NEW JOURNAL OF CHEMISTRY
·
2023
·Vol. 47
·期 23
·11318-11324
·
IF 3.3
Jiazheng Zhu,Chengjie Duan,Sen Ye,Qizhong Zhang,Kun Li,Guangke He,Xiang Liu,Zhiguo Zhang
Exploring synthetic methods and catalysts that are easy to handle, highly active, and low-cost for producing industrially important chemicals is a long-term goal in both science and industry. Herein, we present a general and facile Ni-catalyzed reductive amination of aldehydes/ketones methodology using hydrazine as both nitrogen and hydrogen sources, instead of the traditionally used hydrogen gas and ammonia. The mesostructured alumina-supported Ni catalyst with a relatively high ratio of Ni0 and small-sized Ni nanoparticles plays a critical role in this transformation, resulting in 55 aldehydes/ketones successfully converting to their corresponding primary amines with 61–99% yields. This work outlines a low-cost yet robust catalytic methodology for the facile and general synthesis of primary amines for practical laboratory and industrial application.
研究领域:
有机化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Biomass Conversion and Biorefinery
·
2022
·
IF 4.05
Li Zhengsheng,Shao Shanshan,Hu Xinggang,Li Xiaohua,Cai Yixi
The catalytic conversion of renewable biomass-derived aldehydes and ketones to aviation fuels is very attractive for sustainable development. We provided insight into the production of aviation fuel from typical biomass carbonyl platform compounds (furfural, acetone, butanone, and butyraldehyde) by aldol condensation followed with hydrodeoxygenation over bifunctional catalyst Ni/Mg–Al-O/AC, focusing on the mechanism of condensation reaction. It was found that high temperature is not only conducive to aggravate the depth of aldehyde ketone condensation reaction, further convert dimer to trimer, but also promote its self-condensation. The optimal condensation temperature of aldehydes and ketones under this idea was 170 °C, the carbon number range of the jet fuel intermediates was C7–C14, and the yield of condensates reached 79.23%. In order to explore the mechanism in the aldol condensation of aldehydes and ketones, the evolution law of typical products was studied by controlling the reaction time, and seven main condensation pathways were proposed. The ratios of aldehyde/ketone in the reactant and the ratios of each component within the aldehyde and ketone were adjusted, and it was found that the reaction priority of chain aldehydes is the highest in this reaction system, and the reaction priority of small-molecule ketones with low carbon number is higher than that of high carbon number ketones. The presence of long-chain groups in the hydrogenated oil increased the density of jet fuel, and it has a higher calorific value, which are very promising as aviation fuels or additives of aviation bio-fuels.
研究领域:
能源化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ChemCatChem
·
2022
·Vol. 14
·期 6
·e202101794
·
IF 5.497
Longfei Zhu,Sen Ye,Jing Wang,Jiazheng Zhu,Guangke He,Xiang Liu
Graphical Hydrogen pool : Recyclable Ir/ZnO-catalysed additive-free transfer hydrogenation of aldehydes and ketones using methanol as hydrogen source was achieved at 110 °C, delivering alcohols in up to 98 % yield. The fine cooperation of ZnO and positively charged IrO x enables the complete cleavage of O−H and less reactive C−H bonds of methanol to generate active H for carbonyl hydrogenation. The use of methanol as abundant and low-toxic hydrogen source under mild and clean conditions is promising for the development of safe and sustainable reduction processes, but remains a daunting challenge. This work presents a recyclable ZnO-supported Ir catalyst for the additive-free transfer hydrogenation of aldehydes and ketones using methanol as hydrogen source at 110 °C, delivering alcohols in up to 98 % yield. Mechanistic studies disclose that methanol is first dehydrogenated to formaldehyde and then fully decomposed into active hydrogen species for hydrogenation. The superior performance is related to the high ratio of positively charged IrO x species and their ultrafine dispersion over ZnO. And the delicate cooperation of IrO x and ZnO enhances the catalytic activities for the selective scission of O−H and less reactive C−H bonds in methanol, maintaining a good balance between methanol decomposition and C=O hydrogenation in this green transfer hydrogenation.
