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Acido solfidrico nella letteratura internazionale Studi inseriti in PubMed nel mese di ottobre 2014 aggiornamento al 6 novembre 2014 (1) Macey GP, Breech R, Chernaik M, Cox C, Larson D, Thomas D, et al. Air concentrations of volatile compounds near oil and gas production: a community-based exploratory study. Environ Health 2014;13:82. Abstract: BACKGROUND: Horizontal drilling, hydraulic fracturing, and other drilling and well stimulation technologies are now used widely in the United States and increasingly in other countries. They enable increases in oil and gas production, but there has been inadequate attention to human health impacts. Air quality near oil and gas operations is an underexplored human health concern for five reasons: (1) prior focus on threats to water quality; (2) an evolving understanding of contributions of certain oil and gas production processes to air quality; (3) limited state air quality monitoring networks; (4) significant variability in air emissions and concentrations; and (5) air quality research that misses impacts important to residents. Preliminary research suggests that volatile compounds, including hazardous air pollutants, are of potential concern. This study differs from prior research in its use of a community-based process to identify sampling locations. Through this approach, we determine concentrations of volatile compounds in air near operations that reflect community concerns and point to the need for more fine-grained and frequent monitoring at points along the production life cycle. METHODS: Grab and passive air samples were collected by trained volunteers at locations identified through systematic observation of industrial operations and air impacts over the course of resident daily routines. A total of 75 volatile organics were measured using EPA Method TO-15 or TO-3 by gas chromatography/mass spectrometry. Formaldehyde levels were determined using UMEx 100 Passive Samplers. RESULTS: Levels of eight volatile chemicals exceeded federal guidelines under several operational circumstances. Benzene, formaldehyde, and hydrogen sulfide were the most common compounds to exceed acute and other health-based risk levels. CONCLUSIONS: Air concentrations of potentially dangerous compounds and chemical mixtures are frequently present near oil and gas production sites. Community-based research can provide an important supplement to state air quality monitoring programs (2) Huber B, Drewes JE, Lin KC, Konig R, Muller E. Revealing biogenic sulfuric acid corrosion in sludge digesters: detection of sulfur-oxidizing bacteria within full-scale digesters. Water Sci Technol 2014 Oct;70(8):1405-11. Abstract: Biogenic sulfuric acid corrosion (BSA) is a costly problem affecting both sewerage infrastructure and sludge handling facilities such as digesters. The aim of this study was to verify BSA in full-scale digesters by identifying the microorganisms involved in the concrete corrosion process, that is, sulfate-reducing (SRB) and sulfur-oxidizing bacteria (SOB). To investigate the SRB and SOB communities, digester sludge and biofilm samples were collected. SRB diversity within digester sludge was studied by applying polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) targeting the dsrB-gene (dissimilatory sulfite reductase beta subunit). To reveal SOB diversity, cultivation dependent and independent techniques were applied. The SRB diversity studies revealed different uncultured SRB, confirming SRB activity and H2S production. Comparable DGGE profiles were obtained from the different sludges,

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Page 1: Studi inseriti in PubMed nel mese di ottobre 2014 · potentially dangerous compounds and chemical mixtures are frequently present near oil and gas production sites. Community-based

Acido solfidrico nella letteratura internazionale

Studi inseriti in PubMed nel mese di ottobre 2014

aggiornamento al 6 novembre 2014

(1) Macey GP, Breech R, Chernaik M, Cox C, Larson D, Thomas D, et al. Air concentrations

of volatile compounds near oil and gas production: a community-based exploratory study. Environ Health 2014;13:82. Abstract: BACKGROUND: Horizontal drilling, hydraulic fracturing, and other drilling and well stimulation technologies are now used widely in the United States and increasingly in other countries. They enable increases in oil and gas production, but there has been inadequate attention to human health impacts. Air quality near oil and gas operations is an underexplored human health concern for five reasons: (1) prior focus on threats to water quality; (2) an evolving understanding of contributions of certain oil and gas production processes to air quality; (3) limited state air quality monitoring networks; (4) significant variability in air emissions and concentrations; and (5) air quality research that misses impacts important to residents. Preliminary research suggests that volatile compounds, including hazardous air pollutants, are of potential concern. This study differs from prior research in its use of a community-based process to identify sampling locations. Through this approach, we determine concentrations of volatile compounds in air near operations that reflect community concerns and point to the need for more fine-grained and frequent monitoring at points along the production life cycle. METHODS: Grab and passive air samples were collected by trained volunteers at locations identified through systematic observation of industrial operations and air impacts over the course of resident daily routines. A total of 75 volatile organics were measured using EPA Method TO-15 or TO-3 by gas chromatography/mass spectrometry. Formaldehyde levels were determined using UMEx 100 Passive Samplers. RESULTS: Levels of eight volatile chemicals exceeded federal guidelines under several operational circumstances. Benzene, formaldehyde, and hydrogen sulfide were the most common compounds to exceed acute and other health-based risk levels. CONCLUSIONS: Air concentrations of potentially dangerous compounds and chemical mixtures are frequently present near oil and gas production sites. Community-based research can provide an important supplement to state air quality monitoring programs

(2) Huber B, Drewes JE, Lin KC, Konig R, Muller E. Revealing biogenic sulfuric acid corrosion in sludge digesters: detection of sulfur-oxidizing bacteria within full-scale digesters. Water Sci Technol 2014 Oct;70(8):1405-11. Abstract: Biogenic sulfuric acid corrosion (BSA) is a costly problem affecting both sewerage infrastructure and sludge handling facilities such as digesters. The aim of this study was to verify BSA in full-scale digesters by identifying the microorganisms involved in the concrete corrosion process, that is, sulfate-reducing (SRB) and sulfur-oxidizing bacteria (SOB). To investigate the SRB and SOB communities, digester sludge and biofilm samples were collected. SRB diversity within digester sludge was studied by applying polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) targeting the dsrB-gene (dissimilatory sulfite reductase beta subunit). To reveal SOB diversity, cultivation dependent and independent techniques were applied. The SRB diversity studies revealed different uncultured SRB, confirming SRB activity and H2S production. Comparable DGGE profiles were obtained from the different sludges,

Page 2: Studi inseriti in PubMed nel mese di ottobre 2014 · potentially dangerous compounds and chemical mixtures are frequently present near oil and gas production sites. Community-based

demonstrating the presence of similar SRB species. By cultivation, three pure SOB strains from the digester headspace were obtained including Acidithiobacillus thiooxidans, Thiomonas intermedia and Thiomonas perometabolis. These organisms were also detected with PCR-DGGE in addition to two new SOB: Thiobacillus thioparus and Paracoccus solventivorans. The SRB and SOB responsible for BSA were identified within five different digesters, demonstrating that BSA is a problem occurring not only in sewer systems but also in sludge digesters. In addition, the presence of different SOB species was successfully associated with the progression of microbial corrosion

(3) Zhang Y, Moschandreas D, Pagilla K. Seasonal and influent characteristic effects on hydrogen sulfide generation at a water reclamation plant. Water Sci Technol 2014 Oct;70(8):1322-8. Abstract: Correlations between sulfide generation and seasonal influent wastewater characteristics were identified based on a long-term monitoring program in summer and winter at a water reclamation plant. During summer, the emission rates of hydrogen sulfide (H2S) from the liquid treatment processes increased substantially compared to those during winter due to the increased wastewater temperature. The open tanks/clarifiers were the least significant H2S emission contributors throughout the year. For solids-handling processes, the H2S emission rates did not change during the year due to similar sludge characteristics in the different seasons. The fate of sulfide in liquid treatment processes was investigated as an alternative to estimation of H2S emissions. H2S emission from the wet well and screens was proven to be robustly associated with the wastewater temperature, flow rate, 5-day biochemical oxygen demand and total Kjeldahl nitrogen levels. However, the correlation between influent parameters and H2S emission from aerated grit chambers was not statistically significant

(4) Brenner M. Re: Letter to the editor about "The Vitamin B12 Analog Cobinamide is an Effective Hydrogen Sulfide Antidote in a Lethal Rabbit Model". Clin Toxicol (Phila) 2014 Oct 25;1.

(5) Ma Y, Su H, Kuang X, Li X, Zhang T, Tang B. A Heterogeneous Nano Metal-Organic Framework Fluorescence Probe for Highly Selective and Sensitive Detection of Hydrogen Sulfide in Living Cells. Anal Chem 2014 Oct 24. Abstract: Hydrogen sulfide (H2S) has been regarded as the third important gaseous signaling molecule involved in human physiological and pathological process. Due to the high reactive and diffusible properties of H2S, real-time detection of H2S fluctuations in living biological specimens is crucial. Here, we presented a Cu(II) metalated 3D porous nanoscale metal-organic framework {CuL[AlOH]2}n (PAC, H6L = meso-tetra(4-carboxyl-phenyl)porphyrin) and successfully employed this nano-MOF as a novel heterogeneous fluorescence probe for H2S detection. As far as we know, nano-MOFs have never been used as selective fluorescence probes for H2S detection. Based on the advantages of nano-MOF materials, this biocompatible nano-MOF probe exhibits rapid response, excellent selectivity and hypotoxicity in in-situ detection of H2S, and represents the most sensitive fluorescence probe for selective H2S detection under physiological pH. In addition, the confocal imaging was achieved successfully in living cells

(6) Ge J, Chu J, Jiang J, Yan Y, Yang P. Characteristics of In-substituted CZTS thin film and bifacial solar cell. ACS Appl Mater Interfaces 2014 Oct 23. Abstract: Implementing bifacial photovoltaic devices based on transparent conducting oxides (TCO) as the front and back contacts is highly appealing to improve the efficiency of kesterite solar cells. The p-type In substituted Cu2ZnSnS4 (CZTIS) thin-film solar cell absorber has been fabricated on ITO glass by sulfurizing co-electroplated Cu-Zn-Sn-S precursors in H2S (vol. 5%) atmosphere at 520 degrees C for 30 min. Experimental proof, including X-ray diffraction, Raman spectroscopy, UV-Vis-NIR transmission/reflection spectra, PL spectra and electron microscopies, is presented for the interfacial reaction

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between the ITO back contact and CZTS absorber. This aggressive reaction due to thermal processing contributes to substitutional diffusion of In into CZTS, formation of secondary phases and electrically conductive degradation of ITO back contact. The structural, lattice vibrational, optical absorption, and defective properties of the CZTIS alloy absorber layer have been analyzed and discussed. The new dopant In is desirably capable of improving the open circuit voltage deficit of kesterite device. However, the non-ohmic back contact in the bifacial device negatively limits the open circuit voltage and fill factor, evidencing by illumination-/temperature-dependent J-V and frequency-dependent capacitance-voltage (C-V-f) measurements. A 3.4 % efficient solar cell is demonstrated under simultaneously bifacial illumination from both sides of TCO front and back contacts

