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JOURNAL OF APPLIED POLYMER SCIENCE · 2014 ·Vol. 132 ·期 9 · IF 1.64

Polystyrene/attapulgite nanocomposites prepared via in situ suspension polymerization with redox initiation system

Haicun Yang,Liu Zhang,Wenzhong Ma,Hongting Pu,Fanghong Gong

A series of polymer–clay nanocomposites consisting of polystyrene (PS) and attapuglite (ATP) were prepared successfully. First, silane coupling agent containing aromatic tertiary amine groups was synthesized to functionalize ATP (M-ATP). Then, PS nanocomposites with varied clay loadings were prepared via in situ suspension polymerization process with a redox initiation system consisting of aromatic tertiary amine and benzoyl peroxide. The synthesis of silane coupling agent and functionalization of ATP were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectra, and X-ray photoelectron spectroscopy. Mechanical properties, morphology, thermal stability, and rheological behavior of nanocomposites were investigated to illuminate the effects of M-ATP on the structure and properties of nanocomposites. Field-emission scanning electron microscope images revealed an ideal dispersion of M-ATP and an enhanced toughness of nanocomposites. The improved interface interaction between M-ATP and PS matrix endowed the nanocomposites with outstanding mechanical properties and thermal stability. The formation of hybrid network in the nanocomposites containing 3 wt % M-ATP resulted in higher complex viscosity (η*), storage modulus ( G ′), and lower loss factor (tanδ) compared with the pristine PS and PS/ATP nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 41567.

CAS / MDL: 919-30-2 80-41-1
研究领域: 材料科学 · 高分子化学
✓ 已验证 产品关联 DOI 高影响因子
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Acta Biomaterialia · 2016 · IF 6.008

Synergistic antitumor efficacy of redox and pH dually responsive micelleplexes for co-delivery of camptothecin and genes

Maohua Chen,Yun Zhang,Zhoujiang Chen,Songzhi Xie,Xiaoming Luo,Xiaohong Li

Challenges remain to load and deliver two or multiple drugs of complementary effects for synergistic cancer therapies. In the current study, multiarmed amphiphilic copolymers of 4-arm poly(ethylene glycol) (PEG) and polyaspartate (PAsp) are created for conjugation of camptothecin (CPT) and condensation with tumor necrosis factor-α (TNF) plasmids. Diethylenetriamine (DET) is grafted on PAsp, and CPT is conjugated onto PAsp(DET) by disulfide linkages to form hydrophobic cores of micelles , followed by condensation with TNF plasmids to form micelleplexes. The cis -aconitic linkers are introduced between PEG and PAsp(DET) to remove PEG shells in response to acidic pH, resulting in destabilized micelleplexes and prompted endosomal escape into the cytosol. The micelleplex disintegration in response to reductive stimuli in the cytosol leads to an efficient CPT release and pDNA disassociation. The co-delivery of CPT with TNF plasmids enhances the gene transfection of micelleplexes at low N/P ratios, and shows synergetic cytotoxicities to tumor cells with 2.5 and 8 folds lower IC 50 s compared with those after treatment with CPT or TNF alone, respectively. The micelleplex treatment on 4T1 tumor models dramatically extends the animal survival and suppresses the tumor growth with 2.3 and 3 folds lower in volume compared with CPT or TNF treatment alone, respectively. Histological and biochemical analyses display TNF expressions in tumor tissues after micelleplex treatment, resulting in significantly larger necrotic regions in tumors, higher cell apoptosis rates , and no obvious sign of tumor metastasis in lungs compared with other treatment. Therefore, the multifunctional micelleplexes based on multiarmed PEG-PAsp(DET) copolymers offer the targeted drug/gene delivery, dually responsive drug/gene release and synergistic antitumor efficacy, holding great promises for combination therapies. Statement of Significance Micelleplexes are constructed from multiarmed amphiphilic copolymers with conjugation of captothecin (CPT) and condensation of tumor necrosis factor-α (TNF) plasmid. The pH/redox stimuli realize co-delivery of CPT and pDNA in a sequential manner of folate-mediated endocytosis , endosomal escape induced by PEG cleavage, reduction-sensitive release of CPT in cytosol, and pDNA release from disintegrated polyplexes after CPT release. Compared with CPT or TNF treatment alone, the micelleplexes achieve 2.5 and 8 folds higher cytotoxicities to tumor cells, and suppress the tumor growth with 2.3 and 3 folds lower in volume, respectively. It demonstrates a feasible strategy to develop multifunctional micelleplexes with simultaneous drug conjugation and pDNA condensation, dually responsive drug/gene release and synergistic antitumor efficacy, holding great promise for combinational therapies.

