scholarly journals Promotion of C-S Bond Scission over Solid Catalytic Sulfides by Aromatics and Nitrogen Heterocycles

2021 ◽  
Author(s):  
Edgar M. Morales-Valencia ◽  
Omar J. Vargas-Montañez ◽  
Pablo Alexander Monroy-García ◽  
Lina Avendaño ◽  
Eduard Arley Quintero-Quintero ◽  
...  
Keyword(s):  
Active Sites ◽  
Nitrogen Heterocycles ◽  
Reaction System ◽  
Lone Pair ◽  
Nitrogen Heterocycle ◽  
Inhibitory Effects ◽  
Bond Scission ◽  
Sulfur Heterocycles ◽  
Pi System ◽  
Sulfur Heterocycle

The competitive adsorption of aromatics and nitrogen heterocycles on the active sites of solid catalytic sulfides (Ni(Co)-MoS2 dispersed over oxidic carriers) typically causes inhibitory effects during the hydropurification of sulfur heterocycles. Contrary to this typical behavior, we report herein that it is possible to promote the scission of the C-S bond of refractory dibenzothiophene by co?feeding the above compounds during hydropurification over a conventional Ni-MoS2/Al2O3 catalyst. Particularly, we prove that at temperatures between 240 and 300°C and concentrations of dibenzothiophene between 1.0 and 3.7 wt.%, the desulfurization of dibenzothiophene is promoted by increasing its conversion up to 370% when either naphthalene, indole, or quinoline are co-fed to the reaction system. The work highlights the following: (i) lower temperatures and higher concentrations of the sulfur heterocycle enhanced the cleavage of the C-S bond from dibenzothiophene; (ii) it is possible to promote hydropurification reactions regardless of the nature of the of co-reactants; namely: a fused aromatic ring -naphthalene-, or a fused nitrogen heterocycle with a lone pair belonging to the pi-system -quinoline- or not -indole-.<br><p><a></a></p>

scholarly journals Promotion of C-S Bond Scission over Solid Catalytic Sulfides by Aromatics and Nitrogen Heterocycles

2021 ◽  
Author(s):  
Edgar M. Morales-Valencia ◽  
Omar J. Vargas-Montañez ◽  
Pablo Alexander Monroy-García ◽  
Lina Avendaño ◽  
Eduard Arley Quintero-Quintero ◽  
...  
Keyword(s):  
Active Sites ◽  
Nitrogen Heterocycles ◽  
Reaction System ◽  
Lone Pair ◽  
Nitrogen Heterocycle ◽  
Inhibitory Effects ◽  
Bond Scission ◽  
Sulfur Heterocycles ◽  
Pi System ◽  
Sulfur Heterocycle

The competitive adsorption of aromatics and nitrogen heterocycles on the active sites of solid catalytic sulfides (Ni(Co)-MoS2 dispersed over oxidic carriers) typically causes inhibitory effects during the hydropurification of sulfur heterocycles. Contrary to this typical behavior, we report herein that it is possible to promote the scission of the C-S bond of refractory dibenzothiophene by co?feeding the above compounds during hydropurification over a conventional Ni-MoS2/Al2O3 catalyst. Particularly, we prove that at temperatures between 240 and 300°C and concentrations of dibenzothiophene between 1.0 and 3.7 wt.%, the desulfurization of dibenzothiophene is promoted by increasing its conversion up to 370% when either naphthalene, indole, or quinoline are co-fed to the reaction system. The work highlights the following: (i) lower temperatures and higher concentrations of the sulfur heterocycle enhanced the cleavage of the C-S bond from dibenzothiophene; (ii) it is possible to promote hydropurification reactions regardless of the nature of the of co-reactants; namely: a fused aromatic ring -naphthalene-, or a fused nitrogen heterocycle with a lone pair belonging to the pi-system -quinoline- or not -indole-.<br><p><a></a></p>

Kinetics of the catalytic hydrodesulphurization reaction system; hydrogenolysis of thiophene

1980 ◽  
Vol 45 (10) ◽  
pp. 2728-2741 ◽  
Author(s):  
Pavel Fott ◽  
Petr Schneider
Keyword(s):  
Atmospheric Pressure ◽  
Active Sites ◽  
Flow Reactor ◽  
Kinetic Equations ◽  
Reaction System ◽  
Reaction Products ◽  
Molybdenum Catalyst ◽  
Cobalt Molybdenum Catalyst ◽  
Kinetics Of ◽  
Reaction Schemes

