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CARBOHYDRATE POLYMERS · 2022 · IF 10.723

A facile method of functional derivatization based on starch acetoacetate

Tianhang Weng,Zejian He,Zhaohua Zhang,Yulong Chen,Mi Zhou,Bianying Wen

In the present work, we constructed a methodology to graft starch with special groups, such as alkyl, phenolic, naphthalimide derivatives (ND) and polymer, by a simple reaction under generally mild conditions without catalysts or UV irradiation , based on precursor starch acetoacetate (SAA). The completeness of these reactions has been proved to be ideal. After grafting, the starch derivatives have some common changes, for instance, their solubility is improved in certain solvents. On the other hand, the introduction of different functional groups will also bring some characteristics to the derivatives (e.g. ND brings fluorescence). In addition, part of the derivatives shows excellent machinability, and their hot-pressed samples exhibit great transparency and mechanical strength. Specially, the alkyl grafted starch displays excellent toughness, properties of deformation and self-recovery. In conclusion, this method has good universality and methodological significance, and offers insights into the larger-scale industrial application of starch.

研究领域: 材料科学 · 化学工程 · 高分子化学
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ORGANIC PROCESS RESEARCH & DEVELOPMENT · 2019 · IF 3.327

A Continuous Flow Process for the Synthesis of Hymexazol

Xin-peng Ma,Jin-sha Chen,Xiao-hua Du

Hymexazol is an efficient and low-toxicity soil fungicide. In this work, a fully continuous flow process for the synthesis of hymexazol has been developed. This process begins with combining ethyl acetoacetate and hydroxylamine hydrochloride to form a hydroxamic acid intermediate. The reaction solution is then quenched with concentrated hydrochloric acid to obtain the final product, hymexazol. Under the optimized process conditions, the total yield of the target product reached 86%. In addition, production was successfully scaled-up to a kilogram scale. The continuous flow method not only greatly decreases the reaction time but also significantly inhibits the side reactions.

研究领域: 化学工程 · 农药科学
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LAB ON A CHIP · 2025 · IF 5.4

Integrated Microfluidic Colorimetric Patch with Auto-Framing APP for Multiplex Temporal Detection of Ketone Bodies in Sweat

Tianhao Xue,JiaNing Shen,Wanting Lin,Jiahui Zhou,Xiaofang Zhang,Jen-Tsai Liu,Ching-Jung Chen,Guixian Zhu

Ketone bodies are key products of fat metabolism, primarily consisting of acetoacetate (AcAc), β-hydroxybutyrate (BHB), and acetone (Acetone). Monitoring the concentration of ketone bodies in sweat can reflect the metabolic status of the body, it is also particularly significant in areas such as diabetes management, exercise monitoring, and the evaluation of the ketogenic diet. This paper presents a microfluidic patch for sweat collection and multiplex detection of AcAc, BHB and glucose. The microfluidic patch can achieve time-sequential sensing through Tesla valves, hydrophilic coatings, and unique chamber structural design. The concentrations of the three substances are quantified using colorimetric methods. Additionally, this study has designed a colorimetric app which can achieve automatic framing and detect the grayscale value of the colored area. Experimental results show that the patch can accurately detect changes in the concentrations of the three substances within specific ranges. The linear detection range for AcAc is 0.25 mM to 8 mM, the limit of detection (LOD) is 0.08 mM; for BHB, linear detection range is 0.05 mM to 0.80 mM, LOD is 0.02 mM; and for glucose, linear detection range is 62.50 μM to 1000 μM, LOD is 20.83 μM. In the future, this technology is expected to be applied to portable metabolic monitoring devices, offering a convenient solution for personal health management

研究领域: 生物医学工程 · 代谢监测 · 健康科技
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KINETICS AND CATALYSIS · 2024 · IF 1.3

Crosslinked Cation Exchange Resin with -SO3H Groups as an Efficient Solid Catalyst for the Ketalization of Ethyl Acetoacetate with Glycols

Chen Bo-Jiang,Wu Jian-Ping,Rukhsana,Xiang Fei-Yong,Shen Yong-Miao,Liang Xue-Zheng

