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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Optimizing photocatalytic hydrogen evolution performance by rationally constructing S-scheme heterojunction to modulate the D-band center

Zhiliang Jin,Cheng Yang

The research in the field of photocatalysis has progressed, with the development of heterojunctions being recognized as an effective method to improve carrier separation efficiency in light-induced processes. In this particular study, CuCo 2 S 4 particles were attached to a new cubic CdS surface to create an S-scheme heterojunction, thus successfully addressing this issue. Specifically, owing to the higher conduction band and Fermi level of CuCo 2 S 4 compared to CdS, they serve as the foundation and driving force for the formation of an S-scheme heterojunction. Through in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, the direction of charge transfer in the composite photocatalyst under light exposure was determined, confirming the charge transfer mechanism of the S-scheme heterojunction. By effectively constructing the S-scheme heterojunction, the d-band center of the composite photocatalyst was adjusted, reducing the energy needed for electron filling in the anti-bonding energy band, promoting the transfer of photogenerated carriers, and ultimately enhancing the photocatalytic hydrogen production . performance. After optimization, the hydrogen evolution activity of the composite photocatalyst CdS-C/CuCo 2 S 4 -3 reached 5818.9 μmol g −1 h −1 , which is 2.6 times higher than that of cubic CdS (2272.3 μmol g −1 h −1 ) and 327.4 times higher than that of CuCo 2 S 4 (17.8 μmol g −1 h −1 ), showcasing exceptional photocatalytic activity. Electron paramagnetic resonance and in situ X-ray photoelectron spectroscopy have established a theoretical basis for designing and constructing S-scheme heterojunctions, offering a viable method for adjusting the D-band center to enhance the performance of photocatalytic hydrogen evolution.

CAS / MDL: 13963-58-1
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Nature Communications · 2024 ·Vol. 15 ·期 1 ·1-13 · IF 14.7

Spin occupancy regulation of the Pt d-orbital for a robust low-Pt catalyst towards oxygen reduction

Xue Dongping,Yuan Yifang,Yu Yue,Xu Siran,Wei Yifan,Zhang Jiaqi,Guo Haizhong,Shao Minhua,Zhang Jia-Nan

Disentangling the limitations of O-O bond activation and OH* site-blocking effects on Pt sites is key to improving the intrinsic activity and stability of low-Pt catalysts for the oxygen reduction reaction (ORR). Herein, we integrate of PtFe alloy nanocrystals on a single-atom Fe-N-C substrate (PtFe@Fe SAs -N-C) and further construct a ferromagnetic platform to investigate the regulation behavior of the spin occupancy state of the Pt d -orbital in the ORR. PtFe@Fe SAs -N-C delivers a mass activity of 0.75 A mg Pt −1 at 0.9 V and a peak power density of 1240 mW cm −2 in the fuel-cell, outperforming the commercial Pt/C catalyst, and a mass activity retention of 97%, with no noticeable current drop at 0.6 V for more than 220 h, is attained. Operando spectroelectrochemistry decodes the orbital interaction mechanism between the active center and reaction intermediates. The Pt dz 2 orbital occupation state is regulated to t 2g 6 e g 3 by spin-charge injection, suppressing the OH* site-blocking effect and effectively inhibiting H 2 O 2 production. This work provides valuable insights into designing high-performance and low-Pt catalysts via spintronics-level engineering.

CAS / MDL: 693-98-1
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Ultrathin ternary PtNiRu nanowires for enhanced oxygen reduction and methanol oxidation catalysis via d-band center regulation

Guopu Cai,Chun Hua,Hongji Ren,Renqin Yu,Deying Xu,Muhammad Arif Khan,Jian Guo,Yu Sun,Ya Tang,Huidong Qian,Zhonghong Xia,Daixin Ye,Jiujun Zhang,Hongbin Zhao

