MOLECULES
·
2025
·Vol. 30
·期 5
·1042
·
IF 4.6
Min Zhang,Gaolei Qin,Pengfei Li,Xiangjie Zhang,Hongying Chang,Ziyu Zhou,Wei Zhao,Xumeng Huang,Kui Tang,Yonghe Ning,Chang Song,Peng He
Epoxidation of long-chain α-olefins (LAOs) is a process of paramount importance, particularly in the preparation of epoxides. Traditional epoxidation methods, such as the chlorohydrin method and peracid method, suffer from issues such as poor selectivity, by-product formation, and environmental pollution. Mukaiyama epoxidation, with its mild reaction conditions and exceptional selectivity, has attracted widespread attention and considerable research. Transition metal oxide catalysts show potential in the reaction; however, the catalytic efficiency still require substantial improvement due to dilemma of substance activation. In this study, a synergistic enhancement method was employed, achieved through the creation of oxygen vacancies and the electron-rich nature of Cu. The substitution of Cu with Sn in CuO facilitates the creation of oxygen vacancy (Vo), thereby enhancing absorption and activation of O2. The conversion for O2activation paves the way for the formation of benzoyl peroxy radicals. Moreover, the interaction between Sn and Cu promotes charge transfer from Sn to Cu, resulting in an electron-rich Cu surface that significantly accelerates the dehydrogenation of benzaldehyde. The synergistic enhancement protocol exhibits near-quantitative performance, delivering an oxide yield of 92.9%. This study introduces an innovative dual-promotion catalytic strategy for Mukaiyama epoxidation utilizing readily available O2, providing profound insights into the optimization design of transition metal oxide catalysts and beyond.
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MOLECULAR MEDICINE
·
2024
·Vol. 30
·期 1
·1-14
·
IF 6
Yu Hao,Gan Daojing,Luo Zhen,Yang Qilin,An Dongqi,Zhang Hao,Hu Yingchun,Ma Zhuang,Zeng Qingchun,Xu Dingli,Ren Hao
Background In heart failure (HF), mitochondrial dysfunction and metabolic remodeling lead to a reduction in energy productivity and aggravate cardiomyocyte injury. Supplementation with α-ketoglutarate (AKG) alleviated myocardial hypertrophy and fibrosis in mice with HF and improved cardiac insufficiency. However, the myocardial protective mechanism of AKG remains unclear. We verified the hypothesis that AKG improves mitochondrial function by upregulating NAD + levels and activating silent information regulator 2 homolog 1 (SIRT1) in cardiomyocytes. Methods In vivo, 2% AKG was added to the drinking water of mice undergoing transverse aortic constriction (TAC) surgery. Echocardiography and biopsy were performed to evaluate cardiac function and pathological changes. Myocardial metabolomics was analyzed by liquid chromatography‒mass spectrometry (LC‒MS/MS) at 8 weeks after surgery. In vitro, the expression of SIRT1 or PINK1 proteins was inhibited by selective inhibitors and siRNA in cardiomyocytes stimulated with angiotensin II (AngII) and AKG. NAD + levels were detected using an NAD test kit. Mitophagy and ferroptosis levels were evaluated by Western blotting, qPCR, JC-1 staining and lipid peroxidation analysis. Results AKG supplementation after TAC surgery could alleviate myocardial hypertrophy and fibrosis and improve cardiac function in mice. Metabolites of the malate-aspartate shuttle (MAS) were increased, but the TCA cycle and fatty acid metabolism pathway could be inhibited in the myocardium of TAC mice after AKG supplementation. Decreased NAD + levels and SIRT1 protein expression were observed in heart of mice and AngII-treated cardiomyocytes. After AKG treatment, these changes were reversed, and increased mitophagy, inhibited ferroptosis, and alleviated damage in cardiomyocytes were observed. When the expression of SIRT1 was inhibited by a selective inhibitor and siRNA, the protective effect of AKG was suppressed. Conclusion Supplementation with AKG can improve myocardial hypertrophy, fibrosis and chronic cardiac insufficiency caused by pressure overload. By increasing the level of NAD + , the SIRT-PINK1 and SIRT1-GPX4 signaling pathways are activated to promote mitophagy and inhibit ferroptosis in cardiomyocytes, which ultimately alleviates cardiomyocyte damage.
