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Advanced Materials Technologies · 2022 ·Vol. 8 ·期 4 ·2201223 · IF 8.856

Rapid Preparation of Patterned Conductive Films Based on In Situ Voltaic Cell Templated 3D Controllable Metal Deposition

Lili Xia,Jin Qian,Danting Song,Haoyu Gong,Chunxin Zhu,Zaiyang Zheng,Huibin Sun,Wei Huang

The fabrication of patterned metal films is essential for a wide range of applications. Here, a novel solution-processing method is presented to achieve the area-selective deposition of copper on aluminum substrates via an in situ Al/CuSO 4 /Graphite voltaic cell template. And the copper ions preferentially deposit in the graphite-covered area due to the formed latent image of the potential difference between the graphite-covered area and the blank area on the aluminum surface. Benefiting from the low adhesive force of graphite, the formed copper layer can be easily peeled off and transferred to a flexible substrate to obtain the patterned conductive metal films. By studying the electrochemical properties of different surfaces and the in situ microscopic observation, four stages of electroplating process are proposed. More importantly, a positive correlation between the deposition speed and graphite coverage density is confirmed. This further enables a regional control of deposition thickness in addition to area-selective deposition, which means a 3D controllable metal deposition. Other forms of electroactive carbon are also demonstrated to replace graphite in this method, which offers a versatile and accessible technique to fabricate large-area flexible patterned metal films with defined feature size and controlled resolution from microscale to macroscale.

研究领域: 材料科学 · 电化学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2023 · IF 4.2

Phosphorus-Doped Carbon-Supported Rh Nanoparticles for the Hydroformylation of Styrene with High Regioselectivity

Xingcong Zhang,Hao Zhang,Guanghui Guo,Qingdi Sun,Xiaohui He,Hongbing Ji

Rhodium nanoparticles supported on phosphorus-doped carbon (Rh/PC) are successfully prepared by the ball-milling method with sodium hypophosphite as the phosphorus source. The catalyst exhibits superb conversion (93.6%) and high regioselectivity (branched aldehydes/linear aldehydes = 20.2:1) for the hydroformylation of styrene compared to the phosphorus-free (Rh/C) and metal-free (PC) catalysts.

研究领域: 催化化学 · 材料科学
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LETTERS IN ORGANIC CHEMISTRY · 2023 ·Vol. 20 ·期 12 ·1159-1169 · IF 0.8

Green and Regioselective Alkylation of Dihydropyrimidinthiones through Michael Addition

Yaghoubi Fatemeh,imanzadeh Gholamhassan,Asgharzadeh Roghayyeh,Soltanzadeh Zahra,Öztürk Turan

Dihydropyrimidines are one of the most important heterocyclic ring systems having a serious place in medicinal and organic synthesis. In this paper, a new series of dihydropyrimidines consisting of sulfur atoms were synthesized using inorganic base K2CO3 and TBAB as an organic salt to make high polarity in reaction media. Interestingly, different 3,4-dihydropyrimidin-2(1H)-thiones reacted smoothly with various acrylic esters to afford adducts viahighly regioselective N3-Michael addition reaction was carried out at 100°C in 12 h. result: Unfortunately, the reaction failed with fumaric esters owing steric effects. Avoiding organic solvents during this reaction effectively led to the development of an economic approach. Structures of the new compounds were established on the basis of 1H NMR, 13C NMR, and IR spectral data.

