ChemSusChem
·
2014
·Vol. 7
·期 10
·2889-2897
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IF 7.117
Yong Yang,Mei Wang,Liqin Xue,Fengbo Zhang,Lin Chen,Mårten S. G. Ahlquist,Licheng Sun
Graphical Nickel is the answer: A noble-metal-free molecular system that comprises a Ni complex that bears internal bases, fluorescein as a cheap light harvester, and triethylamine, displays a turnover number up to 3230 in H 2 evolution in aqueous solutions. A Ni complex with internal bases that contain bipyridine-derived ligands, [Ni(L) 2 (H 2 O) 2 ](BF 4 ) 2 ([ 1 ](BF 4 ) 2 , L=2-(2-pyridyl)-1,8-naphthyridine), and a reference complex that bears analogous bipyridine-derived ligands but without an internal base, [Ni(L′) 3 ](BF 4 ) 2 ([ 2 ](BF 4 ) 2 , L′=2-(2-pyridyl)quinoline), were synthesized and characterized. The electrochemical properties of these complexes were studied in CH 3 CN, H 2 O, and a mixture of EtOH/H 2 O. The fluorescence spectroscopic studies suggest that both dynamic and the sphere-of-action static quenching exist in the fluorescein Fl 2− /[ 1 ] 2+ and Fl 2− /[ 2 ] 2+ systems. These noble-metal-free molecular systems were studied for photocatalytic H 2 generation. Under optimal conditions, the turnover number of H 2 evolution reaches 3230 based on [ 1 ] 2+ , whereas [ 2 ] 2+ displays only approximately one third of the turnover of [ 1 ] 2+ . A plausible mechanism for the catalytic H 2 generation by [ 1 ] 2+ is presented based on DFT calculations.
研究领域:
化学
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可再生能源
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催化科学
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DOI
高影响因子
CHINESE JOURNAL OF CHEMISTRY
·
2017
·Vol. 36
·期 2
·147-152
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IF 1.852
Qing-Wen Song,Ping Liu,Li-Hua Han,Kan Zhang,Liang-Nian He
One-pot two-step stepwise reaction of terminal propargylic alcohols, carbon dioxide, and primary/secondary amines for the effective synthesis of various urethanes through robust silver-catalysed C-O/C-N bond formation is reported. Catalytic activities were investigated by controlling catalyst loading, reaction pressure and time, and very high turnover number (turnover frequency) was obtained: 3350 (35 h −1 ) with 0.01 mol% silver catalyst under 0.1 MPa, and up to 13360 (139 h −1 ) with 0.005 mol% silver catalyst under 2.0 MPa at room temperature. The strategy was ingeniously regulated, and synchronously afforded a wide range of β-oxopropylcarbamate and 1,3-oxazolidin-2-one motifs in excellent yields and selectivity together with unprecedented high turnover number (TON) and turnover frequency (TOF) value.
研究领域:
化学
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材料科学
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DOI
高影响因子
ChemCatChem
·
2019
·Vol. 12
·期 4
·989-994
·
IF 4.495
Yunjian Ma,Yongru Li,Shahid Ali,Peilin Li,Wuyuan Zhang,Marine C. R. Rauch,Sébastien J.-P. Willot,Doris Ribitsch,Young Hae Choi,Miguel Alcalde,Frank Hollmann,Yonghua Wang
Graphical Natural Deep Eutectic Solvents : Envisioned bienzymatic cascade for the selective oxyfunctionalisation of ethyl benzene or cis-ß-methylstyrene comprising the evolved peroxygenase from Agrocybe aegerita (r Aae UPO) and choline oxidase from Arthrobacter nicotianae ( An ChOx) to provide r Aae UPO with H 2 O 2 . Natural deep eutectic solvents (NADES) are proposed as alternative solvents for peroxygenase-catalysed oxyfunctionalization reactions. Choline chloride-based NADES are of particular interest as they can serve as solvent, enzyme-stabiliser and sacrificial electron donor for the in situ H 2 O 2 generation. This report provides the first proof-of-concept and basic characterisation of this new reaction system. Highly promising turnover numbers for the biocatalysts of up to 200,000 have been achieved.