Abstract A highly efficient protocol was developed for the synthesis of fructone spice from the ketalization of ethyl acetoacetate with ethylene glycol utilizing the sulfonated polydivinylbenzene (PDVB-SO 3 H) solid acid catalyst. A comparative analysis revealed that PDVB-SO 3 H exhibited better catalytic activity and reusability than conventional H 2 SO 4 and p -toluene sulfonic acid. The impact of reaction conditions, including temperature, reaction time, catalyst dosage, and molar ratio of reactants, was extensively investigated in order to optimize the reaction parameters. The results revealed the remarkable catalytic efficiency of PDVB-SO 3 H in synthesizing apple ester flavor, achieving a conversion rate exceeding 99% under reflux conditions with a ketone to alcohol ratio of 1.5. Furthermore, PDVB-SO 3 H solid acid demonstrated its versatility by enhancing the synthesis of a variety of fruit ketone flavors with high conversion rates. Notably, the catalyst displayed excellent recyclability, remaining active for up to six cycles without any noticeable decline in performance. Therefore, PDVB-SO 3 H solid acid exhibits immense potential for utilization in the chemical industry.

研究领域: 有机化学 · 食品科学
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RSC Advances · 2014 ·Vol. 4 ·期 43 ·22520-22525 · IF 3.708

Facile synthesis of fructone from ethyl acetoacetate and ethylene glycol catalyzed by SO3H-functionalized Brønsted acidic ionic liquids

Yong Liu,Yi-Tao Wang,Tao Liu,Duan-Jian Tao

SO3H-functionalized Brønsted acidic ionic liquids (BAILs) were synthesized and utilized as highly efficient catalysts for the production of fructone via the acetalization reaction of ethyl acetoacetate with ethylene glycol. In comparison with conventional H2SO4 and cation exchange resins, the BAILs N-(4-sulfonic acid) butyl triethylammonium hydrogensulfate ([BSEt3N][HSO4]) of strong acidities exhibited excellent catalytic activities. The effects of various parameters such as different BAILs, reaction temperature, catalyst dosage, and molar ratio of the reactants on the conversion of ethyl acetoacetate were investigated in detail. The experimental results indicated that the catalytic performance of BAILs were closely related to their Hammett acidities. Moreover, it was found that [BSEt3N][HSO4] could be also recovered easily and used repetitively six times without obvious decline in activity and quantity, showing great potential application in industry.

CAS / MDL: 1633-83-6 616-47-7
研究领域: 化学工程 · 有机合成
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APPLIED ENERGY · 2013 · IF 4.781

Ethyl acetoacetate: A potential bio-based diluent for improving the cold flow properties of biodiesel from waste cooking oil

Leichang Cao,Jieni Wang,Kuojin Liu,Sheng Han

Ethyl acetoacetate was investigated as a potential bio-based diluent for improving the cold flow properties of biodiesel from waste cooking oil. Waste cooking oil generally has relatively high saturated fatty acid content, meaning that the cold flow properties of the converted biodiesel are more challenging than the properties of biodiesel from conventional vegetable oils. The cold filter plugging point (CFPP) and pour point (PP) of biodiesel decreased after adding ethyl acetoacetate at 0%, 2.5%, 5%, 10% and 20% (vol). Both PP and CFPP decreased by 4   °C at 20   vol% ethyl acetoacetate. The effect of ethyl acetoacetate on kinematic viscosity, acid value and flash point was determined. Every sample satisfied ASTM D6751 except for the flash point (⩾10   vol% ethyl acetoacetate), but the 5   vol% blends were all acceptable. Oxidative stability was improved with the addition of ethyl acetoacetate. Overall, ethyl acetoacetate appears acceptable as a bio-based diluent for improving the cold flow properties of biodiesel.