Direct methanol fuel cells rely on the efficiency of their anode/cathode electrocatalysts to facilitate the methanol oxidation reaction and oxygen reduction reaction, respectively. Platinum-based nanocatalysts are at the forefront due to their superior catalytic properties. However, the high-cost, scarcity, and low CO tolerance of platinum pose challenges for the scalable application of DMFCs. Herein, we report novel ultrathin ternary PtNiRu alloy nanowires to improve Pt utilization and CO tolerance. These novel electrocatalysts incorporate the oxophilic metal Ru into ultrathin PtNi nanowires, aiming to enhance the intrinsic activity of platinum while leveraging the long-term durability and high utilization efficiency provided by the bimetallic synergistic effect. The PtNiRu NWs significantly enhance both mass activity and specific activity for ORR, performing about 6.9 times and 3.9 times better than commercial Pt/C, respectively. After a rigorous durability test of 10,000 cycles, the PtNiRu NWs only exhibited a 25.2 % loss in mass activity. Additionally, for MOR, the MA and SA of PtNiRu NWs exceed that of Pt/C catalyst by 4.30 and 2.72 times, respectively, and exhibit exceptional resistance to CO poisoning. Theoretical insights from density functional theory calculations suggest that the introduction of Ru modulates the d-band center of the surface Pt atoms, which contributes to decreased binding strength of oxygenated species and an elevated dissolution potential, substantiating the enhanced performance metrics, and the durability enhancement stems from the stronger Pt M bonds than those in PtNiRu NWs resulted from Pt Ru covalent interactions. These findings not only provide a new perspective on platinum-based nanocatalysts but also significantly advance the quest for more efficient and durable electrocatalysts for DMFCs, representing a substantial stride in fuel cell technology.

CAS / MDL: 57-09-0 14040-11-0
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JOURNAL OF ETHNOPHARMACOLOGY · 2024 · IF 4.8

Total alkaloids in Fritillaria cirrhosa D. Don alleviate OVA-induced allergic asthma by inhibiting M2 macrophage polarization

Yu Wang,Meihao Peng,Xin Yang,Liming Tu,Jiamin Liu,Yixi Yang,Rui Li,Xue Tang,Yuqing Hu,Guowu Zhang,Qi Zhao,Qiuxia Lu

ABSTRACT Ethnopharmacological relevance Fritillaria cirrhosa D. Don (FCD) is a traditional Chinese medicine used to treat respiratory disorders, known for its effects in clearing heat, moistening the lungs, resolving phlegm, and relieving cough. Additionally, the total alkaloids extracted from FCD can alleviate asthma symptoms and reduce airway inflammation. However, no studies have investigated the effects of total alkaloids on lung macrophages. Aim of the study This study explored whether the total alkaloids of FCD (TAs-FCD) reduce M2 macrophage polarization and, consequently, attenuate airway remodeling in asthmatic mice. This study further elucidated its mechanism of action in treating allergic asthma. Materials and methods The extracted TAs-FCD was analyzed for its composition using UPLC-Q-TOF/MS. Network pharmacology was employed to identify the active ingredients and potential mechanisms of TAs-FCD in the treatment of allergic asthma. A mouse model of ovalbumin-induced allergic asthma was established, adopted, and validated through in vivo experiments. Hematoxylin-eosin staining (H&E), immunohistochemistry (IHC), immunofluorescence staining (IF), enzyme-linked immunosorbent assay (ELISA), Western blotting (WB), and real-time fluorescence quantitative polymerase chain reaction (q-PCR) were used to investigate the role of TAs-FCD in inhibiting M2 macrophage polarization in the context of allergic asthma. Results A total of 66 active ingredients were screened from 116 compounds using SWISSADME. The targets of these 66 compounds were predicted by SwissTargetPrediction, resulting in 808 unique drug targets after excluding duplicates. Additionally, 1,756 targets related to allergic asthma were identified from the DisGeNET, Genecard, and OMIM databases. This led to 267 cross-targets between the active ingredient targets and allergic asthma targets, including interleukin (IL)-1β, tumor necrosis factor (TNF), and STAT3. Animal experiments demonstrated that TAs-FCD improved histopathological injury in mouse lungs, reduced peri-airway collagen fiber accumulation, airway mucus secretion, and airway smooth muscle proliferation. TAs-FCD also lowered IL-1β, TNF-α and IL-4 levels in lung tissues and alleviated airway inflammation. Furthermore, TAs-FCD significantly reduced levels of Arg1 and CD206, which are closely associated with M2 macrophages, and downregulated the expression of p-STAT3 and p-JAK2. Conclusion TAs-FCD may inhibit M2 macrophage polarization by regulating the JAK2/STAT3 pathway, thereby alleviating airway remodeling and inflammation in allergic asthmatic mice.