(7) Frasdorf B, Radon C, Leimkuhler S. Characterization and Interaction Studies of Two Isoforms of the Dual Localized 3-Mercaptopyruvate Sulfurtransferase TUM1 from Humans. J Biol Chem 2014 Oct 21. Abstract: The human tRNA thiouridine modification protein (TUM1), also designated as 3-mercaptopyruvate sulfurtransferase (MPST), has been implicated in a wide range of physiological processes in the cell. The roles range from an involvement in thiolation of cytosolic tRNAs to the generation of H2S as signaling molecule both in mitochondria and the cytosol. TUM1 is a member of the sulfurtransferase family and catalyzes the conversion of 3-mercaptopyruvate to pyruvate and protein-bound persulfide. Here, we purified and characterized two novel TUM1 splice variants, designated as TUM1-Iso1 and TUM1-Iso2. The purified proteins showed similar kinetic behavior and comparable pH and temperature dependency. Cellular localization studies, however, showed a different localization pattern between the isoforms. TUM1-Iso1 is exclusively localized in the cytosol, while TUM1-Iso2 showed a dual localization both in the cytosol and mitochondria. Interaction studies were performed with the isoforms both in vitro using the purified proteins and in vivo by fluorescence analysis in human cells, using the split-EGFP system. The studies showed that TUM1 interacts with the L-cysteine desulfurase NFS1 and the rhodanese-like protein MOCS3, suggesting a dual function of TUM1 both in sulfur transfer for the biosynthesis of the molybdenum cofactor, and for the thiolation of tRNA. Our studies point to distinct roles of each TUM1 isoform in the sulfur transfer processes in the cell, with different compartmentalization of the two splice variants of TUM1

(8) Zhang J, Wang X, Chen Y, Yao W. Exhaled Hydrogen Sulfide Predicts Airway Inflammation Phenotype in COPD. Respir Care 2014 Oct 21. Abstract: BACKGROUND: The role of exhaled H2S as a marker of airway inflammation and its relationship with COPD severity remain to be determined. METHODS: Airway inflammation was classified in 77 COPD subjects based on the presence of inflammatory cells in induced sputum. We investigated the association between disease phenotype and exhaled H2S, lung function, and plasma levels of several inflammatory factors, including tumor necrosis factor alpha, interleukin-8, and leukotriene B4. RESULTS: In total, 33.77% of enrolled COPD subjects were diagnosed with eosinophilia. These subjects had a longer disease course, smoked fewer cigarettes, and experienced more frequent exacerbation events before study enrollment. However, they also had worse lung function and larger residual volume, they demonstrated greater changes in FEV1 following bronchodilator inhalation. Although levels of plasma inflammatory factors did not significantly differ between subjects with and without eosinophilia, subjects without eosinophilia had significantly higher levels of exhaled H2S (9.19 +/- 2.74 vs 7.24 +/- 1.68 parts per billion, P = .01). Furthermore, exhaled H2S levels were negatively correlated with induced sputum eosinophils (r = -0.45, P = .045), and positively correlated with inspiratory capacity in COPD subjects (r = 0.51, P = .026), but did not correlate significantly with plasma inflammatory factors. A cut-off value of 7.10 parts per billion of exhaled H2S predicted a non-eosinophilic phenotype with 68.6% sensitivity and 77.9% specificity. CONCLUSIONS: Exhaled levels of H2S were lower in subjects with

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eosinophilia. Increased levels of exhaled H2S predicted a non-eosinophilic phenotype in our study population

(9) Varlet V, Giuliani N, Palmiere C, Maujean G, Augsburger M. Hydrogen Sulfide Measurement by Headspace-gas Chromatography-mass Spectrometry (HS-GC-MS): Application to Gaseous Samples and Gas Dissolved in Muscle. J Anal Toxicol 2014 Oct 21. Abstract: The aim of our study was to present a new headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable to the routine determination of hydrogen sulfide (H2S) concentrations in biological and gaseous samples. The primary analytical drawback of the GC/MS methods for H2S measurement discussed in the literature was the absence of a specific H2S internal standard required to perform quantification. Although a deuterated hydrogen sulfide (D2S) standard is currently available, this standard is not often used because this standard is expensive and is only available in the gas phase. As an alternative approach, D2S can be generated in situ by reacting deuterated chloride with sodium sulfide; however, this technique can lead to low recovery yield and potential isotopic fractionation. Therefore, N2O was chosen for use as an internal standard. This method allows precise measurements of H2S concentrations in biological and gaseous samples. Therefore, a full validation using accuracy profile based on the beta-expectation tolerance interval is presented. Finally, this method was applied to quantify H2S in an actual case of H2S fatal intoxication

(10) [Propargylglycine restores endothelium-dependent relaxation of aortic smooth muscles in old rats]. Fiziol Zh 2014;60(4):3-10. Abstract: In the study we investigated the effect of blockade cystathionine-gamma -lyase (CSE), an enzyme of hydrogen sulfide (H2S) (de novo) synthesis on the endothelium-dependent relaxation of aortic smooth muscle (SM) in old rats. It has been shown that an inhibition of CSE by propargylglycine (PAG) results in restoration of a decreased ACh-induced relaxation of aorta in old rats. This effect of PAG was removed by blocking nitric oxide (NO) synthesis in the endothelial cells. Age-related changes in the levels of H2S, NO2- and enzyme activity of the constitutive synthesis of NO (cNOS) in the heart, were determined. It has been shown that PAG introduction elevates a decreased levels of HzS, NO2- and stimulates the suppressed activity of cNOS in old rats. These results suggest that PAG activates alternative ways of H2S synthesis and stimulates the constitutive synthesis of NO. These actions of PAG restore endothelial function in old rats

(11) Zayachkivska O, Havryluk O, Hrycevych N, Bula N, Grushka O, Wallace JL. Cytoprotective effects of hydrogen sulfide in novel rat models of non-erosive esophagitis. PLoS One 2014;9(10):e110688. Abstract: Non-erosive esophagitis is a chronic inflammatory condition of the esophagus and is a form of gastroesophageal reflux disease. There are limited treatment options for non-erosive esophagitis, and it often progresses to Barrett's esophagus and esophageal carcinoma. Hydrogen sulfide has been demonstrated to be a critical mediator of gastric and intestinal mucosal protection and repair. However, roles for H2S in esophageal mucosal defence, inflammation and responses to injury have not been reported. We therefore examined the effects of endogenous and exogenous H2S in rat models of non-erosive esophagitis. Mild- and moderate-severity non-erosive esophagitis was induced in rats through supplementation of drinking water with fructose, plus or minus exposure to water-immersion stress. The effects of inhibitors of H2S synthesis or of an H2S donor on severity of esophagitis was then examined, along with changes in serum levels of a pro- and an anti-inflammatory cytokine (IL-17 and IL-10, respectively). Exposure to water-immersion stress after consumption of the fructose-supplemented water for 28 days resulted in submucosal esophageal edema and neutrophil infiltration and the development of lesions in the muscular lamina and basal cell hyperplasia.

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Inhibition of H2S synthesis resulted in significant exacerbation of inflammation and injury. Serum levels of IL-17 were significantly elevated, while serum IL-10 levels were reduced. Treatment with an H2S donor significantly reduced the severity of esophageal injury and inflammation and normalized the serum cytokine levels. The rat models used in this study provide novel tools for studying non-erosive esophagitis with a range of severity. H2S contributes significantly to mucosal defence in the esophagus, and H2S donors may have therapeutic value in treating esophageal inflammation and injury

(12) Peers C, Boyle JP. Oxidative modulation of K+ channels in the central nervous system in neurodegenerative diseases and ageing. Antioxid Redox Signal 2014 Oct 21. Abstract: Significance. Oxidative stress and damage are well established components of neurodegenerative diseases, contributing to neuronal death during disease progression. Here, we consider key K+ channels as target proteins which can undergo oxidative modulation, describe what is understood about how this influences disease progression, and consider regulation of these channels by gasotransmitters as a means of cellular protection. Recent Advances. Oxidative regulation of the delayed rectifier Kv2.1 and the Ca2+- and voltage-sensitive BK channel are established, but recent studies contest how their redox sensitivity contributes to altered excitability, progression of neurodegenerative diseases and healthy ageing. Critical Issues. Both Kv2.1 and BK channels have recently been established as target proteins for regulation by the gasotransmitters carbon monoxide and hydrogen sulfide. Establishing the molecular basis of such regulation, and exactly how this influences excitability and vulnerability to apoptotic cell death will determine whether such regulation can be exploited for therapeutic benefit. Future Directions. Developing a more comprehensive picture of the oxidative modulation of K+ channels (and indeed other ion channels) within the CNS in health and disease will allow us to better understand processes associated with healthy ageing as well as distinct processes underlying progression of neurodegenerative diseases. Advances in the growing understanding of how gasotransmitters can regulate ion channels, including redox-sensitive K+ channels, are a research priority for this field, and will establish their usefulness in design of future approaches for the treatment of such diseases

(13) Chen Y, Mo HZ, Zheng MY, Xian M, Qi ZQ, Li YQ, et al. Selenium Inhibits Root Elongation by Repressing the Generation of Endogenous Hydrogen Sulfide in Brassica rapa. PLoS One 2014;9(10):e110904. Abstract: Selenium (Se) has been becoming an emerging pollutant causing severe phytotoxicity, which the biochemical mechanism is rarely known. Although hydrogen sulfide (H2S) has been suggested as an important exogenous regulator modulating plant physiological adaptions in response to heavy metal stress, whether and how the endogenous H2S regulates Se-induce phytotoxicity remains unclear. In this work, a self-developed specific fluorescent probe (WSP-1) was applied to track endogenous H2S in situ in the roots of Brassica rapa under Se(IV) stress. Se(IV)-induced root growth stunt was closely correlated with the inhibition of endogenous H2S generation in root tips. Se(IV) stress dampened the expression of most LCD and DCD homologues in the roots of B. rapa. By using various specific fluorescent probes for bio-imaging root tips in situ, we found that the increase in endogenous H2S by the application of H2S donor NaHS could significantly alleviate Se(IV)-induced reactive oxygen species (ROS) over-accumulation, oxidative impairment, and cell death in root tips, which further resulted in the recovery of root growth under Se(IV) stress. However, dampening the endogenous H2S could block the alleviated effect of NaHS on Se(IV)-induced phytotoxicity. Finally, the increase in endogenous H2S resulted in the enhancement of glutathione (GSH) in Se(IV)-treated roots, which may share the similar molecular mechanism for the dominant role of H2S in removing ROS by activating GSH biosynthesis in mammals. Altogether, these data provide the first direct evidences confirming the pivotal role of endogenous H2S in modulating Se(IV)-induced phytotoxicity in roots

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(14) Shi H, Ye T, Han N, Bian H, Liu X, Chan Z. Hydrogen sulfide regulates abiotic stress tolerance and biotic stress resistance in Arabidopsis. J Integr Plant Biol 2014 Oct 20. Abstract: Hydrogen sulfide (H2 S) is an important gaseous molecule in various plant developmental processes and plant stress responses. In this study, the transgenic plants with modulation expressions of two cysteine desulfhydrases and exogenous H2 S donor (sodium hydrosulfide, NaHS) and H2 S scavenger (hypotaurine, HT) pre-treated plants were used to dissect the involvement of H2 S in plant stress responses. The cysteine desulfhydrases overexpressing plants and NaHS pre-treated plants exhibited higher endogenous H2 S level and improved abiotic stress tolerance and biotic stress resistance, while cysteine desulfhydrases knockdown plants and HT pre-treated plants displayed lower endogenous H2 S level and decreased stress resistance. Moreover, H2 S up-regulated the transcripts of multiple abiotic and biotic stress-related genes, and inhibited reactive oxygen species (ROS) accumulation. Interestingly, MIR393-mediated auxin signaling including MIR393a/b and their target genes (TIR1, AFB1, AFB2, and AFB3) was transcriptionally regulated by H2 S, and was related with H2 S-induced antibacterial resistance. Moreover, H2 S regulated 50 carbon metabolites including amino acids, organic acids, sugars, sugar alcohols and aromatic amines. Taken together, these results indicated that cysteine desulfhydrase and H2 S conferred abiotic stress tolerance and biotic stress resistance, via affecting the stress-related gene expressions, ROS metabolism, metabolic homeostasis, and MIR393-targeted auxin receptors

