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RUSSIAN JOURNAL OF GENERAL CHEMISTRY · 2017 ·Vol. 87 ·期 11 ·2643-2647 · IF 0.553

Novel approach to the synthesis of istaroxime

Liang G.-P.,Guo J.-H.,Jiang R.-W.

Istaroxime 1 , a novel cardiotonic agent with high efficiency and low toxicity was synthesized from dehydroepiandrosterone 2 using a novel approach that included epoxidation, ring-opening, substitution, and oximation. The new protocol without gas protection was milder than the reported approaches. The overall yield of the method was 24.1%.

研究领域: 药物化学 · 有机合成
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Catalysts · 2020 ·Vol. 10 ·期 12 ·1419 · IF 3.52

Ring-Opening of Epoxides with Amines for Synthesis of β-Amino Alcohols in a Continuous-Flow Biocatalysis System

Li-Hua Du,Miao Xue,Meng-Jie Yang,Yue Pan,Ling-Yan Zheng,Zhi-Min Ou,Xi-Ping Luo

An efficient method for the preparation of β-amino alcohols catalyzed by lipase TL IM fromThermomyces lanuginosusin a continuous-flow reactor was developed. The eco-friendly biocatalyst combined with continuous-flow reaction technology displayed high efficiency in the synthesis of β-amino alcohols. The benign reaction conditions (35 °C) and short residence time (20 min), together with the use of low cost and readily available starting materials, make this synthetic approach a promising alternative to current β-amino alcohol synthesis.Keywords:enzymatic synthesis;β-amino alcohols;reactor;epoxides;ring-opening reaction

CAS / MDL: 286-20-4 106-89-8
研究领域: 生物化学 · 有机合成 · 绿色化学
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Reaction Chemistry & Engineering · 2021 ·Vol. 6 ·期 11 ·2159-2169 · IF 4.239

Remarkable improvement of epoxide ring-opening reaction efficiency and selectivity with water as a green regulator

Zifei Yan,Chencan Du,Guangsheng Luo,Jian Deng

Glycidyl esters are synthesized through the epoxide ring-opening reactions, and the reaction efficiency must be greatly improved for green and efficient production. In this work, the structure of the side product that caused the decline of selectivity was confirmed by GC-MS and 1H NMR. The formation mechanism of the side product was unraveled, indicating that the relative rates of the parallel competing reactions towards the conversion of an intermediate was a key factor in selectivity. It was found that water as a proton transfer carrier can effectively facilitate the conversion of the intermediate to the target product, thus successfully suppressing the side reactions. The water content of 8–10 wt% in the reaction system was proved to be the optimized range. Relying on the function of water, the ring-opening reaction can be performed at 100 °C instead of 70 °C, and epichlorohydrin (ECH) could be directly fed in the reaction system once instead of dripping for 1 hour. Thus, the reaction time could be reduced from 6 hours to 1 hour, and the product selectivity could be maintained higher than 98%. The industrial production process further proved the effectiveness of this strategy in terms of broadening the temperature range for the highly selective synthesis of glycidyl esters and reducing the scale-up effect.

研究领域: 化学工程 · 绿色化学
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Bioengineering-Basel · 2022 ·Vol. 9 ·期 7 ·307 · IF 5.046

Rapid Degradation of Rhodamine B through Visible-Photocatalytic Advanced Oxidation Using Self-Degradable Natural Perylene Quinone Derivatives—Hypocrellins

Zhixian Huang,Fan Zhang,Yanbo Tang,Yongdi Wen,Zhenqiang Wu,Zhen Fang,Xiaofei Tian

Hypocrellins (HYPs) are natural perylene quinone derivatives from Ascomycota fungi. Based on the excellent photosensitization properties of HYPs, this work proposed a photocatalytic advanced oxidation process (PAOP) that uses HYPs to degrade rhodamine B (RhB) as a model organic pollutant. A synergistic activity of HYPs and H2O2(0.18 mM of HYPs, 0.33%w/vof H2O2) was suggested, resulting in a yield of 82.4% for RhB degradation after 60 min under visible light irradiation at 470–475 nm. The principle of pseudo-first-order kinetics was used to describe the decomposition reaction with a calculated constant (k) of 0.02899 min−1(R2= 0.983). Light-induced self-degradation of HYPs could be activated under alkaline (pH > 7) conditions, promising HYPs as an advanced property to alleviate the current dilemma of secondary pollution by synthetic photocatalysts in the remediation of emerging organic pollutants.Keywords:photocatalytic advanced oxidation;organic pollutants;photosensitizer;ring-opening reaction;self-degradation

