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Accounts of Chemical Research Jun 2021Carbohydrates (glycans, saccharides, and sugars) are essential molecules in all domains of life. Research on glycoscience spans from chemistry to biomedicine, including... (Review)
Review
Carbohydrates (glycans, saccharides, and sugars) are essential molecules in all domains of life. Research on glycoscience spans from chemistry to biomedicine, including material science and biotechnology. Access to pure and well-defined complex glycans using synthetic methods depends on the success of the employed glycosylation reaction. In most cases, the mechanism of the glycosylation reaction is believed to involve the oxocarbenium ion. Understanding the structure, conformation, reactivity, and interactions of this glycosyl cation is essential to predict the outcome of the reaction. In this Account, building on our contributions on this topic, we discuss the theoretical and experimental approaches that have been employed to decipher the key features of glycosyl cations, from their structures to their interactions and reactivity.We also highlight that, from a chemical perspective, the glycosylation reaction can be described as a continuum, from unimolecular S1 with naked oxocarbenium cations as intermediates to bimolecular S2-type mechanisms, which involve the key role of counterions and donors. All these factors should be considered and are discussed herein. The importance of dissociative mechanisms (involving contact ion pairs, solvent-separated ion pairs, solvent-equilibrated ion pairs) with bimolecular features in most reactions is also highlighted.The role of theoretical calculations to predict the conformation, dynamics, and reactivity of the oxocarbenium ion is also discussed, highlighting the advances in this field that now allow access to the conformational preferences of a variety of oxocarbenium ions and their reactivities under S1-like conditions.Specifically, the ground-breaking use of superacids to generate these cations is emphasized, since it has permitted characterization of the structure and conformation of a variety of glycosyl oxocarbenium ions in superacid solution by NMR spectroscopy.We also pay special attention to the reactivity of these glycosyl ions, which depends on the conditions, including the counterions, the possible intra- or intermolecular participation of functional groups that may stabilize the cation and the chemical nature of the acceptor, either weak or strong nucleophile. We discuss recent investigations from different experimental perspectives, which identified the involved ionic intermediates, estimating their lifetimes and reactivities and studying their interactions with other molecules. In this context, we also emphasize the relationship between the chemical methods that can be employed to modulate the sensitivity of glycosyl cations and the way in which glycosyl modifying enzymes (glycosyl hydrolases and transferases) build and cleave glycosidic linkages in nature. This comparison provides inspiration on the use of molecules that regulate the stability and reactivity of glycosyl cations.
Topics: Glycosylation; Ions; Methane; Models, Molecular; Molecular Conformation
PubMed: 33930267
DOI: 10.1021/acs.accounts.1c00021 -
Chemical Reviews Feb 2020In this contribution, we provide a comprehensive overview of C-H activation methods promoted by NHC-transition metal complexes, covering the literature since 2002 (the... (Review)
Review
In this contribution, we provide a comprehensive overview of C-H activation methods promoted by NHC-transition metal complexes, covering the literature since 2002 (the year of the first report on metal-NHC-catalyzed C-H activation) through June 2019, focusing on both NHC ligands and C-H activation methods. This review covers C-H activation reactions catalyzed by group 8 to 11 NHC-metal complexes. Through discussing the role of NHC ligands in promoting challenging C-H activation methods, the reader is provided with an overview of this important area and its crucial role in forging carbon-carbon and carbon-heteroatom bonds by directly engaging ubiquitous C-H bonds.
Topics: Chemistry Techniques, Synthetic; Heterocyclic Compounds; Imidazoles; Methane; Organometallic Compounds; Oxazoles; Palladium; Thiazoles
PubMed: 31967451
DOI: 10.1021/acs.chemrev.9b00634 -
Proceedings of the National Academy of... Oct 2022China is set to actively reduce its methane emissions in the coming decade. A comprehensive evaluation of the current situation can provide a reference point for...
China is set to actively reduce its methane emissions in the coming decade. A comprehensive evaluation of the current situation can provide a reference point for tracking the country's future progress. Here, using satellite and surface observations, we quantify China's methane emissions during 2010-2017. Including newly available data from a surface network across China greatly improves our ability to constrain emissions at subnational and sectoral levels. Our results show that recent changes in China's methane emissions are linked to energy, agricultural, and environmental policies. We find contrasting methane emission trends in different regions attributed to coal mining, reflecting region-dependent responses to China's energy policy of closing small coal mines (decreases in Southwest) and consolidating large coal mines (increases in North). Coordinated production of coalbed methane and coal in southern Shanxi effectively decreases methane emissions, despite increased coal production there. We also detect unexpected increases from rice cultivation over East and Central China, which is contributed by enhanced rates of crop-residue application, a factor not accounted for in current inventories. Our work identifies policy drivers of recent changes in China's methane emissions, providing input to formulating methane policy toward its climate goal.
