ChemSusChem
·
2017
·Vol. 10
·期 4
·711-719
·
IF 7.226
Shanshan Li,Fang Chen,Ning Li,Wentao Wang,Xueru Sheng,Aiqin Wang,Yu Cong,Xiaodong Wang,Tao Zhang
Graphical Green triketones : Renewable C 9 –C 12 triketones with repeating [COCH 2 CH 2 ] units are synthesized in high carbon yields (ca. 90 %) over a cost-effective and reusable Au/TiO 2 catalyst. The triketones as obtained can be used as feedstocks in the production of conducting or semi-conducting polymers. Furthermore, they can also be converted to diketones or jet-fuel range branched cycloalkanes with high densities and low freezing points. A series of renewable C 9 –C 12 triketones with repeating [COCH 2 CH 2 ] units were synthesized in high carbon yields (ca. 90 %) by the aqueous-phase hydrogenation of the aldol-condensation products of 5-hydroxylmethylfurfural (HMF) and ketones over an Au/TiO 2 catalyst. Compared with the reported routes, this new route has many advantages such as being environmentally friendly, having fewer steps, using a cheaper and reusable catalyst, etc. The triketones as obtained can be used as feedstocks in the production of conducting or semi-conducting polymers. Through a solvent-free intramolecular aldol condensation over solid-base catalysts, the triketones were selectively converted to diketones, which can be used as intermediates in the synthesis of useful chemicals or polymers. As another application, the tri- and diketones can also be utilized as precursors for the synthesis of jet-fuel range branched cycloalkanes with low freezing points (224–248 K) and high densities (ca. 0.81 g mL −1 ).
研究领域:
化学工程
·
可再生能源
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2020
·
IF 4.982
Kuan Ding,Hao Zhou,Yiling Wan,Yong Huang,Yuming Zhang,Xun Hu,Hong Zhang,Shu Zhang
Ketonization of biomass-derived oxygenates provides an efficient way for bio-oil upgrading. However, little information on the ketonization of oxygen-rich sugars has been reported, leaving the deep deoxygenation of biomass an unsolved challenge. To address the problem, this paper investigated the catalytic pyrolysis of xylose over nano-CeO 2 using an analytical pyrolyzer . Results showed that upon the addition of CeO 2 , multi-functional oxygenated compounds from xylose pyrolysis were majorly reformed to mono-functional ketonic products, resulting in a 5-fold increase in peak area of ketones . Among them, acetone and 2-butanone presented the highest selectivity of 51% with the CeO 2 to xylose ratio of 10:1 at the temperature of 600 °C. Meanwhile, the short-chain oxygenates, i.e. C 2 -C 3 aldehydes and alcohols, had been converted into C 3 -C 5 ketones, indicating an outstanding ability of chain-increasing over CeO 2 . Both the catalyst dosage and the pyrolysis temperature play a vital role during the ketonization process. The reaction mechanism was proposed according to the experimental results, in which three major reaction pathways were analyzed. This study demonstrates that ketonization of biomass-derived sugars is a promising method for oxygen removal and carbon chain increase, thus improving the bio-oil quality.
研究领域:
生物质能
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Chinese Journal of Natural Medicines
·
2020
·
IF 2.014
Yong-Jiang WANG,Li WANG,Xin HE,Dong-Dong XU,Jun TANG,Ya-Tuan MA,Yi-Jun YAN,Yu-Cheng GU,Jing YANG,Sheng-Xiong HUANG
Inthomycins are polyketide antibiotics which contain a terminal carboxamide group and a triene chain. Inthomycin B ( 1 ) and its two new analogues 2 and 3 were isolated from the crude extract of Streptomyces pactum L8. Identification of the gene cluster for inthomycin biosynthesis as well as the 15 N -labeled glycine incorporation into inthomycins are described. Combined with the gene deletion of the rare P450 domain in the NRPS module, a formation mechanism of carboxamide moiety in inthomycins was proposed via an oxidative release of the assembly chain assisted by the P450 domain.