(15) Zhu L, Wang W, Shi J, Zhang W, Shen Y, Du H, et al. Hydrogen sulfide extends the postharvest life and enhances antioxidant activity of kiwifruit during storage. J Sci Food Agric 2014 Oct;94(13):2699-704. Abstract: BACKGROUND: Exogenous hydrogen sulfide (H2S) treatment can prolong the postharvest life of cut flowers and strawberries. Little work has been done to explore the effects of H2S on respiratory climacteric fruits such as kiwifruits during storage. Therefore the aim of the present study was to evaluate the effects of H2S treatment at concentrations of 15-1000 micromol L-1 on the postharvest life of kiwifruit during 25 degrees C storage and the role of H2S in regulating the antioxidant defensive system of kiwifruit. RESULTS: Treatments with 45 and 90 micromol L-1 H2S significantly inhibited the increase in soluble sugar content and the decrease in vitamin C (Vit C), chlorophyll content and firmness, inhibited ethylene production and both superoxide production rate (O.2-) and hydrogen peroxide content. Kiwifruits with 45 and 90 micromol L-1 H2S exhibited significantly higher activities of superoxide dismutase, catalase and peroxidase. Treatment with 180 micromol L-1 H2S promoted the ripening of kiwifruits. CONCLUSION: Treatments with 45 and 90 micromol L-1 H2S could delay the maturation and senescence of kiwifruits and maintain higher titratable acid (TA) and Vit C during eating-ripe storage by inhibiting ethylene production, improving protective enzyme activities and decreasing the accumulation of reactive oxygen species to protect the cell membrane during storage

(16) Lou Z, Li P, Han K. Selenium as a Versatile Center in Fluorescence Probe for the Redox Cycle Between HClO Oxidative Stress and H2S Repair. Methods Mol Biol 2015;1208:97-110. Abstract: Selenium is a biologically important trace element and acts as an active center of glutathione peroxidase (GPx). GPx is the important antioxidant enzyme to protect organisms from oxidative damage via catalyzing the reaction between ROS and glutathione (GSH). Mimicking the oxidation-reduction cycles of the versatile selenium core in GPx, we can develop fluorescence probes to detect oxidation and reduction events in living systems. The cellular redox balance between hypochloric acid (HClO) and hydrogen sulfide (H2S) has broad implications in human health and diseases, such as Alzheimer's disease (AD). Therefore, to further investigate the roles of this redox balance and understand the pathogenesis of neurodegenerative diseases, it is necessary to detect the redox state between HClO and H2S in real time. We have developed a

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reversible fluorescence probe MPhSe-BOD for imaging of the redox cycle between HClO and H2S based on oxidation and reduction of selenide in living cells

(17) Riahi S, Rowley CN. Why can hydrogen sulfide permeate cell membranes? J Am Chem Soc 2014 Oct 29;136(43):15111-3. Abstract: The high membrane permeability of H2S was studied using polarizable molecular dynamics simulations of a DPPC lipid bilayer. The solubility-diffusion model predicts permeability coefficients of H2S and H2O that are in good agreement with experiment. The computed diffusion coefficient profile shows H2S to diffuse at a lower rate than H2O, but the barrier for H2S permeation on the Gibbs energy profile is negligible. The hydrophobicity of H2S allows it to partition into the paraffinic interior of the membrane readily

(18) Luebke JL, Shen J, Bruce KE, Kehl-Fie TE, Peng H, Skaar EP, et al. The CsoR-like sulfurtransferase repressor (CstR) is a persulfide sensor in Staphylococcus aureus. Mol Microbiol 2014 Oct 16. Abstract: How cells regulate the bioavailability of utilizable sulfur while mitigating the effects of hydrogen sulfide toxicity is poorly understood. CstR (Copper-sensing operon repressor (CsoR)-like sulfurtransferase repressor) represses the expression of the cst operon encoding a putative sulfide oxidation system in Staphylococcus aureus. Here, we show that the cst operon is strongly and transiently induced by cellular sulfide stress in an acute phase and specific response and that cst-encoded genes are necessary to mitigate the effects of sulfide toxicity. Growth defects are most pronounced when S. aureus is cultured in chemically defined media with thiosulfate (TS) as a sole sulfur source, but are also apparent when cystine is used or in rich media. Under TS growth conditions, cells fail to grow as a result of either unregulated expression of the cst operon in a DeltacstR strain or transformation with a non-inducible C31A/C60A CstR that blocks cst induction. This suggests that the cst operon contributes to cellular sulfide homeostasis. Tandem high resolution mass spectrometry reveals derivatization of CstR by both inorganic tetrasulfide and an organic persulfide, glutathione persulfide, to yield a mixture of Cys31-Cys60' interprotomer crosslinks, including di-, tri- and tetrasulfide bonds, which allosterically inhibit cst operator DNA binding by CstR

(19) Mousa HA. Short-term effects of subchronic low-level hydrogen sulfide exposure on oil field workers. Environ Health Prev Med 2014 Oct 15. Abstract: OBJECTIVES: To investigate the short-term effects of low-level hydrogen sulfide (H2S) exposure on oil field workers. MATERIALS AND METHODS: Observational study included 34 patients who work at an oil field. All patients were males with age range of 22-60 years (mean 37 years). The data were collected by systematic questionnaire about symptoms. The inclusion criteria of patients were symptoms related to inhalation of H2S gas in the oil field. The complaints should be frequent and relapsed after each gas exposure and disappeared when there was no gas exposure. Exclusion criteria were the symptoms which experienced with or without H2S exposure. The presence of H2S gas was confirmed by valid gas detector devices. RESULTS: The most frequent presenting symptom was nasal bleeding. It was revealed in 18 patients (52.9 %). This followed by pharyngeal bleeding, gum bleeding, and bloody saliva (mouth bleeding) which were encountered in five cases for each complaint (14.7 %). Other less frequent presenting symptoms were tongue bleeding, bloody sputum, headache, abdominal colic, pharyngeal soreness, fatigue, and sleepiness. CONCLUSIONS: Nasal mucosa was the most vulnerable part to H2S effect. Inhalation of H2S produced upper respiratory tract epithelial damage that led to bleeding from nose, pharynx, gum, tongue, trachea, and bronchi. There were no complaints of asthmatic attack upon exposure to low level of H2S. Sunlight had a significant role in reduction of ambient air H2S level

(20) Yoo D, Kim M, Jeong S, Han J, Cheon J. Chemical synthetic strategy for single-layer transition-metal chalcogenides. J Am Chem Soc 2014 Oct 22;136(42):14670-3.

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Abstract: A solution-phase synthetic protocol to form two-dimensional (2D) single-layer transition-metal chalcogenides (TMCs) has long been sought; however, such efforts have been plagued with the spontaneous formation of multilayer sheets. In this study, we discovered a solution-phase synthetic protocol, called "diluted chalcogen continuous influx (DCCI)", where controlling the chalcogen source influx (e.g., H2S) during its reaction with the transition-metal halide precursor is the critical parameter for the formation of single-layer sheets as examined for the cases of group IV TMCs. The continuous influx of dilute H2S throughout the entire growth period is necessary for large sheet formation through the exclusive a- and b-axial growth processes. By contrast, the burst influx of highly concentrated H2S in the early stages of the growth process forms multilayer TMC nanodiscs. Our DCCI protocol is a new synthetic concept for single-layer TMCs and, in principle, can be operative for wide range of TMC nanosheets

(21) Chen Y, Fan Z, Ma L, Yin J, Luo M, Cai W. Performance of three pilot-scale immobilized-cell biotrickling filters for removal of hydrogen sulfide from a contaminated air steam. Saudi J Biol Sci 2014 Nov;21(5):450-6. Abstract: Hydrogen sulfide (H2S) is a major malodorous compound emitted from wastewater treatment plants. In this study, the performance of three pilot-scale immobilized-cell biotrickling filters (BTFs) spacked with combinations of bamboo charcoal and ceramsite in different ratios was investigated in terms of H2S removal. Extensive tests were performed to determine the removal characteristics, pressure drops, metabolic products, and removal kinetics of the BTFs. The BTFs were operated in continuous mode at low loading rates varying from 0.59 to 5.00 g H2S m(-3) h(-1) with an empty bed retention time (EBRT) of 25 s. The removal efficiency (RE) for each BTF was >99% in the steady-state period, and high standards were met for the exhaust gas. It was found that a multilayer BTF had a slight advantage over a perfectly mixed BTF for the removal of H2S. Furthermore, an impressive amount >97% of the H2S was eliminated by 10% of packing materials near the inlet of the BTF. The modified Michaelis-Menten equation was adopted to describe the characteristics of the BTF, and K s and V m values for the BTF with pure bamboo charcoal packing material were 3.68 ppmv and 4.26 g H2S m(-3) h(-1), respectively. Both bamboo charcoal and ceramsite demonstrated good performance as packing materials in BTFs for the removal of H2S, and the results of this study could serve as a guide for further design and operation of industrial-scale systems

(22) Sieghart D, Liszt M, Wanivenhaus A, Broll H, Kiener H, Klosch B, et al. Hydrogen sulphide decreases IL-1beta-induced activation of fibroblast-like synoviocytes from patients with osteoarthritis. J Cell Mol Med 2014 Oct 14. Abstract: Balneotherapy employing sulphurous thermal water is still applied to patients suffering from diseases of musculoskeletal system like osteoarthritis (OA) but evidence for its clinical effectiveness is scarce. Since the gasotransmitter hydrogen sulphide (H2 S) seems to affect cells involved in degenerative joint diseases, it was the objective of this study to investigate the effects of exogenous H2 S on fibroblast-like synoviocytes (FLS), which are key players in OA pathogenesis being capable of producing pro-inflammatory cytokines and matrix degrading enzymes. To address this issue primary FLS derived from OA patients were stimulated with IL-1beta and treated with the H2 S donor NaHS. Cellular responses were analysed by ELISA, quantitative real-time PCR, phospho-MAPkinase array and Western blotting. Treatment-induced effects on cellular structure and synovial architecture were investigated in three-dimensional extracellular matrix micromasses. NaHS treatment reduced both spontaneous and IL-1beta-induced secretion of IL-6, IL-8 and RANTES in different experimental settings. In addition, NaHS treatment reduced the expression of matrix metallo-proteinases MMP-2 and MMP-14. IL-1beta induced the phosphorylation of several MAPkinases. NaHS treatment partially reduced IL-1beta-induced activation of several MAPK whereas it increased phosphorylation of pro-survival factor Akt1/2. When cultured in spherical micromasses, FLS intentionally established a synovial lining layer-like structure; stimulation with IL-1beta altered the architecture of micromasses leading to hyperplasia of the lining layer