Topics: Agriculture; China; Coal; Methane; Policy
PubMed: 36191196
DOI: 10.1073/pnas.2202742119 -
Archives of Biochemistry and Biophysics Apr 2011Because angiogenesis underlies the pathogenesis of numerous conditions (cancer, psoriasis, macular degeneration), there is a pressing need for continued investigations... (Review)
Review
Because angiogenesis underlies the pathogenesis of numerous conditions (cancer, psoriasis, macular degeneration), there is a pressing need for continued investigations into angiogenic signaling and potential drug targets. Antiangiogenic agents can be classified as either direct or indirect. Direct antiangiogenics act on untransformed endothelial cells to prevent differentiation and proliferation; indirect antiangiogenics act to inhibit factors involved in proangiogenic signaling. Agents currently available with dermatologic indications are few; while several established and novel biologics targeting various proangiogenic factors are currently being investigated for potential dermatologic uses, but the jury is still out on their efficacy and safety. In this review, we highlight our experience with a group of existing and novel, small molecules that combine several modes of action against angiogenesis in addition to other properties--triarylmethane dyes and fulvene derivatives.
Topics: Angiogenesis Inhibitors; Animals; Coloring Agents; Dermatology; Humans; Methane
PubMed: 21172300
DOI: 10.1016/j.abb.2010.12.016 -
Nature Feb 2015The most powerful oxidant found in nature is compound Q, an enzymatic intermediate that oxidizes methane. New spectroscopic data have resolved the long-running...
The most powerful oxidant found in nature is compound Q, an enzymatic intermediate that oxidizes methane. New spectroscopic data have resolved the long-running controversy about Q’s chemical structure.
Topics: Iron Compounds; Methane; Methanol; Oxygenases
PubMed: 25607367
DOI: 10.1038/nature14199 -
Journal of the American Chemical Society May 2022Biocatalytic carbene transfer from diazo compounds is a versatile strategy in asymmetric synthesis. However, the limited pool of stable diazo compounds constrains the...
Biocatalytic carbene transfer from diazo compounds is a versatile strategy in asymmetric synthesis. However, the limited pool of stable diazo compounds constrains the variety of accessible products. To overcome this restriction, we have engineered variants of protoglobin (Pgb) that use diazirines as carbene precursors. While the enhanced stability of diazirines relative to their diazo isomers enables access to a diverse array of carbenes, they have previously resisted catalytic activation. Our engineered Pgb variants represent the first example of catalysts for selective carbene transfer from these species at room temperature. The structure of an Pgb variant, determined by microcrystal electron diffraction (MicroED), reveals that evolution has enhanced access to the heme active site to facilitate this new-to-nature catalysis. Using readily prepared aryl diazirines as model substrates, we demonstrate the application of these highly stable carbene precursors in biocatalytic cyclopropanation, N-H insertion, and Si-H insertion reactions.
Topics: Azo Compounds; Biocatalysis; Catalysis; Diazomethane; Methane
PubMed: 35561334
DOI: 10.1021/jacs.2c02723 -
Proceedings of the National Academy of... Apr 2022Methane has been proposed as an exoplanet biosignature. Imminent observations with the James Webb Space Telescope may enable methane detections on potentially habitable...
Methane has been proposed as an exoplanet biosignature. Imminent observations with the James Webb Space Telescope may enable methane detections on potentially habitable exoplanets, so it is essential to assess in what planetary contexts methane is a compelling biosignature. Methane’s short photochemical lifetime in terrestrial planet atmospheres implies that abundant methane requires large replenishment fluxes. While methane can be produced by a variety of abiotic mechanisms such as outgassing, serpentinizing reactions, and impacts, we argue that—in contrast to an Earth-like biosphere—known abiotic processes cannot easily generate atmospheres rich in CH4 and CO2 with limited CO due to the strong redox disequilibrium between CH4 and CO2. Methane is thus more likely to be biogenic for planets with 1) a terrestrial bulk density, high mean-molecular-weight and anoxic atmosphere, and an old host star; 2) an abundance of CH4 that implies surface fluxes exceeding what could be supplied by abiotic processes; and 3) atmospheric CO2 with comparatively little CO.
