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Small · 2024 · IF 13

D–A Conjugated Polymer/CdS S-Scheme Heterojunction with Enhanced Interfacial Charge Transfer for Efficient Photocatalytic Hydrogen Generation

Yaqi Li,Sijie Wan,Weichen Liang,Bei Cheng,Wang Wang,Yao Xiang,Jiaguo Yu,Shaowen Cao

Owing to the improved charge separation and maximized redox capability of the system, Step-scheme (S-scheme) heterojunctions have garnered significant research attention for efficient photocatalysis of H 2 evolution. In this work, an innovative linear donor–acceptor (D–A) conjugated polymer fluorene-alt-(benzo-thiophene-dione) (PFBTD) is coupled with the CdS nanosheets, forming the organic–inorganic S-scheme heterojunction. The CdS/PFBTD (CP) composite exhibits an impressed hydrogen production rate of 7.62 mmol g −1 h −1 without any co-catalysts, which is ≈14 times higher than pristine CdS. It is revealed that the outstanding photocatalytic performance is attributed to the formation of rapid electron transfer channels through the interfacial Cd─O bonding as evidenced by the density functional theory (DFT) calculations and in situ X-ray photoelectron spectroscopy (XPS) analysis. The charge transfer mechanism involved in S-scheme heterojunctions is further investigated through the photo-irradiated Kelvin probe force microscopy (KPFM) analysis. This work provides a new point of view on the mechanism of interfacial charge transfer and points out the direction of designing superior organic–inorganic S-scheme heterojunction photocatalysts.

研究领域: 材料科学 · 化学工程 · 光化学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2025 · IF 4.1

Kinetic recognition of L-DOPA and D-DOPA by using a clock system

Xiaofeng Wang,Xiao Liu,Lixue Wu,Gang Hu,Zhaohui Fang

Chiral enantiomers of drugs often exhibit distinct pharmacological activities despite their similar physical and chemical properties. Developing efficient methods for their distinguishment is crucial for pharmaceutical quality control. Here, we presented a novel approach using a CTT (Chlorite-Tetramethylammonium Hydroxide-Tetrathionate) clock reaction system for kinetic chiral enantiomer recognition. DOPA enantiomers were selected for this purpose, in which L-DOPA is therapeutic efficacy in treating Parkinson's disease by precursoring dopamine while D-DOPA lacks such a function. By introducing equal amounts of L-DOPA and D-DOPA into the CTT clock system, we observed a more prolonged induction period for L-DOPA compared to D-DOPA, enabling their quick differentiation. Moreover, a linear relationship between the induction period and the concentration (1.190 × 10 −6  mol/L to 4.5238 × 10 −6  mol/L) of L-DOPA or D-DOPA allowed quantitative detection of L-DOPA or D-DOPA samples. This method could also be applied to analyze varying concentration ratios of L-DOPA and D-DOPA mixtures at a fixed total concentration. Study on mechanism indicates that both L-DOPA and D-DOPA react with ClO 2 · radical to finally generate DHICA through oxidation, with their kinetic disparities evident during this process. These kinetic disparities between L-DOPA and D-DOPA oxidation arises from stereospecific hydrogen-bonding interactions in the cyclodopa intermediate. The weaker hydrogen bond in L-DOPA-derived cyclodopa likely facilitates its cleavage during oxidation, thereby accounting for the faster reaction kinetics observed in the clock system compared to D-DOPA. This makes L-DOPA exhibit more fast consumption of chlorine dioxide than D-DOPA, and resulting larger the extension in the induction period with L-DOPA than that with D-DOPA. Such a method coupling CCT clock demonstrates its versatility and potential for broader applications in chiral drug analysis.

