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JOURNAL OF PORPHYRINS AND PHTHALOCYANINES · 2022 · IF 1.914

p-Toluenethiolate manganese(II) porphyrin complexes: Structure and spectroscopic properties

Yiwen Yuan,Jianping Zhao,Jianfeng Li

Utilizing tetraphenylporphyrin (TPP), tetratolylporphyrin (TTP), tetramesitylporphyrin (TMP), and tetra- p -chlorophenylporphyrin (T p ClPP) as ligands, several five-coordinate high-spin p -toluenethiolate Manganese(II) complexes are isolated and studied by UV-vis, single-crystal X-ray and EPR spectroscopies. The crystal structures show noteworthy features including flexible axial p -toluenethiolate ligands and intramolecular C−H ⋅ ⋅ ⋅ π and π - π interactions between ligands and porphyrin planes. All four products are further studied by X-band EPR on both solid and solution states at 4 K which confirmed the S = 2/5 high-spin states. Temperature-dependent EPR and measurements with different equivalents of ligands are also reported for comparison. The work provides new references for the study of the active center of P450s and the biochemical reaction between cysteine residues and heme.

CAS / MDL: 1310-58-3 106-45-6
研究领域: 生物化学 · 配位化学 · 结构化学
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JOURNAL OF NANOBIOTECHNOLOGY · 2022 ·Vol. 20 ·期 1 ·1-18 · IF 9.429

Augmented EPR effect post IRFA to enhance the therapeutic efficacy of arsenic loaded ZIF-8 nanoparticles on residual HCC progression

Chen Xuehua,Huang Yongquan,Chen Hui,Chen Ziman,Chen Jiaxin,Wang Hao,Li Dan,Su Zhongzhen

Background Insufficient radiofrequency ablation (IRFA) can promote the local recurrence and distal metastasis of residual hepatocellular carcinoma (HCC), which makes clinical treatment extremely challenging. In this study, the malignant transition of residual tumors after IRFA was explored. Then, arsenic-loaded zeolitic imidazolate framework-8 nanoparticles (As@ZIF-8 NPs) were constructed, and their therapeutic effect on residual tumors was studied. Results Our data showed that IRFA can dramatically promote the proliferation, induce the metastasis, activate the epithelial–mesenchymal transition (EMT) and accelerate the angiogenesis of residual tumors. Interestingly, we found, for the first time, that extensive angiogenesis after IRFA can augment the enhanced permeability and retention (EPR) effect and enhance the enrichment of ZIF-8 nanocarriers in residual tumors. Encouraged by this unique finding, we successfully prepared As@ZIF-8 NPs with good biocompatibility and confirmed that they were more effective than free arsenic trioxide (ATO) in sublethal heat-induced cell proliferation suppression, apoptosis induction, cell migration and invasion inhibition, and EMT reversal in vitro. Furthermore, compared with free ATO, As@ZIF-8 NPs exhibited remarkably increased therapeutic effects by repressing residual tumor growth and metastasis in vivo. Conclusions This work provides a new paradigm for the treatment of residual HCC after IRFA. Graphical Abstract

研究领域: 肿瘤学 · 纳米技术 · 药理学
✓ 已验证 DOI PubMed 高影响因子
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ACS Applied Energy Materials · 2023 · IF 6.4

Understanding the Improved Fast Charging Performance of Graphite Anodes with a Fluoroethylene Carbonate Additive by In Situ NMR and EPR

