scholarly journals Coupled inter-subunit dynamics enable the fastest CO2-fixation by reductive carboxylases

2019 ◽  
Author(s):  
Hasan DeMirci ◽  
Yash Rao ◽  
Gabriele M. Stoffel ◽  
Bastian Vögeli ◽  
Kristina Schell ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Molecular Mechanisms ◽  
Co2 Fixation ◽  
Catalytic Domains ◽  
Catalytically Active ◽  
Key Enzyme ◽  
Order Of Magnitude ◽  
Conformational Coupling ◽  
Substrate Binding Sites ◽  
Half Site

AbstractEnoyl-CoA carboxylases/reductases (ECRs) are the most efficient CO2-fixing enzymes described to date, outcompeting RubisCO, the key enzyme in photosynthesis in catalytic activity by more than an order of magnitude. However, the molecular mechanisms underlying ECR’s extraordinary catalytic activity remain elusive. Here we used different crystallographic approaches, including ambient temperature X-ray Free Electron Laser (XFEL) experiments, to study the dynamic structural organization of the ECR from Kitasatospora setae. K. setae ECR is a homotetramer that differentiates into a dimer of dimers of open- and closed-form subunits in the catalytically active state, suggesting that the enzyme operates with “half-site reactivity” to achieve high catalytic rates. Using structure-based mutagenesis, we show that catalysis is synchronized in K. setae ECR across the pair of dimers by conformational coupling of catalytic domains and within individual dimers by shared substrate binding sites. Our results provide unprecedented insights into the dynamic organization and synchronized inter- and intra-subunit communications of nature’s most efficient CO2-fixing enzyme during catalysis.

Hydrogen peroxide decomposition on a two-component CuO-Cr2O3 catalyst

1988 ◽  
Vol 53 (8) ◽  
pp. 1636-1646 ◽  
Author(s):  
Viliam Múčka ◽  
Kamil Lang
Keyword(s):  
Hydrogen Peroxide ◽  
Catalytic Activity ◽  
Extreme Values ◽  
Catalytic Properties ◽  
Active Components ◽  
Catalytic Systems ◽  
Heterogeneous Catalytic ◽  
Peroxide Decomposition ◽  
Two Component ◽  
Catalytically Active

Some physical and catalytic properties of the two-component copper(II)oxide-chromium(III)oxide catalyst with different content of both components were studied using the decomposition of the aqueous solution of hydrogen peroxide as a testing reaction. It has been found that along to both basic components, the system under study contains also the spinel structure CuCr2O4, chromate washable by water and hexavalent ions of chromium unwashable by water. The soluble chromate is catalytically active. During the first period of the reaction the equilibrium is being established in both homogeneous and heterogeneous catalytic systems. The catalytic activity as well as the specific surface area of the washed solid is a non-monotonous function of its composition. It seems highly probable that the extreme values of both these quantities are not connected with the detected admixtures in the catalytic system. The system under study is very insensitive with regard to the applied doses of gamma radiation. Its catalytic properties are changed rather significantly after the thermal treatment and particularly after the partial reduction to low degree by hydrogen. The observed changes of the catalytic activity of the system under study are very probably in connection with the changes of the valence state of the catalytically active components of the catalyst.

scholarly journals Role of CO2 During Oxidative Dehydrogenation of Propane Over Bulk and Activated-Carbon Supported Cerium and Vanadium Based Catalysts

2021 ◽  
Author(s):  
Petar Djinović ◽  
Janez Zavašnik ◽  
Janvit Teržan ◽  
Ivan Jerman
Keyword(s):  
Catalytic Activity ◽  
Activated Carbon ◽  
Oxidative Dehydrogenation ◽  
Active Phase ◽  
Lattice Oxygen ◽  
Chemisorbed Oxygen ◽  
Catalytically Active ◽  
Temperature Programmed ◽  
Propane Cracking