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Molecular Catalysis
·
2024
·
IF 3.9
Fukun Li,Ronghe Yang,Jinhang Dai,Hanyue Deng,Junjun Shi,Wucheng Xie,Juanhua Kong,Tingwang Guo
Biomass upgrading, which supplies important biomaterials, chemicals and fuels, is considered as an efficient way to realize the goal of carbon neutralization. Recently, γ-valerolactone (GVL) has gained increasing attention due to its wide applications. In this work, a novel protocol of microwave-assisted cascade catalytic upgrading of α-angelicalactone (α-AL) to GVL over metal triflate using alcohol as the hydrogen donor was proposed. The yield of GVL production from α-AL upgrading is strongly influenced by the Lewis acid strength of the metal triflate and the reduction potential of the employed alcohol. Among all tests, Sc (OTf) 3 showed the best catalytic performance in isopropanol media, giving 96.4 % GVL yield and 100 % α-AL conversion at 433 K within 3.0 h. Meanwhile, kinetic study indicated transfer hydrogenation of isopropyl levulinate to isopropyl 4-hydroxyvalerate was the rate-limited step with the apparent activation energy of 94.5 kJ/mol. This Sc (OTf) 3 catalyst was highly stable and could be reused for five cycles by simple vacuum distillation. In a word, this work provides an alternative for GVL production from biomass upgrading.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yu-Xuan Fu,Shu-Yi Huang,Ming-Shuai Sun,Yan Zhou,Dan-Dan Cai,Wen-Shuai Zhu,Wei Hui,Duan-Jian Tao
Current industrial catalysts for α-pinene hydrogenation suffer from harsh reaction conditions and poor selectivity to cis -pinane, primarily due to their inability to effectively adsorb α-pinene in a specific favorable configuration on the catalyst surface. In this study, a high-specific-surface-area, rod-shaped CeO 2 -supported ultra-fine Ru nanoparticle (average particle size of 4 nm) catalyst was synthesized via hydrothermal method for the highly stereoselective hydrogenation of α-pinene to cis -pinane. The resulting Ru/CeO 2 -H catalyst achieved an α-pinene conversion of 99.3 % and an impressive cis -pinane selectivity of up to 99.6 % under exceptionally low temperature (30°C), 0.6 MPa H 2 and 0.5 h with high TOF (1236 h −1 ). Density functional theory (DFT) calculations indicated that α-pinene preferentially adsorbs onto the Ru surface via the backside of its intramolecular dimethyl bridge. This particular adsorption mode lowers the energy barriers for further hydrogenation to generate cis -pinane. The oriented dimethyl-up configuration of α-pinene and ultra-low activation energy (12.04 kJ/mol obtained from kinetic tests) enable the highly selective production of cis -pinane at ambient temperature. Furthermore, the strong interaction between the CeO 2 -H support and highly dispersed Ru, combined with the ambient-temperature reaction conditions, effectively prevents metal nanoparticle agglomeration and coking, imparting the catalyst with exceptional stability. Notably, the catalyst was reused at least 15 times without observing any significant deactivation, demonstrating its significant potential for practical applications.