研究领域:
化学催化
·
绿色化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
BIOMASS & BIOENERGY
·
2022
·
IF 5.774
Shanshan Shao,Chengyue Liu,Xianliang Xiang,Xiaohua Li,Huiyan Zhang,Rui Xiao
Catalytic upgrading of pyrolysis gas components from cellulose and xylan was investigated over ZrO 2 catalyst to produce aldehydes and ketones . The oxygen content in the bio-oil was reduced by aldol condensation and hydrogenation of aldehydes and ketones. The optimal pyrolysis temperature of cellulose and xylan were determined to be 400 °C and 350 °C and the carbon yields of aldehydes and ketones reached 54.49% and 52.05% respectively. In order to explore the formation mechanism of aldehydes and ketones, the evolution of typical products by controlling the reaction time was studied. The catalytic pyrolysis was complete and the product content was maximum at 20 min H 2 O played a role in providing oxygen atoms and increasing ZrO 2 reaction activity in the carbonylation process. The binding energy of the catalyst was calculated as −15.69 kcal/mol by density functional theory (DFT). It was found that the presence of water can remove the coke on the catalyst surface and increase the activity of ZrO 2 . The yield of aldehydes and ketones reached 58.17% and 55.85% of cellulose and xylan with the presence of 15 wt% H 2 O in the carbonylation process. According to the evolution of the above experimental products, the generation pathways of four main carbonylation products (acetone, methyl ethyl ketone , butyraldehyde and furfural) were proposed. Through this research, the effective utilization of biomass could be realized.
研究领域:
能源与环境科学
·
催化化学
✓ 已验证
DOI
高影响因子
JOURNAL OF CHEMICAL RESEARCH
·
2013
·
IF 0.596
Xiao-Chuan Jia,Jing Li,Zhi-Rui Yu,Yu-Hu Wang,Lei Zhou,Yan-Yan Yu
Deprotection of phenylhydrazones and tosylhydrazones to their parent aldehydes and ketones has been accomplished using iodobenzene as catalyst in the presence of mCPBA as the terminal oxidant at room temperature. The reaction is general, and the target products can be obtained in good to excellent yields.
研究领域:
有机化学
·
合成化学
✓ 已验证
DOI
高影响因子
Systems Microbiology and Biomanufacturing
·
2022
·
IF 0
Zhu Jiufeng,Bai Yajun,Fan Tai-Ping,Zheng Xiaohui,Cai Yujie
Ethyl ( R )-4-chloro-3-hydroxybutyrate (( R )-CHBE), as a chiral intermediate, is widely used in the synthesis of various chiral drugs. In this study, we screened two aldo–keto reductases (LP-AKRs) from the probiotic Lactobacillus plantarum DSM20174, both with a molecular weight of approximately 31 kDa. Both enzymes could reduce 4-chloroacetoacetic acid ethyl ester (COBE) to produce ( R )-CHBE with an enantioselectivity value of 99%. When determining the kinetic parameter, the K m , K cat , and V max of LP-AKR5 and LP-AKR9 were 9.5 mM, 7.6 U/mg, 3.96 s −1 and 8.7 mM, 8.59 U/mg, 4.47 s −1 , respectively. Both LP-AKR5 and LP-AKR9 had an optimal reaction pH of 6 and could maintain a high level of stability at pH 6, allowing them to perform well in an acidic environment. LP-AKR5 and LP-AKR9 had optimal reaction temperatures of 30 °C and 40 °C, respectively. Metal ions had minimal influence on LP-AKR5 and LP-AKR9 enzyme activities. This series of enzymatic properties showed that LP-AKR5 and LP-AKR9 mined from Lactobacillus plantarum DSM20174 could asymmetrically catalyze the synthesis of ( R )-CHBE under weakly acidic circumstances, which could maintain product stability and provide a good foundation for industrial production.