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which was completely inhibited by concomitant exposure to NaHS. These data suggest that H2 S partially antagonizes IL-1beta stimulation via selective manipulation of the MAPkinase and the PI3K/Akt pathways which may encourage development of novel drugs for treatment of OA

(23) Kulkarni GJ, Shetty S, Dharne MS, Shouche YS. Genome sequencing analysis reveals virulence-related gene content of Ochrobactrum intermedium strain 229E, a urease-positive strain isolated from the human gastric niche. FEMS Microbiol Lett 2014 Sep;358(1):12-5. Abstract: Filamentous sulfur bacteria of the genus Thiothrix are able to respire nitrate (NO3--->NO2-) under anaerobic growth. Here, Thiothrix caldifontis (G1(T), G3), Thiothrix unzii (A1(T), TN) and Thiothrix lacustris AS were shown to be capable of further reduction of nitrite and/or nitrous oxides (denitrification). In particular, in the genomes of these strains, excluding T. unzii TN, the nirS gene encoding periplasmic respiratory nitrite reductase was detected, and for T. lacustris AS the nirS expression was confirmed during anaerobic growth. The nirK gene, coding for an alternative nitrite reductase, and the nrfA gene, encoding nitrite reduction to ammonia, were not found in any investigated strains. All Thiothrix species capable of denitrification possess the cnorB gene encoding cytochrome c-dependent NO reductase but not the qnorB gene coding for quinol-dependent NO reductase. Denitrifying capacity ('full' or 'truncated') can vary between strains belonging to the same species and correlates with physical-chemical parameters of the environment such as nitrate, hydrogen sulfide and oxygen concentrations. Phylogenetic analysis revealed the absence of recent horizontal transfer events for narG and nirS; however, cnorB was subjected to gene transfer before the separation of modern species from a last common ancestor of the Thiothrix species

(24) Zhang Y, Weiner JH. A simple semi-quantitative in vivo method using H2S detection to monitor sulfide metabolizing enzymes. Biotechniques 2014;57(4):208-10. Abstract: Here we present a simple in vivo microtiter plate assay using lead acetate [Pb(OAc)2]-soaked filter paper to detect H2S released by Escherichia coli metabolizing cysteine. The released H2S precipitates as brown lead sulfide (PbS) on Pb(OAc)2 soaked filter paper. The PbS stain quantitated by ImageJ software is proportional to the amount of H2S released from the culture. Expression of recombinant Acidithiobacillus ferrooxidans sulfide:quinone oxidoreductase (SQR) converts the H2S to sulfur, resulting in less PbS formation. The in vivo H2S oxidation activity of SQR was calculated based on the density of the PbS stain formed by E. coli expressing SQR compared with cells harboring the empty vector pLM1. The results are consistent with the in vitro activity of SQR measured by decylubiquinone (DUQ) reduction. This assay can be applied to sulfide metabolizing enzymatic studies, mutant screening and high-throughput inhibitor screens

(25) Carrasco-Correa EJ, Ramis-Ramos G, Herrero-Martinez JM, Lammerhofer M. Polymethacrylate monoliths with immobilized poly-3-mercaptopropyl methylsiloxane film for high-coverage surface functionalization by thiol-ene click reaction. J Chromatogr A 2014 Oct 2. Abstract: In this work, new polythiol-functionalized macroporous monolithic polymethacrylate-polysiloxane composite materials are presented which can be useful substrates for highly efficient immobilization of (chiral) catalysts, chromatographic ligands, and other functional moieties by thiol-ene click reaction. Poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) monoliths were coated with a poly-3-mercaptopropyl methylsiloxane (PMPMS) film and subsequently the polymer was covalently immobilized by formation of crosslinks via nucleophilic substitution reaction with pendent 2,3-epoxypropyl groups on the monolith surface. This monolith, though, showed similar levels of surface coverage as a reference monolith obtained by opening of the epoxide groups with sodium hydrogen sulfide. However, a 3-step functionalization by amination of the epoxy monolith, followed by its vinylation with

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allylglycidyl ether and subsequent thiolation by coating of a thin polythiol (PMPMS) film and crosslinking by click reaction furnished a monolith with more than 2-fold elevated thiol coverage. Its further functionalization with a clickable chiral quinine carbamate selector clearly documented the benefit of highly dense thiol surfaces for such reactions and synthesis of functional materials with proper ligand loadings. The new monoliths were chromatographically tested in capillary electrochromatography mode using N-3,5-dinitrobenzoyl-leucine as chiral probe and the capillary column with the monolith having the highest selector coverage, produced from the precursor with the most thiols on the surface, showed the largest separation factor. By performic acid oxidation the surface characteristic could be tuned and strongly altered due to a delicate balance of enantioselective and non-specific interactions

(26) Heshka NE, Hager DB. A multidimensional gas chromatography method for the analysis of hydrogen sulfide in crude oil and crude oil headspace. J Sep Sci 2014 Oct 14. Abstract: Two dimensional heart-cutting gas chromatography is used to analyze dissolved hydrogen sulfide in crude samples. Liquid samples are separated first on an HP-PONA column, and the light sulfur gases are heart-cut to a GasPro column, where hydrogen sulfide is separated from other light sulfur gases and detected with a sulfur chemiluminescence detector. Heart-cutting is accomplished with the use of a Deans switch. Backflushing the columns after hydrogen sulfide detection eliminates any problems caused by high-boiling hydrocarbons in the samples. Dissolved hydrogen sulfide is quantified in 14 crude oil samples, and the results are shown in this work. The method is also applicable to the analysis of headspace hydrogen sulfide over crude oil samples. Gas hydrogen sulfide measurements are compared to liquid hydrogen sulfide measurements for the same sample set. The chromatographic system design is discussed, and chromatograms of representative gas and liquid measurements are shown. This article is protected by copyright. All rights reserved

(27) Bronowicka-Adamska P, Zagajewski J, Wrobel M. An application of RP-HPLC for determination of the activity of cystathionine beta-synthase and gamma-cystathionase in tissue homogenates. Nitric Oxide 2014 Oct 9. Abstract: The RP-HPLC-based method of determination of the activity of cystathionine beta-synthase and gamma-cystathionase was undertaken in mouse liver, kidney and brain. Products of the reactions, such as cystathionine, alpha-ketobutyrate, cysteine and glutathione, were measured using the RP-HPLC method. A difference in the cystathionine level between homogenates with totally CTH-inhibiting concentrations of DL-propargylglycine and without the inhibitor was employed to evaluate the activity of cystathionine beta-synthase. Gamma-cystathionase activity was measured using DL-homoserine as a substrate and a sensitive HPLC-based assay to measure alpha-ketobutyrate. The results confirmed high cystathionine beta-synthase activity and no gamma-cystathionase activity in brain, and high gamma-cystathionase activity in mouse liver. The method presented here allows for evaluating the relative contribution of CBS and CTH to generation of H2S in tissues. Additionally, it provides results, which reflect the redox status (GSH/GSSG) of a tissue

(28) Nghiem LD, Manassa P, Dawson M, Fitzgerald SK. Oxidation reduction potential as a parameter to regulate micro-oxygen injection into anaerobic digester for reducing hydrogen sulphide concentration in biogas. Bioresour Technol 2014 Sep 18. Abstract: This study aims to evaluate the use of oxidation reduction potential (ORP) to regulate the injection of a small amount of oxygen into an anaerobic digester for reducing H2S concentration in biogas. The results confirm that micro-oxygen injection can be effective for controlling H2S formation during anaerobic digestion without disturbing the performance of the digester. Biogas production, composition, and the removal of volatile solids (VS) and chemical oxygen demand (COD) were monitored to assessment the digester's performance. Six days after the start of the micro-oxygen injection, the ORP values increased to between -320 and -270mV, from the natural baseline value of

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-485mV. Over the same period the H2S concentration in the biogas decreased from over 6000ppm to just 30ppm. No discernible changes in the VS and COD removal rates, pH and alkalinity of the digestate or in the biogas production or composition were observed

(29) Giannakoudakis DA, Bandosz TJ. Zinc (hydr)oxide/graphite oxide/AuNPs composites: Role of surface features in HS reactive adsorption. J Colloid Interface Sci 2014 Sep 1;436C:296-305. Abstract: Zinc hydroxide/graphite oxide/AuNPs composites with various levels of complexity were synthesized using an in situ precipitation method. Then they were used as H2S adsorbents in visible light. The materials' surfaces were characterized before and after H2S adsorption by various physical and chemical methods (XRD, FTIR, thermal analysis, potentiometric titration, adsorption of nitrogen and SEM/EDX). Significant differences in surface features and synergistic effects were found depending on the materials' composition. Addition of graphite oxide and the deposition of gold nanoparticles resulted in a marked increase in the adsorption capacity in comparison with that on the zinc hydroxide and zinc hydroxide/AuNP. Addition of AuNPs to zinc hydroxide led to a crystalline ZnO/AuNP composite while the zinc hydroxide/graphite oxide/AuNP composite was amorphous. The ZnOH/GO/AuNPs composite exhibited the greatest H2S adsorption capacity due to the increased number of OH terminal groups and the conductive properties of GO that facilitated the electron transfer and consequently the formation of superoxide ions promoting oxidation of hydrogen sulfide. AuNPs present in the composite increased the conductivity, helped with electron transfer to oxygen, and prevented the fast recombination of the electrons and holes

(30) Ahmed A, Ramma W. Unraveling the theories of preeclampsia: Are the protective pathways the new paradigm? Br J Pharmacol 2014 Oct 10. Abstract: Preeclampsia is a vascular disorder of pregnancy where anti-angiogenic factors, systemic inflammation and oxidative stress predominate, but none can claim to cause preeclampsia. This review provides an alternative to the 'two stage model' of preeclampsia in which abnormal spiral arteries modification leads to placental hypoxia, oxidative stress and aberrant maternal systemic inflammation. Very high maternal soluble fms-like tyrosine kinase-1 (sFlt-1) and very low placenta growth factor (PlGF) are unique to preeclampsia; however, abnormal spiral arteries and excessive inflammation are also prevalent in other placental disorders. Metaphorically speaking pregnancy can be viewed as a car with an accelerator and brakes, where inflammation, oxidative stress and an imbalance in the angiogenic milieu act as 'accelerator'. The 'braking system' includes the protective pathways of heme oxygenase-1 (Hmox1 also referred as HO-1) and cystathionase (Cth, also know as cystathionine gamma-lyase, CSE), which generate carbon monoxide (CO) and hydrogen sulfide (H2 S) respectively. The failure in these pathways (brakes) results in the pregnancy going out of control and the system crashing. Put simply, preeclampsia is an accelerator-brake defect disorder. CO and H2 S hold great promise due to their unique ability to suppress the anti-angiogenic factors sFlt-1 and soluble Endoglin as well as to promote PlGF and endothelial nitric oxide sysnthase activity. The key to finding a cure lies in the identification of cheap, safe and effective drugs that induce the braking system to keep the pregnancy vehicle on track past the finishing line