Topics: Atmosphere; Earth, Planet; Exobiology; Extraterrestrial Environment; Methane; Planets
PubMed: 35353627
DOI: 10.1073/pnas.2117933119 -
Environmental Health Perspectives Jun 1995Chlorinated methanes are important industrial chemicals and significant environmental pollutants. While the highly chlorinated methanes, trichloromethane and... (Review)
Review
Chlorinated methanes are important industrial chemicals and significant environmental pollutants. While the highly chlorinated methanes, trichloromethane and tetrachloromethane, are not productively metabolized by bacteria, chloromethane and dichloromethane are used by both aerobic and anaerobic methylotrophic bacteria as carbon and energy sources. Some of the dehalogenation reactions involved in the utilization of the latter two compounds have been elucidated. In a strictly anaerobic acetogenic bacterium growing with chloromethane, an inducible enzyme forming methyltetrahydrofolate and chloride from chloromethane and tetrahydrofolate catalyzes dehalogenation of the growth substrate. A different mechanism for the nucleophilic displacement of chloride is observed in aerobic methylotrophic bacteria utilizing dichloromethane as the sole carbon and energy source. These organisms possess the enzyme dichloromethane dehalogenase which, in a glutathione-dependent reaction, converts dichloromethane to inorganic chloride and formaldehyde, a central metabolite of methylotrophic growth. Sequence comparisons have shown that bacterial dichloromethane dehalogenases belong to the glutathione S-transferase enzyme family, and within this family to class Theta. The dehalogenation reactions underlying aerobic utilization of chloromethane by a pure culture and anaerobic growth with dichloromethane by an acetogenic mixed culture are not known. It appears that they are based on mechanisms other than nucleophilic attack by tetrahydrofolate or glutathione.
Topics: Bacteria; Bacteria, Anaerobic; Hydrocarbons, Chlorinated; Methane; Methylene Chloride
PubMed: 8565906
DOI: 10.1289/ehp.95103s433 -
Journal of Visualized Experiments : JoVE Jun 2016The use of natural gas continues to grow with increased discovery and production of unconventional shale resources. At the same time, the natural gas industry faces...
The use of natural gas continues to grow with increased discovery and production of unconventional shale resources. At the same time, the natural gas industry faces continued scrutiny for methane emissions from across the supply chain, due to methane's relatively high global warming potential (25-84x that of carbon dioxide, according to the Energy Information Administration). Currently, a variety of techniques of varied uncertainties exists to measure or estimate methane emissions from components or facilities. Currently, only one commercial system is available for quantification of component level emissions and recent reports have highlighted its weaknesses. In order to improve accuracy and increase measurement flexibility, we have designed, developed, and implemented a novel full flow sampling system (FFS) for quantification of methane emissions and greenhouse gases based on transportation emissions measurement principles. The FFS is a modular system that consists of an explosive-proof blower(s), mass airflow sensor(s) (MAF), thermocouple, sample probe, constant volume sampling pump, laser based greenhouse gas sensor, data acquisition device, and analysis software. Dependent upon the blower and hose configuration employed, the current FFS is able to achieve a flow rate ranging from 40 to 1,500 standard cubic feet per minute (SCFM). Utilization of laser-based sensors mitigates interference from higher hydrocarbons (C2+). Co-measurement of water vapor allows for humidity correction. The system is portable, with multiple configurations for a variety of applications ranging from being carried by a person to being mounted in a hand drawn cart, on-road vehicle bed, or from the bed of utility terrain vehicles (UTVs). The FFS is able to quantify methane emission rates with a relative uncertainty of ± 4.4%. The FFS has proven, real world operation for the quantification of methane emissions occurring in conventional and remote facilities.
Topics: Carbon Dioxide; Gases; Greenhouse Effect; Methane; Natural Gas
PubMed: 27341646
DOI: 10.3791/54179 -
The Science of the Total Environment Oct 2021Ventilation Air Methane emissions (VAM) from coal mines lead to environmental concern because their high global warming potential and the loss of methane resources. VAM... (Review)
Review
Ventilation Air Methane emissions (VAM) from coal mines lead to environmental concern because their high global warming potential and the loss of methane resources. VAM upgrading requires pre-concentration processes dealing with high flow rates of very diluted streams (<1% methane). Therefore, methane separation and concentration is technically challenging and has important environmental and safety concerns. Among the alternatives, adsorption on Metal-Organic Frameworks (MOFs) could be an interesting option to methane selective separation, due to its tuneable character and outstanding physical properties. Most of the works devoted to the methane adsorption on MOFs deal with methane storage. Therefore, these works were reviewed to determine the properties governing methane-MOF interactions. In addition, the metallic ions and organic linkers roles have been identified. With these premises, decisive effects in the methane adsorption selectivity in nitrogen/methane lean mixtures have been discussed, since nitrogen is the most concentrated gas in the VAM stream, and it is very similar to methane molecule. In order to fulfill this overview, the effect of other aspects, such as the presence of polar compounds (moisture and carbon dioxide), was also considered. In addition, engineering considerations in the operation of fixed bed adsorption units and the main challenges associated to MOFs as adsorbents were also discussed.
Topics: Carbon Dioxide; Coal Mining; Metal-Organic Frameworks; Methane; Rivers
PubMed: 34111784
DOI: 10.1016/j.scitotenv.2021.148211