MSNs), DOX@MSN-DDA-CL, are prepared. The dextrin grafting on the surface of MSNs is oxidized by KIO 4 to obtain dextrin dialdehyde, which is then cross-linked by tetraethylenepentamine through a pH-sensitive Schiff’s base. Under physiological conditions, the cross-linked dextrin dialdehyde blocks the pores to prevent premature release of model drug doxorubicin hydrochloride (DOX). In the weak acidic environment, pH 6.0 in this work, the Schiff’s base can be hydrolyzed and released the drug. The in vitro drug release studies at different pHs prove the pH-sensitivity of DOX@MSN-DDA-CL. The cytotoxicity and cell internalization behavior are also investigated in detail. In vivo tissue distribution and pharmacokinetics with a H22-bearing mouse animal mode are also studied, prove that DOX@MSN-DDA-CL has a longer retention time than that of pure DOX and can accumulate in tumor region via enhanced permeation and retention and nanomaterials-induced endothelial cell leakiness effects. In conclusion, the pH-sensitive modified dextrin/MSNs complex drug delivery system has a great potential for cancer therapy.

CAS / MDL: 919-30-2 25316-40-9
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DYES AND PIGMENTS · 2015 · IF 3.966

A novel pH fluorescent probe based on indocyanine for imaging of living cells

Weifen Niu,Ming Nan,Li Fan,Man Shing Wong,Shaomin Shuang,Chuan Dong

In this paper, we report a novel pH fluorescent probe , 1,1-dimethyl-2-((E)-2-(pyridin-4-yl)vinyl)-1H-benzo[e]indole (PVBI), for imaging in living cells via ethylene bridging of indole derivatives and pyridine . The pH titration indicated that the probe exhibits sensitive pH-dependent behavior with p K a 3.87 and responded linearly and rapidly to minor pH fluctuations within the range of 3.0–4.6 (linear coefficient of 0.9968). Thus PVBI could be potentially useful for quantitative determination of pH within the acidic window. Also, PVBI displays a notably large Stokes shift of 93 nm which could effectively reduce the excitation interference. Moreover, PVBI possesses highly selective response to H + over various metal ions, good photostability and excellent reversibility . The confocal laser scanning microscope images for PVBI diffusing into cells in real-time and detection of pH in living cells were achieved successfully, suggesting the probe has excellent cell membrane permeability and could be applied to monitor pH fluctuations in living cells.

CAS / MDL: 872-85-5
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MATERIALS LETTERS · 2014 · IF 2.269

Facile fabrication of novel pH-sensitive poly(aspartic acid) hydrogel by crosslinking nanofibers

Caidan Zhang,Shaohua Wu,Xiaohong Qin

Stable pH-sensitive poly(aspartic acid) (PASP) hydrogel in nanofibrous structure was successfully manufactured. Firstly, polysuccinimide (PSI), the intermediate of PASP, was synthesized by thermal polymerization of aspartic acid and electrospun into nanofibrous mat. Secondly, imide rings on the main chains of PSI were partly opened to form crosslinking points by amino groups of ethylenediamine. Eventually, the residual imide rings of PSI were opened to obtain PASP hydrogel nanofibers by hydrolysis. The PASP hydrogel nanofibers exhibited significant hydrogel characteristics with fast swelling, high water absorption and pH-sensitivity. Durability test showed the morphological robustness and stability of PASP hydrogel nanofibers. The swelling ratio of pH-sensitive PASP hydrogel nanofibers ranged from 14.8   g/g to 128.1   g/g with the pH values increasing from 1.0 to 10.0.