(31) Kimura H. Hydrogen Sulfide and Polysulfides as Biological Mediators. Molecules 2014;19(10):16146-57. Abstract: Hydrogen sulfide (H2S) is recognized as a biological mediator with various roles such as neuromodulation, regulation of the vascular tone, cytoprotection, anti-inflammation, oxygen sensing, angiogenesis, and generation of mitochondrial energy. It is produced by cystathionine beta-synthase (CBS), cystathionine gamma-lyase (CSE), and 3-mercaptopyruvate sulfurtransferase (3MST). The activity of CBS is enhanced by S-adenosyl methionine (SAM) and glutathionylation, while it is inhibited by nitric oxide (NO) and carbon monoxide (CO). The activity of CSE and cysteine aminotransferase

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(CAT), which produces the 3MST substrate 3-mercaptopyruvate (3MP), is regulated by Ca2+. H2S is oxidized to thiosulfate in mitochondria through the sequential action of sulfide quinone oxidoreductase (SQR), sulfur dioxygenase, and rhodanese. The rates of the production and clearance of H2S determine its cellular concentration. Polysulfides (H2Sn) have been found to occur in the brain and activate transient receptor potential ankyrin 1 (TRPA1) channels, facilitate the translocation of nuclear factor erythroid 2-related factor 2 (Nrf2) to the nucleus, and suppress the activity of phosphatase and tensin homolog (PTEN) by sulfurating (sulfhydrating) the target cysteine residues. A cross talk between H2S and NO also plays an important role in cardioprotection as well as regulation of the vascular tone. H2S, polysulfides, and their cross talk with NO may mediate various physiological and pathophysiological responses

(32) Blackler RW, Motta JP, Manko A, Workentine M, Bercik P, Surette MG, et al. Hydrogen Sulfide Protects Against NSAID-Enteropathy Through Modulation of Bile and the Microbiota. Br J Pharmacol 2014 Oct 8. Abstract: BACKGROUND AND PURPOSE: Hydrogen sulfide is an important mediator of gastrointestinal mucosal defence. The use of non-steroidal anti-inflammatory drugs (NSAIDs) is significantly limited by their toxicity in the gastrointestinal tract. Particularly concerning is the lack of effective preventative or curative treatments for NSAID-induced intestinal damage and bleeding. We evaluated the ability of a hydrogen sulfide donor to protect against NSAID-induced enteropathy. EXPERIMENTAL APPROACH: Intestinal ulceration and bleeding were induced by oral administration of naproxen. The impact of suppression of endogenous hydrogen sulfide synthesis and administration of a hydrogen sulfide donor (diallyl disulfide) on naproxen-induced enteropathy was examined. Effects of diallyl disulfide on small intestinal inflammation and intestinal microbiota were also assessed. Bile collected after in vivo naproxen and diallyl disulfide administration was evaluated for cytotoxicity in vitro using cultured intestinal epithelial cells. KEY RESULTS: Suppression of endogenous hydrogen sulfide synthesis by beta-cyano-L-alanine exacerbated naproxen-induced enteropathy. Diallyl disulfide co-administration dose-dependently reduced the severity of naproxen-induced small intestinal damage, inflammation and bleeding. Diallyl disulfide administration attenuated naproxen-induced increases in the cytotoxicity of bile on cultured enterocytes, and prevented or reversed naproxen-induced changes in the intestinal microbiota. CONCLUSIONS AND IMPLICATIONS: Hydrogen sulfide protects against NSAID-enteropathy in rats, in part reducing the cytotoxicity of bile and preventing NSAID-induced dysbiosis

(33) Wang YS, Yin CC, Chao SD. Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: An ab initio study. J Chem Phys 2014 Oct 7;141(13):134308. Abstract: We perform an ab initio computational study of molecular complexes with the general formula CF3X-B that involve one trifluorohalomethane CF3X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH3 and PH3), two n-pairs (H2O and H2S), two n-pairs with an unsaturated bond (H2CO and H2CS), and a single pi-pair (C2H4) and two pi-pairs (C2H2). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the sigma-hole model. Upon formation of stable complexes, the C-X bond lengths shorten, while the C-X vibrational frequencies increase, thus rendering blueshifting halogen bonds.

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The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the sigma-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved

(34) Zhang H, Gao Y, Zhao FL, Qiao PF, Yan Y. Hydrogen Sulfide-Induced Processing of the Amyloid Precursor Protein in SH-SY5Y Human Neuroblastoma Cells Involves the PI3-K/Akt Signaling Pathway. Cell Mol Neurobiol 2014 Oct 8. Abstract: Hydrogen sulfide (H2S) has been recently categorized as a gasotransmitter, and it may be involved in the pathology of Alzheimer's disease. However, whether H2S induces amyloid precursor protein (APP) processing remains unknown. In the present study, we tested the ability of H2S to mediate APP processing in SH-SY5Y human neuroblastoma cells. We treated SH-SY5Y human neuroblastoma cells with a range of sodium hydrosulfide (H2S donor) concentrations. Western blot analysis showed that H2S increased the generation of C83 and decreased the production of C99. Meanwhile, H2S increased the levels of a disintegrin and metalloprotease 10 (ADAM10) mRNA and protein, but had no effect on TNF-alpha-converting enzyme (TACE, also known as ADAM17) mRNA and protein levels. H2S also induced a significant decrease of extracellular amyloid-beta42 (Abeta42). Furthermore, SH-SY5Y human neuroblastoma cells were assayed for activation of the phosphoinositide 3-kinase (PI3-K) pathway. H2S activated the PI3-K pathway. Using specific inhibitor of PI3-K, we determined that the effects of H2S on APP processing and Abeta42 were blocked by LY 294002 (PI3-K inhibitor). These data indicate that H2S can induce APP processing, and this effect is dependent on activation of the PI3-K signaling pathway

(35) Liu DH, Huang X, Meng XM, Zhang CM, Lu HL, Kim YC, et al. Exogenous H S enhances mice gastric smooth muscle tension through S-sulfhydration of K 4.3, mediating the inhibition of the voltage-dependent potassium current. Neurogastroenterol Motil 2014 Oct 8. Abstract: BACKGROUND: Hydrogen sulfide (H2 S) has been shown to have an excitatory effect on gastric motility, but the underlying molecular mechanism is unclear. In this study, we aimed to investigate the possible targets of H2 S and determine how H2 S affects its target proteins during H2 S-induced contraction. METHODS: Patch-clamp and potentiometric fluorescence dye were utilized to measure the electrophysiological changes. The Biotin-switch assay was utilized to detect the protein S-sulfhydration. The isometric tension measurement was conducted too. KEY RESULTS: Exogenous H2 S enhanced the tonic contraction of gastric antral smooth muscle, and voltage-dependent potassium channel (KV ) blocker and Dithiothreitol (DTT, a reducing agent) abolished the excitatory effect of NaHS. Exogenous H2 S inhibited the fast inactivation component of the voltage-dependent potassium channel current (IKVfast ) in isolated gastric antral smooth muscle cells. H2 S inhibited the KV 4.3 current in H293 cells with heterologous expression of KV 4.3, but did not inhibit the KV 4.1 and KV 4.2 currents, which together contribute greatly to IKVfast . NaHS significantly decreased the membrane potential in cultured gastric smooth muscle cells, but the NaHS-induced depolarization was suppressed by knockdown of KV 4.3 and N-ethylamaleimide (NEM), a free thiol group blocker. In addition, NaHS sulfhydrated KV 4.3 in H293 cells and in gastric smooth muscle tissue. However, this S-sulfhydration was inhibited by NEM and DTT. Meanwhile the NaHS-induced inhibition of IKVfast and KV 4.3 was also blocked by NEM and DTT. CONCLUSIONS & INFERENCES: These results suggest that exogenous H2 S sulfhydrates KV 4.3 to decrease the membrane potential, thereby enhancing the basal tension of gastric antral smooth muscle

(36) Omel'chuk ST, Aleksiichuk VD, Sokurenko LM. [Biochemical parameters of blood and morpho-functional state of the liver of experimental animals by the actions of lead sulfide nanoparticles in different time study]. Lik Sprava 2014 Mar;(3-4):114-8.

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Abstract: Biochemical studies revealed that alanine aminotransferase levels changing first during short action (30 injections) of lead sulfide nanoparticles of size 10 and 30 nm, and the ionic form of a 400 nm lead while the growth of both enzymes (aspartate aminotransferase and alanine aminotransferase) activity during long-term exposure (60 injections) is the same intensity. It it confirmed by the value of de Ritis coefficient, which is statistically the same as control. Morphological studies also confirm these data--degenerative changes of hepatocytes, reactive changes of the stroma and vascular responses were detected. It is shown that the severity of metabolic and morphological damages in the liver increased with prolonging the duration of lead nanoparticles intake

(37) Swami SK, Chaturvedi N, Kumar A, Chander N, Dutta V, Kumar DK, et al. Spray deposited copper zinc tin sulphide (Cu2ZnSnS4) film as a counter electrode in dye sensitized solar cells. Phys Chem Chem Phys 2014 Nov 21;16(43):23993-9. Abstract: Stoichiometric thin films of Cu2ZnSnS4 (CZTS) were deposited by the spray technique on a FTO coated glass substrate, with post-annealing in a H2S environment to improve the film properties. CZTS films were used as a counter electrode (CE) in Dye-Sensitized Solar Cells (DSCs) with N719 dye and an iodine electrolyte. The DSC of 0.25 cm(2) area using a CE of CZTS film annealed in a H2S environment under AM 1.5G illumination (100 mW cm(-2)) exhibited a short circuit current density (JSC) = 18.63 mA cm(-2), an open circuit voltage (VOC) = 0.65 V and a fill factor (FF) = 0.53, resulting in an overall power conversion efficiency (PCE) = 6.4%. While the DSC using as deposited CZTS film as a CE showed the PCE = 3.7% with JSC = 13.38 mA cm(-2), VOC = 0.57 V and FF = 0.48. Thus, the spray deposited CZTS films can play an important role as a CE in the large area DSC fabrication

(38) Li X, Yang C, Wu K, Hu Y, Han Y, Liang SH. A highly specific probe for sensing hydrogen sulfide in live cells based on copper-initiated fluorogen with aggregation-induced emission characteristics. Theranostics 2014;4(12):1233-8. Abstract: Here we reported the first fluorescent probe with aggregation-induced emission characteristics, namely AIE-S, for the detection of hydrogen sulfide (H2S) in live cells. The detection system is selective for complicated biological application and the response is fast enough to complete within seconds. Moreover, the probe exhibits the unique advantage of being immune to aggregation-caused quenching which is a detrimental phenomenon limiting the application of most current available H2S fluorescent probes. The detection mechanism was investigated and postulated to be S(2-) initiated de-coordination and thereafter aggregation of the AIE-S complex

(39) Kurian GA, Pemaih B. Standardization of in vitro Cell-based Model for Renal Ischemia and Reperfusion Injury. Indian J Pharm Sci 2014 Jul;76(4):348-53. Abstract: Renal ischemia reperfusion injury contributes patho-physiological imbalance of acute renal failure that comprises of generation of reactive oxygen species, nitric oxide and peroxynitrite and inflammation involving cytokine/adhesion molecule cascade, finally leads to cell death. Oxygen deprival associated with ischemia that in turn lead to decline ATP production is the characteristic feature usually addressed in the development of in vitro cell based ischemic model. In order to create oxygen deficit in the cell lines different approaches like chemical induction, enzymatic induction and anaerobic chamber models are widely used. However efficiencies of these models were varied and the present study was aimed to compare the suitability of these models in creating in vitro ischemia reperfusion in cell culture. In the chemical induced method we used different concentrations of rotenone, antimycin and sodium azide to inhibit electron transport chain and thereby reduced the ATP production, measured indirectly by cell viability assay. Among the chemical induced model, antimycin mediated cell injury was more reliable for ischemia reperfusion study. In the enzymatic model, comprises of glucose oxidase (3mM/s) and catalase (998 s(-1) at 10:1 ratio) was used and found to be best among the three approaches as it can create injury in short experimental time and are reproducible.