CAS / MDL: 9006-59-1
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Inorganic Chemistry Frontiers · 2025 · IF 6.4

Defect-rich high-entropy alloy AuCuAgRuNi nanofibers based on d-orbital overlap for biomass value-added conversion

Ruichen Geng,Lin Su,Xiaojun Chu,Zhihan Zhang,Ranran Wei,Yinglong Wang,Shuli Yin

Developing electrocatalysts with high activity and selectivity to promote the oxidation of 5-hydroxymethylfurfural (HMF) holds substantial importance yet presents challenges in the realm of biomass upgrading. Herein, the defect-rich high-entropy alloy AuCuAgRuNi nanofibers (AuCuAgRuNi NFs) were synthesized via a facile one-pot wet chemical synthesis. Remarkably, the AuCuAgRuNi NFs demonstrate exceptional electrocatalytic performance for HMF-to-FDCA conversion under ambient conditions, achieving 97.15% yield and 98.40% selectivity with outstanding stability. Theoretical calculations reveal that defect-induced electronic modulation optimizes reactant adsorption, while d-orbital hybridization among multi-metallic components facilitates electron redistribution, synergistically enhancing catalytic activity. Furthermore, HMF oxidation has been successfully integrated with hydrogen evolution in a flow electrolysis cell, and an energy-efficient coupled system has been established, which holds promise for scalable biomass valorization. This research provides valuable insights into the innovative synthesis and inherent catalytic mechanisms of high-entropy alloy systems.

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Plasmonics · 2025 · IF 4.3

Sensitivity Enhanced SPR Biosensor Based on Au Nanoparticles and Polydopamine Co-modified D-shaped Photonic Crystal Fiber

Zhang Yirui,Wang Zhiyang,Zhang Ailing,Chang Pengxiang,Li Zhen,Shi Yanmei

In this paper, a fiber-optic biosensor with the structure of both Au film and Au nanoparticles (AuNps) co-modified on D-shaped photonic crystal fiber (PCF) by adhesion with polydopamine (PDA) is proposed and experimentally fabricated, where the electric field near the sensing surface is increased and thus the sensitivity is improved by coupling the surface plasmon resonance (SPR) in Au film with the localized surface plasmon resonance (LSPR) in Au nanoparticles (AuNps), D-shaped PCF as well as high refractive index of PDA. In addition, due to excellent adhesion and biocompatibility properties of PDA, an extra layer of PDA is modified on the surface of AuNps to anchor a layer of goat anti-rabbit IgG on it, which is a bioassay for rabbit IgG. The experimental results show that the sensor obtains a high sensitivity of 4301.49 nm/RIU in the refractive index (RI) range of 1.335 ~ 1.365, which is 2.4 times the RI sensitivity of the PCF-Au sensor. The bio-sensitivity of the sensor for rabbit IgG reaches 1.017 nm/(µg/ml), and the limit of detection (LOD) is 0.019 µg/ml. This sensitized fiber-optic biosensor based on the SPR-LSPR coupling effect has a potential application in clinical disease diagnosis and immunoassay.

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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Highly selective and efficient recognition of tyrosine enantiomers at Au NPs/D-sorbitol/GCE-based chiral sensor

Jing Zhang,Ye Yang,Yi-Ping Liu,Guo-Cong Liu,Xi Zhu,Xin-Yu Jiang,Jin-Gang Yu

Electrochemical sensors have been considered as one of the most important methods to determine amino acid (AA) enantiomers. An interesting and highly-efficient electrochemical sensor, gold nanoparticles/D-sorbitol modified glass carbon electrode (Au NPs/D-sorbitol/GCE), was developed for the chiral recognition of Tyrosine (Tyr) enantiomers. Au NPs/D-sorbitol/GCE sensor exhibited excellent chiral recognition efficiency for Tyr enantiomers (I L /I D  = 1.99, ∆Ep = 36 mV) by square wave voltammetry (SWV). The possible recognition mechanism was also proposed by cyclic voltammetry (CV) at different scanning rates, wettability measurements, and density-functional theory (DFT) calculations. The smaller steric hindrance and more suitable molecular distance are beneficial to the selective formation of hydrogen bonds between L-Tyr and the chiral interface of the sensor. The energy difference caused by the formation of hydrogen bonds between the chiral interface and Tyr enantiomers can be expressed as different peak currents to achieve chiral recognition. The redox peak current of Tyr enantiomers at Au NPs/D-sorbitol/GCE showed good linear relationship with their concentration, and the limits of detection (LOD) were calculated to be 4.12 μM and 8.07 μM for L-Tyr and D-Tyr, respectively. Importantly, Au NPs/D-sorbitol/GCE can also predict the mass ratios of L-Tyr in the enantiomeric mixtures. In addition, the sensor has shown good anti-interference ability, high stability, and excellent reproducibility.