Shinuo Kang,Fushan Geng,Xiaobing Lou,Guozhong Lu,Yuxin Liao,Ming Shen,Bingwen Hu

The extreme fast charging (XFC) capability of graphite anodes is becoming increasingly important with the development of electric vehicles due to the usage and safety requirement. In this work, the XFC performance of the graphite anodes is improved by simply adding fluoroethylene carbonate (FEC) into the electrolyte. This robust system is studied by in situ nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) experiments to unravel the kinetic mechanism. The Li local environments in the graphite are detected by in situ NMR, which reveals the phase transitions during XFC without and with the FEC additive and the corresponding Li-ion mobility. The graphite conductivity variation is estimated by in situ EPR, and the plated Li can be clearly observed in the later period of XFC. The kinetics of graphite lithiation is deduced to be surface-controlled during the dilute stages and bulk-controlled during the dense stages. The solid electrolyte interphase (SEI) formed with FEC is more homogeneous and richer in LiF, which delivers a faster Li+ transport ability and results in the improvement of the surface kinetics. The major advantage of FEC additive is in the optimization of the Li plating behavior. Without FEC, the Li deposits grow locally, while the FEC additive consumes more currents to form the SEI and facilitate the uniform deposition of metallic Li on graphite during XFC. These results display the versatility of in situ NMR and EPR technologies in the research of XFC kinetics.

研究领域: 电化学 · 电池技术 · 材料科学 · 原位表征 · 储能
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Nanoscale · 2016 ·Vol. 9 ·期 1 ·314-325 · IF 7.76

A pH-responsive sequential-disassembly nanohybrid for mitochondrial targeting

Lijia Li,Wei Sun,Lian Li,Yuanyuan Liu,Lei Wu,Fengling Wang,Zhou Zhou,Zhirong Zhang,Yuan Huang

Cationic materials have been reported as promising tools for targeting to mitochondria which are the “power houses” and “metabolic garbage keepers” of cells. However, their positive nature also restricts their in vivo application due to the quick clearance. Herein, we fabricated a nanohybrid consisting of the pH-responsive N-(2-hydroxypropyl)methacrylamide (HPMA) co-polymer (R-P) shells and positive mesoporous silica nanoparticle cores via electrostatic interaction. The anticancer drug, docetaxel (DTX), was encapsulated in the positive MSN cores (MSN–DTX). Once concealed by the anionic R-P shield, the assembled nanohybrid R-P@MSN–DTX will achieve prolonged blood circulation thereby leading to an enhanced EPR effect. At mildly acidic tumor environmental pH, first-stage charge reversion took place due to the hydrolysis of the amide bond on HPMA co-polymers. The de-attachment of the HPMA co-polymer occurred because of the positive charge repulsion and partial exposure of the positively charged MSN core promoted the cell internalization. The second-stage pH-responsiveness in the endo/lysosomes with a more acidic environment accelerates the disassembly of the nanohybrid and the leakage of the core facilitated the endo/lysosome escape and mitochondrial targeting with the help of intracellular compartmental acidity. Gathering up the characteristics of neutralized charge and stepwise pH-responsiveness, the R-P@MSN–DTX acquired a good tumor inhibition rate of 72.6% on nude mice. Our report provided a reference for systemic mitochondrial targeting achieved by the union of “assembly–disassembly”.

研究领域: 药学 · 纳米技术 · 癌症研究
✓ 已验证 DOI PubMed 高影响因子
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Advanced Healthcare Materials · 2018 ·Vol. 7 ·期 24 ·1801094 · IF 5.609

Enhancing the Accumulation of Polymer Micelles by Selectively Dilating Tumor Blood Vessels with NO for Highly Effective Cancer Treatment

Guoqing Wei,Yi Wang,Xuehui Huang,Guang Yang,Jingya Zhao,Shaobing Zhou

The accumulation of nanoparticles in tumors by the enhanced permeability and retention (EPR) effect is effective and well known. However, how to maximize accumulation is still a bottleneck in the development of nanomedicine. Herein, a tumor vascular-targeted hybrid polymeric micelle, which has a great capacity to selectively augment the EPR effect of nanoparticles by dilating tumor blood vessels via the activity of nitric oxide (NO), is presented. Under neutral conditions, the micelle is stable, with a long blood circulation half-life due to the carboxylated poly(ethylene glycol) (PEG) layer; in mildly acidic tumor tissues, the micelle can selectively target the tumor blood vessels by the exposed cyclic Arg-Gly-Asp peptide (cRGD) peptides, which is realized with a pH-dependent hydrolysis of the monomethoxy PEG layer. Simultaneously, exposed copper ions catalyze the decomposition of endogenous NO donors, which generates NO in situ, leading to vasodilation and increased tumor vascular permeability. As a result, the accumulation of nanoparticles is significantly enhanced, and a high accumulation of doxorubicin in tumors is achieved at 48 h after injection. This high dose of therapeutic agent produces a large inhibition of tumor growth (94%) in cancer treatment, and shows no general toxicity, with 100% of the mice surviving the treatment regimen.