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However anaerobic chamber method was not suitable for ischemia reperfusion study as it need more time to induce significant cell injury

(40) Ferreira V, Bueno M, Franco-Luesma E, Cullere L, Fernandez-Zurbano P. Key Changes in Wine Aroma Active Compounds during Bottle Storage of Spanish Red Wines under Different Oxygen Levels. J Agric Food Chem 2014 Oct 15;62(41):10015-27. Abstract: Samples from 16 Spanish red wines have been stored for 6 months at 25 degrees C under different levels of oxygen (0-56 mg/L). Amino acids, metals, and phenolic compounds were analyzed and related to the production or depletion of key oxidation- and reduction-related aroma compounds. Oxidation brings about sensory-relevant increases in Strecker aldehydes, 1-octen-3-one, and vanillin. Formation of Strecker aldehydes correlates to the wine content on the corresponding amino acid precursor, Zn, and caffeic acid ethyl ester and negatively to some flavonols and anthocyanin derivatives. Formation of most carbonyls correlates to wine-combined SO2, suggesting that part of the increments are the result of the release of aldehydes forming bisulfite combinations once SO2 is oxidized. Methanethiol (MeSH) and dimethylsulfide (DMS), but not H2S levels, increase during storage. MeSH increments correlate to methionine levels and proanthocyanidins and negatively to resveratrol and aluminum. H2S, MeSH, and DMS levels all decreased with oxidation, and for the latter two, there are important effects of Mn and pH, respectively

(41) Shadlinskii VB, Gasymova TM, Nikitiuk DV. [Morphological changes of lymphoid apparatus of the larynx after experimental exposure to various balneal factors]. Morfologiia 2014;145(2):21-5. Abstract: The aim of this investigation was to detect the structural changes of lymphoid components of rat pharynx in an experiment after a course of exposure to various balneal procedures. The studies were performed on 90 outbred mature 3 month-old male rats (20 animals in each experimental group and 10 animals in each control groups). The animals were exposed to a course of weakly mineralized organic bituminous, thermal iodobromine and strong (concentrated) sulfide baths present on the territory of Azerbaijan. The experiments performed have shown a significant sensitivity of the lymphoid structures of the rat pharynx to the balneal procedures. After exposure to iodobromine and bituminous baths, the signs of lymphocytopoiesis activation were noted. The exposure to strong sulfide baths resulted in a morphological regression of lymphoid apparatus of rat larynx, which raises the question on the expediency of the use of these procedures in practical balneology

(42) Ge X, Yang L, Sheets JP, Yu Z, Li Y. Biological conversion of methane to liquid fuels: Status and opportunities. Biotechnol Adv 2014 Oct 2. Abstract: Methane is the main component of natural gas and biogas. As an abundant energy source, methane is crucial not only to meet current energy needs but also to achieve a sustainable energy future. Conversion of methane to liquid fuels provides energy-dense products and therefore reduces costs for storage, transportation, and distribution. Compared to thermochemical processes, biological conversion has advantages such as high conversion efficiency and using environmentally friendly processes. This paper is a comprehensive review of studies on three promising groups of microorganisms (methanotrophs, ammonia-oxidizing bacteria, and acetogens) that hold potential in converting methane to liquid fuels, and their habitats, biochemical conversion mechanisms, performance in liquid fuels production, and genetic modification to enhance the conversion were also discussed. To date, methane-to-methanol conversion efficiencies (moles of methanol produced per mole methane consumed) of up to 80% have been reported. A number of issues that impede scale-up of this technology, such as mass transfer limitations of methane, inhibitory effect of H2S in biogas, usage of expensive chemicals as electron donors, and lack of native strains capable of converting methane to liquid fuels other than methanol, are also discussed. Future perspectives and strategies in addressing these challenges are also addressed

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(43) Basic A, Dahlen G. Hydrogen sulfide production from subgingival plaque samples. Anaerobe 2014 Sep 30. Abstract: Periodontitis is a polymicrobial anaerobe infection. Little is known about the dysbiotic microbiota and the role of bacterial metabolites in the disease process. It is suggested that the production of certain waste products in the proteolytic metabolism may work as markers for disease severity. Hydrogen sulfide (H2S) is a gas produced by degradation of proteins in the subgingival pocket. It is highly toxic and believed to have pro-inflammatory properties. We aimed to study H2S production from subgingival plaque samples in relation to disease severity in subjects with natural development of the disease, using a colorimetric method based on bismuth precipitation. In remote areas of northern Thailand, adults with poor oral hygiene habits and a natural development of periodontal disease were examined for their oral health status. H2S production was measured with the bismuth method and subgingival plaque samples were analyzed for the presence of 20 bacterial species with the checkerboard DNA-DNA hybridization technique. In total, 43 subjects were examined (age 40-60 years, mean PI 95 +/- 6.6%). Fifty-six percent had moderate periodontal breakdown (CAL > 3 < 7 mm) and 35% had severe periodontal breakdown (CAL > 7 mm) on at least one site. Parvimonas micra, Filifactor alocis, Porphyromonas endodontalis and Fusobacterium nucleatum were frequently detected. H2S production could not be correlated to periodontal disease severity (PPD or CAL at sampled sites) or to a specific bacterial composition. Site 21 had statistically lower production of H2S (p = 0.02) compared to 16 and 46. Betel nut chewers had statistically significant lower H2S production (p = 0.01) than non-chewers. Rapid detection and estimation of subgingival H2S production capacity was easily and reliably tested by the colorimetric bismuth sulfide precipitation method. H2S may be a valuable clinical marker for degradation of proteins in the subgingival pocket

(44) Hajihashemi R, Rashidi AM, Alaie M, Mohammadzadeh R, Izadi N. The study of structural properties of carbon nanotubes decorated with NiFe2O4 nanoparticles and application of nano-composite thin film as H2S gas sensor. Mater Sci Eng C Mater Biol Appl 2014 Nov 1;44:417-21. Abstract: Nano-composite of multiwall carbon nanotube, decorated with NiFe2O4 nanoparticles (NiFe2O4-MWCNT), was synthesized using the sol-gel method. NiFe2O4-MWCNTs were characterized using different methods such as X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM) and vibrating sample magnetometer (VSM). The average size of the crystallites is 23.93nm. The values of the saturation magnetization (MS), coercivity (HC) and retentivity (MR) of NiFe2O4-MWCNTs are obtained as 15emug(-1), 21Oe and 5emug(-1), respectively. In this research, NiFe2O4-MWCNT thin films were prepared with the spin-coating method. These thin films were used as the H2S gas sensor. The results suggest the possibility of the utilization of NiFe2O4-MWCNT nano-composite, as the H2S detector. The sensor shows appropriate response towards 100ppm of H2S at 300 degrees C

(45) nis-Oliveira RJ, Carvalho F, Moreira R, Proenca JB, Santos A, Duarte JA, et al. Clinical and forensic signs related to chemical burns: A mechanistic approach. Burns 2014 Oct 1. Abstract: This manuscript highlights and critically analyses clinical and forensic signs related to chemical burns. Signs that may lead to suspicion of a particular chemical are thoroughly discussed regarding its underlying mechanisms. Burns due to sulfuric, hydrofluoric, nitric, hydrochloric (muriatic) and acetic (including derivatives) acids, hydrogen sulphide, sodium (caustic soda) and calcium (cement) hydroxides, paraquat, burns after inflation and rupture of airbags, povidone-iodine, chlorhexidine/alcohol (in preterm infants), laxatives, and vesicants (warfare agents), will be reviewed since these are the most common agents found in daily practice, for which relevant and timed information may be helpful in formulating an emergency treatment protocols and toxicological analysis

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(46) Wang CM, Yang YJ, Zhang JT, Liu J, Guan XL, Li MX, et al. Regulation of emotional memory by hydrogen sulfide: role of GluN2B-containing NMDA receptor in the amygdala. J Neurochem 2014 Oct 3. Abstract: As an endogenous gaseous molecule, hydrogen sulfide (H2 S) has attracted extensive attention because of its multiple biological effects. However, the effect of H2 S on amygdala-mediated emotional memory has not been elucidated. Here, by employing Pavlovian fear conditioning, an animal model widely used to explore the neural substrates of emotion, we determined whether H2 S could regulate emotional memory. It was shown that the H2 S levels in the amygdala of rats were significantly elevated after cued fear conditioning. Both intraamygdala and systemic administrations of H2 S markedly enhanced amygdala-dependent cued fear memory in rats. Moreover, it was found that H2 S selectively increased the surface expression and currents of NMDA-type glutamate receptor subunit 2B (GluN2B)-containing NMDA receptors (NMDARs) in lateral amygdala of rats, whereas blockade of GluN2B-containing NMDARs in lateral amygdala eliminated the effects of H2 S to enhance amygdalar long-term potentiation and cued fear memory. These results demonstrate that H2 S can regulate amygdala-dependent emotional memory by promoting the function of GluN2B-containing NMDARs in amygdala, suggesting that H2 S-associated signaling may hold potential as a new target for the treatment of emotional disorders. In our study, the effect of hydrogen sulfide (H2 S) on amygdala-mediated emotional memory was investigated. It was found that H2 S could enhance amygdala-dependent emotional memory and long-term potentiation (LTP) in rats by selectively increasing the function of GluN2B-containing NMDA receptors in the amygdala. These results suggest that H2 S-associated signaling may be a new target for the treatment of emotional disorders

(47) Ostrakhovitch EA, Akakura S, Sanokawa-Akakura R, Goodwin S, Tabibzadeh S. Dedifferentiation of cancer cells following recovery from a potentially lethal damage is mediated by HS-Nampt. Exp Cell Res 2014 Sep 30. Abstract: Recently, we reported that cancer cells that recover from a potentially lethal damage gain new phenotypic features comprised of mitochondrial structural remodeling associated with increased glycolytic dependency and drug resistance. Here, we demonstrate that a subset of cancer cells, upon recovery from a potentially lethal damage, undergo dedifferentiation and express genes, which are characteristic of undifferentiated stem cells. While these cells are competent in maintaining differentiated progeny of tumor, they also exhibit transdifferentiation potential. Dedifferentiation is characterized by accumulation of hydrogen sulfide (H2S), which triggers up-regulation of nicotinamide phosphoribosyltransferase (Nampt) accompanied by changes in the redox state. The molecular events triggered by Nampt include elevated production of NAD+ and up-regulation of H2S producing enzymes, cystathionine beta synthase (CBS) and cystathionase (CTH) with 3-mercaptopyruvate sulfurtransferase (MST) being detectable only in 3D spheroids. Suppression of Nampt, or inactivation of H2S producing enzymes, all reduce H2S production and reverse the ability of cells to dedifferentiate. Moreover, H2S induced stem cell markers in parental cancer cells in a manner similar to that observed in damage recovered cells. These data suggest of existence of a positive feedback loop between H2S and Nampt that controls dedifferentiation in cancer cells that recover from a potentially lethal damage