研究领域: 药剂学 · 肿瘤学 · 生物材料科学
✓ 已验证 DOI PubMed 高影响因子
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RSC Advances · 2016 ·Vol. 6 ·期 17 ·14120-14127 · IF 3.289

Preparation of core–shell attapulgite particles by redox-initiated surface reversible addition–fragmentation chain transfer polymerization via a “graft from” approach

Haicun Yang,Sheng Xue,Ji Pan,Fanghong Gong,Hongting Pu

Nanoclay attapulgite (ATP) was first activated with hydrochloric acid to enhance the surface reactivity, and was then allowed to react with a synthetic aromatic tertiary amine coupling agent to introduce electron-donor groups. Subsequently, the surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization of methyl methacrylate (MMA) was carried out in the presence of a free RAFT agent cyanoisopropyl dithiobenzoate (CPDB) initiated by a redox pair made up of benzoyl peroxide (BPO) and aromatic tertiary amine functionalized ATP (ATP-ATA). The grafting process was verified by 1H nuclear magnetic resonance, UV-visible spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermo gravimetric analysis, transmission electron microscopy and gel permeation chromatography. Kinetic behavior indicated that polymerization using this redox initiation system displayed a living/controlled nature. Both the grafted and free polymers were grown in a controlled manner, and the RAFT polymerization proceeded with 37.6% monomer conversion achieved within 10 h at 50 °C, yielding about 47.4% grafting ratio of polymer relative to hybrid particles with high affinity to organic media.

研究领域: 材料科学 · 高分子化学
✓ 已验证 DOI 高影响因子
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ACS Sustainable Chemistry & Engineering · 2025 · IF 7.3

Modulating Mn3+/Mn4+ Redox Couples in Pd/OMS-2 through Pd–O–Mn Interfacial Chemical Bonds for Boosting Electrocatalytic Oxygen Reduction and Methanol Oxidation

Jun Zhang,Lanyu Luo,Jiankun Wang,Xinlan Xu,Tiantian Peng,Boyu Liu,Lingying Jiang,Meng Jin,Weimin Wu,Laizheng Luo,Huan Yi,Shi-Yu Lu

Optimizing the electronic configuration presents a promising approach to enhance intrinsic activity and minimize noble metal use in direct methanol fuel cells (DMFCs). Metal–support interactions, commonly employed to induce interfacial charge redistribution, play a crucial role in this optimization. This study successfully synthesized a Pd/O-OMS-2 electrocatalyst characterized by Pd–O–Mn interfacial chemical bonds and Mn3+/Mn4+ redox couples, serving as a stable bifunctional catalyst for both the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). Unlike the mixed Pd–O/Mn bonds in Pd/O/Mn-OMS-2, the Pd–O–Mn bonds in Pd/O-OMS-2 not only enhance metal–support interactions and promote uniform dispersion of Pd nanoparticles but also facilitate electron transfer and the conversion between Mn3+ and Mn4+. These structural and compositional advantages endow the Pd/O-OMS-2 catalyst with superior ORR and MOR performance. The catalyst achieves a higher half-wave potential (E1/2) of 0.901 V, a mass activity of 0.937 A mgPd–1, and enhanced methanol permeability, outperforming Pd/O/Mn-OMS-2, Pd/OMS-2 and commercial Pd/C catalysts. Moreover, in an alkaline electrolyte, the Pd/O-OMS-2 catalyst follows a typical four-electron reaction pathway for ORR (O2 to H2O) and promotes faster reaction kinetics and charge transfer rates. In terms of durability, the Pd/O-OMS-2 catalyst exhibits minimal E1/2 decay (8 mV) and retains its structural integrity even after 10,000 cyclic voltammetry (CV) cycles. Additionally, it demonstrates the highest mass activity and stability during the MOR process. The exceptional ORR/MOR performance can be attributed to the synergistic effect of strong metal–support interactions, high Pd nanoparticle dispersion, and increased Mn3+ active species. The construction of interfacial chemical bonds offers a prospective strategy to optimize electronic configurations and develop advanced bifunctional electrocatalysts for ORR and MOR.