研究领域: 有机化学 · 药物化学
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BIOTECHNOLOGY AND BIOPROCESS ENGINEERING · 2019 ·Vol. 24 ·期 2 ·326-336 · IF 1.438

Preparation of High-purity 1,3-Diacylglycerol Using Performance-enhanced Lipase Immobilized on Nanosized Magnetite Particles

Zhao Jiong-feng,Tao-Wang,Lin Jian-ping,Yang Li-rong,Wu Mian-Bin

Early research on the nutritional value of 1,3-diacylglycerols (1,3-DAGs) has resulted in a significant interest in their synthesis. 1,3-DAGs can be produced chemically and biologically. In this work, a regioselective lipase from Rhizopus oryzae was efficiently immobilized on nanosized magnetite particles (NSM) in an oriented way, resulting in significant enhancement of activity. The specific hydrolytic and esterification activities of the immobilized enzyme were 1,660% and 260% of those of the free enzyme, respectively. The immobilized enzyme was then used to catalyze the esterification of oleic acid with glycerol in a solvent-free system for preparation of 1,3-DAG in a 1 L reactor. The catalytic process was studied in detail, the final concentration of 1,3-DAG reached >76% under the optimal condition when the molar ratio of oleic acid to glycerol was 2.8:1. The regioselectivities of free and immobilized enzyme were both >97%. The immobilized enzyme was reused for 55 cycles with only ∼30% activity loss at 30°C. The purity of 1,3-DAG was up to ∼95% (w/w) after a simple purification step with the recovery ratio ∼85%. This is the first report of efficient 1,3-DAG purification by neutralization without acyl migration.

CAS / MDL: 56-81-5 112-80-1
研究领域: 生物化学 · 食品科学
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CARBOHYDRATE RESEARCH · 2018 · IF 2.074

Preparation and structural characterization of regioselective 4-O/6-O-desulfated chondroitin sulfate

Wenwei Han,Quancai Li,Youjing Lv,QingChi Wang,Xia Zhao

The sulfation pattern plays a crucial role in chondroitin sulfate (CS) biological activity, and preparation of CS with defined structure is essential for accurate pharmacological study. In this study, we focused on the preparation of regioselective 4- O /6- O -desulfated CS derived from porcine, employing a dimethyl sulfoxide-methanol (DMSO-MeOH) method and an N-methyl-N-(trimethylsilyl) -trifluoroacetamide (MTSTFA) method CS, respectively. Results showed that the sulfate at C4 position (4- O -S) of N-acetylgalactosamine (GalNAc) was selectively removed by the DMSO-MeOH method, and the sulfate at C6 position (6- O -S) of GalNAc was selectively removed by the MTSTFA method. Structures of desulfated CS were characterized by means of FT-IR, NMR and disaccharide composition analysis. The preparations of regioselective 4- O /6- O -desulfated CS are powerful for the study of structure-activity relationship of CS.

CAS / MDL: 24589-78-4
研究领域: 生物化学 · 药理学
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CATALYSIS LETTERS · 2020 ·Vol. 150 ·期 7 ·1841-1848 · IF 2.482

Catalytic Performance of a Robust Whole-Cell Biocatalyst in the Regioselective Synthesis of Helicid Esters Under Optimized Processing Conditions

Wu Ting-Ting,Zhao Xiang-Jie,Yang Rong-Ling,Bilal Muhammad,Wang Zhao-Yu,Luo Hong-Zhen,Xu Ning-Ning,Nie Ze-Kun

In this study, lyophilized Pseudomonas aeruginosa based whole-cell biocatalyst was used in the highly efficient and regioselective acylation of helicid with fatty acid vinyl esters in organic solvents. P. aeruginosa whole-cell catalyst showed high biomass and biocatalytic performance using 0.1% (w/v) soybean oil and 0.2% (w/v) tryptone as the carbon and nitrogen source, respectively. The biomass (0.72 g/L) cultivated for 36 h under the optimized conditions was 2-folds higher than that obtained by the use of the initial conditions (0.36 g/L). In addition, the optimized medium was found to be suitable for P. aeruginosa cultured in 3.5-L scale fermentation with high biomass (0.71 g/L) obtained at 24 h. Besides, a high substrate conversion efficiency (ranged from 92 to 99%) and excellent regioselectivity (99%) was achieved when P. aeruginosa whole-cell biocatalyst was applied to synthesize an array of 6′-esters of helicid. The reaction rate varies with varying acyl donors because of their differential interactions with the catalytic site of the enzyme from the whole cells of P. aeruginosa . Taken together, P. aeruginosa whole-cell catalyst obtained using optimal culture medium manifest a promising and highly-regioselective alternative to purified enzymes for the regioselective formation of 6′-esters derivatives of helicid in non-aqueous solvents. Graphic Abstract