(48) Belle AJ, Lansing S, Mulbry W, Weil RR. Anaerobic co-digestion of forage radish and dairy manure in complete mix digesters. Bioresour Technol 2014 Sep 16. Abstract: Pilot-scale digesters (850L) were used to quantify CH4 and H2S production when using forage radish cover crops as a co-digestion feedstock in dairy manure-based digesters. During two trials, triplicate mixed digesters were operated in batch mode with manure-only or radish+manure (27% and 13% radish by wet weight in Trial 1 and 2, respectively). Co-digestion increased CH4 production by 11% and 39% in Trial 1 and 2, respectively. As H2S production rapidly declined in the radish+manure digesters, CH4 production increased reaching high levels of CH4 (67%) in the biogas. Over time, radish

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co-digestion lowered the H2S concentration in the biogas (0.20%) beyond that of manure-only digestion (0.34-0.40%), although cumulative H2S production in the radish+manure digesters was higher than manure-only. Extrapolated to a farm-scale (200 cows) continuous mixed digester, co-digesting with radish could generate 3150m3CH4/month, providing a farmer additional revenue up to $3125/month in electricity sales

(49) Pan Z, Wang H, Liu Y, Yu C, Zhang Y, Chen J, et al. Involvement of CSE/ H2S in high glucose induced aberrant secretion of adipokines in 3T3-L1 adipocytes. Lipids Health Dis 2014;13(1):155. Abstract: BACKGROUND: Deregulated secretion of adipokines contributes to subclinical systemic inflammation associated with type 2 diabetes mellitus (T2DM). However, the mechanisms underlying are not fully understood. Hydrogen sulfide (H2S), as an endogenous gasotransmitter, possesses an anti-inflammation activity. The aim of this study was to examine the possible involvement of H2S in high glucose induced adipokine secretion in 3T3-L1 adipocytes. METHODS: The expression of cystathionine-gamma-lyase (CSE), the H2S-forming enzyme, was evaluated by Western-blotting and real-time PCR. The secretion of TNF-alpha, MCP-1 and adiponectin was determined by radioimmunoassay and enzyme-linked immunosorbent assay (ELISA), respectively. Lentiviral empty vector and vector expressing mouse CSE were used for in vitro transduction. RESULTS: High glucose (HG) significantly decreased CSE expression at both protein and mRNA levels in mature 3T3-L1 adipocytes. In parallel, HG significantly increased secretion of MCP-1 while decreasing secretion of adiponectin, but had no effect on secretion of TNF-alpha. HG induced changes in MCP-1 and adiponectin secretion were partly attenuated by forced expression of CSE or sodium hydrosulfide (NaHS), a source of exogenous H2S. CONCLUSION: High glucose induces aberrant secretion of adipokines in mature 3T3-L1 adipocytes, favoring inflammation. The mechanism is partly related to inhibition of CSE/ H2S system

(50) Yang CT, Zhao Y, Xian M, Li JH, Dong Q, Bai HB, et al. A novel controllable hydrogen sulfide-releasing molecule protects human skin keratinocytes against methylglyoxal-induced injury and dysfunction. Cell Physiol Biochem 2014;34(4):1304-17. Abstract: BACKGROUND/AIM: Delayed wound healing is a common skin complication of diabetes, which is associated with keratinocyte injury and dysfunction. Levels of methylglyoxal (MGO), an alpha-dicarbonyl compound, are elevated in diabetic skin tissue and plasma, while levels of hydrogen sulfide (H2S), a critical gaseous signaling molecule, are reduced. Interestingly, the gas has shown dermal protection in our previous study. To date, there is no evidence demonstrating whether MGO affects keratinocyte viability and function or H2S donation abolishes these effects and improves MGO-related impairment of wound healing. The current study was conducted to examine the effects of MGO on the injury and function in human skin keratinocytes and then to evaluate the protective action of a novel H2S-releasing molecule. METHODS: An N-mercapto-based H2S donor (NSHD)-1 was synthesized and its ability to release H2S was observed in cell medium and cells, respectively. HaCaT cells, a cell line of human skin keratinocyte, were exposed to MGO to establish an in vitro diabetic wound healing model. NSHD-1 was added to the cells before MGO exposure and the improvement of cell function was observed in respect of cellular viability, apoptosis, oxidative stress, mitochondrial membrane potential (MMP) and behavioral function. RESULTS: Treatment with MGO decreased cell viability, induced cellular apoptosis, increased intracellular reactive oxygen species (ROS) content and depressed MMP in HaCaT cells. The treatment also damaged cell behavioral function, characterized by decreased cellular adhesion and migration. The synthesized H2S-releasing molecule, NSHD-1, was able to increase H2S levels in both cell medium and cells. Importantly, pretreatment with NSHD-1 inhibited MGO-induced decreases in cell viability and MMP, increases in apoptosis and ROS accumulation in HaCaT cells. The pretreatment was also able to improve adhesion and migration function. CONCLUSION: These results demonstrate that the novel synthesized H2S donor is able

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to protect human skin keratinocytes against MGO-induced injury and behavior dysfunction. We believe that more reasonable H2S-releasing molecules will bring relief to patients suffering from delayed wound healing in diabetes mellitus in the future. (c) 2014 S. Karger AG, Basel

(51) Yin L, Chen D, Cui X, Ge L, Yang J, Yu L, et al. Normal-pressure microwave rapid synthesis of hierarchical SnO2@rGO nanostructures with superhigh surface areas as high-quality gas-sensing and electrochemical active materials. Nanoscale 2014 Oct 24;6(22):13690-700. Abstract: Hierarchical SnO2@rGO nanostructures with superhigh surface areas are synthesized via a simple redox reaction between Sn(2+) ions and graphene oxide (GO) nanosheets under microwave irradiation. XRD, SEM, TEM, XPS, TG-DTA and N2 adsorption-desorption are used to characterize the compositions and microstructures of the SnO2@rGO samples obtained. The SnO2@rGO nanostructures are used as gas-sensing and electroactive materials to evaluate their property-microstructure relationship. The results show that SnO2 nanoparticles (NPs) with particle sizes of 3-5 nm are uniformly anchored on the surfaces of reduced graphene oxide (rGO) nanosheets through a heteronucleation and growth process. The as-obtained SnO2@rGO sample with a hierarchically sesame cake-like microstructure and a superhigh specific surface area of 2110.9 m(2) g(-1) consists of 92 mass% SnO2 NPs and approximately 8 mass% rGO nanosheets. The sensitivity of the SnO2@rGO sensor upon exposure to 10 ppm H2S is up to 78 at the optimal operating temperature of 100 degrees C, and its response time is as short as 7 s. Compared with SnO2 nanocrystals (5-10 nm), the hierarchical SnO2@rGO nanostructures have enhanced gas-sensing behaviors (i.e., high sensitivity, rapid response and good selectivity). The SnO2@rGO nanostructures also show excellent electroactivity in detecting sunset yellow (SY) in 0.1 M phosphate buffer solution (pH = 2.0). The enhancement in gas-sensing and electroactive performance is mainly attributed to the unique hierarchical microstructure, high surface areas and the synergistic effect of SnO2 NPs and rGO nanosheets

(52) Qu Z, Jiang Y, Wu BQ, Duan YF, Sun ZD, Luo GH. Cystathionine-gamma-lyase inhibitor attenuates acute lung injury induced by acute pancreatitis in rats. Arch Med Sci 2014 Aug 29;10(4):825-9. Abstract: INTRODUCTION: Acute pancreatitis (AP) is known to induce injuries to extrapancreatic organs. Because respiratory dysfunction is the main cause of death in patients with severe AP, acute pancreatitis-associated lung injury (APALI) is a great challenge for clinicians. This study aimed to investigate the potential role of hydrogen sulfide (H2S) in the pathogenesis of APALI. MATERIAL AND METHODS: Fifty-four SD rats were randomly divided into three groups: the AP group of rats that received injection of sodium deoxycholate into the common bile duct, the control group that underwent a sham operation, and the treatment group made by intraperitoneal injection of propargylglycine (PAG), an inhibitor of cystathionine-gamma-lyase (CSE), into rats with AP. Histopathology of the lung was examined and the expression of CSE and TNF-alpha mRNA in lung tissue was detected by real-time polymerase chain reaction. The H2S level in the serum was detected spectrophotometrically. RESULTS: The serum concentration of H2S and CSE and TNF-alpha expression in the lung were increased in AP rats modeled after 3 h and 6 h than in control rats (p < 0.05). Intraperitoneal injection of PAG could reduce the serum concentration of H2S, reduce CSE and TNF-alpha expression, and alleviate the lung pathology (p < 0.05). CONCLUSIONS: Taken together, our findings suggest that the H2S/CSE system is crucially involved in the pathological process of APALI and represents a novel target for the therapy of APALI

(53) Cui W, Chen H, Zhu K, Jin Q, Xie Y, Cui J, et al. Cadmium-Induced Hydrogen Sulfide Synthesis Is Involved in Cadmium Tolerance in Medicago sativa by Reestablishment of Reduced (Homo)glutathione and Reactive Oxygen Species Homeostases. PLoS One 2014;9(10):e109669.