Kinetics have been studied of the reaction system taking place during the reaction of thiophene on the cobalt-molybdenum catalyst in a gradientless circulation flow reactor at 360 °C and atmospheric pressure. Butane has been found present in a small amount in the reaction products even at very low conversion. In view of this, consecutive and parallel-consecutive (triangular) reaction schemes have been proposed. In the former scheme the appearance of butane is accounted for by rate of desorption of butene being comparable with the rate of its hydrogenation. According to the latter scheme part of the butane originates from thiophene via a different route than through hydrogenation of butene. Analysis of the kinetic data has revealed that the reaction of thiophene should be considered to take place on other active sites than that of butene. Kinetic equations derived on this assumption for the consecutive and the triangular reaction schemes correlate experimental data with acceptable accuracy.

scholarly journals Heterogeneous Catalytic Synthesis of 2-Methylbenzimidazole from 2-Nitroaniline and Ethanol Over Mg Modified Cu-Pd/γ-Al2O3

Catalysts ◽  
2018 ◽  
Vol 9 (1) ◽  
pp. 8 ◽  
Author(s):  
Feng Feng ◽  
Yaqin Deng ◽  
Zheng Cheng ◽  
Xiaoliang Xu ◽  
Qunfeng Zhang ◽  
...  
Keyword(s):  
Active Sites ◽  
Hydrogen Transfer ◽  
High Efficiency ◽  
Simple Procedure ◽  
Direct Synthesis ◽  
Reaction System ◽  
Simple Method ◽  
Heterogeneous Catalytic ◽  
Coupled Reaction ◽  
Al2o3 Catalyst

The direct synthesis of benzimidazoles from 2-nitroaniline and ethanol over Cu-Pd/γ-Al2O3 catalysts has the advantages of requiring easily available starting materials, having high efficiency, and a simple procedure. The modification by Mg of the Cu-Pd/γ-Al2O3 catalyst could improve the catalytic activity significantly. The addition of Mg to the Cu-Pd/γ-Al2O3 catalyst could maintain and promote the formation of CuPd alloy active sites. Meanwhile, the basicity of the support was enhanced appropriately by Mg, which generated more basic sites (Al-Oδ−) to accelerate the dehydrogenation of alcohol and increased the rate of the whole coupled reaction. The 2-nitroaniline was completely converted over Cu-Pd/(Mg)γ-Al2O3 after reacting for six hours, and the yield of 2-methylbenzimidazole was 98.8%. The results of this work provide a simple method to develop a more efficient catalyst for the “alcohol-dehydrogenation, hydrogen transfer and hydrogenation” coupled reaction system.

Studies on the Mechanism of NAD-photoreduction by Chromatophores of the Facultative Phototroph, Rhodopseudomonas capsulata

1969 ◽  
Vol 24 (1) ◽  
pp. 67-76 ◽  
Author(s):  
J.-H. Klemme
Keyword(s):  
Nicotinamide Adenine Dinucleotide ◽  
Molecular Hydrogen ◽  
Reaction System ◽  
Electron Donors ◽  
Rhodopseudomonas Capsulata ◽  
Antimycin A ◽  
Inhibitory Effects ◽  
Carbonyl Cyanide ◽  
Cyclic Photophosphorylation ◽  
Energy Dependent

The light-driven and the ATP-driven reduction of nicotinamide adenine dinucleotide (NAD) catalyzed by the chromatophore fraction of Rhodopseudomonas capsulata was investigated. Efficient electron donors for the photoreduction of NAD are molecular hydrogen and succinate. In the ATP-dependent reaction system, succinate is a more efficient electron donor than H2. The energydependent NAD-reduction is driven by ATP, but not by pyrophosphate or ADP. Oligomycin stimulates the NAD-photoreductions and completely inhibits the ATP-driven NAD-reductions. Rotenone and piericidin A are inhibitors for both the light-driven and the ATP-driven NAD-reductions. Antimycin A is an inhibitor only for the light-driven reductions. The H2-linked NAD-photoreduction is less sensitive to these inhibitors and to the uncoupler desaspidin than the succinate-linked reduction. Atebrine, carbonyl cyanide-m-chlorophenylhydrazone, 2,4-dinitrophenol and phenazonium methosulfate are inhibitors for the light-driven and the ATP-driven reductions. Some of the compounds used as inhibitors of the NAD-reduction were also investigated with concerns to their inhibitory effects on cyclic photophosphorylation and O2-linked oxidations of reduced NAD, succinate and H2. Based on the results of these inhibitor studies, the relationships between cyclic photophosphorylation, light-induced noncyclic electron transport and energy-dependent NAD-reduction are discussed.

scholarly journals Effects of NO<sub>2</sub> and C<sub>3</sub>H<sub>6</sub> on the heterogeneous oxidation of SO<sub>2</sub> on TiO<sub>2</sub> in the presence or absence of UV–Vis irradiation