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AQUATIC TOXICOLOGY · 2024 · IF 4.1

Study on low concentration deltamethrin toxicity mediated by phospholipase D in Chinese mitten crab (Eriocheir sinensis) ovary

Qi Sun,Jun Dong,Zehui Su,Xuanyun Huang,Xiaoning Gao,Kun Hu,Xiaoling Gong

This study evaluates the impact of environmentally relevant, low-concentration deltamethrin exposure to Eriocheir sinensis ovaries. Our findings revealed that even at a concentration of 0.05 µg/L, deltamethrin exposure can induce significant ovarian toxicity through a 5-day exposure, with gradual amplification detected with time, demonstrating the toxicity amplification effect. Hematoxylin and Eosin staining revealed that low-concentration deltamethrin exposure produces pathological damage consistent with acute toxicity—yolk granules were dissolved and oocyte membranes were ruptured. High-throughput RNA-sequencing data indicated that the acute and low-concentration exposure groups involved completely different pathways and molecular functions, suggesting distinct mechanisms for their toxic effects. Following the identification of phospholipase D (PLD) as a potential core factor regulating the toxicity amplification effect of low concentration deltamethrin, we delved into subsequent mechanism studies using quantitative real-time PCR, immunofluorescence and enzyme-linked immunosorbent assay. Through the GnRH signaling pathway, increased PLD indirectly stimulates augmented estradiol secretion, subsequently inducing apoptosis by upregulating Cathepsin D, which can activate the key executioners of apoptosis—caspases (CASP3 and CASP7). In conclusion, low-concentration deltamethrin exposures can induce significant ovarian damage through apoptosis mediated by the upregulation of PLD in the ovaries of Eriocheir sinensis at environmentally relevant concentrations, which lays the preliminary theoretical groundwork for further elucidating the mechanism of toxicity amplification effect of pesticide exposure at low concentrations.

CAS / MDL: 52918-63-5
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Nature Communications · 2022 ·Vol. 13 ·期 1 ·1-10 · IF 17.694

Breaking scaling relationships in alkynol semi-hydrogenation by manipulating interstitial atoms in Pd with d-electron gain

Yang Yang,Zhu Xiaojuan,Wang Lili,Lang Junyu,Yao Guohua,Qin Tian,Ren Zhouhong,Chen Liwei,Liu Xi,Li Wei,Wan Ying

Pd catalysts are widely used in alkynol semi-hydrogenation. However, due to the existence of scaling relationships of adsorption energies between the key adsorbed species, the increase in conversion is frequently accompanied by side reactions, thereby reducing the selectivity to alkenols. We report that the simultaneous increase in alkenol selectivity and alkynol conversion is achieved by manipulating interstitial atoms including B, P, C, S and N in Pd catalysts. A negative linear relationship is observed between the activation entropies of 2-methyl-3-butyn-2-ol and 2-methyl-3-buten-2-ol which is highly related to the filling of d -orbital of Pd catalysts by the modification of p -block elements. A catalyst co-modified by B and C atoms has the maximum d charge of Pd that achieves a 17-fold increase in the turn-over frequency values compared to the Lindlar catalysts in the semi-hydrogenation of 2-methyl-3-butyn-2-ol. When the conversion is close to 100%, the selectivity can be as high as 95%.

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Frontiers in Bioscience-Landmark · 2024 ·Vol. 29 ·期 11 ·389 · IF 3.3

Protective Role of Vitamin D Receptor in Cerebral Ischemia/Reperfusion Injury In Vitro and In Vivo Model

Jie Dai,Haiyan Huang,Liucheng Wu,Mei Ding,Xiangyang Zhu

Background: Vitamin D receptor (VDR) can prevent myocardial ischemia reperfusion injury (MIRI). Hence, we aimed to illuminate the effect of VDR on cerebral ischemia/reperfusion injury (CIRI). Methods: C57BL/6 mice and SK-N-SH cells were utilized to establish CIRI and cellular oxygen deprivation/reoxygenation (OGD/R) models. Mice were injected with 1 μg/kg Calcitriol or 1 μg/kg Paricalcitol (PC) and adenovirus-mediated VDR overexpression or knockdown plasmids. 2,3,5-triphenyl-tetrazolium chloride (TTC) and Terminal deoxynucleotidyl transferase dUTP nick end labeling (TUNEL) assays were performed to measure the brain infarct volume and the apoptosis of cerebral cells. SK-N-SH cells were treated with 5 mM N-acetyl-L-cysteine (NAC) and transfected with VDR knockdown plasmid. Flow cytometry and Cell Counting Kit-8 (CCK-8) assays were employed to assess the apoptosis and cell viability. Enzyme-Linked Immunosorbent Assay (ELISA), quantitative Reverse Transcription Polymerase Chain Reaction (qRT-PCR) and Western blot were exploited to quantify the levels of reactive species oxygen (ROS), other oxidative stress-related factors, VDR and apoptosis-related factors. Results: The level of VDR in mouse cerebral tissue was elevated by CIRI (p < 0.001). CIRI-induced cerebral infarction (p < 0.001) and the apoptosis of cerebral cells (p < 0.001) in mice were mitigated by the activation of VDR. VDR overexpression abrogated while VDR silencing enhanced CIRI-induced infarction, oxidative stress and apoptosis of cerebral cells (p < 0.05). Furthermore, VDR silencing aggravated the oxidative stress and apoptosis in OGD/R-treated SK-N-SH cells (p < 0.05). NAC, a scavenger of oxidative stress, could reverse the effects of VDR silencing on apoptosis and oxidative stress in OGD/R-treated SK-N-SH cells (p < 0.01). Conclusion: VDR alleviates the oxidative stress to protect against CIRI.