研究领域:
生物化学
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酶工程
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绿色化学
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DOI
高影响因子
DALTON TRANSACTIONS
·
2016
·Vol. 45
·期 9
·3814-3819
·
IF 4.177
L. L. Zhang,Y. Gao,Z. Liu,X. Ding,Z. Yu,L. C. Sun
A trinuclear ruthenium complex, 3, was designed and synthesized with the ligand 2,2′-bipyridine-6,6′-dicarboxylic acid (bda) and we found that this complex could function as a highly efficient molecular catalyst for water oxidation in homogeneous systems. This trinuclear molecular water oxidation catalyst, 3, displayed much higher efficiencies in terms of turnover numbers and initial oxygen evolution rate than its counterparts, a binuclear catalyst, 2, and a mononuclear catalyst, 1, in both chemically driven and photochemically driven water oxidation based on either the whole catalytic molecules or just the active Ru centers. The reasons for the superior performance of catalyst 3 were discussed and we believe that multiple Ru centers in a single molecule are indeed beneficial for increasing the probability of the formation of O–O bonds through an intramolecular radical coupling pathway.
研究领域:
化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
He Huang,Huahua Fan,Yuzhen Ge,Wanyue Ye,Yingcen Liu,Caicheng Song,Hua Lin,Xiaotong Zhang,Bing Li,Xiaowa Nie,Shufen Zhang,Rongwen Lu
The selective oxidation of the primary C H bonds in hydrocarbons to corresponding high-valued oxygenates is highly desired but challenging to realize. The difficulty arises from the high homolytic bond dissociation enthalpy of the C H bond, the relatively high reactivity of oxygenated intermediates, and the diversity of resultant products. Herein, we reported the in situ confinement of Au clusters in Silicalite-1 for the selective solvent-free oxidation of toluene to benzaldehyde. The doping of an alkali metal (K or Na) resulted in the formation of electron-rich Au species, which readily facilitate the activation of oxygen, In turn, toluene is activated by the produced reactive oxygen species in a single step, as confirmed through density functional theory (DFT) calculations. At optimal alkali metal doping, the selectivity to benzaldehyde could reach > 90 %, with the toluene conversion being 19.8 %. Remarkably, the total turnover number (TTN) of Au@Silicalite-1–0.2 K was found to be 29,658, which is one or two orders of magnitudes higher than the previously reported values. These findings are expected to inspire the design of highly efficient catalysts for the activation of fundamental feedstock with C H bonds.
研究领域:
催化
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化学工程
·
材料科学
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产品关联
DOI
高影响因子
TALANTA
·
2021
·
IF 6.057
Lijun Xu,Dongguo Xue,Jialin Sai,Lu Zhou,Renjun Pei,Aihua Liu
Although enzyme mimics have been widely developed, limited catalytic efficiency is still a bottleneck, especially under neutral condition. Herein, we reported the bioactive quinaldic acid (QA) significantly boosted the peroxidase-like activity of Co 2+ in the presence of bicarbonate (HCO 3 − ). With 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonate) (ABTS) as the substrate, the catalytic activity of Co 2+ (1 μM) was increased by over 300 times upon adding 100 μM QA. The formed Co 2+ complex had much higher turnover number (5.52 min −1 ) than that of cobalt-based nanozymes (0.011–0.51 min −1 ) in decomposing H 2 O 2 . Based on this system, ultrasensitive colorimetric methods for the detection of Co 2+ , bicarbonate and urease activity were achieved with limits of detection of 4.6 nM, 40 μM and 0.00125 U/mL, respectively. For the first time, this work established an ultrasensitive method for the detection of urease activity by activating a peroxidase-like mimic with the produced HCO 3 − .
研究领域:
分析化学
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生物化学
·
催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Saudi Chemical Society
·
2019
·
IF 2.759
Pengwei Gao,Yongmei Xiao,Zhenhua Dong,Hongguo Pan,Wentao Wang
By using urea linked porous organic polymers as template, a new nano palladium catalyst with low Pd loading can be easily prepared (1.0 wt% Pd only). Although such less amount of Pd was contained in this new catalyst, it is still an effective catalyst for the Suzuki-Miyaura coupling of aryl iodines and aryl boric acids, affording biphenyl products in excellent yields with outstandingly enhanced turnover numbers (up to 10,536) under green solvent (water).