研究领域:
生物化学
·
分子生物学
·
工业微生物学
✓ 已验证
DOI
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Lingzhi Zhang,Rui Zhou,Dekai Liu,Meinan Zhu,Guangya Zhang,Lijuan Zhang,Shu-Feng Zhou,Wei Jiang
Given their outstanding efficiency and selectivity, enzymes are integral in various domains such as drug synthesis, the food industry, and environmental management. However, the inherent instability of natural enzymes limits their widespread industrial application. In this study, we underscore the efficacy of enhancing protein thermal stability through comprehensive protein design strategies, encompassing elements such as the free energy of protein folding, internal forces within proteins, and the overall structural design. We also demonstrate the efficiency and precision of combinatorial screening in the thermal stability design of aldo-keto reductase (AKR7-2-1). In our research, three single-point mutations and five combinatorial mutations were strategically introduced into AKR7-2-1, using multiple computational techniques. Notably, the E12I/S235I mutant showed a significant increase of 25.4 °C in its melting temperature ( Tm ). Furthermore, the optimal mutant, E12V/S235I, maintained 80 % of its activity while realizing a 16.8 °C elevation in Tm . Remarkably, its half-life at 50 °C was increased to twenty times that of the wild type. Structural analysis indicates that this enhanced thermal stability primarily arises from reduced oscillation in the loop region and increased internal hydrogen bonding. The promising results achieved with AKR7-2-1 demonstrate that our strategy could serve as a valuable reference for enhancing the thermal stability of other industrial enzymes.
研究领域:
生物化学
·
分子生物学
·
工业酶工程
✓ 已验证
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Yalin Yang,Zheyan Chen,Hanlin Huang,Yuxin Liu,Junhua Zou,Shuqi Shen,Jiawei Yan,Jinshui Zhang,Zanyong Zhuang,Zhongzhen Luo,Chengkai Yang,Yan Yu,Zhigang Zou
Halide perovskites and derivatives have been used as emerging photocatalysts due to their unique optoelectronic and structural diversity. However, compared with the well-explored photophysical processes for light-driven more energetic carriers to trigger redox reactions, catalytic effects on the surface of halide perovskite or their derivatives for chemical transformations between reactive species are seldom addressed, which is equally important for improving the efficiency for halide perovskite-based photocatalysts. Here, we demonstrate that Cs 3 Bi 2 Br 9 sites in the Cs 3 Bi 2 Br 9 /CdS heterojunction, not only participate in light-driven processes, but also play a vital role for the activation and conversion of key intermediates during C(sp 3 )-H bond transformation, via a more thermodynamically and kinetically favorable surface reaction pathway. Besides, various aromatic hydrocarbons can be effectively photocatalytic converted to corresponding aldehydes/ketones as major products. This work highlights the importance of surface catalysis mechanism in photocatalysis not only for halide perovskites but also for other semiconductors.
研究领域:
材料科学
·
化学工程
·
光化学
✓ 已验证
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Qianqian Xu,Xueru Sheng,Na Li,Jian Zhang,Haiqiang Shi,Meihong Niu,Qingwei Ping,Ning Li
For the first time, ball-milling was introduced as an efficient process for the condensation of biomass-derived cyclopentanone using commercial CaO as a catalyst. Compared with traditional magnetic stirring methods (“heat input” methods), ball-milling is an alternative “energy input” method. CaO dosage, rotation speed, and reaction time were investigated for optimal condition screening, and the ball-milling method could achieve a high yield (98.9%) and a high selectivity (99.2%) under lower energy demand conditions at mild temperature (∼40 °C). Moreover, the power hypothetically needed for dimer per mole (E2) of the ball-milling method was comparable or even lower than that for the magnetic stirring method after our assessment. In addition, we also explored the applicability of the ball-milling method for the condensation of other biomass-derived aldehydes and ketones. Competitive yield was obtained using heterogeneous CaO as a catalyst. Due to the intense stirring in ball-milling, the CaO catalyst was mixed uniformly with reactants, and higher surface area was also obtained due to the decrease of the particle size during the ball-milling method, which may also benefit the reaction and increase the catalytic activity. This way would tally with the concept of green chemistry and economic efficiency, which has the potential for industrial applications.