AbstractCeO2, V2O5 and CeVO4 were synthesised as bulk oxides, or deposited over activated carbon, characterized by XRD, HRTEM, CO2-TPO, C3H8-TPR, DRIFTS and Raman techniques and tested in propane oxidative dehydrogenation using CO2. Complete oxidation of propane to CO and CO2 is favoured by lattice oxygen of CeO2. The temperature programmed experiments show the ~ 4 nm AC supported CeO2 crystallites become more susceptible to reduction by propane, but less prone to re-oxidation with CO2 compared to bulk CeO2. Catalytic activity of CeVO4/AC catalysts requires a 1–2 nm amorphous CeVO4 layer. During reaction, the amorphous CeVO4 layer crystallises and several atomic layers of carbon cover the CeVO4 surface, resulting in deactivation. During reaction, V2O5 is irreversibly reduced to V2O3. The lattice oxygen in bulk V2O5 favours catalytic activity and propene selectivity. Bulk V2O3 promotes only propane cracking with no propene selectivity. In VOx/AC materials, vanadium carbide is the catalytically active phase. Propane dehydrogenation over VC proceeds via chemisorbed oxygen species originating from the dissociated CO2. Graphic Abstract

From Ru nanoparticle-encapsulated metal–organic frameworks to highly catalytically active Cu/Ru nanoparticle-embedded porous carbon

2017 ◽  
Vol 5 (10) ◽  
pp. 4835-4841 ◽  
Author(s):  
Pradip Pachfule ◽  
Xinchun Yang ◽  
Qi-Long Zhu ◽  
Nobuko Tsumori ◽  
Takeyuki Uchida ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
High Temperature ◽  
Porous Carbon ◽  
Metal Organic Frameworks ◽  
Ammonia Borane ◽  
Carbon Composites ◽  
High Catalytic Activity ◽  
Catalytically Active ◽  
Metal Organic

High-temperature pyrolysis of Ru nanoparticle-encapsulated MOF (Ru@HKUST-1) afforded ultrafine Cu/Ru nanoparticle-embedded porous carbon composites (Cu/Ru@C), which show high catalytic activity for ammonia borane hydrolysis.

Catalytic activity of Co-åkermanite and Co-pyroxene in oxidation reactions

2011 ◽  
Vol 89 (8) ◽  
pp. 939-947 ◽  
Author(s):  
Irena Mihailova ◽  
Dimitar Mehandjiev
Keyword(s):  
Catalytic Activity ◽  
Solid Phase ◽  
Sol Gel ◽  
Cobalt Content ◽  
Octahedral Coordination ◽  
Tetrahedral Coordination ◽  
Oxidation Reactions ◽  
Oxidation Of Co ◽  
Phase Synthesis ◽  
Catalytically Active

Two calcium–cobalt silicates were synthesized in which cobalt occupies different structural positions. The crystal phases belong to two main structural silicate types. In the Co-åkermanite structure (Ca2CoSi2O7), cobalt cations take tetrahedral coordination toward oxygen atoms. In the Co-pyroxene structure of CaCoSi2O6, cobalt displays octahedral coordination. Ca2CoSi2O7 was prepared by solid-phase synthesis and CaCoSi2O6 was prepared by sol–gel method. The synthesis of the phases was confirmed by XRD, FTIR, and EPR data. On the basis of the XPS analysis, it can be concluded that Co2+ cations exist in the studied silicates. Thus, it is possible to study the catalytic activity of two silicate phases containing Co2+ cations in different coordinations: tetrahedral and octahedral. It was found that cobalt silicates with crystal structures corresponding to pyroxene and åkermanite possess catalytic activity in the reactions of complete oxidation of CO and toluene. Co-pyroxene exhibits higher catalytic activity than Co-åkermanite, but the higher cobalt content on the surface of Co-pyroxene should also be taken into account. Then, it turns out that catalytically active complexes with Со2+ ions in tetrahedral coordination are more efficient than those with such ions in octahedral coordination when equal concentrations of cobalt were used on the surface of the catalysts.

scholarly journals MARCKS domain phosphorylation regulates the differential interaction of Diacylglycerol Kinase ζ with Rac1, RhoA and Syntrophin

2020 ◽  
Author(s):  
Ryan Ard ◽  
Jean-Christian Maillet ◽  
Elias Daher ◽  
Michael Phan ◽  
Radoslav Zinoviev ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Molecular Mechanisms ◽  
Rho Gtpase ◽  
Pdz Domain ◽  
Diacylglycerol Kinase ◽  
Binding Motif ◽  
Membrane Blebbing ◽  
Rhoa Activity ◽  
C Terminus ◽  
Mechanistic Basis

