LANGMUIR
·
2025
·
IF 3.9
Xiaoru An,Xiaonan Du,Hong Li,Fei Gao,Yue Hua,Xiuling Zhang,Jingsen Zhang,Lanbo Di
Electrochemical nitrate reduction reaction (eNO3RR) with Co-based catalysts provides a sustainable and efficient approach to wastewater purification and nitrogen recovery. However, their inevitable and uncontrollable reconstruction during the eNO3RR leads to uncertain actual active sites and a confused understanding of the mechanism. Herein, the active sites and structural evolution of α-Co(OH)2/CC during the eNO3RR process were investigated via in situ and ex situ characterizations. The results show that α-Co(OH)2 nanosheets are converted to β-Co(OH)2 in a strongly alkaline electrolyte and then act as active sites to adsorb NO3– and spontaneously react to generate CoOOH. Whereas CoOOH is swiftly reduced to β-Co(OH)2 at negative cathodic potential, realizing a nitrate-electrically mediated cyclic evolution process and synergistically catalyzing the eNO3RR. Consequently, α-Co(OH)2/CC achieves a Faradaic efficiency as high as 92% at −0.1 V vs RHE and a high NH3 yield rate of 338 mmol·gcat–1·h–1 under −0.6 V vs RHE. This work offers novel insight into the structural evolution and catalytic behavior of Co-based catalysts in eNO3RR.
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JOURNAL OF CATALYSIS
·
2025
·
IF 6.5
Huacheng Ying,Zeyu Wen,Jia Yao,Mowei Zhou,Yongtao Wang,Haoran Li
Constructing N−O bond in amines via aerobic oxidation is of high interest for producing cyclohexanone oxime; however, the mechanism remains disputed. Concerning TiO 2 /NHPI co-catalyzed aerobic oxidation of cyclohexylamine, here a convincing mechanism involving α-C radical and oxaziridine as key intermediates is demonstrated. All the evidences from electron paramagnetic resonance, mass spectrometry, and product analysis with methylated substrates lead to the same story about the mechanism, where both radical translocation of cyclohexylamino radical and epoxidation of 1-hydroperoxycyclohexylamine are mediated by double proton transfer and are the key to convert amine into oxime. Near IR analysis indicate that surface hydroxyl groups on TiO 2 facilitate the double proton transfer process. Here the unveiled role of surface hydroxyl on TiO 2 highlights its potential for broader applications in amine activation. Additionally, the well-established radical mechanism provides valuable insight into the construction of N−O bonds in amines.
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
·
2024
·Vol. 25
·期 3
·1937
·
IF 4.9
Ye Yuan,Siqi Zhang,Kang Duan,Yong Xu,Kaixuan Guo,Cheng Chen,Somboon Chaemchuen,Dongfeng Cao,Francis Verpoort
α-Hydroxy ketones are a class of vital organic skeletons that generally exist in a variety of natural products and high-value chemicals. However, the traditional synthetic route for their production involves toxic Hg salts and corrosive H2SO4as catalysts, resulting in harsh conditions and the undesired side reaction of Meyer–Schuster rearrangement. In this study, CO2-promoted hydration of propargylic alcohols was achieved for the synthesis of various α-hydroxy ketones. Notably, this process was catalyzed using an environmentally friendly and cost-effective biomass-based ionic liquids/CuCl system, which effectively eliminated the side reaction. The ionic liquids utilized in this system are derived from natural biomass materials, which exhibited recyclability and catalytic activity under 1 bar of CO2pressure without volatile organic solvents or additives. Evaluation of the green metrics revealed the superiority of this CuCl/ionic liquid system in terms of environmental sustainability. Further mechanistic investigation attributed the excellent performance to the ionic liquid component, which exhibited multifunctionality in activating substrates, CO2and the Cu component.