2019 ◽  
Vol 19 (23) ◽  
pp. 14777-14790 ◽  
Author(s):  
Biwu Chu ◽  
Yali Wang ◽  
Weiwei Yang ◽  
Jinzhu Ma ◽  
Qingxin Ma ◽  
...  
Keyword(s):  
Active Sites ◽  
Heterogeneous Reaction ◽  
Reaction System ◽  
Heterogeneous Reactions ◽  
Heterogeneous Oxidation ◽  
Inorganic Species ◽  
Sulfate Formation ◽  
Dark Conditions ◽  
Diffuse Reflectance Infrared ◽  
Reaction Processes

Abstract. The heterogeneous reactions of SO2 in the presence of NO2 and C3H6 on TiO2 were investigated with the aid of in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) under dark conditions or with UV–Vis irradiation. Sulfate formation with or without the coexistence of NO2 and/or C3H6 was analyzed with ion chromatography (IC). Under dark conditions, SO2 reacting alone resulted in sulfite formation on TiO2, while the presence of parts per billion (ppb) levels of NO2 promoted the oxidation of SO2 to sulfate. The presence of C3H6 had little effect on sulfate formation in the heterogeneous reaction of SO2 but suppressed sulfate formation in the heterogeneous reaction of SO2 and NO2. UV–Vis irradiation could significantly enhance the heterogeneous oxidation of SO2 on TiO2, leading to copious generation of sulfate, while the coexistence of NO2 and/or C3H6 significantly suppressed sulfate formation in experiments with UV–Vis lights. Step-by-step exposure experiments indicated that C3H6 mainly competes for reactive oxygen species (ROS), while NO2 competes with SO2 for both surface active sites and ROS. Meanwhile, the coexistence of NO2 with C3H6 further resulted in less sulfate formation compared to introducing either one of them separately to the SO2–TiO2 reaction system. The results of this study highlighted the complex heterogeneous reaction processes that take place due to the ubiquitous interactions between organic and inorganic species and the need to consider the influence of coexisting volatile organic compounds (VOCs) and other inorganic gases in the heterogeneous oxidation kinetics of SO2.

Kinetics of the catalytic hydrodesulphurization reaction system; hydrogenation of ethylene and butene

1980 ◽  
Vol 45 (10) ◽  
pp. 2742-2750 ◽  
Author(s):  
Pavel Fott ◽  
Petr Schneider
Keyword(s):  
Atmospheric Pressure ◽  
Active Sites ◽  
Flow Reactor ◽  
Reaction System ◽  
Circulation Flow ◽  
Kinetic Description ◽  
Molybdenum Catalyst ◽  
Cobalt Molybdenum Catalyst ◽  
Kinetics Of ◽  
Hydrogenation Of Ethylene

Hydrogenation has been studied of ethylene and butene in a circulation flow reactor on a cobalt-molybdenum catalyst at 360 °C and atmospheric pressure. The effect has been investigated of simultaneous hydrodesulphurization of thiophene on the hydrogenation. The results have confirmed that different active sites for hydrogenation and hydrodesulphurization must be considered in the kinetic description of simultaneous hydrogenation of ethylene and hydrodesulphurization of thiophene. For isolated hydrogenation of ethylene and butene the absence of hydrogen sulphide in the reaction mixture considerably enhances the hydrogenation activity of the catalyst due to the change of its state.

scholarly journals Active sites and mechanisms for H2O2 decomposition over Pd catalysts

2016 ◽  
Vol 113 (14) ◽  
pp. E1973-E1982 ◽  
Author(s):  
Anthony Plauck ◽  
Eric E. Stangland ◽  
James A. Dumesic ◽  
Manos Mavrikakis
Keyword(s):  
Active Sites ◽  
Density Functional ◽  
Mean Field ◽  
Pd Catalyst ◽  
Pd Catalysts ◽  
H2o2 Decomposition ◽  
Bond Scission ◽  
Flow Through ◽  
Key Aspects ◽  
Supported Pd

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity.

Herbacetin Broadly Blocks the Activities of CYP450s by Different Inhibitory Mechanisms

Planta Medica ◽  
2021 ◽  
Author(s):  
Jianchang Qian ◽  
Yinghui Li ◽  
Xiaodan Zhang ◽  
Daoxing Chen ◽  
Mingming Han ◽  
...  
Keyword(s):  
Wide Spectrum ◽  
Reaction System ◽  
Human Liver Microsome ◽  
Inhibitory Effects ◽  
In Silico Docking ◽  
Structure Activity ◽  
Inhibitory Mechanisms ◽  
Good Agreement