CAS / MDL: 13820-53-6 7785-87-7
研究领域: 电化学 · 催化材料 · 能源材料
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Nature Communications · 2025 ·Vol. 16 ·期 1 ·1-11 · IF 15.7

Proton-coupled electron transfer controls peroxide activation initiated by a solid-water interface

Chen Jian-Hua,Li Wan-Ting,Cai Kun-Yu,Tu Hui-Jie,Long Zi-Tong,Akhtar Shoaib,Liu Lin-Dong

Decentralized water treatment technologies, designed to align with the specific characteristics of the water source and the requirements of the user, are gaining prominence due to their cost and energy-saving advantages over traditional centralized systems. The application of chemical water treatment via heterogeneous advanced oxidation processes using peroxide (O–O) represents a potentially attractive treatment option. These processes serve to initiate redox processes at the solid-water interface. Nevertheless, the oxidation mechanism exemplified by the typical Fenton-like persulfate-based heterogeneous oxidation, in which electron transfer dominates, is almost universally accepted. Here, we present experimental results that challenge this view. At the solid-liquid interface, it is demonstrated that protons are thermodynamically coupled to electrons. In situ quantitative titration provides direct experimental evidence that the coupling ratio of protons to transferred electrons is almost 1:1. Comprehensive thermodynamic analyses further demonstrate that a net proton-coupled electron transfer occurs, with both protons and electrons entering the redox cycle. These findings will inform future developments in O–O activation technologies, enabling more efficient redox activity via the tight coupling of protons and electrons.

研究领域: 环境科学 · 化学工程 · 材料科学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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Energy & Environmental Science · 2024 ·Vol. 17 ·期 12 ·4104-4114 · IF 32.4

Ultra-high performance of ionic thermoelectric-electrochemical gel cells for harvesting low grade heat

Yongbin Zhu,Cheng-Gong Han,Jiawei Chen,Lijuan Yang,Yingming Ma,Hongyu Guan,Dongxue Han,Li Niu

Gel-based ionic thermoelectric (i-TE) conversion systems have attracted more attention to harvest energy from ambient waste heat to power sensors in IoT systems, due to their high ionic thermopower, cost-effectiveness, and environmental friendliness. However, their thermoelectric performance, particularly output power density, remains low, hindering their further application. To date, there is still a lack of an effective strategy to reverse this serious situation. Herein, we originally designed an ionic thermoelectric-electrochemical (i-TE-EC) cell by combining two asymmetric gels into a double sandwich structure, resulting in high thermoelectric performance. By tailoring gel compositions, including the concentration and ratio of redox couples as well as additive contents, a maximum output power density Pmax/(ΔT)2 of 10.0 mW m−2 K−2, a cell ionic thermopower of 5.2 mV K−1, and an energy density of 3.4 J m−2 K−2 in two hours were obtained at 313 K for the i-TE-EC cell Gp | G-m/n FeCN4−/3− | Gp | G-x/y I−/I3−-z CF3SO3K | Gp (m/n = 0.175/0.025 M, x/y = 0.10/0.05 M, z = 0.4 M). Moreover, Pmax/(ΔT)2 increased to a higher value of 20.5 mW m−2 K−2 for the i-TE-EC cell using a CEM as a built-in electrode. A gel-device assembled by nine single i-TE-EC cells connected in series generated a voltage of 1.55 V and a high Pmax/(ΔT)2 of 5.2 mW m−2 K−2 at 313 K and ΔT = 5 K. This work provides a promising route for improving the gel-based thermoelectric performance, available for other energy conversion systems.