CAS / MDL: 107-88-0
研究领域: 环境科学 · 生物化学
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JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART A · 2019 ·Vol. 107 ·期 11 ·2458-2467 · IF 3.221

Structure and antimicrobial properties of long-chain branched poly (lactic acid)

Zhengqiu Li,Lei Liu,Baoshu Chen,Tianbao Zhao,Longchang Ran,Xiaodie Yuan,Zhiwen Cao,Ting Wu

Long-chain branched poly (lactic acid) (LCB-PLA) with antimicrobial functional group was fabricated through a two-step ring-opening reactive processing for improving antimicrobial properties and broadening the PLA processing window. A combination of linear viscoelasticity and the branch-on-branch (BOB) model predicted probable compositions and chain topologies of the products. It is also explored the antimicrobial properties of LCB-PLA to provide a theoretical basis for broadening the possible applications.

CAS / MDL: 89-32-7
研究领域: 材料科学 · 微生物学
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TRIBOLOGY INTERNATIONAL · 2021 · IF 4.872

Fluid-like graphene oxide organic hybrid materials as efficient anti-wear and friction-reducing additive of polyethylene glycol

Tao Cai,Dan Liu,Shenggao Liu

Achieving graphene-based lubricants with simultaneous excellent dispersibility and tribological performance remains challenging as graphene tends to agglomerate in lubricating oils. Herein, a fluid-like graphene oxide (FL-GO) was developed based on covalent grafting and epoxide ring-opening reactions, which exhibited obviously improved dispersion ability and tribological behaviors in polyethylene glycol (PEG). The dispersion stability of FL-GO was demonstrated by sedimentation experiment and the 0.5% of FL-GO reduced wear volume of 91.1% and friction coefficient of 43.7%. This well-dispersed graphene helps continue to generate an uneven lubricating film on the rubbing surface, thereby improving the friction and wear performance of the lubricating oils.

CAS / MDL: 25322-68-3
研究领域: 材料科学 · 润滑工程
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Polymer Chemistry · 2023 ·Vol. 14 ·期 32 ·3679-3685 · IF 4.6

Ring-opening mechanism of epoxides with alcohol and tertiary amines

Yongzhuang Du,Xiaoqiang Xue,Qimin Jiang,Wenyan Huang,Hongjun Yang,Li Jiang,Bibiao Jiang,Sridhar Komarneni

The ring-opening mechanism of epoxides in the presence of tertiary amines was studied in this work. Gas chromatography (GC) and size-exclusion chromatography (SEC) were used to measure the monomer conversion and molecular weights of the polymers. Nuclear magnetic resonance (NMR) spectroscopy was used to analyze the polymer structures. It has been found that only in the system where tertiary amines and hydroxyl-containing compounds coexist can the ring-opening reaction occur, indicating that there is an interaction between tertiary amines and the hydroxyl groups, which is confirmed by the NMR analysis of a mixture of triethylamine (TEA) and ethanol (EtOH), and the polymerization of TEA and glycidol (GL). As for normal epoxides, such as propylene oxide, polymers contained tertiary amine moieties before and after dialysis, suggesting that the tertiary amine moieties were covalently linked with the polymer backbone but were not present as the counter ions, and this is the first NMR proof confirming that tertiary amine initiates the ring-opening reaction of epoxides. In sharp contrast, a reaction at huge excesses of EtOH and TEA was carried out at [GL]0/[EtOH]0/[TEA]0 = 1/50/50, and a model compound with only one GL unit was obtained. The NMR analysis of this model compound confirms that the alkoxy anion from ethanol rather than TEA attacks and opens the epoxy ring of GL. The presence and absence of the tertiary amine moiety in the polymers from GL/tertiary amine before and after dialysis further support the reaction mechanism that an alkoxy anion initiates the polymerization, and the positively charged tertiary amine units are present only as counter ions and are removed by dialysis. These demonstrate that the ring-opening mechanisms catalyzed by tertiary amine for epoxides will be different from each other depending on their structures.

