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JOURNAL OF MATERIALS SCIENCE · 2019 ·Vol. 54 ·期 13 ·9983-9994 · IF 3.442

Light- and pH-responsive self-healing hydrogel

Yang Meng,Wang Linlin,Cheng Yongbin,Ma Ke,Wei Xinran,Jia Pengxiang,Gong Yongkuan,Zhang Yang,Yang Jingfa,Zhao Jiang

A self-healing hydrogel was synthesized via the multi-component reaction of azobenzene-methacrylamide, β-CD and 3-methacrylamido phenylboronic acid. The orthogonal method was applied to analyze the influence of host–guest inclusion complexation, cross-linker and phenylboronic acid monomers content on mechanical properties and healing efficiency of the hydrogel. The results indicated that hydrogel showed autonomic self-healing behavior. The hydrogel demonstrated light-switchable self-healing ability and pH-sensitive swelling ratio. It was found that hydrogel showed high elongation, excellent resilience and low elastic hysteresis. The design of the combined host–guest interactions and boronate esters on the hydrogel showed advantage for improving the mechanical, self-healing and recovery properties simultaneously.

研究领域: 材料科学 · 化学
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Signal Transduction and Targeted Therapy · 2024 ·Vol. 9 ·期 1 ·1-25 · IF 40.8

Malate initiates a proton-sensing pathway essential for pH regulation of inflammation

Chen Yu-jia-nan,Shi Rong-chen,Xiang Yuan-cai,Fan Li,Tang Hong,He Gang,Zhou Mei,Feng Xin-zhe,Tan Jin-dong,Huang Pan,Ye Xiao,Zhao Kun,Fu Wen-yu,Li Liu-li,Bian Xu-ting,Chen Huan,Wang Feng,Wang Teng,Zhang Chen-ke,Zhou Bing-hua,Chen Wan,Liang Tao-tao,Lv Jing-tong,Kang Xia,Shi You-xing,Kim Ellen,Qin Yin-hua,Hettinghouse Aubryanna,Wang Kai-di,Zhao Xiang-li,Yang Ming-yu,Tang Yu-zhen,Piao Hai-long,Guo Lin,Liu Chuan-ju,Miao Hong-ming,Tang Kang-lai

Metabolites can double as a signaling modality that initiates physiological adaptations. Metabolism, a chemical language encoding biological information, has been recognized as a powerful principle directing inflammatory responses. Cytosolic pH is a regulator of inflammatory response in macrophages. Here, we found that L-malate exerts anti-inflammatory effect via BiP-IRF2BP2 signaling, which is a sensor of cytosolic pH in macrophages. First, L-malate, a TCA intermediate upregulated in pro-inflammatory macrophages, was identified as a potent anti-inflammatory metabolite through initial screening. Subsequent screening with DARTS and MS led to the isolation of L-malate-BiP binding. Further screening through protein‒protein interaction microarrays identified a L-malate-restrained coupling of BiP with IRF2BP2, a known anti-inflammatory protein. Interestingly, pH reduction, which promotes carboxyl protonation of L-malate, facilitates L-malate and carboxylate analogues such as succinate to bind BiP, and disrupt BiP-IRF2BP2 interaction in a carboxyl-dependent manner. Both L-malate and acidification inhibit BiP-IRF2BP2 interaction, and protect IRF2BP2 from BiP-driven degradation in macrophages. Furthermore, both in vitro and in vivo, BiP-IRF2BP2 signal is required for effects of both L-malate and pH on inflammatory responses. These findings reveal a previously unrecognized, proton/carboxylate dual sensing pathway wherein pH and L-malate regulate inflammatory responses, indicating the role of certain carboxylate metabolites as adaptors in the proton biosensing by interactions between macromolecules.

研究领域: 免疫学 · 细胞生物学 · 代谢研究 · 炎症研究
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TALANTA · 2014 · IF 3.511

A profluorescent ratiometric probe for intracellular pH imaging

Qingqing Zhang,Ming Zhou

A ratiometric pH probe composed of a fluorescein moiety and an ionic near-infrared-emitting phosphorescent cyclometalated iridium(III) complex bis(6-(benzo[b]thien-2-yl)phenanthridinato)(4-(3-carboxypropyl)-4′-methyl-2,2′-bipyridine)iridium(III) was synthesized. With good cell permeability, the probe demonstrated a linear ratiometric response to the pH variation in the physiological range in HeLa cell assay.