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Abstract: Until now, physiological mechanisms and downstream targets responsible for the cadmium (Cd) tolerance mediated by endogenous hydrogen sulfide (H2S) have been elusive. To address this gap, a combination of pharmacological, histochemical, biochemical and molecular approaches was applied. The perturbation of reduced (homo)glutathione homeostasis and increased H2S production as well as the activation of two H2S-synthetic enzymes activities, including L-cysteine desulfhydrase (LCD) and D-cysteine desulfhydrase (DCD), in alfalfa seedling roots were early responses to the exposure of Cd. The application of H2S donor sodium hydrosulfide (NaHS), not only mimicked intracellular H2S production triggered by Cd, but also alleviated Cd toxicity in a H2S-dependent fashion. By contrast, the inhibition of H2S production caused by the application of its synthetic inhibitor blocked NaHS-induced Cd tolerance, and destroyed reduced (homo)glutathione and reactive oxygen species (ROS) homeostases. Above mentioned inhibitory responses were further rescued by exogenously applied glutathione (GSH). Meanwhile, NaHS responses were sensitive to a (homo)glutathione synthetic inhibitor, but reversed by the cotreatment with GSH. The possible involvement of cyclic AMP (cAMP) signaling in NaHS responses was also suggested. In summary, LCD/DCD-mediated H2S might be an important signaling molecule in the enhancement of Cd toxicity in alfalfa seedlings mainly by governing reduced (homo)glutathione and ROS homeostases

(54) Ozturk I, Sagdic O. Biodiversity of Yeast Mycobiota in "Sucuk," a Traditional Turkish Fermented Dry Sausage: Phenotypic and Genotypic Identification, Functional and Technological Properties. J Food Sci 2014 Oct 1. Abstract: In this study, yeasts from Turkish fermented sucuks were identified and their functional and technological properties were evaluated. Two hundred fifty-five yeast isolates were obtained from 35 different sucuk samples from different regions of Turkey. The yeast isolates were determined as genotypic using 2 different polymerase chain reaction (PCR) methods (rep-PCR and RAPD-PCR). Functional and technological properties of including proteolytic, lipolytic, and catalase activities, tolerance to NaCl and bile, as well as growing rates at different temperature and pH conditions selected yeast strains were also evaluated. Candida zeylanoides and Debaryomyces hansenii were dominant strains in sucuk samples. All C. zeylanoides and D. hansenii tested could grow at the condition of 15% NaCl and 0.3% bile salt. However, none of the strains were able to grow at 37 degrees C, even though catalase activity, weak proteolytic and lipolytic activities was still observed. D. hansenii were able to grow only at pH 3, while some of C. zeylanoides could grow at lower pH levels (pH 2). Three and 4 strains of C. zeylanoides showed beta-hemolysis activity and nitrate reduction ability to nitrite, respectively. D. hansenii did not have properties, which are beta-hemolysis, nitrate reduction, or hydrogen sulfide production. Overall, diverse yeast mycobiota present in Turkish fermented sucuk and their functional and technological properties were revealed with this study

(55) Surzhik MA, Shmidt AE, Glazunov EA, Firsov DL, Petukhov MG. [Introduction of additional thiol groups into glucoamylase in Aspergillus awamori and their effect on the thermal stability and catalytic activity of the enzyme]. Prikl Biokhim Mikrobiol 2014 Mar;50(2):139-46. Abstract: Five mutant forms of glucoamylase (GA) from the filamentous fungus Aspergillus awamori with artificial disulfide bonds (4D-G137A¥A14C, 6D-A14C¥Y419C¥G137A, 10D-V13C¥G396C, 11D-V13C¥G396C¥A14C¥Y419C¥G137A, and 20D-G137A¥A246C¥A14C) were constructed using computer simulation and experimentally tested for thermostability. The introduction of two additional disulfide bonds between its first and thirteenth alpha-helices and that of the loop located close to a catalytic residue--E400--made it possible to assess the effects of disulfide bridges on protein thermostability. The mutant proteins with combined amino acid substitutions G137A¥A14C, V13C¥G396C¥A14C¥Y419C¥G137A, and G137A¥A246C¥A14C showed higher thermal stability as compared to the wild-type

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protein. At the same time, new disulfide bridges in the mutant A14C¥Y419C¥G137A and V13C¥G396C proteins led to the destabilization of their structure and the loss of thermal stability

(56) Krayzelova L, Bartacek J, Kolesarova N, Jenicek P. Microaeration for hydrogen sulfide removal in UASB reactor. Bioresour Technol 2014 Sep 20;172C:297-302. Abstract: The removal of hydrogen sulfide from biogas by microaeration was studied in Up-flow Anaerobic Sludge Blanket (UASB) reactors treating synthetic brewery wastewater. A fully anaerobic UASB reactor served as a control while air was dosed into a microaerobic UASB reactor (UMSB). After a year of operation, sulfur balance was described in both reactors. In UASB, sulfur was mainly presented in the effluent as sulfide (49%) and in biogas as hydrogen sulfide (34%). In UMSB, 74% of sulfur was detected in the effluent (41% being sulfide and 33% being elemental sulfur), 10% accumulated in headspace as elemental sulfur and 9% escaped in biogas as hydrogen sulfide. The efficiency of hydrogen sulfide removal in UMSB was on average 73%. Microaeration did not cause any decrease in COD removal or methanogenic activity in UMSB and the elemental sulfur produced by microaeration did not accumulate in granular sludge

(57) Kafle GK, Chen L, Neibling H, Brian HB. Field evaluation of wood bark-based down-flow biofilters for mitigation of odor, ammonia, and hydrogen sulfide emissions from confined swine nursery barns. J Environ Manage 2014 Sep 27;147C:164-74. Abstract: Two down-flow wood bark-based biofilters were evaluated for their effectiveness in treating odor, NH3 and H2S under actual swine farm conditions. The water requirement for maintaining proper media moisture contents (MC) under different ventilation rates and intervals were determined. The effect of media depth and MC on the biofilters' performance was also evaluated. The aerodynamic resistance on biofilters was studied using computational fluid dynamics (CFD) software. Water requirements for biofilters were obtained in the range of 3.8-556.0 L/m3/d for ventilation duration of 1-24 h/d (depending on the age of the pig and environmental conditions). The highest reductions in odor, NH3 and H2S, obtained in this study at empty bed residence times (EBRT) of 1.6-3.1 s, were 73.5-76.9%, 95.2-97.9% and 95.8-100.0%, respectively. The pressure drop was 28.8-68.8 Pa for a media depth of 381 mm at an EBRT of 1.6-3.1 s and an MC of 64-65%. The pressure drop followed a secondary order polynomial line with both airflow rate and media MC (R2 = 0.927-0.982). The results of odor, NH3 and H2S reduction efficiency and pressure drop suggest a media depth of >/=254 mm, MC >/= 35-50% and EBRT of 2-3 s for successful operations of the wood bark-based biofilters. A high correlation was found between the measured and predicted pressured drops obtained using CFD software (R2 = 0.921, RMSE = 0.145)

(58) Stubbert D, Prysyazhna O, Rudyk O, Scotcher J, Burgoyne JR, Eaton P. Protein Kinase G Ialpha Oxidation Paradoxically Underlies Blood Pressure Lowering by the Reductant Hydrogen Sulfide. Hypertension 2014 Sep 29. Abstract: Dysregulated blood pressure control leading to hypertension is prevalent and is a risk factor for several common diseases. Fully understanding blood pressure regulation offers the possibility of developing rationale therapies to alleviate hypertension and associated disease risks. Although hydrogen sulfide (H2S) is a well-established endogenous vasodilator, the molecular basis of its blood-pressure lowering action is incompletely understood. H2S-dependent vasodilation and blood pressure lowering in vivo was mediated by it catalyzing formation of an activating interprotein disulfide within protein kinase G (PKG) Ialpha. However, this oxidative activation of PKG Ialpha is counterintuitive because H2S is a thiol-reducing molecule that breaks disulfides, and so it is not generally anticipated to induce their formation. This apparent paradox was explained by H2S in the presence of molecular oxygen or hydrogen peroxide rapidly converting to polysulfides, which have oxidant properties that in turn activate PKG by inducing the disulfide. These observations are relevant in vivo because transgenic

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knockin mice in which the cysteine 42 redox sensor within PKG has been systemically replaced with a redox-dead serine residue are resistant to H2S-induced blood pressure lowering. Thus, a primary mechanism by which the reductant molecule H2S lowers blood pressure is mediated somewhat paradoxically by the oxidative activation of PKG

(59) Wolin MS. Novel Role for Protein Kinase G Oxidative Activation in the Vasodilator and Antihypertensive Actions of Hydrogen Sulfide. Hypertension 2014 Sep 29.

(60) Terada Y, Fujimura M, Nishimura S, Tsubota M, Sekiguchi F, Kawabata A. Roles of Ca 3.2 and TRPA1 channels targeted by hydrogen sulfide in pancreatic nociceptive processing in mice with or without acute pancreatitis. J Neurosci Res 2014 Sep 30. Abstract: Hydrogen sulfide (H2 S), formed by multiple enzymes, including cystathionine-gamma-lyase (CSE), targets Cav 3.2 T-type Ca2+ channels (T channels) and transient receptor potential ankyrin-1 (TRPA1), facilitating somatic pain. Pancreatitis-related pain also appears to involve activation of T channels by H2 S formed by the upregulated CSE. Therefore, this study investigates the roles of the Cav 3.2 isoform and/or TRPA1 in pancreatic nociception in the absence and presence of pancreatitis. In anesthetized mice, AP18, a TRPA1 inhibitor, abolished the Fos expression in the spinal dorsal horn caused by injection of a TRPA1 agonist into the pancreatic duct. As did mibefradil, a T-channel inhibitor, in our previous report, AP18 prevented the Fos expression following ductal NaHS, an H2 S donor. In the mice with cerulein-induced acute pancreatitis, the referred hyperalgesia was suppressed by NNC 55-0396 (NNC), a selective T-channel inhibitor; zinc chloride; or ascorbic acid, known to inhibit Cav 3.2 selectively among three T-channel isoforms; and knockdown of Cav 3.2. In contrast, AP18 and knockdown of TRPA1 had no significant effect on the cerulein-induced referred hyperalgesia, although they significantly potentiated the antihyperalgesic effect of NNC at a subeffective dose. TRPA1 but not Cav 3.2 in the dorsal root ganglia was downregulated at a protein level in mice with cerulein-induced pancreatitis. The data indicate that TRPA1 and Cav 3.2 mediate the exogenous H2 S-induced pancreatic nociception in naive mice and suggest that, in the mice with pancreatitis, Cav 3.2 targeted by H2 S primarily participates in the pancreatic pain, whereas TRPA1 is downregulated and plays a secondary role in pancreatic nociceptive signaling. (c) 2014 Wiley Periodicals, Inc

(61) Scuffi D, Nunez A, Laspina N, Gotor C, Lamattina L, Garcia-Mata C. Hydrogen sulfide generated by L-cysteine desulfhydrase acts upstream of nitric oxide to modulate ABA-dependent stomatal closure. Plant Physiol 2014 Sep 29. Abstract: Abscisic acid (ABA) is a well-studied regulator of stomatal movement. Hydrogen sulfide (H2S), a small signaling gas molecule involved in key physiological processes in mammals, has been recently reported as a new component of ABA signaling network in stomatal guard cells. In Arabidopsis, H2S is enzymatically produced in the cytosol through the activity of L-cysteine desulfhydrase (DES1). In the present work, we used DES1 knock-out Arabidopsis mutant plants (des1) to study the participation of DES1 in the crosstalk between H2S and nitric oxide (NO) in the ABA-dependent signaling network in guard cells. The results show that ABA did not close the stomata in isolated epidermal strips of des1 mutants, effect that was restored by the application of exogenous H2S. qRT-PCR analysis demonstrated that ABA induces DES1 expression in guard cell-enriched RNA extracts from wild type Arabidopsis plants. Furthermore, stomata from isolated epidermal strips of Arabidopsis ABA receptor mutant pyr1/pyl1/pyl2/pyl4 close in response to exogenous H2S suggesting that this gasotransmitter is acting downstream, although acting independently of ABA receptor cannot be rule out with the present data.. However Arabidopsis clade-A PP2C mutant abi1-1 do not close the stomata when epidermal strips are treated with H2S suggesting that H2S required a functional ABI1. Further studies to unravel the cross-talk between H2S and NO indicate that: (i) H2S promotes NO production, (ii) DES1 is required for ABA-dependent NO production, and

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(iii) NO is downstream of H2S in ABA-induced stomatal closure. Altogether, data indicate that DES1 is a novel component of ABA signaling in guard cells