研究领域: 分析化学 · 手性药物分析 · 药学 · 化学动力学 · 生物化学
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RSC Advances · 2015 ·Vol. 5 ·期 47 ·37574-37580 · IF 3.84

A D–π–A–π–A type dye for highly efficient dye-sensitized solar cells

Chao-Feng Du,Lei Jiang,Lei Sun,Nian-Yu Huang,Wei-Qiao Deng

We synthesized a D–π–A–π–A type dye and demonstrated its application in dye-sensitized solar cells (DSSCs). This D–π–A–π–A type dye, named C321, consisted of a triphenylamine as a donor, a 3,4-ethylenedioxythiophene (EDOT) as a π-bridge, and a benzothiazole (BTDA)–phenyl-cyanoacrylic acid as an A–π–A group. Compared with DSSCs based on a traditional D–π–A type dye C311, the DSSCs based on C321 exhibited a significant enhancement of cell performance. A power conversion efficiency of 8.2% was achieved for DSSCs based on C321, which was 9 times higher than that for DSSCs based on C311 (0.9%). The theoretical calculations and electrochemical impedance spectroscopy investigations revealed the mechanism of the enhancement of cell performance.

研究领域: 材料科学 · 能源技术 · 有机化学
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Small · 2024 · IF 13

Distinctive p-d Orbital Hybridization in CuSb Porous Nanonetworks for Enhanced Nitrite Electroreduction to Ammonia

Min Yan,Ranran Wei,Ruifan Zhang,Xiaoying Zhang,Shiqin Sun,Xuewen Wei,Xianlong Wang,Shuli Yin,Yinglong Wang

Electrochemical nitrite reduction reaction ( NO 2 − RR ${\mathrm{NO}}_{\mathrm{2}}^{\mathrm{ - }}{\mathrm{RR}}$ ), as a green and sustainable ammonia synthesis technology, has broad application prospects and environmental friendliness. Herein, an unconventional p - d orbital hybridization strategy is reported to realize the fabrication of defect-rich CuSb porous nanonetwork (CuSb PNs) electrocatalyst for NO 2 − RR ${\mathrm{NO}}_{\mathrm{2}}^ - {\mathrm{RR}}$ . The crystalline/amorphous heterophase structure is cleverly introduced into the porous nanonetworks, and this defect-rich structure exposes more atoms and activated boundaries. CuSb PNs exhibit a large NH 3 yield ( r N H 3 ${{r}_{{\mathrm{N}}{{{\mathrm{H}}}_{\mathrm{3}}}}}$ ) of 946.1 µg h −1 m cat − 1 ${\mathrm{m}}_{{\mathrm{cat}}}^{ - {\mathrm{1}}}$ and a high faradaic efficiency (FE) of 90.7%. Experimental and theoretical studies indicate that the excellent performance of CuSb PNs results from the defect-rich porous nanonetworks structure and the p-d hybridization of Cu and Sb elements. This work describes a powerful pathway for the fabrication of p - d orbital hybrid defect-rich porous nanonetworks catalysts, and provides hope for solving the problem of nitrogen oxide pollution in the field of environment and energy.

研究领域: 材料科学 · 环境科学 · 电化学
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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

FeCo alloy encased in nitrogen-doped carbon for efficient formaldehyde removal: Preparation, electronic structure, and d-band center tailoring

Dandan Zhu,Meijuan Chen,Yu Huang,Rong Li,Tingting Huang,Jun-ji Cao,Zhenxing Shen,Shun Cheng Lee

Formaldehyde is a typical indoor air pollutant that has posed severely adverse effects on human health. Herein, a novel FeCo alloy nanoparticle-embedded nitrogen-doped carbon (FeCo@NC) was synthesized with the aim of tailoring the transition-metal d-band structure toward an improved formaldehyde oxidation activity for the first time. A unique core@shell metal–organic frameworks (MOFs) architecture with a Fe-based Prussian blue analogue core and Co-containing zeolite imidazole framework shell was firstly fabricated. Then, Fe and Co ion alloying was readily achieved owing to the inherent MOF porosity and interionic nonequilibrium diffusion occurring during pyrolysis . High-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectra confirm that small FeCo alloys in situ form in FeCo@NC, which exhibits a higher formaldehyde removal efficiency (93%) than the monometallic Fe-based catalyst and a remarkable CO 2 selectivity (85%) at room temperature. Density functional theory calculations indicate the number of electrons transferred from the metal core to the outer carbon layer is altered by alloying Fe and Co. More importantly, a downshift in the d-band center relative to the Fermi level occurs from − 0.93 to − 1.04 eV after introducing Co, which could alleviate the adsorption of reaction intermediates and greatly improve the catalytic performance.