CAS / MDL: 56-84-8 7664-38-2
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TALANTA · 2014 · IF 3.511

A two-photon ratiometric fluorescent probe enables spatial coordinates determination of intracellular pH

Junjie Wang,Yuming Sun,Weijia Zhang,Yong Liu,Xiaoqiang Yu,Ning Zhao

We reported a two-photon ratiometric fluorescent probe for detecting intracellular pH. When excited with 800   nm laser, an optimal output of laser as the routine equipment of two-photon fluorescence microscopy , the two-photon excited fluorescence of this probe showed distinct emission peak shift as large as 109   nm upon the change of pH values in vitro. Very importantly, the experiment results show that this probe has large two-photon absorption cross-section at pH 4.5 at 800   nm of 354   g, which ranks it as one of the best two-photon ratiometric fluorescent pH probes, and its working pH value is between 4.0 and 8.0 which could fit the intracellular pH range. Moreover, utilizing this probe, the two-photon ratiometric fluorescent images in living cells have been obtained, and the spatial coordinates of intracellular pH can be mapped. At the same time, the probe also exhibited selectivity, photostability and membrane permeability. And the photophysical properties of this probe in various solvents indicated that these photophysical properties variations are due to an intramolecular charge transfer process. At last, the imaging depth of the probe in liver biopsy slices was investigated. The experimental results demonstrated the maximum imaging depth can arrive 66   µm in living rat liver tissues.

CAS / MDL: 137-07-5
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SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

Thiazole-based ratiometric fluorescence pH probe with large Stokes shift for intracellular imaging

Wen-Jia Zhang,Li Fan,Zeng-Bo Li,Ting Ou,Hua-Jin Zhai,Jun Yang,Chuan Dong,Shao-Min Shuang

A ratiometric fluorescent pH probe 4-((1E, 3E)-4-(benzo[d]thiazol-2-yl)buta-1, 3-dienyl)- N , N -dimethylbenzenamine ( BTDB ) was synthesized via ethylene bridging of thiazol and cinnamaldehyde for extremely acidic sensing. BTDB exhibits ratiometric fluorescence emission ( I 425   nm / I 595   nm ) characteristics with p K a of 2.34 and a large Stokes shift of 177   nm under acidic conditions. The linear response to pH is in the range of 2.3–4.0. Quantum chemical calculations with the B3LYP exchange functional theory demonstrated that the ratiometric response of the probe to acidic pH was due to H + binding with the N of cinnamaldehyde and the induced decreases of the intramolecular charger transfer (ICT) process. The as-prepared probe displayed excellent cell membrane permeability was further applied successfully to monitor pH fluctuations in live cells with excellent lysosomal targeting ability, and extreme acidity in Escherichia coli cells.

CAS / MDL: 6203-18-5
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JOURNAL OF MEMBRANE SCIENCE · 2017 · IF 6.035

Dual pH- and ammonia-vapor-responsive electrospun nanofibrous membranes for oil-water separations

Wenjing Ma,Sangram Keshari Samal,Zhongche Liu,Ranhua Xiong,Stefaan C. De Smedt,Bharat Bhushan,Qilu Zhang,Chaobo Huang

In the last few years, the amount of industrial oily wastewater discharge and number of oil spill accidents have increased exponentially, spurring the development of highly efficient, cost-effective oil-water separation technologies. In this study, a dual pH- and ammonia-vapor-responsive polyimide (PI)-based nanofibrous membrane with high permeate flux and stability was developed for oil-water separations. The membrane was prepared by successively dip-coating electrospun PI in decanoic acid (DA)-TiO 2 and silica nanoparticles (SNPs). The novel SNP/DA-TiO 2 /PI membrane exhibits superhydrophobicity in air and superoleophilicity in neutral aqueous environments (e.g., at pH 6.5). However, the membrane becomes hydrophilic and superoleophobic in basic aqueous environments (e.g., at pH 12), resulting in only water permeation during oil-water separations. The oil-water separation potential of this innovative dual-responsive membrane was investigated using several model oil-water mixtures. The membrane has extremely high flux (6500±100   L   m −2   h −1 ) and separation efficiency (>99%) and is reusable. In addition, thermal stability and abrasion resistance tests show that the membrane is highly stable under extreme conditions. This dual-responsive electrospun nanofibrous membrane has potential for use in industrial oil-polluted water and oil spill treatment and in systems that require selective oil-water permeation. Furthermore, changes in the surface wettability can also be induced by exposure to ammonia vapor, which might facilitate remote-controlled oil-water separations.

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