CAS / MDL: 129-00-0
研究领域: 药学 · 肿瘤学 · 纳米医学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

A multifunctional manipulation to stabilize oxygen redox and phase transition in 4.6 V high-voltage LiCoO2 with sXAS and EPR studies

Bei Hu,Fushan Geng,Ming Shen,Chong Zhao,Qing Qiu,Yang Lin,Changxin Chen,Wen Wen,Shun Zheng,Xiaoshi Hu,Chao Li,Bingwen Hu

LiCoO 2 , as a domain cathode material of Li-ion batteries, faces a great deal of challenges due to the limited cycling stability at high voltage (>4.35 V vs. Li/Li + ). These issues are tentatively addressed here by a multifunctional self-stabilization modification strategy, involving trace Mg bulk doping, surface gradient Ti doping and BaTiO 3 dot coating in LiCoO 2 . The multifunctional synergy is verified to overcome the detrimental irreversible phase transition and the growth of impedance of LiCoO 2 cycling at 4.6 V. By using soft X-ray absorption spectroscopy (sXAS) and electron paramagnetic resonance (EPR) techniques, we also elucidate that Ti surface gradient doping can reinforce the structure rigidity of the particles while significantly attenuates the irreversible oxygen redox at high voltage. All these strategies promote the prolonged cyclic performance of LiCoO 2 under 4.6 V high-voltage through different mechanism. This elaborate investigation provides an instructive contribution in the advancement of high-voltage LiCoO 2 .

研究领域: 材料科学 · 电化学
✓ 已验证 DOI 高影响因子
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Journal of Physical Chemistry Letters · 2025 · IF 4.6

A Ring-Shaped Lithium Metal Anode Enables High-Performance All-Solid-State Batteries Revealed by In Situ L-Band EPR Imaging

Jiaxing Lv,Ying Jiang,Guozhong Lu,Xiaobing Lou,Bingwen Hu

In traditional operations of all-solid-state lithium metal batteries (ASSLMBs), a small thin lithium metal circular disk is employed as a lithium metal anode (LMA). However, ASSLMBs with a circular-disk LMA often fail in <150 cycles with low capacity retention. In this work, we developed a new ring-shaped LMA to improve cyclability. Full cells consisting of a ring-shaped LMA, a LiCoO2 cathode, and a Li6PS5Cl electrolyte maintain good capacity retention of 83.65% at 0.3C after 300 cycles. Moreover, in situ L-band electron paramagnetic resonance imaging (EPRI) showed that fewer Li dendrites are formed on a ring-shaped LMA. This work highlights the importance of the design of the shape of the LMA to mitigate the growth of lithium dendrites and shows that L-band EPRI is a useful technique for ASSLMBs.

CAS / MDL: 554-13-2
研究领域: 材料科学 · 电化学 · 储能技术 · 电池技术
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2018 ·Vol. 316 ·期 2 ·685-690 · IF 1.181

Preparation and biodistribution of 131I-labeled graphene quantum dots

Song Hu,Wang Yunhan,Wang Jing,Wang Guanquan,He Jiaheng,Wei Hongyuan,Luo Shunzhong

For the superiority of graphene quantum dots (GQDs) in bioimaging and drug delivery carrier, GQDs bring new opportunities for theranostics of diseases. In this study, GQDs were successfully prepared and labeled with 131 I. The in vitro properties, biodistribution and SPECT imaging of 131 I-GQDs were investigated. The uptake of 131 I-GQDs at tumor sites can be clearly observed via SPECT imaging and T/B and T/M ratios increase with increasing time, which can contribute to enhanced permeability and retention (EPR) effect.