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Food Bioscience
·
2025
·
IF 5.9
Xin Wang,Bailiang Xue,Rong Zhang,Lin Shi,Wei Jia
To enable the precision production and identification of bioactive selenium peptides from selenium-biofortified rice proteins, this study developed an approach combining controlled enzymatic hydrolysis, ultrafiltration, and high-resolution mass spectrometry. Rice proteins were subjected to chymotrypsin/trypsin digestion, followed by ultrafiltration to enrich low-molecular-weight selenium peptides. A selenium-specific peptide database was constructed by systematically replacing methionine (Met) and cysteine (Cys) with selenized forms in UniProtKB Oryza sativa L. protein sequences (195,302 entries), generating 88,176 unique selenium peptide entries to overcome limitations in traditional database annotations. Ultra-performance liquid chromatography coupled with quadrupole-Orbitrap (UHPLC-Q-Orbitrap) and dynamic mass calibration enabled high-confidence screening of selenium peptides under EU 2002/657/EC guidelines, identifying 104 candidate selenium peptides. Among these, 14 high-confidence peptides (coverage score >5 %) were sequenced de novo using mMass 5.5.0. Parallel reaction monitoring (PRM) and multidimensional validation (fragment ion matching and modification site localization) confirmed the structure and bioactivity of key selenium peptides, such as Leu-{Se-Met}-Ala-Lys, which exhibited strong binding affinity to dipeptidyl peptidase IV (DPP-IV) active sites (binding energy: −64.54 kcal mol −1 ). Research findings demonstrate that selenium peptides can be precisely isolated from biofortified crops and characterized for their functional properties. The dynamic database and high-resolution analysis framework can be expanded to include selenium morphology analysis, bioactive peptide discovery and precise nutrition research, promoting the development of data-driven functional food.
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Synthetic and Systems Biotechnology
·
2025
·
IF 4.4
Wei Li,Di Liu,Linbo Gou,Shengfang Wu,Xiuwen Zhou,Tai-Ping Fan,Long Wang,Yujie Cai
(-)-α-Bisabolol, a valuable monocyclic sesquiterpene alcohol, has garnered significant attention in the pharmaceutical and cosmetic industries due to its remarkable anti-inflammatory, antibacterial, and skin-care properties. In this study, Serratia marcescens HBQA7 ( S. marcescens HBQA7), a non-model strain resistant to terpenoid toxicity, was used as the production host, and the expression intensities of different integration sites were screened. The complete (-)-α-bisabolol synthesis pathway was integrated into these sites, achieving a production titer of 3.5 g L −1 . On this basis, by knocking out competitive pathway genes (such as slaB and adhE ) and global regulatory factors ( arcA and iclR ), and introducing efficient glucose transport and activation ( glf and glk ), the shake flask fermentation titer was increased to 7.21 g L −1 . Through optimization of fermentation culture by orthogonal experiments and others, the titer was further increased to 9.90 g L −1 . Finally, through the fed-batch fermentation process conducted in a 50 L bioreactor, a titer of 102.3 g L −1 was achieved after 110 h of cultivation. The productivity reached 0.93 g L −1 h −1 . This study not only establishes the most efficient microbial production system for (-)-α-bisabolol reported to date, but also demonstrates the outstanding potential of S. marcescens as a chassis for terpenoid biosynthesis. It provides a novel strategy for the industrial production of high-value terpenoids.
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npj Science of Food
·
2025
·Vol. 9
·期 1
·262
·
IF 7.8
Mou Linyun,Li Jianlong,Lu Ya
Cherries are highly susceptible to spoilage after harvest due to physiological and biochemical changes. This poses considerable challenges to food safety. Common fungal pathogens responsible for decay include Aspergillus niger and Cladosporium cladosporioides . Citral, an efficient antifungal agent, is thought to combat these pathogens through interactions with phytase (phyA) and N-myristoyltransferase (NMT), a hypothesis explored through molecular docking simulations. Using the Independent Gradient Model based on Hirshfeld partition (IGMH) analysis, it was found that citral encapsulated within α -cyclodextrin metal-organic frameworks ( α -CD-MOFs) forms strong van der Waals forces and exhibits hydrogen bonding. These interactions enhance the stability of the composite material. Incorporating citral-loaded α -CD-MOFs into a matrix of sodium alginate and pullulan resulted in a novel composite film. This film exhibits significantly improved flexibility and tensile properties, which is beneficial for fruit packaging. Meanwhile, the Higuchi and Ritger–Peppas models both indicate that citral is released by diffusion from a uniform polymeric matrix. When applied to cherry preservation, the film exhibited significantly better cherry preservation at 4 °C than at 30 °C ( P < 0.05). Simultaneously, the combination of low temperature with the film’s barrier properties and sustained antimicrobial release synergistically inhibited microbial growth and fruit metabolism, effectively delaying spoilage and supporting its application in both cold-chain and ambient-temperature transport.