研究领域: 材料科学 · 能源技术
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ChemPhotoChem · 2024 · IF 3

Reversing Reprogramming of Cancer Cell Metabolism by Singlet Oxygen Triggered Release of Dichloroacetate Enhances Photodynamic Cytotoxicity

Zhenyan Zhou,Lei Wang,ShouCai Yan,Ziang Liu,Rensong Sun,Yuan Qiao,Engin Umut Akkaya

Cancer cells change their glucose metabolism towards lactic acid production for various defensive and proliferative advantages.  Dichloroacetate (DCA) is an inhibitor of a key enzyme and thus, changes back the OX-PHOS to glycolysis ratio.  We designed and synthesized a singlet oxygen triggered source of dichloroacetate which releases this inhibitor during photodynamic singlet oxygen generation.  Synergistic action of DCA and singlet oxygen results in significant enhancement of photocytotoxicity.  The results suggest that this approach could offer significant improvement in the therapeutic outcome of PDT.

CAS / MDL: 84-65-1 79-36-7
研究领域: 肿瘤学 · 药理学 · 生物医学工程 · 细胞生物学
✓ 已验证 产品关联 DOI 高影响因子
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ACS Applied Polymer Materials · 2022 · IF 4.855

Increasing the Production of Reactive Oxygen Species through a Ferroptosis Pathway Disrupts the Redox Balance of Tumor Cells for Cancer Treatment

Fan Yang,Chenggang Song,Ruixuan Ji,Xiaoyi Song,Bin Yang,Yin Lv,Zhong Wei

Disruption of the balance of cellular redox can increase the cellular concentration of reactive oxygen species (ROS), which leads to oxidative stress-induced apoptosis in cancer cells, therefore minimizing the toxic effects on normal cells. However, this strategy is incomplete in programmable anticancer drug delivery. On the basis of this strategy, we designed, synthesized, and successfully functionalized an amphiphilic copolymer [poly(ethylene glycol) monomethyl ether (mPEG)-b-poly(hydroxyethyl methylacrylate)(PHEMA))-g-SS-hydroxybenzenoborate pinanol ester(HPBAe)/hydroxyethylferrocene (Fc)] that can form stable micelles in water and effectively load the hydrophobic drug doxorubicin (DOX). 1H NMR was used to confirm the structure of the polymers. Transmission electron microscopy (TEM) revealed that the blank or drug-loaded micelles were spherical. Blank micelles displayed negligible cytotoxicity. Ferrocene reacted with H2O2 to form hydroxyl radicals (·OH) through a Fenton or Fenton-like reaction for an enhanced antioxidant ability of cancer cells. H2O2-induced self-destruction of PHEMA can then release quinone methide (QM), which depletes glutathione (GSH) and suppresses the antioxidant capacity of tumor cells. This process can effectively attack cancerous cells through the synergistic effects of DOX, thus maximizing the therapeutic impact. Confocal microscopy also displayed that the drug could be efficiently delivered and released by micelles. Finally, the nano drug loading system containing ferrocene and pinacol phenylborate can actively increase the level of ROS in 4T1 cells and effectively kill 4T1 cells. This amphiphilic copolymer micelle is a stimuli-responsive nanomaterial and a promising therapeutic approach for cancer.