研究领域:
微生物学
·
生物化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Jiayuan Sun,Shanshan Shao,Xinggang Hu,Xiaohua Li,Huiyan Zhang
The aqueous fraction of bio-oil from biomass fast pyrolysis mainly contains low-molecular-weight oxygenates such as carboxylic acids, ketones, aldehydes, phenols, and furans. In this study, the full components of aqueous bio-oil are directionally converted into carbonyl groups such as aldehydes and ketones, and then the oxygen-containing precursors of aviation fuel are prepared through coupling, focusing on exploring the mechanism of carbonylation and C–C coupling. Studies have revealed that propionic acid, furfural, and phenol can be directionally converted into ketones, in which reaction 3-pentanone, cyclopentanone, and cyclohexanone were formed via ketonization and hydrogenation in the aqueous phase. Then the two components of 3-pentanone, cyclopentanone, cyclohexanone, acetone, and acetaldehyde were subjected to aldol condensation to explore the C–C coupling mechanism in the preparation of the C7–C18 precursor of aviation fuel. The mechanism in the high-quality utilization of all components of the aqueous phase bio-oil fraction was explored, which was favorable for the synthesis of biomass-based aviation fuel.
研究领域:
化学工程
·
可再生能源
·
生物质转化
✓ 已验证
产品关联
DOI
高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Shanshan Shao,Pengfei Zhang,Xianliang Xiang,Xiaohua Li,Huiyan Zhang
Ketonization of bagasse pyrolysis gas was performed over red mud-based oxides. The maximum yield of ketones in the catalytic conversion of bagasse pyrolysis gas over original red mud was 18.66% at 420 °C. To promote the oxidability of red mud and obtain a higher yield of ketones, the effect of metal oxides (CeO 2 , MnO 2 , TiO 2 , CaO, ZrO 2 ) loading and loading amount of CeO 2 on red mud on ketonization of bagasse pyrolysis gas were studied. The highest yield of ketones of 27.86% was obtained over red mud-based oxides with 40 wt% CeO 2 loading. The oxidability of the catalyst was enhanced greatly by the high loading of CeO 2 , leading to the peroxidation of acetone as the side reaction. To control the oxidability and cut costs, bimetallic oxides were loaded on red mud. The yield of ketones reached 30.12% over the composite red mud catalyst with the loading of 20 wt% CeO 2 and 20 wt% MnO 2 . The rough coating of MnO 2 on the surface of red mud was beneficial to the loading of CeO 2 , resulting in smaller and more uniform grains. This study provides the efficient utilization of red mud and biomass as solid wastes for high-valued chemicals and fuels.
研究领域:
能源与环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2021
·
IF 5.455
Zijun Yang,Qiang Yu,Yonghua Guo,Xiaoxia Wu,Hua Wang,Jinyu Han,Qingfeng Ge,Xinli Zhu
Heteroatom metal-zeolite, with heteroatom metal (oxide) dispersed in the zeolite framework, enables the reactions typically catalyzed by bulk metal oxide counterpart but with maximized the atomic utilization. However, the distribution of heteroatoms in the framework is strongly influenced by the preparation method. In this work, Ti-Beta zeolites were postsynthesized using the recrystallization (Ti-Beta-Re) and solid-state ion-exchange (Ti-Beta-SSIE) methods. Characterizations showed that more Ti species were incorporated in the tetrahedral framework site of Ti-Beta-Re to form Lewis acid sites than in that of Ti-Beta-SSIE. In addition, intra-crystallite mesopores were developed in Ti-Beta-Re due to partial dissolution of BEA framework during alkaline etching and subsequent recrystallization of the etched framework. These zeolites were then tested for ketonization of biomass derived propionic acid at 350 °C and atmospheric pressure. The turnover frequency of ketonization was found to be 25% higher on Ti-Beta-Re (0.25 min −1 ) than on Ti-Beta-SSIE (0.20 min −1 ), whereas the apparent activation energy of 80 kJ/mol on Ti-Beta-Re is lower than 95 kJ/mol on Ti-Beta-SSIE. Moreover, the selectivity of 3-pentanone kept > 95% on Ti-Beta-Re while it dropped to ∼63% on Ti-Beta-SSIE with increase of reaction time at a space time of 2 h. This work demonstrated that the tetrahedrally coordinated Ti species are the active sites and the presence of intra-crystallite mesopores facilitates selective ketonization of carboxylic acids.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2022
·
IF 8.129
Yiling Wan,Kuan Ding,Jason Chun-Ho Lam,Daoxu Zhong,Shu Zhang