研究领域:
催化
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材料科学
·
有机化学
✓ 已验证
DOI
高影响因子
Chemistry-An Asian Journal
·
2021
·Vol. 16
·期 23
·3957-3962
·
IF 4.568
Lijun Xu,Jialin Sai,Dongguo Xue,Lu Zhou,Renjun Pei,Aihua Liu
Graphical The complex formed by Co 2 + , 8 - hydroxyquinoline and HCO 3 − could act as a robust peroxidase mimic in neutral pH at room temperature. This system provided a universal method for the ultrasensitive colorimetric detection of various 8-hydroxyquinoline-based drugs (e. g., clioquinol) by activating the catalytic activity of Co 2+ . 8-Hydroxyquinoline (8HQ) and its derivatives display diverse bioactivities and therapeutic potentials. In this study, we unveiled that 8HQ can boost the peroxidase-like activity of Co 2+ in the presence of bicarbonate (HCO 3 − ) in neutral pH at room temperature. With 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulphonate) (ABTS) as the substrate, the formed Co 2+ /8HQ/HCO 3 − complex shows robust catalytic activity with the turnover number ( k cat ) tens to hundreds of times higher than that of Co 3 O 4 and other Co 2+ complexes in terms of per cobalt ion. This system was used to design colorimetric sensors for ultrasensitive detection of 8HQ-based drugs by activating the activity of Co 2+ . Take detecting clioquinol as an example, a detection limit of 2.4 nM clioquinol with a linear range from 0.01 to 0.2 μM was obtained. This work not only revealed a new kind of ligand that activated the activity of Co 2+ , but also provided a facile, low-cost, ultrasensitive, easy-to-use, and universal strategy for sensing various 8HQ-based drugs. Further development of this catalytic system might be beneficial to overcome drug resistance by combined medication.
研究领域:
分析化学
·
生物化学
·
药物检测
·
酶模拟
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产品关联
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2018
·Vol. 9
·期 3
·659-671
·
IF 5.365
Yanliang Zhai,Shaolong Zhang,Yunshan Shang,Yu Song,Wenxuan Wang,Tong Ma,Luoming Zhang,Yanjun Gong,Jun Xu,Feng Deng
Herein, a specific core–shell MFI zeolite was designed for the methanol to propylene (MTP) reaction. The core–shell structure of Al-ZSM-5@B-ZSM-5 and Al-ZSM-5@silicalite-1 were easily obtained via a two-step procedure, in which Al-ZSM-5 aggregate acted as the core and B-ZSM-5 or silicalite-1 as the shell. Their core–shell structures, acidity distribution and pore properties were characterized systemically, and new insights were gained into the synergetic effect of acid property and diffusion on the MTP reaction. The Al-ZSM-5@B-ZSM-5 zeolite exhibited a superior catalytic performance with a lifetime of 350 h (WHSV = 3 h−1), propylene selectivity of 49% and high turnover number of 4.3 × 106, while for the Al-ZSM-5 core, the corresponding values were 210 h, 43% and 5.2 × 105, respectively. Al-ZSM-5@silicalite-1 displayed the second best performance with the values of 250 h, 45% and 2.9 × 106, respectively. Gradient strong acid reduction from the core to the shell via the epitaxial growth of the silicalite-1 or B-ZSM-5 shell combined with an appropriate strong/weak acid ratio plays a vital role in inhibiting the hydrogen transfer reaction and thus gives a low consumption of propylene and low coke deposition. For the hydrogen transfer reaction of alkenes to form alkanes and aromatics, strong acid sites are required. Moreover, the acid sites originally existing on the external surface of the Al-ZSM-5 core were converted into internal acid sites due to the formation of an interface zone in the core–shell zeolite, possessing micropore characteristics, which in turn improve the shape selectivity and suppress coke deposition. Especially, the Al-ZSM-5@B-ZSM-5 zeolite displayed more weak acid sites and few strong acid sites on its shell surface, which are beneficial for the low formation of external coke and also account for the highest utilization of acid sites in the MTP reaction, high propylene selectivity and long lifetime.