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MOLECULES
·
2025
·Vol. 31
·期 1
·79
·
IF 4.6
Ziqian Zhang,Xue Bai,Qian Du,Jianhong Yang
Diabetic cardiomyopathy (DCM) is a severe complication of diabetes, in which ferroptosis is a key pathogenic mechanism. This study examines how alpha-linolenic acid (ALA), a plant-derived omega-3 polyunsaturated fatty acid, protects against damage from ferroptosis in DCM. Using an in vitro model of H9C2 cardiomyocytes treated with high glucose/palmitate, combined with a high-fat diet and mouse model of low-dose streptozotocin (STZ)-induced diabetes, this research demonstrates for the first time that ALA significantly alleviates cardiac dysfunction and prevents ferroptosis. Mechanistically, ALA inhibits STAT3 phosphorylation by activating the AMPK signaling pathway, thereby reducing NCOA4-mediated ferritinophagy and mitigating mitochondrial iron overload and reactive oxygen species accumulation. It also enhances the function of the SLC7A11/GSH/GPX4 axis, reducing lipid peroxidation (LPO)-induced ferroptosis. Collectively, these findings indicate that ALA protects against diabetic cardiomyopathy by coordinating the regulation of ferritinophagy and antioxidant defense through the AMPK-STAT3 pathway, offering a potential therapeutic strategy for disease management.
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Foods
·
2021
·Vol. 10
·期 2
·315
·
IF 4.35
Zhenxing Wang,Zongcai Tu,Xing Xie,Hao Cui,Kin Weng Kong,Lu Zhang
This study aims to evaluate the bioactive components, in vitro bioactivities, and in vivo hypoglycemic effect ofP. frutescensleaf, which is a traditional medicine-food homology plant.P. frutescensmethanol crude extract and its fractions (petroleum ether, chloroform, ethyl acetate, n-butanol fractions, and aqueous phase residue) were prepared by ultrasound-enzyme assisted extraction and liquid–liquid extraction. Among the samples, the ethyl acetate fraction possessed the high total phenolic (440.48 μg GAE/mg DE) and flavonoid content (455.22 μg RE/mg DE), the best antioxidant activity (the DPPH radical, ABTS radical, and superoxide anion scavenging activity, and ferric reducing antioxidant power were 1.71, 1.14, 2.40, 1.29, and 2.4 times higher than that of control Vc, respectively), the most powerful α-glucosidase inhibitory ability with the IC50value of 190.03 μg/mL which was 2.2-folds higher than control acarbose, the strongest proliferative inhibitory ability against MCF-7 and HepG2 cell with the IC50values of 37.92 and 13.43 μg/mL, which were considerable with control cisplatin, as well as certain inhibition abilities on acetylcholinesterase and tyrosinase. HPLC analysis showed that the luteolin, rosmarinic acid, rutin, and catechin were the dominant components of the ethyl acetate fraction. Animal experiments further demonstrated that the ethyl acetate fraction could significantly decrease the serum glucose level, food, and water intake of streptozotocin-induced diabetic SD rats, increase the body weight, modulate their serum levels of TC, TG, HDL-C, and LDL-C, improve the histopathology and glycogen accumulation in liver and intestinal tissue. Taken together,P. frutescensleaf exhibits excellent hypoglycemic activity in vitro and in vivo, and could be exploited as a source of natural antidiabetic agent.Keywords:P. frutescensleaf;phytochemical composition;antioxidant activity;enzyme inhibitory;anticancer ability;antidiabetic activity
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CERAMICS INTERNATIONAL
·
2024
·
IF 5.1
Siyi Li,Pinyi Wang,Jianyun Hu,Guangcan Yang,Youjun Lu,Zhenxia Yuan,Xiao Zhang,Sen Liang
γ-AlOOH nanopowder synthesized using hydrothermal-assisted freeze-drying was employed as a precursor, with AlF₃ as a sintering aid, to explore the preparation of α-Al₂O₃ with a high specific surface area at elevated temperatures. The γ-AlOOH nanopowder produced in this study exhibited superior dispersion, achieving a specific surface area of 198.06 m 2 /g and a zeta potential of 45.8 mV. At a calcination temperature of 1200 °C, the resulting α-Al₂O₃, synthesized from γ-AlOOH and AlF₃, maintained a specific surface area of 27.72 m 2 /g, significantly higher than the typical values reported in the literature (generally below 10 m 2 /g). The α-phase purity exceeded 99 %, and the [AlO₆] proportion was 95.07 %. Furthermore, at a calcination temperature of 1150 °C, the specific surface area of the α-Al₂O₃ reached 50.48 m 2 /g. Using this α-Al₂O₃ as a carrier, a composite TiO₂ catalyst was prepared via a sol-gel and hydrothermal method. This catalyst demonstrated a photocatalytic degradation rate of over 98 % for rhodamine B (10 mg/L) within 30 min of irradiation, under the illumination of a 300 W mercury lamp in proximity to the light source.