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Polymers
·
2025
·Vol. 18
·期 1
·64
·
IF 4.9
Ruijun Zhang,Ziyi Dong,Qiqi He,Junhua Li,Yuexin Hu,Jianhua Qian
Accurate knowledge of phase behavior in polyolefin–solvent mixtures is critical for ensuring stable operation and safe scale-up of industrial solution polymerization processes. The binary (n-hexane + ethylene/1-octene copolymer, POE96k-10) and ternary (α-olefin +n-hexane + POE96k-10) phase behaviors were investigated via a visual high-pressure cell (POE96k-10:Mw= 96 kg·mol–1,Mw/Mn= 3.87, 1-octene mole fraction = 10.31 mol%) at temperatures of 380~480 K and pressures as high as 14 MPa. To systematically analyze the effects of α-olefin mass fraction and type on phase transition, four industrially relevant α-olefins (ethylene, 1-butene, 1-hexene, and 1-octene) were investigated. The results show that the phase transition temperature and pressure for liquid–liquid and liquid–vapor transitions show an approximately linear dependence on α-olefin mass fraction. Ethylene, 1-butene, and 1-hexene lower the phase transition temperature, whereas 1-octene increases it. Ethylene exhibits a strong anti-solvent effect, significantly lowering the transition temperature while increasing the phase transition pressure. The modified Sanchez-Lacombe equation of state (MSL EOS) effectively correlates and reproduces the phase equilibrium data of the α-olefin +n-hexane + POE96k-10 ternary systems, though its accuracy decreases with increasing α-olefin chain length.
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LANGMUIR
·
2025
·
IF 3.9
Peng Wang,Qianpeng Dong,Chenyu Gao,Lianlian Wang,Ruiliang Wang,Dianming Chu,Wenjuan Bai,Yan He
This research presents a regulation strategy of constructing a heterogeneous bilayer catalyst of Fe and Al2O3, namely, Fe–Al2O3, through interfacial interaction and particle nucleation, in order to modulate the size and catalytic activity of Fe sites and achieve the growth of carbon nanotubes (CNTs). Through temperature control, the noncatalytically active Fe2O3 clusters on the surface of Al2O3 are exposed, inducing multiple nucleation of Fe clusters on its surface. Under the synergistic effect of the confinement at the Fe–Al2O3 interface, the fabrication of small Fe nanoparticles is accomplished. The results indicate that the catalytically active Fe nanoparticles have a diameter of approximately 10 nm, and the grown CNTs have a diameter of approximately 15 nm. Based on the systematic characterization results, the nonactive Fe2O3 clusters confined by strong interfacial interaction induce multiple nucleation of Fe on their surface during multiple loading processes, facilitating the formation of nanoparticles. Additionally, the strong interaction between Al2O3 and Fe induces the formation of FeAl4O8, thereby enhancing the thermal stability of the nanoparticles. In conclusion, the targeted regulation of the interfacial interaction of the catalyst active sites offers guidance for the low-cost and large-scale preparation of small nanoparticle catalyst particles.
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Results in Chemistry
·
2025
·
IF 4.2
Yan Liu,Zhao Jiankan,Minzhen Si
This study employs Fourier Transform Infrared Spectroscopy (FTIR) to quantitatively analyze the distribution patterns and metabolic roles of α-solanine across different organs (roots, stems, leaves, flowers, and fruits) of Solanum nigrum . By extracting absorbance values from key characteristic peaks (2923 cm −1 , 2853 cm −1 , 1639 cm −1 , 1152 cm −1 , and 1072 cm −1 ) and applying a normalization ratio method for quantitative assessment, our results reveal that fruits serve as the primary accumulation site of α-solanine, followed by flowers and leaves, whereas the lowest concentrations are detected in roots and stems. Further analysis suggests that the high accumulation in fruits is likely associated with defensive functions and seed protection, while leaves and flowers function as the primary sites for α-solanine biosynthesis and signaling regulation, respectively. In contrast, roots and stems mainly facilitate transport and storage. This study highlights FTIR as a rapid, non-destructive technique for the quantitative analysis of plant secondary metabolites, demonstrating its potential in botanical research and biochemical profiling. Moreover, these findings provide valuable insights into the ecological roles of Solanaceae secondary metabolites and their potential applications in agriculture and pharmaceutical sciences.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2017