CAS / MDL: 124-09-4 24424-99-5
研究领域: 生物化学 · 细胞生物学
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EUROPEAN POLYMER JOURNAL · 2022 · IF 5.546

Multicyclic topology-enhanced micelle stability and pH-sensitivity

Wei Ma,Shuang Li,Li-Wei Ma,Cui-Yun Yu,Hua Wei

Cyclic polymers have been reported to show unique properties and often better performance than linear analogues due to the absence of polymer chain ends, therefore great efforts have been devoted to the development of various cyclic polymers for biomedical applications. However, the effect of multicyclic topology on the stimuli-responsiveness of polymers has not been elucidated so far, to our knowledge, likely due to the lack of an efficient and powerful strategy for the controlled preparation of multicyclic polymers with well-defined structures and compositions. Clarification of this structure–property relationship will not only contribute to the rational design and development of novel cyclic polymer-derived materials with better properties for biomedical applications, but also promote greatly the clinical translations of these cyclic topology-based materials. A panel of amphiphilic pH-responsive multicyclic polymers (MCPs) were prepared via reversible addition-fragmentation chain-transfer (RAFT) copolymerization of a cyclic macromonomer, poly(oligoethylene glycol methacrylate) (M− c POEGMA) and N,N -dimethyl aminoethyl methacrylate (DMAEMA). The effect of multicyclic topology on the colloidal stability and stimuli-responsiveness of the resulting self-assembled micelles was investigated in detail. Interestingly, MCP1 micelles with a polymer composition of P(DMAEMA 50 - st -(M− c POEGMA 7 ) 3 ) showed much greater stability with a CMC value as low as 130.5 nM and more complete acidic pH-triggered disassembly than the single cyclic polymers (SCPs)-based micelle counterparts, which further endows the doxorubicin (DOX)-loaded MCP1 micelles with an approximately twofold lower IC 50 value (greater in vitro cytotoxicity) than that of the SCP-based analogues. This study therefore highlights for the first time the incorporation of multicyclic topology as a useful and efficient alternative to the simultaneously enhanced colloidal stability and stimuli-responsiveness of polymeric self-assemblies for controlled release application.

CAS / MDL: 78-67-1
研究领域: 生物材料 · 高分子化学 · 药物递送
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POLYMER · 2020 · IF 4.231

Fluorescent cellulose films with pH response and polarized emission

Tao Shi,Yun Lu

As one of the most abundant renewable and biodegradable materials in nature, cellulose is difficult to dissolve in common organic and inorganic liquids. Here, a series of regenerated cellulose films were prepared by using a specific tetra-butylammonium hydroxide TBAH/H 2 O/DMSO ternary solvent system. Especially, the fluorescent cellulose film was obtained successfully via a ring-opening grafting reaction between a modified fluorescein molecule with 3-expoxypropoxy and cellulose. The fluorescent cellulose films exhibited excellent fluorescence stability and pH sensitivity to the aqueous solutions with different degree of acid and alkaline. Moreover, the anisotropic fluorescein cellulose film was obtained for the first time by stretching and further drying the initial fluorescence cellulose hydrogel, and displayed a novel polarized emission. This work provided a simple, low-cost and environment-friendly pathway to fabricate fluorescent cellulose films, showing potential applications in packaging, decoration materials and other functional materials such as anti-counterfeiting paper.

研究领域: 材料科学 · 化学工程
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JOURNAL OF LUMINESCENCE · 2013 · IF 2.144

Optical properties of pH-sensitive carbon-dots with different modifications

Weiguang Kong,Huizhen Wu,Zhenyu Ye,Ruifeng Li,Tianning Xu,Bingpo Zhang

Carbon dots with unique characters of chemical inertness, low cytotoxicity and good biocompatibility, demonstrate important applications in biology and optoelectronics . In this paper we report the optical properties of pH-sensitive carbon dots with different surface modifications. The as-prepared carbon dots can be well dispersed in water by modifying with acid, alkali or metal ions though they tend to form a suspension when being directly dispersed in water. We find that the carbon dots dispersed in water show a new emission and absorption character which is tunable due to the pH-sensitive nature. It is firstly proved that the addition of bivalent copper ions offers a high color contrast for visual colorimetric assays for pH measurement. The effect of surface defects with different modification on the performances of the carbon dots is also explored with a core–shell model. The hydro-dispersed carbon dots can be potentially utilized for cellular imaging or metal ion probes in biochemistry.