研究领域:
催化
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化学工程
·
材料科学
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产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-10
·
IF 16.6
Lei Qinqin,Yuan Huiqing,Du Jiehao,Ming Mei,Yang Shuang,Chen Ya,Lei Jingxiang,Han Zhiji
The direct utilization of solar energy to convert CO 2 into renewable chemicals remains a challenge. One essential difficulty is the development of efficient and inexpensive light-absorbers. Here we show a series of aminoanthraquinone organic dyes to promote the efficiency for visible light-driven CO 2 reduction to CO when coupled with an Fe porphyrin catalyst. Importantly, high turnover numbers can be obtained for both the photosensitizer and the catalyst, which has not been achieved in current light-driven systems. Structure-function study performed with substituents having distinct electronic effects reveals that the built-in donor-acceptor property of the photosensitizer significantly promotes the photocatalytic activity. We anticipate this study gives insight into the continued development of advanced photocatalysts for solar energy conversion.
研究领域:
化学
·
材料科学
·
环境科学
·
太阳能转换
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DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Ting Liang,Han Liu,Lanjing Li,Ru Huan,Chunshan Gui
Human organic anion transporting polypeptide 1B3 (OATP1B3) and 1B1 are two liver-specific and highly homologous uptake transporters, whose structures consist of 12 transmembrane domains. The present study showed that OATP1B3 is more heavily N-glycosylated than OATP1B1 in extracellular loop 2 (EL2) and EL5. OATP1B3 has six N-glycosylation sites, namely N134, N145, N151, N445, N503, and N516, which is twice of that of OATP1B1. Single removal of individual N-glycans seems to have minimal influence on the surface expression and function of OATP1B3. However, simultaneous removal of all N-glycans will lead to OATP1B3's large retention in the endoplasmic reticulum and cellular degradation and thus significantly disrupts its surface expression. While N-glycosylation plays a crucial role in the surface expression of OATP1B3, it also has some effect on the transport function of OATP1B3 per se , which is not due to a decrease of substrate binding affinity but due to a reduced transporter's turnover number. Taken together, N-glycosylation is essential for normal surface expression and function of OATP1B3. Its disruption by some liver diseases such as NASH might alter the pharmacokinetic/pharmacodynamic properties of OATP1B3's substrate drugs.
研究领域:
药理学
·
分子生物学
·
细胞生物学
✓ 已验证
DOI
PubMed
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Xiangquan Qin,Yiping Jiang,Jie Chen,Fuquan Yao,Longyi Jin,Zhiqi Cong
Selective hydroxylation of C( sp 3 )–H bonds is a long-standing challenge in the organic synthesis field. We herein report an artificial P450 peroxygenase system facilitated by ω-pyridyl fatty acyl amino acids that can hydroxylate broad-spectrum alkanes, including linear and cyclic alkanes and benzylic and allylic alkane chains. Compared with the previously reported dual-functional small molecule (DFSM) with imidazole as a catalytic group (Im-DFSM), pyridyl DFSM (Pyd-DFSM) produced substantially higher total turnover numbers (TTNs) for the hydroxylation of medium-chain alkanes and cycloalkanes (C6–C8), e.g., 12.0-fold and 17.1-fold increased TTNs of P450 mutant F87A/T268V for heptane and cycloheptane , respectively. In addition, Pyd-DFSM altered the enantioselectivity of benzylic hydroxylation, e.g., it almost inverted the configuration observed in the benzylic hydroxylation of ethylbenzene and tetralin . More importantly, Pyd-DFSM showed excellent regioselectivity for allylic hydroxylation over epoxidation of terminal alkenes and cycloalkenes , e.g., up to 94% allylic hydroxylation of 1-hexene was observed. This work significantly enhances the catalytic toolbox of the DFSM-facilitated P450 peroxygenase system; it not only substantially expands the chemical space of P450 enzymes, but also provides an alternative solution for the selective hydroxylation of C( sp 3 )–H bonds.
研究领域:
有机化学
·
生物化学
·
催化
·
酶工程
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）