研究领域: 环境科学 · 材料科学 · 化学
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RSC Advances · 2015 ·Vol. 5 ·期 86 ·70139-70146 · IF 3.84

Catalytic dehydration of D-xylose to furfural over a tantalum-based catalyst in batch and continuous process

Xing-Long Li,Tao Pan,Jin Deng,Yao Fu,Hua-Jian Xu

Furfural is a biomass-based bulk chemical and its derivatives have potential applications as renewable fuels and chemicals. A water-tolerant and stable solid acid catalyst modified hydrated tantalum oxide (TA-p) was developed for catalytic conversion of D-xylose to furfural in water–organic solvent biphasic system. This process was performed both in a batch reactor and a continuous fixed-bed reactor. In the batch process, D-xylose conversion and furfural yield were significantly affected by the organic solvent, reaction temperature and reaction time. 1-Butanol, which could be obtained through the fermentation of biomass-based carbohydrates, was selected as organic phase and the highest furfural yield of 59% was achieved with D-xylose conversion of 96% at 180 °C in the continuous process. Moreover, the long-time stability test for 80 h under the optimal conditions showed the excellent stability of TA-p catalyst.

研究领域: 生物化学 · 催化化学
✓ 已验证 DOI 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Single-atom Co sites with upshifted d-band center efficiently boost transfer hydrogenation for selective imines synthesis

Ting Zhang,Wantong Zhao,Shiyan Li,Wenguang Cui,Baojun Wang,Yuefeng Liu,Riguang Zhang,Zhongkui Zhao

Selective transfer hydrogenation coupling of nitroarenes with benzyl alcohol is one of the most reliable strategies to access functionalized imines, but challenges remain, such as the multiple and complicated operate process, low reactivity, poor selectivity results from deep hydrogenation. Constructing highly efficient catalyst is critical for this organic transformation process. Herein, we propose a unique single-atom Co-N 4 sites on N-doped carbon, with significantly upshifted d -band center, fabricated by a one-pot solid-phase carbonization strategy, which generates an excellent catalyst for one-pot selective transfer hydrogenation coupling of nitroarenes with benzyl alcohol to various functionalized imines. Experimental and theoretical investigations demonstrate the clear linear correlation among the nitrobenzene turnover number ( TON ) and d -band center over the as-prepared Co based samples, indicating the vital effect of electronic structure of Co sites on catalytic performances. Furthermore, owing to the upshifted d -band center of Co-N 4 sites, thedesorption of aniline and N -benzylideneaniline is promoted, which accelerates the spontaneous condensation coupling of aniline with benzaldehyde and inhibits the deep hydrogenation of N -benzylideneaniline. Consequently, an outstanding catalytic performance with high activity and selectivity in transfer hydrogenation coupling for imine synthesis has been realized. This work not only presents a highly efficient non-precious metal catalyst for functionalized imines production, but also illustrates the critical effect of electron structure of metallic active site on catalytic properties and opens a new avenue for fabricating diverse single-atom catalysts for selective hydrogenation reactions.

CAS / MDL: 102-71-6
研究领域: 化学 · 材料科学 · 催化反应
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2023 · IF 8.2

High hydrostatic pressure (HHP) reinforces solid encapsulation of d-limonene into V-type starch and its application in strawberry storage