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POLYMERS FOR ADVANCED TECHNOLOGIES
·
2015
·Vol. 27
·期 2
·169-177
·
IF 1.757
Jie Liu,Ru Cheng,Jianping Deng,Youping Wu
Chiral, pH-responsive hydrogels are constructed by poly(ethylene glycol) diacrylate/ α -cyclodextrin (PEGDA/ α -CD) inclusion complex and L- N -acryloyl-alanine or D- N -acryloyl-alanine (L-NAA or D-NAA) by an effective free radical polymerization approach. PEGDA containing two C=C end groups was used simultaneously to introduce α -CD units in the resulting hydrogels and to serve as a cross-linking agent, by which forming the designed hydrogels in quantitative yield. Hydrophilic α -CD moieties acted as pore-forming agent, while the L(D)-NAA-based polymer chains bearing –COOH groups enabled the hydrogels to display remarkable swelling–deswelling behavior in response to pH variation. The chiral NAA monomer-derived polymer chains rendered the hydrogels with intriguing optical activity, according to circular dichroism spectra. Scanning electron microscopy revealed the uniformly porous microstructures of hydrogels. More remarkably, the L-NAA-based hydrogels preferentially adsorbed trans -4-hydroxy- d -proline and preferentially released trans -4-hydroxy- l -proline, while D-NAA-based hydrogels provided opposite results. The hydrogels also demonstrated remarkable enantioselective release ability towards chiral drug ibuprofen. Copyright © 2015 John Wiley & Sons, Ltd.
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CHINESE JOURNAL OF CATALYSIS
·
2019
·
IF 4.914
Zhi-Hua Zhou,Xiao Zhang,Yong-Fu Huang,Kai-Hong Chen,Liang-Nian He
Inexpensive and efficient Cu(I) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO 2 , and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO 2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO 2 as a crucial cocatalyst under mild conditions.
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ELECTROCHIMICA ACTA
·
2014
·
IF 4.086
Shuaiyuan Han,Baohua Yue,Liuming Yan
The poly(vinylphosphonic acid) (PVPA), poly(4-(α-methyl)vinyl-1 H -1,2,3-triazole) (PMVTri), and poly(VPA- co -MVTri) were synthesized, and proton exchange membranes were prepared based on the acid-base polymeric composite of PVPA and PMVTri, and acid-base amphoteric copolymer of poly(VPA- co -MVTri). The overall performances of PVPA, proton conductivity, thermal and oxidative stability, and water resistance, are greatly improved by compositing of PMVTri or copolymerization with 4-(α-methyl)vinyl-1 H -1,2,3-triazole (MVTri). About four or eight folds improvement in maximum proton conductivity was observed in the polymeric composite of PVPA/PMVTri or acid-base amphoteric copolymer poly(VPA- co -MVTri) because of the redistribution of ions in the heterostructures of PVPA and PMVTri, respectively, compared with the pristine PVPA. At the same time, the oxidative stability and the water resistance of PVPA were also greatly improved attributing to the absent of α-H in the main chain of PMVTri and the acid-base interaction between the phosphonic acid groups and the triazolyl groups, respectively.
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