研究领域: 生物化学 · 酶工程 · 工业微生物学
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JOURNAL OF CHEMICAL SCIENCES · 2017 ·Vol. 129 ·期 3 ·289-294 · IF 1.235

1,2,3-Triazole N(2)-coordinated C–O coupling: Access to ortho aryloxyl 1,4-diaryl 1,2,3-triazoles

LIU YAOWEN,ZHAO FEN,ZHOU HAOHUA,XIE KAI,JIANG YUBO

CuI-catalyzed selective Ullmann C–O coupling of 1,4-disubstituted 1,2,3-triazole bromides with phenols were achieved through the coordination of N(2) atom. The ortho C–Br bond in N(1) aryl can be selectively coupled with phenols, while other C–Br bonds remain inert, generating ortho aryloxyl 1,4-diaryl 1,2,3-triazoles. CuI-catalyzed selective Ullmann C–O couplings of 1,4-disubstituted 1,2,3-triazole bromides with phenols were achieved through the coordination of N(2) atom in triazole. The ortho C-Br bond in N(1) of aryl can be selectively coupled with phenols, while other C-Br bonds remain inert, generating ortho -aryloxyl 1,4-diaryl 1,2,3-triazoles.

研究领域: 有机化学 · 药物化学 · 生物有机化学 · 催化化学 · 合成方法学
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APPLIED ORGANOMETALLIC CHEMISTRY · 2022 ·Vol. 37 ·期 1 ·e6951 · IF 4.072

Highly dispersed nano-copper catalyst on porous polyvinyl chloride for highly regioselective borylation of alkynes

Wenna Xie,Shiwen Liu

We developed a highly regioselective synthesis of multi-substituted alkenylboronates via a heterogeneous ligand-free nano-copper catalyst that was highly dispersed and supported on the porous polyvinyl chloride. In this catalytic system, substituents on the terminal alkynes could affect the configuration of products. Terminal alkynes and general internal alkynes gave β-selective borylation products, whereas heteroatom-substituted alkynes like alkynamides, thioacetylenes, and ynol ethers gave α-selective borylation products in good chemical yields with exclusive regioselectivity.

研究领域: 有机化学 · 催化化学
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INORGANIC CHEMISTRY · 2025 · IF 4.7

Revisiting the Origins of Reactivity and Selectivity in the Pd6L4-Cage-Catalyzed Diels–Alder Reactions: A Combined Computational and Experimental Study

Hui-Mei Shan,Lin Li,Qian Wang,Li-Ping Xu

Supramolecular metal–organic cages (MOCs) have gained attention as versatile catalytic platforms due to their self-assembled architectures and well-defined cavities, which mimic enzyme active sites and enable spatial confinement. This confinement modulates the reaction pathways and enhances the catalytic performance. Recent studies highlight their catalytic potential in various organic transformations, but the factors governing the MOC-catalyzed reactions remain incompletely understood. This work builds on prior computational studies of Diels–Alder reactions catalyzed by palladium-based MOCs, showing that the common view of transition-state stabilization via π–π interactions is not valid. Instead, we find that π–π interactions between the substrate and the ligands destabilize the transition state. Additionally, theoretical studies of regioselectivity, validated experimentally, suggest that substrate encapsulation efficiency is key to determining reaction selectivity. These findings provide new insights into the mechanisms of MOC-catalyzed reactions.