AbstractHerbacetin is a bioactive flavanol compound that has various pharmacological effects. However, the pharmacokinetic characteristics have not been thoroughly investigated. Previously, we screened a natural compound library and identified herbacetin as a potent CYP blocker. Herein, we aimed to mechanistically determine the inhibitory effects of herbacetin on CYP450 and its potential application. A human liver microsome incubation system was developed based on a UPLC-MS/MS method. Moreover, an in silico docking assay and a human CYP recombinase reaction system were developed and used to investigate binding affinity and inhibitory efficacy. Subsequently, the effects of the combination of herbacetin and sorafenib on HepG2 cells were assessed by MTT and immunoblotting assays. The concentration of sorafenib and its main metabolite were measured by UPLC-MS/MS after incubation with or without herbacetin. As a result, we found herbacetin almost completely inhibited the functions of major CYPs at 100 µM. Moreover, through analysis of the structure-activity relationship, we found 4-, 6-, and 8-hydroxyl were essential groups for the inhibitory effects. Herbacetin inhibited CYP3A4, CYP2B6, CYP2C9, and CYP2E1 in a mixed manner, but non-competitively blocked CYP2D6. These results are in good agreement with the recombinase reaction in vitro results, with an IC50 < 10 µM for each tested isoenzyme. Interestingly, the stimulatory effects of sorafenib on HepG2 cell apoptosis were significantly enhanced by combining with herbacetin, which was associated with increased sorafenib exposure. In summary, herbacetin is a potent inhibitor of a wide spectrum of CYP450s, which may enhance the exposure of drugs in vivo.

scholarly journals Inhibitory effects on the HMG-CoA Reductase in the chemical constituents of the Cassia mimosoides Linn

2016 ◽  
Vol 24 (4) ◽  
pp. 413-422 ◽  
Author(s):  
Chuangpeng Shen ◽  
Liping Huang ◽  
Hua Xiang ◽  
Minzhen Deng ◽  
Huahong Gao ◽  
...  
Keyword(s):  
Oleanolic Acid ◽  
Reductase Activity ◽  
Chemical Constituents ◽  
Dynamic Change ◽  
Reaction System ◽  
Inhibitory Effect ◽  
Inhibitory Effects ◽  
Hmg Coa Reductase ◽  
Ancient Times ◽  
Coa Reductase

Abstract Cassia mimosoides Linn has been used from ancient times and used for treating hepatitis for its supposedly medically beneficial properties. In this study, different constituents of the Cassia mimosoides Linn (β-Sitosterol, Oleanolic Acid, Emodin, Carotene, Resorcinol, Luteolin, and α-L-Rhamnose) were evaluated for potential anti-HMG-CoA reductase effect. The inhibitory effects of HMG-CoA reductase of Cassia mimosoides Linn extracts and Pravastatin inhibitor at different concentrations (at doses of 1, 5, 25 or 125 μg/mL, respectively) in reaction system (70 mmol/L phosphate buffer, 200mmol/L NADPH, 5 μg HMG-CoA reductase, 2 mmol/L EDTA, 2 mmol/L cysteamine, 0.06% BSA) into 37°C preheat HMG-CoA for initiating this reaction, and then determined the change of HMG-CoA reductase activity (ΔAΔt) at 340 nm, the inhibition ratio of HMG-CoA reductase activity and its dynamic change of inhibitory effect within 15 min and the descent rate of NADPH. Emodin, Luteolin, β-Sitosterol, Oleanolic Acid, α-L-Rhamnose and Carotene showed good inhibition of HMG-CoA reductase activity. Among them, only the Emodin (1 and 5 μg/mL) groups showed a significant decrease of HMG-CoA reductase activity compared to the Pravastatin (1 and 5 μg/mL) groups respectively. In addition, the HMG-CoA reductase activity in the Emodin and Luteolin (25 and 125 μg/mL) groups was clearly lower than the Pravastatin (25 and 125 μg/mL) groups respectively. And the Emodin and Luteolin (1, 5, 25 or 125 μg/mL) groups exhibited a stable effect on inhibiting the HMG-CoA reductase within 15 min. These findings further support the exploration of Cassia mimosoides Linn as a potential agent for the treatment of hepatitis in future studies.

scholarly journals Secondary brown carbon formation via the dicarbonyl imine pathway: nitrogen heterocycle formation and synergistic effects

2016 ◽  
Vol 18 (27) ◽  
pp. 18353-18364 ◽  
Author(s):  
C. J. Kampf ◽  
A. Filippi ◽  
C. Zuth ◽  
T. Hoffmann ◽  
T. Opatz
Keyword(s):  
Synergistic Effects ◽  
Nitrogen Heterocycles ◽  
Nitrogen Heterocycle ◽  
Carbon Formation ◽  
Brown Carbon ◽  
Reaction Systems

We observe nitrogen heterocycles to be common secondary brown carbon chromophores formed by dicarbonylsviathe imine pathway, and synergistic effects in mixed dicarbonyl reaction systems.

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