研究领域: 生物技术 · 材料科学 · 光学
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Soft Matter · 2022 ·Vol. 18 ·期 16 ·3157-3167 · IF 4.046

Rational design of a supramolecular hydrogel with customizable pH-responsiveness on the basis of pH-induced ionization/protonation transition of BSA

Zhouxuan Xiang,Ting Liu,Huimin Wang,Genxin Chen,Xiongbin Zhu,Tonghui Hao,Jiabing Ran,Changying Yang

Developing customizable pH-responsiveness for supramolecular hydrogels is of great significance and has drawn tremendous attention. Through systematic simulation analysis, we formulated a simple supramolecular hydrogel (i.e., poly(AAm-co-NaSS)/BSA on the basis of electrostatic interaction between the sulfonate groups of poly(AAm-co-NaSS) and the protonated side groups of BSA, and proposed a novel pH-responsive mode for it: changing the internal electric charge composition of the hydrogel through pH-induced ionization/protonation transition of BSA, thereby regulating the structural stability/shrinkage/extension of the supramolecular network. On basis of this theory, the pH-responsiveness of the poly(AAm-co-NaSS)/BSA hydrogel, in principle, could be pre-designed by adjusting the initial BSA/NaSS ratio. In this regard, we fabricated a poly(AAm-co-NaSS)/BSA hydrogel prototype with a BSA/NaSS ratio of 1/57 and investigated its rheological/swelling/disassembling behavior under different pH conditions (1.7, 4.7, 7.7, 10.7, and 13.7). In addition, we also prepared two capecitabine-loaded poly(AAm-co-NaSS)/BSA hydrogel prototypes with BSA/NaSS ratios of 1/57 and 1/102 respectively at pH 4.0, and compared their drug release behavior in SGF and SIF. Finally, the experimental results fitted well with our theoretical expectations, which testified the rationality of our assumption. Thus, we believed that the poly(AAm-co-NaSS)/BSA supramolecular hydrogel could find diverse applications in the future.

CAS / MDL: 79-06-1 154361-50-9
研究领域: 生物材料学 · 药物递送系统 · 高分子化学
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EUROPEAN JOURNAL OF PHARMACEUTICAL SCIENCES · 2018 · IF 3.466

The ratiometric fluorescence nanoparticle based on SiRB for pH detection of tumor

Qinghui Wang,Xiaoyu Ding,Yuhui Wang,Qian Du,Tianguo Xu,Bin Du,Hanchun Yao

Tumor pH detection and pH value change monitoring have been of great interest in the field of nanomedicine . In this study, a pH-sensitive near-infrared fluorescence probe SiRB (Si-rhodamine and Boronic acid group) was synthesized by introducing a boronic acid group into the silicon rhodamine structure. ICG (Indocyanine green) as the fluorescence internal standard and SiRB were loaded into PLGA (poly lactic- co -glycolic acid) to form PLGA-SiRB-ICG nanoparticle . The experiments showed that the size of the nanoparticle was about 90 nm, which can reach tumor passively by enhancing permeability and retention effect. PLGA in the acidic environment will accelerate the release of cleavage, and the fluorescence ratio of the two probes can reflect the specific pH value in the tumor. The results indicated that the nanoparticle could quantitatively measure the pH value of the tumor site, which is expected to be used in tumor research and treatment.

研究领域: 纳米医学 · 生物化学 · 肿瘤学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2017 ·Vol. 35 ·期 10 ·1243-1252 · IF 1.692

Dual thermal- and pH-responsive polypeptide-based hydrogels

Meng Fan-dong,Ni Yun-xia,Ji Si-fan,Fu Xiao-hui,Wei Yu-han,Sun Jing,Li Zhi-bo

Smart hydrogels have received increasing attention for their great potential for the applications in many fields. Herein, we report a facile approach to prepare a class of dual-responsive hydrogels assembled from synthetic statistical/block thermal-responsive copoly(L-glutamate)s copolymerized with poly(ethylene glycol), which were prepared by ring-opening polymerization (ROP) and post-modification strategy. The incorporation of oligo(ethylene glycol) (OEG) and glutamic acid residues offers the gels with thermal- and pH-responsive properties simultaneously. We have systematically studied the influence of both temperature and pH on the gelation behaviors of these copolymers. It is found that the increase of glutamic acid content and solution pH values can significantly suppress the gelation ability of the samples. Circular dichroism (CD) results show that the α -helix conformation appears to be the dominant secondary conformation. More interestingly, the gelation property of the block copolymer with statistical thermal-responsive copoly(L-glutamate)s shows greater dependence on pH as compared to that with block segments due to the distinct morphology of the self-assemblies. The obtained hydrogels exhibit pH-dependent and thermal-responsive gelation behaviors, which enable them as an ideal smart hydrogel system for biomedical applications.

