scholarly journals Peroxide-Mediated Oxygenation of Organic Compounds by Fungal Peroxygenases

Antioxidants ◽  
2022 ◽  
Vol 11 (1) ◽  
pp. 163
Author(s):  
Martin Hofrichter ◽  
Harald Kellner ◽  
Robert Herzog ◽  
Alexander Karich ◽  
Jan Kiebist ◽  
...  
Keyword(s):  
Filamentous Fungi ◽  
Organic Compounds ◽  
Active Site ◽  
High Efficiency ◽  
Radical Formation ◽  
Organic Substrates ◽  
Phenoxy Radical ◽  
Wide Range ◽  
Molecular Phylogenetic

Unspecific peroxygenases (UPOs), whose sequences can be found in the genomes of thousands of filamentous fungi, many yeasts and certain fungus-like protists, are fascinating biocatalysts that transfer peroxide-borne oxygen (from H2O2 or R-OOH) with high efficiency to a wide range of organic substrates, including less or unactivated carbons and heteroatoms. A twice-proline-flanked cysteine (PCP motif) typically ligates the heme that forms the heart of the active site of UPOs and enables various types of relevant oxygenation reactions (hydroxylation, epoxidation, subsequent dealkylations, deacylation, or aromatization) together with less specific one-electron oxidations (e.g., phenoxy radical formation). In consequence, the substrate portfolio of a UPO enzyme always combines prototypical monooxygenase and peroxidase activities. Here, we briefly review nearly 20 years of peroxygenase research, considering basic mechanistic, molecular, phylogenetic, and biotechnological aspects.

scholarly journals Exploring the Role of Phenylalanine Residues in Modulating the Flexibility and Topography of the Active Site in the Peroxygenase Variant PaDa-I

2020 ◽  
Vol 21 (16) ◽  
pp. 5734
Author(s):  
Joaquin Ramirez-Ramirez ◽  
Javier Martin-Diaz ◽  
Nina Pastor ◽  
Miguel Alcalde ◽  
Marcela Ayala
Keyword(s):  
Hydrogen Peroxide ◽  
Cytochrome P450 ◽  
Active Site ◽  
Bulk Solution ◽  
Computational Studies ◽  
Organic Substrates ◽  
Oxidation Reactions ◽  
Heme Group ◽  
Wide Range

Unspecific peroxygenases (UPOs) are fungal heme-thiolate enzymes able to catalyze a wide range of oxidation reactions, such as peroxidase-like, catalase-like, haloperoxidase-like, and, most interestingly, cytochrome P450-like. One of the most outstanding properties of these enzymes is the ability to catalyze the oxidation a wide range of organic substrates (both aromatic and aliphatic) through cytochrome P450-like reactions (the so-called peroxygenase activity), which involves the insertion of an oxygen atom from hydrogen peroxide. To catalyze this reaction, the substrate must access a channel connecting the bulk solution to the heme group. The composition, shape, and flexibility of this channel surely modulate the catalytic ability of the enzymes in this family. In order to gain an understanding of the role of the residues comprising the channel, mutants derived from PaDa-I, a laboratory-evolved UPO variant from Agrocybe aegerita, were obtained. The two phenylalanine residues at the surface of the channel, which regulate the traffic towards the heme active site, were mutated by less bulky residues (alanine and leucine). The mutants were experimentally characterized, and computational studies (i.e., molecular dynamics (MD)) were performed. The results suggest that these residues are necessary to reduce the flexibility of the region and maintain the topography of the channel.

Synthesis of Elaborate Benzofuran-2-Carboxamide Derivatives Through a Combination of 8-Aminoquinoline Directed C–H Arylations and Transamidations

2019 ◽  
Author(s):  
Michael Oschmann ◽  
Linus Johansson Holm ◽  
Oscar Verho
Keyword(s):  
Small Molecule ◽  
High Efficiency ◽  
Synthetic Strategy ◽  
Small Molecule Screening ◽  
Physiological Properties ◽  
Wide Range ◽  
Directing Group ◽  
Synthetic Sequence