·
IF 3.582
Yu-pei Li,Fa-tang Li,Xiao-jing Wang,Jun Zhao,Jiang-nan Wei,Ying-juan Hao,Ying Liu
A quantum-sized hematite iron oxide (α-Fe 2 O 3 )/graphitic carbon nitride (g-C 3 N 4 ) hybrids have been designed and constructed through a facile in situ calcination treatment. The α-Fe 2 O 3 /g-C 3 N 4 hybrids were analyzed via various characterization techniques including XRD , TEM , UV–Vis DRS , XPS , and their photocatalytic efficiencies were evaluated by visible light-driven hydrogen evolution . The results reveal that the cooperation of α-Fe 2 O 3 and g-C 3 N 4 during fabrication process leads to synergy effects of not only the morphology but also the microstructure. These hybrids exhibit much higher hydrogen evolution efficiency than pure g-C 3 N 4 under visible-light illumination due to their improved light harvesting capability, enhancement of surface areas , predominant (110) facet exposure of α-Fe 2 O 3 as well as a prominent quantum size effect , and highly efficient electron transfer and separation. A proposed Z-scheme mechanism was further verified experimentally.
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JOURNAL OF CHROMATOGRAPHY A
·
2011
·Vol. 1218
·期 48
·8664-8671
·
IF 4.194
L.Y. Kong,B.G. Su,Z.B. Bao,H.B. Xing,Y.W. Yang,Q.L. Ren
A simple and direct reversed-phase high performance liquid chromatography (RP-HPLC) method with UV detection was developed and validated for the determination of mono- and di- d -α-tocopherol polyethylene glycol 1000 succinate (TPGS 1000) in TPGS mixture. Before the HPLC analysis, mono- and di-TPGS 1000 were separated by simulated moving bed (SMB) chromatography system and characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The mass spectrometric results confirmed that the molar mass distribution of TPGS prepared in our laboratory was very close to that of the product of Eastman Chemical Company with similar n ¯ (average polymerization degree), M n ¯ (number-average molecular weight) and M w ¯ (weight-average molecular weight). The HPLC analysis was carried out on a C30 analytical column with mobile phases comprised of acetonitrile (A) and isopropanol (B) in gradient conditions. Validation of the analytical method was done on the following parameters: system suitability, linearity, limits of detection and quantification, accuracy and precision, method robustness and solution stability. The linearity of the calibration curves for mono- and di-TPGS 1000 from both sources was found to be good ( r 2 > 0.9996). The recovery values were from 94.6% to 103.3% for mono-TPGS, and 93.5% to 103.3% for di-TPGS. This method could be successfully used in the direct quantification of mono- and di-TPGS in TPGS 1000 mixture using TPGS standards with similar molecular mass distributions although derived from different sources.
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RSC Advances
·
2017
·Vol. 7
·期 52
·32682-32691
·
IF 3.108
He Zhang,Lei Chen,Xiao Han,Feng Jiang,Haoyang Sun,Dazhi Sun
Nylon6 nanocomposites containing pristine layered α-zirconium phosphate (ZrP) nanoplatelets of various sizes have been fabricated by a simple and direct melt-compounding method without adding intercalation or exfoliation agents. Owing to the excellent compatibility between the nanofillers and Nylon6, the pristine ZrP nanoplatelet nanocrystallites were well dispersed and homogeneously distributed into the polymer matrices during the melt processing, but still maintained their original layered state as observed by scanning electron microscopy and X-ray diffraction. Tensile testing and dynamic mechanical analysis on the Nylon6/ZrP nanocomposites illustrate that the size and concentration of the pristine ZrP nanoplatelets have a profound effect on the mechanical properties of such prepared polymer nanocomposites. The improvement of the mechanical reinforcement for the Nylon6 nanocomposites does not show a steady increase with the increase in the size and concentration of the embedded pristine ZrP nanoplatelets, but displays the maximum for the pristine ZrP nanoplatelets with a size ranging from 600 nm to 800 nm at a concentration of ∼3.0–5.0% in the polymer matrices. The mechanisms that are responsible for the mechanical reinforcement of thermoplastic polymer matrices by the embedded pristine ZrP nanoplatelets, as well as their comparisons with corresponding epoxy nanocomposites, are also discussed.