研究领域:
化学工程
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Shanshan Shao,Yu Cao,Zian Ye,Xiaohua Li,Huiyan Zhang,Rui Xiao
This work proposes an effective method for the utilization of agricultural residues and red mud (RM) to produce the carbonyl platform compounds for the synthesis of high-value biofuels. The carbonyl platform compounds were synthesized by catalytic upgrading of pyrolysis vapor from holocellulose over RM composite catalyst. The maximized yield of aldehydes and ketones was obtained with the cellulose-to-hemicellulose mass ratio of 3:2, which was consistent with that of bagasse. Two types of RM were selected for the carbonylation of pyrolysis vapors, in which the type prepared by Bayer process containing more Fe 2 O 3 exhibited better carbonylation performance. The ZrO 2 -loaded RM composite catalyst was prepared, and it was found that the yield of aldehydes and ketones was greatly boosted. Finally, RM composite catalysts supported by five individual metal oxide were prepared, the correlation between the oxidizability of catalyst and the aldehyde/ketone mole ratio was established, and it was revealed that the stronger oxidizability of the composite catalysts was usually accompanied with the decreased aldehydes/ketones mole ratio. Biomass and RM wastes were used as resources in this study, this waste-to-energy idea contributes to optimizing the utilization of waste and promoting the production of biofuels.
研究领域:
能源与环境科学
·
催化化学
✓ 已验证
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 9
·4464-4471
·
IF 3.591
Bo Li,Yanxin Wang,Quan Chi,Ziliang Yuan,Bing Liu,Zehui Zhang
The selective synthesis of imines from biomass-derived chemicals over heterogeneous non-noble metal catalysts is of great importance for organic transformation. Herein, non-noble heterogeneous nitrogen-doped carbon supported Ni catalysts (abbreviated as Ni/CN–MgO-T, where T represents the pyrolysis temperature) have been facilely prepared from the simple pyrolysis of Ni precursors and biomass, and Ni/CN–MgO-600 with the smallest size of Ni nanoparticles demonstrated the highest catalytic activity. The reductive coupling of nitroarenes and carbonyl compounds could be performed under mild conditions (80 °C, and 10 bar H2), affording structurally-diverse imines with high to excellent yields (84.2–98.1%). Thanks to the mild reaction conditions, the developed method showed good tolerance to other functional groups such as nitriles, halogen and vinyl groups.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
Royal Society Open Science
·
2019
·Vol. 6
·期 2
·
IF 2.515
Xiu Chen,Quan Shi,Xibin Zhou,Xuezheng Liu
Aldehydes and ketones (AKs) in cigarette smoke are risk to humans and environment. Due to the complexity of itself and the interference of the smoke tar matrix, the aldehydes and ketones in particle phase (AKPs) of mainstream smoke (MSS) and sidestream smoke (SSS) have not been well investigated. In this study, the AKPs of MSS and SSS were derivatized into polar products by reaction with Girard T reagent. The derivatives were isolated rapidly by column chromatography and analysed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Fifteen species of aldehydes and ketones were detected by positive ion electrospray ionization (ESI) FT-ICR MS: O1–6, N1O1–4, N2O1–3 and N3O2–3. The total number of AKPs obtained by ESI FT-ICR MS in MSS and SSS is about 1100 and 970, respectively. After hydrolysis, the original AKPs were obtained and 63 carbonyls were identified and quantified by gas chromatography–mass spectrometry (GCMS). The nitrogen-containing and high-oxygen AKPs were further characterized by Orbitrap mass spectrometry. Structures of compounds with high relative abundance in the mass spectrum were speculated (e.g. a series of degradants of cembrenediol) by comparison with the results of GCMS.
研究领域:
化学
·
环境科学
·
公共卫生
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）