Carbonyl Sulfide Hydrolase from <i>Thiobacillus thioparus</i> Strain THI115 Is One of the β-Carbonic Anhydrase Family Enzymes

Ogawa, Takahiro; Noguchi, Keiichi; Saito, M.; Nagahata, Yoshiko; Kato, Hiromi; Ohtaki, Akashi; Nakayama, Hiroshi; Dohmae, Naoshi; Matsushita, Yasuhiko; Odaka, Masafumi; Yohda, Masafumi; Nyunoya, Hiroshi; Katayama, Yoko

doi:10.1021/ja307735e

Cited by 89 publications

(124 citation statements)

References 58 publications

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“…We will assume that such a catalysed reaction by CA-containing organisms can be described by Michaelis-Menten kinetics, as was observed for OCS in several marine algae species (Blezinger et al, 2000;ProtoschillKrebs et al, 1995) and one flour beetle (Haritos and Dojchinov, 2005). Because of the low concentrations of OCS in ambient air (500 ppt) and the comparatively high values of the Michaelis-Menten coefficient for OCS (K m , see Ogawa et al (2013);Protoschill-Krebs et al, 1995 the catalysed uptake rate S cat (mol m −3 s −1 ) can be approximated:…”

Section: Consumption and Production Ratesmentioning

confidence: 97%

“…For example Smeulders et al found a carbon disulfide hydrolase from an acido-thermophilic archaeon that was very efficient at catalysing OCS hydrolysis but did not have CO 2 as one of its substrates (Smeulders et al, 2012). More recently, Ogawa et al (2013) found in Thiobacillus thioparus, a sulfur-oxidising bacterium widely distributed in soils and freshwaters, an enzyme that shared a high similarity with β-CAs and was able to catalyse OCS hydrolysis with a similar efficiency (K M = 60 µM, k cat = 58 s −1 at pH 8.5 and 30 • C) but whose CO 2 hydration activity was 3-4 orders of magnitude smaller than that of β-CAs. For this reason they called this enzyme carbonyl sulfide hydrolase (COSase).…”

Section: Can the Proposed Model Explain Observations Realistically?mentioning

confidence: 99%

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A new mechanistic framework to predict OCS fluxes from soils

Ogée¹,

et al. 2016

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Abstract.Estimates of photosynthetic and respiratory fluxes at large scales are needed to improve our predictions of the current and future global CO 2 cycle. Carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere and has been proposed as a new tracer of photosynthetic gross primary productivity (GPP), as the uptake of OCS from the atmosphere is dominated by the activity of carbonic anhydrase (CA), an enzyme abundant in leaves that also catalyses CO 2 hydration during photosynthesis. However soils also exchange OCS with the atmosphere, which complicates the retrieval of GPP from atmospheric budgets. Indeed soils can take up large amounts of OCS from the atmosphere as soil microorganisms also contain CA, and OCS emissions from soils have been reported in agricultural fields or anoxic soils. To date no mechanistic framework exists to describe this exchange of OCS between soils and the atmosphere, but empirical results, once upscaled to the global scale, indicate that OCS consumption by soils dominates OCS emission and its contribution to the atmospheric budget is large, at about one third of the OCS uptake by vegetation, also with a large uncertainty. Here, we propose a new mechanistic model of the exchange of OCS between soils and the atmosphere that builds on our knowledge of soil CA activity from CO 2 oxygen isotopes. In this model the OCS soil budget is described by a first-order reaction-diffusion-production equation, assuming that the hydrolysis of OCS by CA is total and irreversible. Using this model we are able to explain the observed presence of an optimum temperature for soil OCS uptake and show how this optimum can shift to cooler temperatures in the presence of soil OCS emission. Our model can also explain the observed optimum with soil moisture content previously described in the literature as a result of diffusional constraints on OCS hydrolysis. These diffusional constraints are also responsible for the response of OCS uptake to soil weight and depth observed previously. In order to simulate the exact OCS uptake rates and patterns observed on several soils collected from a range of biomes, different CA activities had to be invoked in each soil type, coherent with expected physiological levels of CA in soil microbes and with CA activities derived from CO 2 isotope exchange measurements, given the differences in affinity of CA for both trace gases. Our model can be used to help upscale laboratory measurements to the plot or the region. Several suggestions are given for future experiments in order to test the model further and allow a better constraint on the large-scale OCS fluxes from both oxic and anoxic soils.