研究领域: 核医学 · 放射学 · 材料科学 · 生物医学工程
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RSC Advances · 2016 ·Vol. 6 ·期 17 ·13698-13709 · IF 3.289

The evaluation of cellular uptake efficiency and tumor-targeting ability of MPEG–PDLLA micelles: effect of particle size

Ying Hao,YiXing Huang,YunQi He,JinRong Peng,LiJuan Chen,Xun Hu,ZhiYong Qian

In this study, we successfully prepared MPEG–PDLLA polymer micelles with two different particle sizes, A and B. DLS and TEM assays demonstrated that the particle sizes of the polymer micelles A and polymer micelles B were about 25 nm and 150 nm respectively. The stability of the MPEG–PDLLA polymer micelles in vitro revealed that the free Cy5.5 dye had been successfully loaded into the polymer micelles as a fluorescence marker and the fluorescence wasn’t quenched until 72 h. The cellular uptake of the polymer micelles was time-dependent and micelles A (particle size 25 nm) showed a higher efficiency to be internalized into the cytoplasm of MCF-7 cells than micelles B (particle size 150 nm). Furthermore, in vivo and in vitro biodistribution and tumor-targeting of polymer micelles MPEG–PDLLA were investigated in female MCF-7 tumor-bearing balb/cA-nu mice with an IVIS imaging system. The results showed that polymer micelles A (particle size 25 nm) had a time dependent biodistribution and tumor site accumulation in mice bearing MCF-7 tumors. Meanwhile, the NIR fluorescence intensity of polymer micelles B (particle size 150 nm) in tumor sites showed a pattern of a rise, a peak and then a decline. What’s more, the distribution of the polymer micelles in the tissue slices demonstrated the same results. Consequently, the results indicated that the micelles with a smaller particle size (25 nm) could be more efficiently internalized into cells and increase the enhanced permeation and retention (EPR) effect in tumor tissue. Therefore, a reasonable small size of micelles may be a key factor for a high-performance anti-cancer drug delivery system.

CAS / MDL: 64-17-5
研究领域: 药剂学 · 肿瘤学 · 生物医学工程
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Journal of Materials Chemistry A · 2020 ·Vol. 8 ·期 32 ·16515-16526 · IF 11.301

Anionic redox reactions and structural degradation in a cation-disordered rock-salt Li1.2Ti0.4Mn0.4O2 cathode material revealed by solid-state NMR and EPR

Fushan Geng,Bei Hu,Chao Li,Chong Zhao,Olivier Lafon,Julien Trébosc,Jean-Paul Amoureux,Ming Shen,Bingwen Hu

The burgeoning Li-rich cation-disordered rock-salt (DRX) materials have great potential to serve as the cathodes for rechargeable lithium ion batteries. They generally possess high capacities thanks to the participation of both cationic and anionic redox reactions. However, most DRX materials are subject to a large irreversible capacity loss during the first cycle and an undesirable voltage hysteresis between charge and discharge. In this work, solid-state NMR spectroscopy is employed to resolve the manifold local environments in Li1.2Ti0.4Mn0.4O2 as a model sample, and electron paramagnetic resonance (EPR) spectroscopy is used to investigate its electronic properties. Very broad resonances are observed in the 7Li and 17O NMR spectra. The paramagnetic and diamagnetic Li environments are distinguished, and the loss of the diamagnetic Li signal is observed after the first cycle. The degradation mechanism involved with oxygen loss and transition metal migration is discussed. The formation of the (O2)n− species and electron holes on oxygen at high voltage is suggested by EPR, and the voltage hysteresis is attributed to the difficulty in reducing the stable O–O bonds. These findings may enrich the understanding of DRX materials to better design high-performance DRX cathodes.