Benzofurans are everywhere in nature and they have been extensively studied by medicinal chemists over the years because of their chemotherapeutic and physiological properties. Herein, we describe a strategy that can be used to access elaborate benzo-2-carboxamide derivatives, which involves a synthetic sequence of 8-aminoquinoline directed C–H arylations followed by transamidations. For the directed C–H arylations, Pd catalysis was used to install a wide range of aryl and heteroaryl substituents at the C3 position of the benzofuran scaffold in high efficiency. Directing group cleavage and further diversification of the C3-arylated benzofuran products were then achieved in a single synthetic operation through the utilization of a two-step transamidation protocol. By bocylating the 8-aminoquinoline amide moiety of these products, it proved possible to activate them towards aminolysis with different amine nucleophiles. Interestingly, this aminolysis reaction was found to proceed efficiently without the need of any additional catalyst or additive. Given the high efficiency and modularity of this synthetic strategy, it constitute a very attractive approach for generating structurally-diverse collections of benzofuran derivatives for small molecule screening.

Strongly Coupled Redox-Linked Conformational Switching at the Active Site of the Non-Heme Iron-Dependent Dioxygenase, TauD

2019 ◽  
Author(s):  
Christopher John ◽  
Greg M. Swain ◽  
Robert P. Hausinger ◽  
Denis A. Proshlyakov
Keyword(s):  
Active Site ◽  
Structural Model ◽  
Heme Iron ◽  
Chemical Transformations ◽  
Experimental Conditions ◽  
Strongly Coupled ◽  
Non Heme Iron ◽  
Reversible Redox ◽  
Wide Range ◽  
Complex Structural

2-Oxoglutarate (2OG)-dependent dioxygenases catalyze C-H activation while performing a wide range of chemical transformations. In contrast to their heme analogues, non-heme iron centers afford greater structural flexibility with important implications for their diverse catalytic mechanisms. We characterize an <i>in situ</i> structural model of the putative transient ferric intermediate of 2OG:taurine dioxygenase (TauD) by using a combination of spectroelectrochemical and semi-empirical computational methods, demonstrating that the Fe (III/II) transition involves a substantial, fully reversible, redox-linked conformational change at the active site. This rearrangement alters the apparent redox potential of the active site between -127 mV for reduction of the ferric state and 171 mV for oxidation of the ferrous state of the 2OG-Fe-TauD complex. Structural perturbations exhibit limited sensitivity to mediator concentrations and potential pulse duration. Similar changes were observed in the Fe-TauD and taurine-2OG-Fe-TauD complexes, thus attributing the reorganization to the protein moiety rather than the cosubstrates. Redox difference infrared spectra indicate a reorganization of the protein backbone in addition to the involvement of carboxylate and histidine ligands. Quantitative modeling of the transient redox response using two alternative reaction schemes across a variety of experimental conditions strongly supports the proposal for intrinsic protein reorganization as the origin of the experimental observations.

To the 70th anniversary of World Meteorological Organization. Scientific and technical cooperation of Hydrometeorological Center of the USSR/Russia in the Programs of World Meteorological Organization

2020 ◽  
pp. 117-138
Author(s):  
S.V. Borshch ◽  
◽  
R.M. Vil’fand ◽  
D.B. Kiktev ◽  
V.M. Khan ◽  
...  
Keyword(s):  
Environmental Monitoring ◽  
High Efficiency ◽  
World Meteorological Organization ◽  
70Th Anniversary ◽  
Technical Level ◽  
Technical Cooperation ◽  
Wide Range

The paper presents the summary and results of long-term and multi-faceted experience of international scientific and technical cooperation of Hydrometeorological Center of Russia in the field of hydrometeorology and environmental monitoring within the framework of WMO programs, which indicates its high efficiency in performing a wide range of works at a high scientific and technical level. Keywords: World Meteorological Organization, major WMO programs, representatives of Hydrometeorological Center of Russia in WMO

Integrated Design and Multi-Objective Optimization of a Single Stage Heat-Pump Turbocompressor

2013 ◽  
Author(s):  
J. Schiffmann
Keyword(s):  
Design Optimization ◽  
High Efficiency ◽  
Integrated Design ◽  
Heat Pumps ◽  
Small Scale ◽  
Multi Objective Optimization ◽  
Design Constraints ◽  
Multi Objective ◽  
Wide Range ◽  
Standard Design