研究领域: 生物化学 · 癌症治疗 · 材料科学
✓ 已验证 DOI 高影响因子
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Journal of Energy Storage · 2024 · IF 8.9

A highly water-soluble phenoxazine quaternary ammonium compound catholyte for pH-neutral aqueous organic redox flow batteries

Mengna Qin,Guibao Wu,Kai Zheng,Xiaofei Yu,Juan Xu,Jianyu Cao

The pH-neutral aqueous redox flow battery (ARFB) is one of the most attractive flow batteries due to its non-corrosiveness, low-cost, and wider electrochemical stability window compared to those with acidic or alkaline electrolytes. However, there are few families of organic redox-active molecules available as catholyte materials for pH-neutral ARFBs. Herein, through incorporation of quaternary ammonium moiety into the redox-active phenoxazine nucleus, an organic catholyte material, N , N , N -trimethyl-2-(10H-phenoxazin-10-yl) ethan-1-aminium chloride (NEt-POZ) is achieved for pH-neutral ARFBs. The NEt-POZ has a high redox potential of 0.79 V versus SHE and rapid redox kinetics (0.23 cm s −1 ) as well as high water-solubility (∼2.6 M in H 2 O). Paired with a methyl viologen (MV) anolyte in the pH-neutral aqueous electrolyte, a viologen-phenoxazine ARFB full cell is assembled, which shows an open circuit voltage of ∼1.23 V. However, the results of long-term cycling experiments indicate low Coulomb efficiency and rapid declining capacity of the NEt-POZ catholyte. The mechanism analysis unveils that the unstable doubly oxidized tri-cations (NEt-POZ 3+ ) formed via the disproportionation of radical di-cations (NEt-POZ 2+ ) in solution readily react with chloride anions to form poly-chlorinated derivatives, which precipitate from the catholyte due to their poor water solubility, leading to a rapid decrease in capacity. When there is no chloride present in the electrolyte solution, highly reactive NEt-POZ 3+ cations can interact with other counter-anions (such as sulfate and carbonate ions) and even water to form complex adducts.

研究领域: 能源化学 · 电化学 · 材料科学
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Biology Open · 2017 ·Vol. 6 ·期 4 ·489-495 · IF 2.095

Tanshinone IIA suppresses the progression of atherosclerosis by inhibiting the apoptosis of vascular smooth muscle cells and the proliferation and migration of macrophages induced by ox-LDL

Wang Baocai,Ge Zhenwei,Cheng Zhaoyun,Zhao Ziniu

The profound inhibitory effect of Tanshinone IIA (Tan IIA) on atherosclerosis has been demonstrated, whereas the latent mechanism is not completely cleared. This study aimed to investigate the cellular and molecular mechanisms underlying Tan IIA protecting against atherosclerosis. Oil Red O staining and ELISA assay showed that Tan IIA suppressed the progress of atherosclerosis and reduced the levels of inflammatory cytokines in serum of apolipoprotein E deficient (ApoE –/– ) mice. Flow cytometry assay revealed that Tan IIA inhibited oxidized LDL (ox-LDL)-induced apoptosis of VSMCs. MTT and transwell assay indicated that Tan IIA suppressed the ox-LDL-stimulated proliferation and migration of RAW264.7 cells. Moreover, Tan IIA ameliorated inflammatory cytokine upregulation elicited by ox-LDL in RAW264.7 cells. Additionally, Tan IIA inhibited the apoptosis of VSMCs and decreased the levels of MMP-2, MMP-9 in ApoE –/– mice. In conclusion, our study demonstrated Tan IIA suppressed the progression of atherosclerosis by inhibiting vascular inflammation, apoptosis of VSMCs and proliferation and migration of macrophages induced by ox-LDL.