研究领域: 能源科学 · 环境科学 · 化学工程
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CHEMICAL ENGINEERING SCIENCE · 2022 · IF 4.889

Process performance and kinetics of the esterification of diketene to methyl acetoacetate in helical continuous-flow microreactors

Hui Zhou,Xian Tang,Zilai Wang,Yunhao Sun,Xiang Ling

The esterification of 4-methyleneoxetan-2-one (diketene) and methanol to obtain methyl acetoacetate (MAA) was conducted in a helical continuous-flow microreactor with triethylamine and 4-methylbenzenesulfonic acid (TsOH) as the catalyst in the absence of a solvent. The effects of the initial molar ratios of methanol to diketene and catalyst to diketene, reaction temperature, and residence time on the esterification reaction were also investigated and optimized. Under optimal conditions, the yield and selectivity of the reaction system for MAA exceeded 97% with only 120 s. In addition, a kinetic model of the esterification reaction inside helical continuous-flow microreactor was established with acceptable model performance. This work demonstrates that the combination of helical continuous flow and esterification, which is designed to provide researchers with a unique process, is also key to assessing the relevant esterification mechanism.

CAS / MDL: 121-44-8
研究领域: 化学工程 · 催化化学
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CELLULOSE · 2020 ·Vol. 28 ·期 2 ·691-701 · IF 4.21

Enzymatic graft polymerization from cellulose acetoacetate: a versatile strategy for cellulose functionalization

Wang Ruochun,Rong Liduo,Ni Shujing,Wang Qiankun,Wang Bijia,Mao Zhiping,Feng Xueling,Yuan Jinying,Sui Xiaofeng

A novel approach was developed to prepare cellulose acetoacetate- graft -copolymers via horseradish peroxidase (HRP)-mediated polymerization. Cellulose acetoacetate (CAA), the macroinitiator, was obtained by transesterification between tert -butyl acetoacetate ( t -BAA) and cellulose in ionic liquid. The CAA- graft -polyacrylamide (CAA- g -PAM) was synthesized using a ternary initiator system consisting of CAA, HRP and hydrogen peroxide (H 2 O 2 ). The results of surface-initiated polymerization showed that the formation of free polymers could be inhibited in this process. The kinetics exhibited that this method is a powerful tool for obtaining graft copolymers. The effects of H 2 O 2 concentration and reaction temperature were investigated to explore the optimal conditions for the process of enzymatic initiation. The synthesized copolymers were characterized by FT IR, NMR, TGA and elemental analysis to confirm the successful grafting of polyacrylamide chains onto the cellulose backbones. Furthermore, generality of the HRP-mediated graft polymerization approach was demonstrated using various monomers, including 2-hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA) and sulfobetaine methacrylate (SBMA). This efficient and robust strategy has great potential in fabrication of cellulose-based functional polymers. Graphic abstract Enzymatic grafting polymerization from cellulose acetoacetate

研究领域: 材料科学 · 生物化学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2016 ·Vol. 408 ·期 17 ·4661-4667 · IF 3.125

A GC/MS method for determination of succinylacetone in Arabidopsis thaliana

Zhou Lizi,Yang Zhaoguang,Zhi Tiantian,Zhou Zhou,Wang Xiaochen,Ren Chunmei,Qiu Bo

Succinylacetone was known to be a toxic metabolite of tyrosine in human and animals caused by blockage of the final step in tyrosine degradation pathway, but its existence in plant was unclear though the metabolic disturbance of tyrosine was also found in plant. A GC-MS method for determination of succinylacetone in Arabidopsis thaliana was developed for the first time. Both oximation and silylation were applied in the derivation procedure, and a low-temperature condition before completion of oximation was found to be necessary to obtain good linearity of the calibration curve due to the thermolability of succinylacetone. The specific chromatogram pattern formed by the four isomers of succinylacetone derivatives provided a helpful feature for its identification. The detection limit of the proposed method was 0.25 ppm in A. thaliana . The recoveries were between 95.4 and 109.3 % with the coefficient of variation ranging from 4.36 to 7.81 % for intra-day assays and 6.47 to 8.52 % for inter-day assays. Application to wild-type and the short-day sensitive cell death 1 mutant of A. thaliana represented an obvious correlation between the measured amount of succinylacetone and wilting symptom, suggesting the proposed method could be a powerful tool in further study on toxicology of succinylacetone and tyrosine catabolism in plants.