Catalytic pyrolysis of biomass over CeO 2 to prepare ketonic chemicals is an important way to achieve carbon emission reduction, whereas the role of catalyst structure has long been overlooked. In this work, nano-CeO 2 with different crystal shapes, namely nanorods (R-CeO 2 ), nano-polyhedra (P-CeO 2 ), and nanocubes (C-CeO 2 ), were synthesized and then tested in catalytic ketonization of xylan . Results showed that among all the three catalysts, C-CeO 2 produced the highest yield of ketones . Characterization results revealed that C-CeO 2 presented the lowest content of oxygen vacancies while exhibiting the highest proportion of {100} facets, proving that the {100} facets made a greater contribution to the total yield of ketones . On the other hand, P-CeO 2 and R-CeO 2 displayed a better selectivity to linear ketones, which was beneficial to improving the product quality. The relative contents of {111} facets of these catalysts were higher than C-CeO 2 , demonstrating that the {111} facets could selectively produce linear ketones. The proposed mechanism indicated that P-CeO 2 and R-CeO 2 principally enhanced the ketonic deoxygenation reactions, while C-CeO 2 also promoted the recyclization reaction, producing more cyclic ketones . These findings disclose that the {111} facets of CeO 2 are more favorable to producing valuable linear ketones.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
·
2020
·
IF 4.192
Yu-Qi Gao,Shuang-Tian Du,Jian Xiao,Da-Cheng Wang,Wen-Bo Han,Qiang Zhang,Jin-Ming Gao
Two biosynthetically related new metabolites, eucalyptacid A (1) and eucalactam B (2), along with six known compounds (3–8), eugenitol (3), cytosporone C (4), 4-hydroxyphenethyl alcohol (5), 1-(4-hydroxyphenyl)ethane-1,2-diol (6), N-(2-hydroxy-2-phenylethyl)acetamide (7), and phomopene (8), were isolated from the solid rice cultures of the endophytic fungus Diaporthe eucalyptorum KY-9 that had been isolated from Melia azedarach. Also, two further new derivatives (2a, 2b) were prepared from 2. The structures were elucidated by exhaustive analysis of NMR and ESIMS data and chemical methods such as Marfey’s protocol. Compound 1 was identified as a rare polyketide fatty acid, (8E)-3,5,11-trihydroxy-2,10,12-trimethyltetradecenoic acid, and 2 was determined to be the first cyclic depsipeptide containing the same fatty acid unit as 1 and a Gly-Gly-Thr tripeptide chain. Its N-terminal end is N-acylated by an 11-hydroxy fatty acid with a branch alkyl chain of 14:1. The 11-hydroxyl group connects to the carboxylic group of the C-terminal amino acid to form a 22-membered lactone ring. A hypothetical biosynthetic pathway for the new polyketides is proposed. The isolated compounds were assayed for their inhibition against four plant pathogenic fungi, Alternaria solani, Botrytis cinerea, Fusarium solani, and Gibberella saubinettii. Compounds 1, 4, 6, and 7 exhibited antifungal activities against Alternaria solani, with minimal inhibitory concentration (MIC) values from 6.25 to 50 μM. Thus, strain KY-9 represents an untapped source for the development of biological control agents to prevent the infection of pathogenic fungus A. solani.
研究领域:
植物学
·
微生物学
·
药理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MOLECULES
·
2021
·Vol. 26
·期 8
·2115
·
IF 4.412
Jiayong Huang,Zhenshuo Yan,Peiling Qiu,Yufeng Mo,Qizhen Cao,Qiuhong Li,Lini Huo,Lichun Zhao
A new coumarin-acridone fluorescent probe S was designed and synthesized, and the structure was confirmed with1H/13C NMR spectrometry, single-crystal X-ray diffraction, and high-resolution mass spectrometry. This probe has high sensitivity and selectivity for Fe3+over other testing metal ions at 420 or 436 nm in acetonitrile–MOPS (3-Morpholinopropanesulfonic Acid) buffer solution (20.0 μM, pH = 6.9, 8:2 (v/v)). Under physiological conditions, the probe displayed satisfying time stability with a detection limit of 1.77 µM. In addition, probe S was successfully used to detect intracellular iron changes through a fluorescence-off mode, and the imaging results of cells and zebrafish confirmed their low cytotoxicity and satisfactory cell membrane permeability, as well as their potential biological applications.Keywords:Fe3+detection;bioimaging;coumarin-acridone compound
研究领域:
分析化学
·
生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Shanshan Shao,Xianliang Xiang,Xiaohua Li,Huiyan Zhang,Rui Xiao,Yixi Cai