AbstractCells can switch between Rac1, lamellipodia-based and RhoA, blebbing-based migration modes but the molecular mechanisms regulating this choice are not fully understood. Diacylglycerol kinase ζ (DGKζ), which phosphorylates diacylglycerol to yield phosphatidic acid, forms independent complexes with Rac1 and RhoA, selectively dissociating each from RhoGDI. DGKζ catalytic activity is required for Rac1 dissociation but is dispensable for RhoA dissociation. Instead, DGKζ functions as a scaffold that stimulates RhoA release by enhancing RhoGDI phosphorylation by protein kinase Cα (PKCα). Here, PKCα-mediated phosphorylation of the DGKζ MARCKS domain increased DGKζ association with RhoA and decreased its interaction with Rac1. The same modification increased binding of the DGKζ C-terminus to the α1-syntrophin PDZ domain. Expression of a phosphomimetic DGKζ mutant stimulated membrane blebbing in mouse embryonic fibroblasts and C2C12 myoblasts, which was augmented by inhibition of endogenous Rac1. DGKζ expression in differentiated C2 myotubes, which have low endogenous Rac1 levels, also induced substantial membrane blebbing via the Rho-ROCK pathway. These events were independent of DGKζ catalytic activity, but dependent upon a functional C-terminal PDZ-binding motif. Rescue of RhoA activity in DGKζ-null cells required the PDZ-binding motif, suggesting syntrophin interaction is necessary for optimal RhoA activation. Collectively, our results define a switch-like mechanism involving DGKζ phosphorylation by PKCα that favours RhoA-driven blebbing over Rac1-driven lamellipodia formation and macropinocytosis. These findings provide a mechanistic basis for the effect of PKCα signaling on Rho GTPase activity and suggest PKCα activity plays a role in the interconversion between Rac1 and RhoA signaling that underlies different migration modes.

Molecular mechanisms regulating hormone-sensitive lipase and lipolysis

2003 ◽  
Vol 31 (6) ◽  
pp. 1120-1124 ◽  
Author(s):  
C. Holm
Keyword(s):  
Lipid Droplet ◽  
Molecular Mechanisms ◽  
Hormone Sensitive Lipase ◽  
Glucose Disposal ◽  
Triacylglycerol Lipase ◽  
Insulin Resistant ◽  
Lipolytic Action ◽  
Key Enzyme ◽  
Hormone Sensitive

HSL (hormone-sensitive lipase) is a key enzyme in the mobilization of fatty acids from acylglycerols in adipocytes as well as non-adipocytes. In adipocytes, catecholamines stimulate lipolysis mainly through PKA (protein kinase A)-mediated phosphorylation of HSL and perilipin, a protein coating the lipid droplet. The anti-lipolytic action of insulin is mediated mainly via lowered cAMP levels, accomplished through activation of phosphodiesterase 3B. Phosphorylation of HSL by PKA occurs at three sites, the serines 563, 659 and 660, both in vitro and in primary rat adipocytes. Phosphorylation of Ser-659 and -660 is required for in vitro activation as well as translocation from the cytosol to the lipid droplet, whereas the role of the third PKA site remains elusive. Adipocytes isolated from homozygous HSL-null mice, generated in our laboratory, exhibit completely blunted catecholamine-induced glycerol release and reduced fatty acid release, suggesting the presence of additional, although not necessarily hormone-activatable, triacylglycerol lipase(s). Basal hyperinsulinaemia, release of exaggerated amounts of insulin during glucose challenges and retarded glucose disposal during insulin tolerance tests suggest that HSL-null mice are insulin resistant. Liver, adipose tissue and skeletal muscle appear all to be sites of impaired insulin sensitivity in HSL-null mice.

scholarly journals Microsecond-timescale simulations suggest 5-HT–mediated preactivation of the 5-HT3Aserotonin receptor

2019 ◽  
Vol 117 (1) ◽  
pp. 405-414 ◽  
Author(s):  
Nicholas B. Guros ◽  
Arvind Balijepalli ◽  
Jeffery B. Klauda
Keyword(s):  
Serotonin Receptor ◽  
Molecular Mechanisms ◽  
Transmembrane Domain ◽  
Allosteric Regulation ◽  
Md Simulations ◽  
Binding Pocket ◽  
Careful Examination ◽  
Dynamic Binding ◽  
Order Of Magnitude ◽  
Membrane Bound