Yanan Sun,Xiangze Jia,Chin Ping Tan,Bin Zhang,Xiong Fu,Qiang Huang

The formation of inclusion complexes (ICs) between V-type starch and flavors is traditionally conducted in an aqueous system. In this study, limonene was solid encapsulated into V6-starch under ambient pressure (AP) and high hydrostatic pressure (HHP). The maximum loading capacity reached 639.0 mg/g after HHP treatment, and the highest encapsulation efficiency was 79.9 %. X-ray Diffraction (XRD) results showed that the ordered structure of V6-starch was ameliorated with limonene, which avoided the reduction of the space between adjacent helices within V6-starch generated by HHP treatment. Notably, HHP treatment may force molecular permeation of limonene from amorphous regions into inter-crystalline amorphous regions and crystalline regions as the Small-angle X-ray scattering (SAXS) patterns indicated, leading to better controlled-release behavior. Thermogravimetry analysis (TGA) revealed that the solid encapsulation of V-type starch improved the thermal stability of limonene. Further, the release kinetics study showed that a complex prepared with a mass ratio of 2:1 under HHP treatment sustainably released limonene over 96 h and exhibited a preferable antimicrobial effect, which could extend the shelf life of strawberries.

研究领域: 食品科学 · 生物学
✓ 已验证 DOI PubMed 高影响因子
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Extensive gene mining and facile engineering of a novel carbonyl reductase for asymmetric synthesis of anti-aging (S)-Pro-Xylane from d-xylose

Zhe Dou,Pei-Ru Hu,Lin-Lin Song,Yi-Cheng Wang,Hao-Nan Tang,Zhen-Qi Weng,Ya-Jun Wang,Yuan-Qiang Cai

Carbonyl reductases (CRs) are promising biological macromolecules for the asymmetric synthesis of chiral secondary alcohols. A novel CR was evolved for efficient conversion of d -xylose into anti-aging ( S )-Pro-Xylane. Through extensive gene mining, an active carbonyl reductase Zm CR was identified from Zygofabospora marxiana with high reductive activity towards d -xylose-derived 1-C-(β- d -xylopyranosyl)-acetone (XPSA) and in situ cofactor regeneration capability. Using a three-round of concise engineering strategy, a hextuple mutant C85V/V128C/S129A/V161S/Y166H/T217A (M6) was identified from merely 157 mutants with specific activity of 46.00 U·mg −1 , about 306 folds of WT. The Shannon-Wiener index of M6 was 2.21, much higher than WT, indicating its extended substrate scope. M6 could efficiently catalyze the asymmetric reduction of 190 g·L −1 XPSA into ( S )-XPSP. The k cat / K M XPSA of M6 was 203.84 s −1 ·mM −1 , about 910 folds of WT. More non-bonded interactions were monitored in M6, contributing to the stabilization of reactive catalytic conformation. This study provides a promising biocatalyst for the chemoenzymatic synthesis of value-added anti-aging ( S )-Pro-Xylane from lignocellulosic d -xylose.

研究领域: 生物化学 · 酶工程 · 合成生物学
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CATALYSIS TODAY · 2014 · IF 3.309

A modified biphasic system for the dehydration of d-xylose into furfural using SO42−/TiO2-ZrO2/La3+ as a solid catalyst

Huiling Li,Aojie Deng,Junli Ren,Changyu Liu,Wenju Wang,Feng Peng,Runcang Sun

One of the most promising strategies for furfural production is to extract continually the target product from the aqueous solution utilizing organic solvents. With the aim to develop an ecologically viable catalytic pathway for furfural production without the addition of mineral acids, we presented a modified biphasic system using a solid acid (SO 4 2− /TiO 2 -ZrO 2 /La 3+ ) as catalyst for producing furfural from xylose. Different kinds of aprotic organic solvents (DMSO, DMF and DMI) in water phase and 2-butanol in organic phase (MIBK) were investigated as reaction media. Furfural yield and xylose conversion efficiency were dependent on the amounts of aprotic organic solvents and 2-butanol, the solid/liquid ratio, and the volume ratio of the organic phase and the aqueous phase as well as the reaction temperature and time. As a result, DMI showed the best performance on improving furfural yield during the furfural production. 3563.3   μmol of furfural/g of xylose with 97.9% xylose conversion efficiency was obtained after 12   h at 180   °C when the volume ratios of water to DMI and MIBK to 2-butanol were 8:2 and 7:3, respectively.