研究领域: 药理学 · 心血管疾病 · 分子生物学
✓ 已验证 DOI 高影响因子
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INTERNATIONAL JOURNAL OF MOLECULAR MEDICINE · 2016 ·Vol. 38 ·期 6 ·1871-1878 · IF 2.348

Paeonol promotes microRNA-126 expression to inhibit monocyte adhesion to ox-LDL-injured vascular endothelial cells and block the activation of the PI3K/Akt/NF-κB pathway

Xusheng Yuan,Junjun Chen,Min Dai

Paeonol (2'-hydroxy-4'-methoxyacetophenone) is an active component isolated from the root of Paeonia Suffruticosa Andrews. We previously found that paeonol inhibited vascular cell adhesion molecule-1 (VCAM‑1) expression, and thus may be useful for the prevention and treatment of rabbit atherosclerosis (AS); however, the underlying mechanisms are not yet well known. Recently, microRNAs (miRNAs or miRs) have been reported to play an important role in the pathogenesis of AS. In the present study, we examined the effects of paeonol on miRNA-126 (miR‑126) expression, and its ability to inhibit monocyte adhesion to oxidized low-density lipoprotein (ox-LDL)-injured vascular endothelial cells (VECs). VECs were isolated from the rat thoracic aorta and stimulated with ox-LDL (20 mg/l) in the presence of paeonol. We found that miR‑126 had a lower expression in the ox-LDL-injured VECs, and VCAM‑1 was identified as a target gene of miR‑126. Furthermore, paeonol promoted miR‑126 expression and suppressed VCAM‑1 expression at the mRNA and protein level. It also inhibited monocyte adhesion to ox-LDL-injured VECs through the promotion of miR‑126 expression. Furthermore, it was demonstrated that paeonol blocked the activation of the phosphatidylinositol 3-kinase (PI3K)/protein kinase B (Akt)/nuclear factor-κB (NF-κB) signaling pathway by promoting miR-126 expression. Taken together, and to the best of our knowledge, the findings of this study provide the first evidence that paeonol promotes miR‑126 expression to inhibit monocyte adhesion to ox-LDL-injured VECs and block the activation of the PI3K/Akt/NF-κB signaling pathway. Our data suggest that miR‑126 plays a crucial role in vascular inflammation and may be an important therapeutic target in the treatment of AS with the use of paeonol.

CAS / MDL: 632-69-9
研究领域: 药理学 · 分子生物学 · 心血管疾病
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF HAZARDOUS MATERIALS · 2018 · IF 6.434

Heterogeneous activation of peroxymonosulfate by LaCo1-xCuxO3 perovskites for degradation of organic pollutants

Sen Lu,Guanlong Wang,Shuo Chen,Hongtao Yu,Fei Ye,Xie Quan

Recently cobalt-based heterogeneous catalysts have been widely investigated for peroxymonosulfate (PMS) activation in sulfate radical-based advanced oxidation processes. However, the improvement of the catalytic performance for PMS activation remains to be a challenge. As the limiting step, the rapid transformation of Co II /Co III redox pairs is crucial for PMS activation. Perovskites attract increasing attention due to their controllable oxidation state of B-site metal and formation of oxygen vacancies, which accelerates the cycle of redox pairs. LaCo 1-x M x O 3 (M = Cu, Fe and Mn) perovskites as heterogeneous catalysts of PMS were synthesized for the degradation of phenol. The results showed that LaCo 0.4 Cu 0.6 O 3 exhibited the highest catalytic activity. The pseudo first-order kinetic constant of phenol degradation on LaCo 0.4 Cu 0.6 O 3 is 0.302 min −1 , being about 5 times as high as Co 2+ with same molar concentration of cobalt in LaCo 0.4 Cu 0.6 O 3 . XPS analysis confirmed that substitution of copper could promote the cycle of Co II /Co III , thus enhance the catalytic efficiency for PMS activation. The facilitated cycle of Co II /Co III played a crucial role in the generation of sulfate radicals, hydroxyl radicals and singlet oxygen. And sulfate radical was the primary radical responsible for pollutants degradation. The results provide insights into constructing novel perovskite catalysts for the removal of organic pollutants in water.

研究领域: 环境科学 · 化学工程
✓ 已验证 DOI PubMed 高影响因子
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