研究领域: 植物学 · 分析化学 · 毒理学
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INDUSTRIAL CROPS AND PRODUCTS · 2022 · IF 6.449

Preparation of high-strength dynamic polysaccharide nanocomposite hydrogels and their application towards dye adsorption

Fang Wang,Kexin Huang,Ziqi Xu,Fangyu Cao,Cheng Chen,Fengna Shi,Naipin Chen

The preparation and application of natural dynamic polysaccharide hydrogels have been attractive in recent years. Herein, carboxymethyl chitosan (CMCht) and oxidized acetoacetate cellulose (OCAA) were used to prepare polysaccharide nanocomposite hydrogel for dye adsorbent by one pot method mixing glutaraldehyde (GA) and cellulose nanofibers (CNFs), and mechanical, rheological, self-healing and dye adsorption properties were investigated. Consequently, compared with CMCht/OCAA hydrogel, the addition of GA crosslinker together with 1 % CNF increased strengths by ∼520 %, tensile strengths from 259 KPa to 1.35 MPa and compressive strength from 450 KPa to 2.35 MPa, respectively. The nanocomposite hydrogels demonstrated excellent anti-fatigue performance, and its experimental modulus result was fit Halpin-Kardos and Ouali model. Moreover, the freeze-dried gels showed a good removal effect for methylene blue dye from water, and its adsorption capacity and removal efficiency could reach up to 564.64 mg/g and 94 % due to the presence of dynamic covalent and hydrogen bonds in the composite hydrogel. This work developed a high-strength dynamic polysaccharide hydrogels incorporation of CNFs, which shows promising applications in environmental fields especially water pollution adsorption treatment.

研究领域: 材料科学 · 环境科学 · 生物化学
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CATALYSIS LETTERS · 2019 ·Vol. 149 ·期 2 ·610-618 · IF 2.372

A Novel Thermal Stable Carbonyl Reductase from Bacillus cereus by Gene Mining as Biocatalyst for β-Carbonyl Ester Asymmetric Reduction Reaction

Qin Yan-Li,Ruan Tao,Hou He-Shuai,Hou Ya-Li,Yang Zhong-Hua,Quan Can

Carbonyl reductase, as biocatalyst, is very important to chiral alcohols production through asymmetric reduction of carbonyl compound. A novel thermal stable carbonyl reductase from Bacillus cereus (BcCR) dependant on NADPH was obtained through a new genome mining strategy proposed in this work. By analyzing its amino acid sequence and structure, the BcCR should be a thermal stability and wide pH tolerance carbonyl reductase. Its gene was cloned by PCR with B. cereus genomic DNA as template. Its heterologous expression system, E. coli BL21 (DE3) plysS/pET28a- bccr , was constructed, and BcCR was successfully expressed. Enzymatic properties show that at 57.5 °C and pH 7.0 it can reach maximum reaction rate. Its K m and V max to ethyl 4-chloroacetoacetate is 1.85 mmol/L and 0.22 µmol/(min·mg protein ), respectively. It can catalyze the asymmetric reduction of the β-carbonyl compound, such as ethyl 4-chloroacetoacetate to ethyl S -4-chloro-3-hydroxybutyrate. This paper proposes a practical method for discovery of new carbonyl reductases, and provides a novel enzyme as biocatalyst for asymmetric reduction of β-carbonyl compound.

研究领域: 生物化学 · 酶工程 · 合成生物学
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APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY · 2024 · IF 3.1

Solvent-Free Enzymatic Synthesis of Ethyl 3-Oxobutyrate Derivative: Characterization and Optimization of Reaction Condition

Wang Yun,Chen Li-Mao,Liao Xiao-qing,Zhang Guo-huan,Zhang Jie

It was first found that porcine pancreatic lipase (PPL) could catalyze the Knoevenagel condensation of aromatic aldehydes and ethyl acetoacetate under solvent-free conditions in this paper. Under solvent-free conditions, the highest yield of PPL catalytic reaction was 99.38%, and the Z/E selectivity of the product was 3.93. In addition, the reaction conditions were optimized, and the factors affecting the product structure were studied.

CAS / MDL: 67-48-1 147-85-3
研究领域: 生物化学 · 酶工程
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