研究领域: 材料科学 · 电化学 · 储能 · 电池技术 · 固体谱学
✓ 已验证 DOI 高影响因子
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CHEMOSPHERE · 2024 · IF 8.1

A new strategy to construct MOF-on-MOF derivatives for the removal of tetracycline hydrochloride from water by activation of peroxymonosulfate

Fengtao Hu,Shunyan Ning,Zengzhiqiang Li,Hao Zhu,Toyohisa Fujita,Xiangbiao Yin,Lifeng Chen,Deqian Zeng,Mohammed F. Hamza,Yuezhou Wei,Xinpeng Wang

A MOF-on-MOF composite derivative material named ZIF-67@Ce-MOF-600 was designed and synthesized. The preparation of ZIF-67@Ce-MOF-600 was optimized from the aspects of the ratio of metal and ligand, heat-treatment temperature. It was demonstrated by XRD , FT-IR, SEM-EDS and TEM . The optimum conditions for the activation of PMS by ZIF-67@Ce-MOF-600 for the degradation of tetracycline (TC) were investigated by adjusting the catalyst dosage, TC, pH, peoxymonosulfate (PMS) concentration, and different kinds of water, co-existing anions and pollution. Under optimal conditions (20 mg catalysts and 50 mg PMS added) in 100 mL of tetracyclines (TC) solvent (20 mg TC/L), the removal rate could reach up to 99.2% and after five cycles was 70.5%. The EPR results indicated the presence of free radicals and non-free radical, among which free radicals intended to play a major role in the degradation process. Its possible degradation pathways and attack sites were analyzed by liquid-phase mass spectrometry and DFT analysis.

CAS / MDL: 10294-41-4 10026-22-9
研究领域: 环境科学 · 材料科学 · 化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF NANOBIOTECHNOLOGY · 2021 ·Vol. 19 ·期 1 ·1-18 · IF 10.435

Co-administration of combretastatin A4 nanoparticles and anti-PD-L1 for synergistic therapy of hepatocellular carcinoma

Zhao Bonan,Dong Zhipeng,Liu Weixing,Lou Fangning,Wang Qiyan,Hong Hao,Wang Yue

Background According to data estimated by the WHO, primary liver cancer is currently the fourth most common malignant tumor and the second leading cause of death around the world. Hepatocellular carcinoma (HCC) is one of the most common primary liver malignancies, so effective therapy is highly desired for HCC. Results In this study, the use of poly( l -Aspartic acid)-poly(ethylene glycol)/combretastatin A4 (CA4-NPs) was aimed to significantly disrupt new blood vessels in tumor tissues for targeted hepatic tumor therapy. Here, PEG-b-PAsp-g-CA4 showed significantly prolonged retention in plasma and tumor tissue. Most importantly, CA4-NPs were mainly distributed at the tumor site because of the triple target effects—enhanced permeability and retention (EPR) effect, acid-sensitive (pH = 5.5) effect to the tumor microenvironment (TME), and good selectivity of CA4 for central tumor blood vessel. Considering that CA4-NPs might induce severe hypoxic conditions resulting in high expression of HIF-1α in tumor tissues, which could induce the overexpression of PD-L1, herein we also used a programmed death-ligand 1 antibody (aPD-L1) to prevent immunosuppression. This way of complementary combination is able to achieve an ideal treatment effect in tumor site where CA4-NPs and aPD-L1 could respond to the inner area and peripheral area, respectively. As a result, a significant decrease in tumor volume and weight was observed in the combination group of CA4-NPs plus aPD-L1 compared with CA4-NPs or aPD-L1 monotherapy in subcutaneous Hepa1-6 hepatic tumor models. Conclusions We presented a new idea that co-administration of CA4-NPs and aPD-L1 possessed notable anti-tumor efficacy for HCC treatment. Graphic abstract

CAS / MDL: 32315-10-9
研究领域: 肿瘤学 · 药学 · 免疫疗法
✓ 已验证 产品关联 DOI PubMed 高影响因子
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