Acetic acid, n-butyraldehyde, furfural, n-butanol, and ethyl acetate as model compounds of biomass pyrolysis vapors were selected as reactants for ketonization over CeO2. Catalytic conversion of single components was conducted to understand their ketonization characteristics and also to obtain the overlapped temperature range. The results showed that the yield of acetone from directional ketonization of acetic acid reached a maximum of 97.4% at 360 °C over CeO2 with numerous oxygen vacancies, while n-butyraldehyde, n-butanol, and ethyl acetate performed the best at 420 °C with limited yield of ketones of 47.2, 35.1, and 85.4%, respectively. At the overlapped 420 °C, owing to the dehydration of acetic acid molecules, the ketonization of n-butyraldehyde was promoted with the largest overall yield of ketones of 96.5%. A mixture of furfural/acetic acid (1:4) brought about a lower yield of ketones of 78.8%, indicating a negative synergism due to active sites occupation by furfural adsorption.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2023
·
IF 7.3
Zijun Yang,Qiang Yu,Hua Wang,Qingfeng Ge,Xinli Zhu
Ketonization of propionic acid has been investigated on Lewis acidic TS-1 and Ti-Beta zeolites to understand the reaction mechanism and effects of pore topology and hydrophobicity. Characterizations showed that TS-1 and Ti-Beta (Si/Ti = 40) exhibited a similar acidity whereas TS-1 was more hydrophobic than the silanol-rich Ti-Beta. TS-1 showed higher activity, selectivity, stability and was more resistance to H 2 O than Ti-Beta. A combination of infrared spectroscopic, isotopic and kinetic studies showed that the molecularly adsorbed monodentate propionic acid is the most abundant reactive intermediate, and C-C coupling is the rate-determining step. The mechanism of ketonization of propionic acid at isolated tetrahedral Ti centers can be described by a Langmuir-Hinshelwood model. The turnover rate on TS-1-40 is ∼ 1.3 times higher than that on Ti-Beta-40, which is consistent with the lower fitted free activation energy, i.e., the energy difference between C-C coupling transition state and two co-adsorbed propionic acids at a Ti center. The slightly lower activation enthalpy on Ti-Beta-40 than TS-1-40 is over-compensated by much larger entropy penalty, due to more silanol groups and hydrogen bonded propionic acids in close proximity to the Ti center for Ti-Beta-40, which impose additional steric hindrance to bulkier C-C coupling complex at transition state and outweigh the difference of steric hindrance of pore confinement between MFI and BEA frameworks. This work provides insight into the ketonization mechanism on Lewis acidic zeolites, and indicates that moderate pore size with hydrophobic property promotes ketonization of carboxylic acid at isolated tetrahedral Ti centers confined in zeolites.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
·
2021
·
IF 5.279
Jia-Xu Nan,Jing-Fang Yang,Hong-Yan Lin,Yao-Chao Yan,Shao-Meng Zhou,Xue-Fang Wei,Qiong Chen,Wen-Chao Yang,Ren-Yu Qu,Guang-Fu Yang
Exploring novel p-hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD) inhibitors has become one of the most promising research directions in herbicide innovation. On the basis of our tremendous interest in exploiting more powerful HPPD inhibitors, we designed a family of benzyl-containing triketone-aminopyridines via a structure-based drug design (SBDD) strategy and then synthesized them. Among these prepared derivatives, the best active 3-hydroxy-2-(3,5,6-trichloro-4-((4-isopropylbenzyl)amino)picolinoyl)cyclohex-2-en-1-one (23, IC50 = 0.047 μM) exhibited a 5.8-fold enhancement in inhibiting Arabidopsis thaliana (At) HPPD activity over that of commercial mesotrione (IC50 = 0.273 μM). The predicted docking models and calculated energy contributions of the key residues for small molecules suggested that an additional π–π stacking interaction with Phe-392 and hydrophobic contacts with Met-335 and Pro-384 were detected in AtHPPD upon the binding of the best active compound 23 compared with that of the reference mesotrione. Such a molecular mechanism and the resulting binding affinities coincide with the proposed design scheme and experimental values. It is noteworthy that inhibitors 16 (3-hydroxy-2-(3,5,6-trichloro-4-((4-chlorobenzyl)amino)picolinoyl)cyclohex-2-en-1-one), 22 (3-hydroxy-2-(3,5,6-trichloro-4-((4-methylbenzyl)amino)picolinoyl)cyclohex-2-en-1-one), and 23 displayed excellent greenhouse herbicidal effects at 150 g of active ingredient (ai)/ha after postemergence treatment. Furthermore, compound 16 showed superior weed-controlling efficacy against Setaria viridis (S. viridis) versus that of the positive control mesotrione at multiple test dosages (120, 60, and 30 g ai/ha). These findings imply that compound 16, as a novel lead of HPPD inhibitors, possesses great potential for application in specifically combating the malignant weed S. viridis.
研究领域:
植物学
·
药理学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）