Aided by efforts to improve their speed and efficiency, molecular dynamics (MD) simulations provide an increasingly powerful tool to study the structure–function relationship of pentameric ligand-gated ion channels (pLGICs). However, accurate reporting of the channel state and observation of allosteric regulation by agonist binding with MD remains difficult due to the timescales necessary to equilibrate pLGICs from their artificial and crystalized conformation to a more native, membrane-bound conformation in silico. Here, we perform multiple all-atom MD simulations of the homomeric 5-hydroxytryptamine 3A (5-HT3A) serotonin receptor for 15 to 20 μs to demonstrate that such timescales are critical to observe the equilibration of a pLGIC from its crystalized conformation to a membrane-bound conformation. These timescales, which are an order of magnitude longer than any previous simulation of 5-HT3A, allow us to observe the dynamic binding and unbinding of 5-hydroxytryptamine (5-HT) (i.e., serotonin) to the binding pocket located on the extracellular domain (ECD) and allosteric regulation of the transmembrane domain (TMD) from synergistic 5-HT binding. While these timescales are not long enough to observe complete activation of 5-HT3A, the allosteric regulation of ion gating elements by 5-HT binding is indicative of a preactive state, which provides insight into molecular mechanisms that regulate channel activation from a resting state. This mechanistic insight, enabled by microsecond-timescale MD simulations, will allow a careful examination of the regulation of pLGICs at a molecular level, expanding our understanding of their function and elucidating key structural motifs that can be targeted for therapeutic regulation.

scholarly journals Agasicles hygrophila attack increases nerolidol synthase gene expression in Alternanthera philoxeroides, facilitating host finding

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Yuanxin Wang ◽  
Yanhong Liu ◽  
Xingchun Wang ◽  
Dong Jia ◽  
Jun Hu ◽  
...  
Keyword(s):  
Host Plants ◽  
Molecular Mechanisms ◽  
Host Finding ◽  
Alternanthera Philoxeroides ◽  
Terpene Synthase ◽  
Mechanical Wounding ◽  
Plant Volatile ◽  
Egg Deposition ◽  
Key Enzyme ◽  
Plant Volatile Compounds

Abstract Herbivorous insects use plant volatile compounds to find their host plants for feeding and egg deposition. The monophagous beetle Agasicles hygrophila uses a volatile (E)-4,8-dimethyl-1,3,7-nonanetriene (DMNT) to recognize its host plant Alternanthera philoxeroides. Alternanthera philoxeroides releases DMNT in response to A. hygrophila attack and nerolidol synthase (NES) is a key enzyme in DMNT biosynthesis; however, the effect of A. hygrophila on NES expression remains unclear. In this study, the A. philoxeroides transcriptome was sequenced and six putative NES genes belonging to the terpene synthase-g family were characterized. The expression of these NES genes was assayed at different times following A. hygrophila contact, feeding or mechanical wounding. Results showed that A. hygrophila contact and feeding induced NES expression more rapidly and more intensely than mechanical wounding alone. This may account for a large release of DMNT following A. hygrophila feeding in a previous study and subsequently facilitate A. hygrophila to find host plants. Our research provides a powerful genetic platform for studying invasive plants and lays the foundation for further elucidating the molecular mechanisms of the interaction between A. philoxeroides and its specialist A. hygrophila.

Enhanced catalytic activity of cobalt catalysts for Fischer–Tropsch synthesis via carburization and hydrogenation and its application to regeneration

2016 ◽  
Vol 6 (12) ◽  
pp. 4594-4600 ◽  
Author(s):  
Geunjae Kwak ◽  
Du-Eil Kim ◽  
Yong Tae Kim ◽  
Hae-Gu Park ◽  
Seok Chang Kang ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Active Material ◽  
Catalytic Performance ◽  
Tropsch Synthesis ◽  
Cobalt Catalysts ◽  
Fischer Tropsch ◽  
Fischer Tropsch Synthesis ◽  
Cobalt Carbide ◽  
Catalytically Active

In Fischer–Tropsch synthesis (FTS), cobalt carbide (Co2C) is not a catalytically active material, but rather an undesired cobalt phase associated with low catalytic performance.

Sign in / Sign up

Export Citation Format

Share Document