Small scale turbomachines in domestic heat pumps reach high efficiency and provide oil-free solutions which improve heat-exchanger performance and offer major advantages in the design of advanced thermodynamic cycles. An appropriate turbocompressor for domestic air based heat pumps requires the ability to operate on a wide range of inlet pressure, pressure ratios and mass flows, confronting the designer with the necessity to compromise between range and efficiency. Further the design of small-scale direct driven turbomachines is a complex and interdisciplinary task. Textbook design procedures propose to split such systems into subcomponents and to design and optimize each element individually. This common procedure, however, tends to neglect the interactions between the different components leading to suboptimal solutions. The authors propose an approach based on the integrated philosophy for designing and optimizing gas bearing supported, direct driven turbocompressors for applications with challenging requirements with regards to operation range and efficiency. Using previously validated reduced order models for the different components an integrated model of the compressor is implemented and the optimum system found via multi-objective optimization. It is shown that compared to standard design procedure the integrated approach yields an increase of the seasonal compressor efficiency of more than 12 points. Further a design optimization based sensitivity analysis allows to investigate the influence of design constraints determined prior to optimization such as impeller surface roughness, rotor material and impeller force. A relaxation of these constrains yields additional room for improvement. Reduced impeller force improves efficiency due to a smaller thrust bearing mainly, whereas a lighter rotor material improves rotordynamic performance. A hydraulically smoother impeller surface improves the overall efficiency considerably by reducing aerodynamic losses. A combination of the relaxation of the 3 design constraints yields an additional improvement of 6 points compared to the original optimization process. The integrated design and optimization procedure implemented in the case of a complex design problem thus clearly shows its advantages compared to traditional design methods by allowing a truly exhaustive search for optimum solutions throughout the complete design space. It can be used for both design optimization and for design analysis.

scholarly journals Low Power Cusped Field Thruster Developed for the Space-Borne Gravitational Wave Detection Mission in China

2021 ◽  
Vol 11 (14) ◽  
pp. 6549
Author(s):  
Hui Liu ◽  
Ming Zeng ◽  
Xiang Niu ◽  
Hongyan Huang ◽  
Daren Yu
Keyword(s):  
Low Power ◽  
Gravitational Wave ◽  
Attitude Control ◽  
High Efficiency ◽  
Experimental Investigations ◽  
Attitude Control System ◽  
Gravitational Wave Detection ◽  
Wave Detection ◽  
Wide Range ◽  
Institute Of Technology

The microthruster is the crucial device of the drag-free attitude control system, essential for the space-borne gravitational wave detection mission. The cusped field thruster (also called the High Efficiency Multistage Plasma Thruster) becomes one of the candidate thrusters for the mission due to its low complexity and potential long life over a wide range of thrust. However, the prescribed minimum of thrust and thrust noise are considerable obstacles to downscaling works on cusped field thrusters. This article reviews the development of the low power cusped field thruster at the Harbin Institute of Technology since 2012, including the design of prototypes, experimental investigations and simulation studies. Progress has been made on the downscaling of cusped field thrusters, and a new concept of microwave discharge cusped field thruster has been introduced.

scholarly journals Responses to Ecopollutants and Pathogenization Risks of Saprotrophic Rhodococcus Species

Pathogens ◽  
2021 ◽  
Vol 10 (8) ◽  
pp. 974
Author(s):  
Irina B. Ivshina ◽  
Maria S. Kuyukina ◽  
Anastasiia V. Krivoruchko ◽  
Elena A. Tyumina
Keyword(s):  
Survival Strategies ◽  
Complex Life Cycle ◽  
Anthropogenic Pressure ◽  
Resting Cells ◽  
Organic Substrates ◽  
Negative Effects ◽  
Anthropogenic Pollutants ◽  
Rhodococcus Species ◽  
Wide Range ◽  
Rigid Cell Wall