CAS / MDL: 7722-84-1
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JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE · 2024 · IF 3.3

Purification and characterization of limonin D-ring lactone hydrolase from sweet orange (Citrus sinensis (L.) Osbeck) seeds

Nawei Zhang,Yang Xu,Xiao Jia,Xiao Li,Jingnan Ren,Siyi Pan,Gang Fan,Jinchu Yang

BACKGROUND Citrus products often suffer from delayed bitterness, which is generated from the conversion of non-bitter precursors (limonoate A-ring lactone, LARL) to limonin under the catalysis of limonin D-ring lactone hydrolase (LDLH). In this study, LDLH was isolated and purified from sweet orange seeds, and a rapid and accurate high-performance liquid chromatography method to quantify LARL was developed and applied to analyze the activity and enzymatic properties of purified LDLH. RESULTS Purified LDLH (25.22 U mg −1 ) showed bands of 245 kDa and 17.5 kDa molecular weights in native polyacrylamide gel electrophoresis (PAGE) and sodium dodecyl sulfate PAGE analysis respectively. After a 24 h incubation under strongly acidic (pH 3) or strongly alkaline (pH 9) conditions, LDLH still retained approximately 100% activity. Moreover, LDLH activity was not impaired by thermal treatment at 50 °C for 120 min. Enzyme inhibition assays showed that LDLH was inactivated only after ethylenediaminetetraacetic acid treatment, and other enzyme inhibitors showed no significant effect on its activity. In addition, the LDLH activity of calcium ion (Ca 2+ ) intervention was 108% of that in the blank group, and that of zinc ion (Zn 2+ ) intervention was 71%. CONCLUSION LDLH purified in this study was a multimer containing 17.5 kDa monomer with a wide pH tolerance range (pH 3–9) and excellent thermal stability. Moreover, LDLH might be a metallopeptidase, and its activity was stimulated by Ca 2+ and significantly inhibited by Zn 2+ . These findings improve our understanding of LDLH and provide some important implications for reducing the bitterness in citrus products in the future. © 2024 Society of Chemical Industry.

CAS / MDL: 9003-39-8
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2025 · IF 3.8

WSe2 nanosheets with peroxidase-mimetic activity and carbon dots based ratiometric fluorescent strategy for d-galactose sensing

Wang Sikai,Liu Weiping,Wang Lei,Lv Lin,Liu Xiangqin,Luo Xiaojun,Zhang Guoqi,Zhao Yan

d -Galactose (D-Gal), an essential monosaccharide, plays multiple physiological roles in living organisms. Abnormal fluctuations in its concentration are closely associated with various genetic metabolic disorders, such as galactosemia and galactose deficiency. Therefore, the development of an efficient, sensitive, and accurate method for D-Gal detection is critical for disease diagnosis and treatment. In this study, a ratiometric fluorescence-based sensing platform was constructed for the quantitative detection of D-Gal. Galactose oxidase can catalyze the oxidation of D-Gal, resulting in the generation of hydrogen peroxide (H 2 O 2 ). When combined with WSe 2 nanosheets prepared via liquid-phase exfoliation and functioning as nanozymes, in the presence of H 2 O 2 , the substrate o -phenylenediamine (OPD) undergoes oxidation to generate 2,3-diaminophenazine (DAP), which exhibits a fluorescence peak at 570 nm. Simultaneously, DAP quenches the fluorescence of carbon dots (CDs) at 430 nm via an inner filter effect, thereby enabling ratiometric detection with enhanced accuracy and sensitivity. The method exhibits a Limit of detection of 0.004 mM, Linear ranges spanning from 0.01 to 1 mM and from 1 to 300 mM, with recoveries ranging between 91.0 and 100.4%. Furthermore, the proposed method was effectively utilized for the detection of D-Gal in human serum specimens, demonstrating excellent selectivity and reliability. This research presents a novel method for D-Gal detection based on WSe 2 nanosheets and CDs, offering potential applications in the biomedical and biosensing fields. Graphical abstract

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