研究领域: 有机化学 · 高分子化学
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JOURNAL OF SEPARATION SCIENCE · 2017 ·Vol. 41 ·期 4 ·856-867 · IF 2.557

Synthesis and chromatographic evaluation of phenyl/tetrazole bonded stationary phase based on thiol-epoxy ring opening reaction

Gaowa Jin,Yanming Liu,Fan Yang,Dongping Yu,Jingyu Yan,Weijia Zhou,Zhimou Guo,Jianhua Zhu,Xinmiao Liang

A silica-based reversed-phase stationary phase bonding with phenyl and tetrazole groups was synthesized by thiol-epoxy ring opening reaction. The bonded groups could not only provide hydrophobic interaction, but also π–π, hydrogen bonding, electrostatic interactions, and so on. The results of characterization with elemental analysis and solid-state 13 C cross-polarization magic-angle-spinning NMR spectroscopy indicated the successful preparation of phenyl/tetrazole sulfoether bonded stationary phase. Chromatographic evaluation revealed that phenyl/tetrazole sulfoether bonded stationary phase behaved well under the reversed-phase mode. The column parameters ( H , S *, A , B , and C ) showed different selectivity compared with some typical commercial columns, and it was validated by the separation of estrogen, ginsenoside, alkaloid samples. Based on the different selectivity between phenyl/tetrazole sulfoether bonded stationary phase and C18 columns, phenyl/tetrazole sulfoether bonded stationary phase also showed potential to construct a 2D reversed-phase liquid chromatography system with C18. And it was verified by the separation of corydalis tuber and curcuma zedoary extracts.

CAS / MDL: 20651-71-2 62-56-6
研究领域: 分析化学 · 色谱技术
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INDUSTRIAL CROPS AND PRODUCTS · 2022 · IF 6.449

Preparation of biopolyols by pyrrolidone ionic liquid-catalyzed ring-opening of epoxidized soybean oils

Jun Li,Yongyan Kuang,Yanlan Bi,Shangde Sun,Dan Peng

The effects of N-methyl pyrrolidone hydrogen sulfate ([Hnmp]HSO 4 ), α-pyrrolidone hydrogen sulfate ([Hnhp]HSO 4 ), and dinucleated pyrrolidone hydrogen sulfate ([[Hnhp]HSO 4 ] 2 ) on ring-opening of epoxidized soybean oils (ESO) was comparatively investigated. Results showed that [Hnhp]HSO 4 had stronger catalytic activity than the other two. Under the optimal conditions ([Hnhp]HSO 4 loading of 6%, water-epoxy group ratio of 9:1 (mol/mol), reaction temperature of 45 °C, and reaction time of 4 h), the resulting di-hydroxylated soybean oils (DSO) with an epoxy content of 0.87% and hydroxyl value (OHV) of 213.41 mg KOH/g was achieved, which corresponded to a conversion rate of OHV of 57.98%. In-situ Fourier transform infrared spectroscopy (In-situ FTIR) and FTIR analyses indicated that the rapid ring-opening of ESO and formation of DSO mainly occurred at 2–3.5 h. The increase of polarity and molecular weight after ring-opening and the formation of hydrogen bonds resulted in the higher viscosity of DSO than ESO. ESO and DSO were thermally stable at up to 350 °C. The effectiveness of [Hnhp]HSO 4 in catalyzing the ring-opening of ESO was comparable to that of inorganic acids. Almost complete ring-opening of epoxy groups with much less etherification leads biopolyols to have more available hydroxyl groups. Thus, the resulting biopolyols can be processed as chemical intermediates under more flexible parameter conditions.