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Section: Consumption and Production Ratesmentioning

confidence: 97%

Section: Can the Proposed Model Explain Observations Realistically?mentioning

confidence: 99%

A new mechanistic framework to predict OCS fluxes from soils

Ogée¹,

et al. 2016

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“…Sun et al: Soil COS, CO, and CO 2 fluxes at Hyytiälä COS participates in land carbon cycle processes due to its chemical similarities to CO 2 (Kettle et al, 2002;Montzka et al, 2007;Berry et al, 2013). In leaf chloroplasts and soil microbes, COS as a substrate of carbonic anhydrase is hydrolyzed irreversibly to CO 2 and H 2 S (Protoschill-Krebs and Kesselmeier, 1992;Protoschill-Krebs et al, 1996;Stimler et al, 2010Stimler et al, , 2011Kesselmeier et al, 1999;Saito et al, 2002;Kato et al, 2008;Ogawa et al, 2013). The hydrolysis occurs in parallel to CO 2 hydration, the main physiological function of carbonic anhydrase (Badger and Price, 1994;Henry, 1996).…”

mentioning

confidence: 99%

“…Soil CO uptake is primarily due to microbial activity (Inman et al, 1971;Conrad and Seiler, 1980;Whalen and Reeburgh, 2001) and involves more diverse metabolic pathways compared with those in COS uptake (Mörsdorf et al, 1992;King and Weber, 2007;Ogawa et al, 2013). The key environmental factors controlling CO uptake rates include soil moisture and temperature (Conrad and Seiler, 1985;King, 1999;Yonemura et al, 2000a).…”

mentioning

confidence: 99%

Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland

et al. 2018

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Abstract. Soil is a major contributor to the biosphereatmosphere exchange of carbonyl sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify terrestrial photosynthesis based on the coupled leaf uptake of COS and CO 2 , but such use requires separating soil COS flux, which is unrelated to photosynthesis, from ecosystem COS uptake. For CO, soil is a significant natural sink that influences the tropospheric CO budget. In the boreal forest, magnitudes and variabilities of soil COS and CO fluxes remain poorly understood. We measured hourly soil fluxes of COS, CO, and CO 2 over the 2015 late growing season (July to November) in a Scots pine forest in Hyytiälä, Finland. The soil acted as a net sink of COS and CO, with average uptake rates around 3 pmol m −2 s −1 for COS and 1 nmol m −2 s −1 for CO. Soil respiration showed seasonal dynamics controlled by soil temperature, peaking at around 4 µmol m −2 s −1 in late August and September and dropping to 1-2 µmol m −2 s −1 in October. In contrast, seasonal variations of COS and CO fluxes were weak and mainly driven by soil moisture changes through diffusion limitation. COS and CO fluxes did not appear to respond to temperature variation, although they both correlated well with soil respiration in specific temperature bins. However, COS : CO 2 and CO : CO 2 flux ratios increased with temperature, suggesting possible shifts in active COS-and CO-consuming microbial groups. Our results show that soil COS and CO fluxes do not have strong variations over the late growing season in this boreal forest and can be represented with the fluxes during the photosynthetically most active period. Well-characterized and relatively invariant soil COS fluxes strengthen the case for using COS as a photosynthetic tracer in boreal forests.

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“…In general the catalytic efficiency of the γ-, δ-and ζ-CAs is low compared to the β-and η-CAs, which in turn are less efficient catalysts compared to many bacterial α-CAs [6,9,11,17]. Interestingly, γ-CAs use only CO 2 as substrate, while β-CAs can hydrolyze CO 2, H 2 S and COS [18]. Furthermore, α-CAs not only hydrate CO 2 , CS 2 but also possess esterase activity, with a range of esters of carboxylic, sulfonic or phosphate acids [6,9,11,17,19,20].…”

Section: Carbonic Anhydrasesmentioning

confidence: 99%

Inhibition of Bacterial Carbonic Anhydrases as a Novel Approach to Escape Drug Resistance

Capasso

Supuran

2017

CTMC

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Background: Clinically used antibiotics act through one of these four mechanisms: cell wall biosynthesis inhibition, inhibition of protein biosynthesis, interference with DNA and RNA synthesis and the folate pathway. Objective:The metalloenzymes carbonic anhydrases (CAs, EC 4.2.1.1) widespread in microorganisms and present as three genetically distinct families may be considered for the design of antiinfective agents with a different mechanism of action compared to the clinically used antibiotics. CAs are crucial for the life cycle of the pathogen, interfering with pH regulation and biosynthetic processes in which CO 2 or bicarbonate are substrates. CA inhibition was shown to lead to debilitation or growth defects of several pathogenic bacteria. Method:CAs catalyzes the interconversion between carbon dioxide to bicarbonate, leading to the formation of protons, and thus affecting pH homeostasis. Several classes of CA inhibitors (CAIs) are known to date, among which the metal complexing anions, the unsubstituted sulfonamides, the dithiocarbamates, etc., which bind to the Zn(II) ion of the enzyme either by substituting the non-protein zinc ligand or add to the metal coordination sphere.Results: Effective inhibitors for many bacterial CAs belonging to the α-, β-, and γ-CA classes were detected, some of which inhibited bacterial growth in vivo. Few of the inhibitors investigated so far were also selective for the bacterial over the human CA isoforms, which may pose problems for their wide clinical applications. Conclusion:Structure-based drug design campaigns might lead to the achievement of the desired selectivity/potency for preferentially inhibiting bacterial but not the host CAs.

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Carbonyl Sulfide Hydrolase from Thiobacillus thioparus Strain THI115 Is One of the β-Carbonic Anhydrase Family Enzymes

Cited by 89 publications

References 58 publications

A new mechanistic framework to predict OCS fluxes from soils

A new mechanistic framework to predict OCS fluxes from soils

Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland

Inhibition of Bacterial Carbonic Anhydrases as a Novel Approach to Escape Drug Resistance

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