Under conditions of increasing environmental pollution, true saprophytes are capable of changing their survival strategies and demonstrating certain pathogenicity factors. Actinobacteria of the genus Rhodococcus, typical soil and aquatic biotope inhabitants, are characterized by high ecological plasticity and a wide range of oxidized organic substrates, including hydrocarbons and their derivatives. Their cell adaptations, such as the ability of adhering and colonizing surfaces, a complex life cycle, formation of resting cells and capsule-like structures, diauxotrophy, and a rigid cell wall, developed against the negative effects of anthropogenic pollutants are discussed and the risks of possible pathogenization of free-living saprotrophic Rhodococcus species are proposed. Due to universal adaptation features, Rhodococcus species are among the candidates, if further anthropogenic pressure increases, to move into the group of potentially pathogenic organisms with “unprofessional” parasitism, and to join an expanding list of infectious agents as facultative or occasional parasites.

scholarly journals A general approach to high-efficiency perovskite solar cells by any antisolvent

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Alexander D. Taylor ◽  
Qing Sun ◽  
Katelyn P. Goetz ◽  
Qingzhi An ◽  
Tim Schramm ◽  
...  
Keyword(s):  
Solar Cells ◽  
High Efficiency ◽  
Perovskite Solar Cells ◽  
Precursor Solution ◽  
Microstructural Characterization ◽  
Application Rate ◽  
Perovskite Layer ◽  
Highly Efficient ◽  
Application Procedure ◽  
Wide Range

AbstractDeposition of perovskite films by antisolvent engineering is a highly common method employed in perovskite photovoltaics research. Herein, we report on a general method that allows for the fabrication of highly efficient perovskite solar cells by any antisolvent via manipulation of the antisolvent application rate. Through detailed structural, compositional, and microstructural characterization of perovskite layers fabricated by 14 different antisolvents, we identify two key factors that influence the quality of the perovskite layer: the solubility of the organic precursors in the antisolvent and its miscibility with the host solvent(s) of the perovskite precursor solution, which combine to produce rate-dependent behavior during the antisolvent application step. Leveraging this, we produce devices with power conversion efficiencies (PCEs) that exceed 21% using a wide range of antisolvents. Moreover, we demonstrate that employing the optimal antisolvent application procedure allows for highly efficient solar cells to be fabricated from a broad range of precursor stoichiometries.

scholarly journals Octane Index Applicability over the Pressure-Temperature Domain

Energies ◽  
2021 ◽  
Vol 14 (3) ◽  
pp. 607
Author(s):  
Tommy R. Powell ◽  
James P. Szybist ◽  
Flavio Dal Forno Chuahy ◽  
Scott J. Curran ◽  
John Mengwasser ◽  
...  
Keyword(s):  
High Efficiency ◽  
National Laboratory ◽  
Operating Conditions ◽  
Dominant Factor ◽  
Compression Ignition ◽  
Oak Ridge ◽  
Operating Modes ◽  
Wide Range ◽  
Thermodynamic Conditions ◽  
Si Engines

Modern boosted spark-ignition (SI) engines and emerging advanced compression ignition (ACI) engines operate under conditions that deviate substantially from the conditions of conventional autoignition metrics, namely the research and motor octane numbers (RON and MON). The octane index (OI) is an emerging autoignition metric based on RON and MON which was developed to better describe fuel knock resistance over a broader range of engine conditions. Prior research at Oak Ridge National Laboratory (ORNL) identified that OI performs reasonably well under stoichiometric boosted conditions, but inconsistencies exist in the ability of OI to predict autoignition behavior under ACI strategies. Instead, the autoignition behavior under ACI operation was found to correlate more closely to fuel composition, suggesting fuel chemistry differences that are insensitive to the conditions of the RON and MON tests may become the dominant factor under these high efficiency operating conditions. This investigation builds on earlier work to study autoignition behavior over six pressure-temperature (PT) trajectories that correspond to a wide range of operating conditions, including boosted SI operation, partial fuel stratification (PFS), and spark-assisted compression ignition (SACI). A total of 12 different fuels were investigated, including the Co-Optima core fuels and five fuels that represent refinery-relevant blending streams. It was found that, for the ACI operating modes investigated here, the low temperature reactions dominate reactivity, similar to boosted SI operating conditions because their PT trajectories lay close to the RON trajectory. Additionally, the OI metric was found to adequately predict autoignition resistance over the PT domain, for the ACI conditions investigated here, and for fuels from different chemical families. This finding is in contrast with the prior study using a different type of ACI operation with different thermodynamic conditions, specifically a significantly higher temperature at the start of compression, illustrating that fuel response depends highly on the ACI strategy being used.

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