CAS / MDL: 865-49-6
研究领域: 化学 · 理论计算化学 · 有机合成化学
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Research · 2021 · IF 0

Programmable Self-Assembly of Gold Nanoarrows via Regioselective Adsorption

Cheng Chen,Liheng Zheng,Fucheng Guo,Zheyu Fang,Limin Qi

Programing the self-assembly of colloidal nanoparticles into predetermined superstructures represents an attractive strategy to realize functional assemblies and novel nanodevices, but it remains a challenge. Herein, gold nanoarrows (GNAs) showing a distinct convex-concave structure were employed as unique building blocks for programmable self-assembly involving multiple assembly modes. Regioselective adsorption of 1,10-decanedithiol on the vertexes, edges, and facets of GNAs allowed for programmable self-assembly of GNAs with five distinct assembly modes, and regioselective blocking with 1-dodecanethiol followed by adsorption of 1,10-decanedithiol gave rise to programmable self-assembly with six assembly modes including three novel wing-engaged modes. The assembly mode was essentially determined by regioselective adsorption of the dithiol linker dictated by the local curvature together with the shape complementarity of GNAs. This approach reveals how the geometric morphology of nanoparticles affects their regioselective functionalization and drives their self-assembly.

研究领域: 纳米技术 · 材料科学 · 化学
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APPLIED MICROBIOLOGY AND BIOTECHNOLOGY · 2023 ·Vol. 107 ·期 18 ·5727-5737 · IF 5

Prokaryotic expression and characterization of artificial self-sufficient CYP120A monooxygenases

Ye Ru-Yi,Song Juan,Zhang Zhi-Jun,Yu Hui-Lei

Abstract Cytochrome P450 monooxygenases CYP120As are the unique non-membrane P450s, which are extensively involved in retinoid biodegradation. As the O -functionalized 1,3,3-trimethylcyclohex-1-ene moiety exists in many bioactive compounds which could only be catalyzed by Class II P450s, exploration of the catalytic repertoire of CYP120As is therefore highly attractive. However, up to date, only one bacteriogenic candidate (CYP120A1) was demonstrated for the hydroxylation of C16 and C17 of retinoic acid, by utilizing the integral membrane protein cytochrome P450 reductase redox partner for the electron transfer. Herein, we provided an efficient prokaryotic functional expression system of CYP120As in E. coli by expression of the CYP120A1 coupled with several reductase partners. Fusion redox partners to the C -terminal of the heme-domain are also working on other CYP120A members. Among them, the fusion protein of CYP120A29 and FAD/FMN reductase from Bacillus megaterium P450 BM3 (CYP101A2) showed the highest expression level. Based on the available translational fusion systems, the regioselectivity and the substrate scope of the CYP120As have also been explored. This work represents a good starting point for further expanding the catalytic potential of CYP120 family. Key Points • Characterization of CYP120As in E. coli is firstly achieved by constructing fusion proteins. • The feasibility of three P450 reductase domains to CYP120As was evaluated. • Hydroxylated products of retinoic acid by six CYP120As were sorted and analyzed. Graphical Abstract

CAS / MDL: 7775-14-6
研究领域: 生物化学 · 分子生物学
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TETRAHEDRON · 2017 · IF 2.651

Synthesis of imidazol[1,2-α]pyridine thioethers via using sulfur powder and halides as reactants

Wei Wu,Yingcai Ding,Ping Xie,Qiujie Tang,Charles U. Pittman,Aihua Zhou

Structure containing the C S bond exist widely in nature, drugs and chemical materials . Here, a novel sulfenylation protocol employing an aryl or alkyl halide and odorless and cheap S as reagents was developed, generating regioselective alkyl-S- and Ar-S-substituted imidazol[1,2-α]pyridine derivatives in good yields under relatively environmentally friendly and mild conditions. This protocol enriches current thioether-producing methods, making up for the shortcomings of previous sulfenylation methods which can only make MeS- and ArS-substituted imidazol[1,2-α]pyridine derivatives.

研究领域: 有机化学 · 药物化学
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