研究领域: 生物化学 · 催化化学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2025 · IF 21.1

Breaking trade-off between catalytic activity and carbon deposit by tailoring d-band center of NiFe alloy for dry reforming of carbonate

Su Li,Jinkai Qiu,Zijun Bian,Bin Shao,Zhicheng Liu,Cheng Lian,Honglai Liu,Jun Hu

The dry reforming of carbonate with methane (CaDRM) can be one of the breakthrough technologies to address the challenge of mitigating inevitable CO 2 emissions into value-added chemicals but remains great challenges for efficient catalysts design. In this study, we break the trade-off between the catalytic activity and the carbon deposit by tailoring the d-band center of Ni through Fe doping, which matches the energy level of CH 4 * dehydrogenation but is far away from that of the over cleavage of CH* . In this light, the porous spherical Fe x Ni/Al 2 O 3 catalysts with Ni 3 Fe alloy nanoaggregates are obtained through a one-step spray drying method. The optimized Fe 0.6 Ni/Al 2 O 3 catalyst shows an excellent catalytic activity with a superior CO selectivity of 91.75 % at a complete CaCO 3 conversion at 700°C, and successfully prevents the carbon deposit to maintain its excellent stability. Moreover, the extremely low activation energy of 45.2 kJ/mol and the good porosity of Fe x Ni/Al 2 O 3 ensure its fast dynamics. Therefore, this tailoring d-band center approach through the formation of alloy catalysts supplied a novel strategy for effectively cracking hydrogen species while avoiding over cleavage of CH x * in the thermal catalysis, which promoted the CaDRM technology to be a promising solution for carbon neutrality in industrial sectors in near future.

CAS / MDL: 471-34-1
研究领域: 化学工程 · 材料科学
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Current Molecular Pharmacology · 2024 ·Vol. 17 ·期 1 ·e18761429267000 · IF 2.4

Co-treatment of Astragaloside IV with Vitamin D in Diabetic Peripheral Neuropathic Rats: Protective Effects and Potential Mechanisms

Fengyan Tang,Bo Zhao,Li Zhang,Faisal Raza,Hajra Zafar,Shao Zhong,Lin Li,Wenhua Zhu,Lingna Fang,Bing Lu,Liwen Shen,Ping Guo,Nengxing Yu,Quanmin Li

Objective: The potential mechanism underlying the protective effect of Astragaloside IV (AS-IV) co-treatment with 1, 25-dihydroxy-vitamin D (Vit-D) on neuropathy in diabetic high-fat rats was investigated. Methods: The rat diabetic hyperlipidemia (DH) model was established via streptozotocin and a high-fat diet (HFD). After co-treatment (of AS-IV and Vit-D at respective doses of 50 mg/kg via oral gavage and 30000 IU/kg via intramuscular injection), blood glucose levels, markers of inflammation and oxidative stress, as well as apoptosis and histopathology were evaluated with appropriate techniques. Results: Co-treatment could effectively reduce blood glucose levels substantially (p< 0.01), improve weight loss, and decrease oral glucose tolerance. Reduced respective sensory and motor nerve conduction velocities in rats were substantially improved (p<0.01) after co-treatment. Also, we observed obvious improvement in DH-induced injured nerve fiber myelin structure and other organ pathologies in co-treated rats. Besides, we observed up-regulated expressions of peroxisomal-proliferator activated receptor-alpha (PPAR-α) and Vit-D receptors (VDR) (p< 0.01) through the western blotting technique. Using the same technique, we also discovered reduced levels of interleukin (IL)1 beta, IL-6, and tumor necrosis factor-alpha, coupled with increased IL-10 and superoxide dismutase levels (p< 0.01). Importantly, co-treatment could effectively exert anti-oxidative and anti-inflammatory effects. Also, co-treatment resulted in the up-regulation of PPAR-α and VDR expressions, inhibition of the renin–angiotensin–aldosterone system, and promotion of β-cell sensitivity to insulin. Conclusion: The combined application of AS-IV and Vit-D exhibited health effects such as anti-oxidation, regulation of inflammatory factors, and promotion of cell repair, which may be considered as the mechanisms underlying treatment of diabetic peripheral neuropathy and improvement in biochemical indicators.

研究领域: 药理学 · 内分泌学 · 神经科学
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