CAS / MDL: 24650-42-8 112-35-6
研究领域: 生物材料学 · 高分子化学 · 生物医药工程
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Materials Today Chemistry · 2018 · IF 0

pH-Regulated supramolecular chirality of phenylalanine-based hydrogels

A. Kousar,J. Liu,N. Mehwish,F. Wang,A.Y. Dang-i,C. Feng

To achieve desired physicochemical and biochemical activities of optically active molecules at targetted sites in biological systems, tuning of chiral sense by varying internal conditions (e.g., pH) is of utmost importance. However, it has been a challenge to gain the balance of non-covalent interactions required for chiral transformations merely by deviations in biochemical environment. Herein, pH-controlled chirality of supramolecular nanostructures obtained from coassembly of phenylalanine-derived gelator and achiral cationic polyacrylamide has successfully been achieved. Specifically, any changes in the pH remarkably influence the chirality of these nanostructures. For instance, coassembled hydrogels possessing l -enantiomer provide right-handed nanostructures at pH < 7; whereas at pH ≥ 7, handedness of nanostructures switches to the left-handed nanostructures. Moreover, viscoelastic properties and twist pitch were also regulated under the influence of pH change. This study may provide a methodology to control chirality by simply varying biochemical conditions, which points toward its potential to be used in biological systems as a key to gain preferential chiral sense in different sites of living systems.

研究领域: 材料科学 · 生物学 · 化学
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CARBON · 2023 · IF 10.9

Carbon nanotube field-effect transistor based pH sensors

Kemin Wang,Xiaofeng Liu,Zijun Zhao,Luyao Li,Jiajun Tong,Qian Shang,Yiwei Liu,Zhiyong Zhang

Field-effect transistor (FET) biosensor has received widespread attention due to their unique high-sensitivity properties. In conventional FET biosensors, the complicated interaction between the sample solution and the semiconductor channel always results in poor stability. Especially for FET-based pH sensors, the interface failure caused by the harsh acid-base working environment makes accurate, continuous, and low hysteresis pH measurement quite challenging. Here, we report a carbon nanotube (CNT)-FET pH sensor with enhanced environmental stability by introducing HfO 2 film into the gate insulator. The proposed devices show desired immunity to environmental interference including various chemical and physical factors. More importantly, we verified the feasibility of this CNT-FET device for continuous pH sensing, which demonstrates a sensitivity of 67.62 mV/pH, a wide pH range of 1.34–12.68, and low hysteresis of 500 pA with pH switching loops of 4.22–10.24. This work not only realizes a high-performance pH sensor but also paves the way for the development of FET biosensors with high environmental stability, which is of great significance for FET biosensors to maintain normal working performance in complex systems.

研究领域: 生物传感技术 · 材料科学
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ACS Applied Materials & Interfaces · 2016 · IF 7.145

pH-Sensitive ZnO Quantum Dots–Doxorubicin Nanoparticles for Lung Cancer Targeted Drug Delivery

Xiaoli Cai,Yanan Luo,Weiying Zhang,Dan Du,Yuehe Lin

In this paper, we reported a ZnO quantum dots-based pH-responsive drug delivery platform for intracellular controlled release of drugs. Acid-decomposable, luminescent aminated ZnO quantum dots (QDs) were synthesized as nanocarriers with ultrasmall size (∼3 nm). The dicarboxyl-terminated poly(ethylene glycol) (PEG) had been introduced to NH2–ZnO QDs, which rendered it stable under physiological fluid. Moreover, a targeting ligand, hyaluronic acid (HA), was conjugated to ZnO QDs for specifically binding to the overexpressed glycoprotein CD44 by cancer cells. Doxorubicin (DOX) molecules were successfully loaded to PEG functionalized ZnO QDs via formation of metal–DOX complex and covalent interactions. The pH-sensitive ZnO QDs dissolved to Zn2+ in acidic endosome/lysosome after uptake by cancer cells, which triggered dissociation of the metal–drug complex and a controlled DOX release. As result, a synergistic therapy was achieved due to incorporation of the antitumor effect of Zn2+ and DOX.

CAS / MDL: 919-30-2 25316-40-9
研究领域: 纳米技术 · 药学 · 癌症研究 · 材料科学
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