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JOURNAL OF INHERITED METABOLIC DISEASE
·
2026
·Vol. 49
·期 2
·e70168
·
IF 3.8
Siwu He,Li Yang,Ke Wan,Zhaoyue Zheng,Mi Leng,Chunmei Gan,Yu Liu,Lin Xiao,Jingya Ye,Zhian Chen,Jiao Zhou,C Alexander Valencia,Aliah Abuammah,Hoi Yee Chow,Biao Dong,Yucheng Chen
Fabry disease is an X‐linked lysosomal storage disorder caused by mutations in the GLA gene, leading to deficient α‐galactosidase A (α‐Gal A) activity and pathological accumulation of globotriaosylceramide (Gb3) and globotriaosylsphingosine (Lyso‐Gb3) in various organs. To enhance α‐Gal A expression and secretion for recombinant adeno‐associated viral (rAAV) gene therapy, the signal peptide was engineered in HepG2 cells. Among 22 heterogeneous signal peptides, sp21 was identified and validated for this purpose. The enzyme activity of GLA with sp21 in conditioned media was 2.3 times higher than that with the wild‐type signal peptide. Furthermore, the human GLA gene was codon optimized (hGLAco), aiming to achieve increased hepatic expression and prevent gene silencing. The secreted α‐Gal A activity of hGLAco increased approximately 4‐fold in vitro. Finally, the hGLAco transgene with sp21 driven by a liver‐specific promoter was packaged in rAAV8 vectors and injected into Fabry mice. Compared with the wild‐type cDNA, the engineered GLA gene resulted in a 6.9‐fold increase in secreted α‐Gal A activity in Fabry mice, and toxic Lyso‐Gb3 accumulation in plasma and key tissues was effectively cleared. These findings demonstrate a promising strategy to develop a more efficient rAAV gene therapy for Fabry disease.
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CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Wenna Tang,Letao Guo,Lixia Yang,Liewei Qiu,Hongchen Liu,Mei Yang
Ester enolates, generated by lithium diisopropylamide (LDA)-mediated deprotonation of the α-hydrogen of esters, serve as highly reactive intermediates for C-C bond formation. However, they readily undergo self-condensation and decomposition, substantially reducing product yields, particularly in reactions with electrophiles that exhibit intrinsically slow kinetics. However, the key factors governing these side reactions, especially across esters with diverse structural features, remain insufficiently understood, limiting the rational design of effective suppression strategies. Here, we systematically studied the consumption behavior of enolates derived from esters with diverse structural features and developed tailored strategies to maintain high enolate concentrations over extended reaction times, several of which leveraged microreactor-based enolate generation. Using ethyl acetate (EA)-derived enolates, the most susceptible to side reactions, as a model, key factors governing enolate depletion in batch operation were identified, including insufficient mixing, excessive LDA consumption, and localized alkaline environments. Guided by these insights, a hybrid strategy operable under cryogenic conditions that coupled continuous-flow enolate generation with batch reaction time extension for EA-derived enolates were developed. Rapid mixing in continuous flow efficiently engaged most of the LDA in EA-derived enolate formation, thereby suppressing both self-condensation and decomposition. This hybrid approach sustained elevated EA-derived enolate concentrations for more than 60 min, outperforming conventional batch protocols. Subsequently, ester-specific enolate generation and preservation strategies for structurally diverse esters based on their distinct consumption pathways were established. Finally, using EA as a representative case, this tailored strategy significantly improved the yield of slow-kinetic Claisen condensation to the corresponding β-keto ester within 60 min.
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