CAS / MDL: 616-45-5
研究领域: 化学工程 · 可再生资源化学 · 绿色化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

A new “off–on” fluorescent probe for Pd2+ in aqueous solution and live-cell based on spirolactam ring-opening reaction

Qi Huang,Yanmei Zhou,Qingyou Zhang,Enze Wang,Yinghao Min,Han Qiao,Junli Zhang,Tongsen Ma

Based on spirolactam ring-opening reaction, a chromogenic and “off–on” fluorescent sensor for determination of palladium (II) was developed in this paper. The novel sensor was easily synthesized from rhodamine B hydrazide and diacetyl monoxime named RBM. The structure of the sensor has been characterized by ESI-MS and NMR. EDTA-adding experiment indicated that the binding of chemosensor RBM and Pd 2+ was chemically reversible. The fluorescence intensity and absorbance of the sensor showed a good linearity with the concentration of Pd 2+ in the range of 0–15   μM and 0–17   μM, respectively, with detection limits of 0.015   μM and 0.200   μM. Moreover, it has been successfully applied to detect Pd 2+ in palladium-containing catalyst, natural water samples and imaging of Pd 2+ in living cells with satisfying results. The study indicated that this novel sensor could be an attractive approach to detect Pd 2+ in environmental systems and biological systems.

研究领域: 分析化学 · 环境科学 · 生物无机化学 · 分子影像 · 化学生物学
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Catalysis Science & Technology · 2017 ·Vol. 7 ·期 3 ·725-733 · IF 5.773

A novel strategy for constructing mesoporous solid superbase catalysts: bimetallic Al–La oxides supported on SBA-15 modified with KF

Ning Liu,Zhimin Wu,Meng Li,Shanshan Li,Yongfei Li,Rongdong Yu,Langsheng Pan,Yuejin Liu

Bimetallic Al–La oxides were conjointly precoated on SBA-15 prior to the introduction of potassium fluoride to achieve solid superbases at low temperature by a modified wetness impregnation method. This breaks the tradition of decomposition of KNO3 at high temperature and gives rise to a new approach to generating superbasic sites on SBA-15. The physico-chemical characteristics of the prepared KF/Al–La@SBA-15 materials were investigated using FT-IR, XRD, TG-DTG, N2 adsorption–desorption, TEM, SEM-EDS, acid–base titration, Hammett indicators and CO2-TPD measurements. The results demonstrated that the addition of Al species promoted the dispersion behavior of La species inside the channels, and the bimetallic species could synergistically protect the mesoporous structures of SBA-15 against KF corrosion. With increasing Al content, KF/Al–La@SBA-15 exhibited a long-range ordering of the pores with relatively narrow pore size distribution as well as high specific surface area. The research results showed that the KF/Al–La@SBA-15 (0.4) catalyst possessed a total basicity up to 0.79 mmol g−1 and superbasicity with a strength of 26.5. The catalytic activity of the prepared materials was evaluated in the ring-opening reaction of propylene oxide with methanol. Compared with the SBA-15 supported monometallic oxide (Al or La) catalysts, KF/Al–La@SBA-15 (0.4) exhibited the highest catalytic activity for the ring-opening reaction of propylene oxide with methanol. This is associated with the synergistic effects between Al and La species and the high dispersion of active components on the SBA-15 support.

研究领域: 催化化学 · 材料科学
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Sustainable Chemistry and Pharmacy · 2023 · IF 6

Two approaches for bio-lubricant production from soybean oil with organosilicon

Qingli Zhu,Xiao Chen,Heng Gu,Zhi Yun

With the rapid increasing of environmental pollution concerns and declining petroleum assets, bio-based lubricants industry has aroused increasingly more attention and study. The present paper proposed two methods (a two-step process and a direct hydrosiylation process) for the production of biolubricant from soybean oil with organosilicon. At first, soybean oil was subjected to transesterification with potassium hydroxide under certain conditions. Then, the transesterified soybean oil was undergone urea inclusion for obtaining unsaturated fatty acid methyl esters (UFAMEs). After urea inclusion, the content of UFAMEs was increased to 88.1%. Next, the chemical modification of UFAMEs by the two-step process (epoxidation and ring-opening reaction) and the direct hydrosiylation process (with triethylsilane in present of catalyst) were systematically studied, respectively. With the optimal conditions, the conversions of UFAMEs in the two-step process and direct hydrosiylation process were 86.1% and 82.1%, respectively. In addition, the structure characteristics of material and products were determined by Fourier-transformed infrared (FTIR) spectroscope and 29 Si-Nuclear magnetic resonance ( 29 Si-NMR) spectrascopy. The lubrication performances of the two products were proved to be much better than soybean oil according to industry standards. Therefore, both of the two processes appeared to be feasible for bio-lubricant production.

研究领域: 环境科学 · 化学工程 · 材料科学
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