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1.
Mechanism of Sulfide Binding by Ferric Hemeproteins.
Boubeta, FM, Bieza, SA, Bringas, M, Estrin, DA, Boechi, L, Bari, SE
Inorganic chemistry. 2018;(13):7591-7600
Abstract
The reaction of hydrogen sulfide (H2S) with hemeproteins is a key physiological reaction; still, its mechanism and implications are not completely understood. In this work, we propose a combination of experimental and theoretical tools to shed light on the reaction in model system microperoxidase 11 (MP11-FeIII) and myoglobin (Mb-FeIII), from the estimation of the intrinsic binding constants of the species H2S and hydrosulfide (HS-), and the computational description of the overall binding process. Our results show that H2S and HS- are the main reactive species in Mb-FeIII and MP11-FeIII, respectively, and that the magnitude of their intrinsic binding constants are similar to most of the binding constants reported so far for hemeproteins systems and model compounds. However, while the binding of HS- to Mb-FeIII was negligible, the binding of H2S to MP11-FeIII was significant, providing a frame for a discriminated analysis of both species and revealing differential mechanistic aspects. A joint inspection of the kinetic data and the free energy profiles of the binding processes suggests that a dissociative mechanism with the release of a coordinated water molecule as rate limiting step is operative in the binding of H2S to Mb-FeIII and that the binding of HS- is prevented in the access to the protein matrix. For the MP11-FeIII case, where no access restrictions for the ligands are present, an associative component in the mechanism seems to be operative. Overall, the results suggest that if accessing the active site then both H2S and HS- are capable of binding a ferric heme moiety.
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2.
Maize straw decorated with sulfide for tylosin removal from the water.
Guo, X, Yin, Y, Yang, C, Dang, Z
Ecotoxicology and environmental safety. 2018;:16-23
Abstract
MS-ZnS and MS-ZnS:Mn complexes were synthesized via a simple method. The results showed that sulfide was successfully loaded on the maize straw. The results of fitting the experimental data showed that the sorption conforms to the pseudo-second-order kinetics, and the TYL sorption on MS fit the Henry model well, but the Freundlich model was more suited to MS-ZnS and MS-ZnS:Mn. In addition, the kf values of MS-ZnS (206.0(mg/kg)/(mg/L)n) and MS-ZnS:Mn (382.5(mg/kg)/(mg/L)n) were significantly greater than that of MS (72.2(mg/kg)/(mg/L)n), indicating that ZnS and ZnS:Mn could improve the sorption capacity of TYL on MS. The pH, ionic strength and temperature influence the sorption process, and the sorption ability of TYL on MS-ZnS and MS-ZnS:Mn showed little change when the solution pH was > 5; the amount of TYL sorption on the adsorbents gradually decreased with the increasing concentration of KNO3. Electrostatic interactions, H bonding and hydrophobic interactions are involved in the sorption of TYL on MS, MS-ZnS and MS-ZnS:Mn, and compared with MS, the main mechanism is surface complexation. This research can provide technical support for the utilization of biomass and the restoration of water polluted by antibiotics.
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3.
Hydrothermal chimneys host habitat-specific microbial communities: analogues for studying the possible impact of mining seafloor massive sulfide deposits.
Han, Y, Gonnella, G, Adam, N, Schippers, A, Burkhardt, L, Kurtz, S, Schwarz-Schampera, U, Franke, H, Perner, M
Scientific reports. 2018;(1):10386
Abstract
To assess the risk that mining of seafloor massive sulfides (SMS) from extinct hydrothermal vent environments has for changing the ecosystem irreversibly, we sampled SMS analogous habitats from the Kairei and the Pelagia vent fields along the Indian Ridge. In total 19.8 million 16S rRNA tags from 14 different sites were analyzed and the microbial communities were compared with each other and with publicly available data sets from other marine environments. The chimneys appear to provide habitats for microorganisms that are not found or only detectable in very low numbers in other marine habitats. The chimneys also host rare organisms and may function as a vital part of the ocean's seed bank. Many of the reads from active and inactive chimney samples were clustered into OTUs, with low or no resemblance to known species. Since we are unaware of the chemical reactions catalyzed by these unknown organisms, the impact of this diversity loss and bio-geo-coupling is hard to predict. Given that chimney structures can be considered SMS analogues, removal of sulfide deposits from the seafloor in the Kairei and Pelagia fields will most likely alter microbial compositions and affect element cycling in the benthic regions and probably beyond.
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4.
Modelling the long-term effect of wastewater compositions on maximum sulfide and methane production rates of sewer biofilm.
Sun, J, Ni, BJ, Sharma, KR, Wang, Q, Hu, S, Yuan, Z
Water research. 2018;:58-65
Abstract
Reliable modelling of sulfide and methane production in sewer systems is required for efficient sewer emission management. Wastewater compositions affect sulfide and methane production kinetics through both its short-term variation influencing the substrate availability to sewer biofilms, and its long-term variation affecting the sewer biofilm structure. While the short-term effect is well considered in existing sewer models with the use of Monod or half-order equations, the long-term effect has not been explicitly considered in current sewer models suitable for network modelling. In this study, the long-term effect of wastewater compositions on sulfide and methane production activities in rising main sewers was investigated. A detailed biofilm model was firstly developed, and then calibrated and validated using experimental data measured during the entire biofilm development period of a laboratory sewer reactor. Based on scenario simulations using the detailed biofilm model, empirical equations describing the long-term effect of sulfate and sCOD (soluble chemical oxygen demand) concentrations on kH2S (the maximum sulfide production rate of sewer biofilm) and kCH4 (the maximum methane production rate of sewer biofilm) were proposed. These equations require further verification in future studies before their potential integration into network-wide sewer models.
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5.
Vortioxetine exerts anti-inflammatory and immunomodulatory effects on human monocytes/macrophages.
Talmon, M, Rossi, S, Pastore, A, Cattaneo, CI, Brunelleschi, S, Fresu, LG
British journal of pharmacology. 2018;(1):113-124
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Abstract
BACKGROUND AND PURPOSE A crosstalk between the immune system and depression has been postulated, with monocytes/macrophages and cytokines having a key role in this interaction. In this study, we examined whether vortioxetine, a multimodal anti-depressive drug, was endowed with anti-inflammatory and antioxidative activity, leading to immunomodulatory effects on human monocytes and macrophages. EXPERIMENTAL APPROACH Human monocytes were isolated from buffy coats and used as such or differentiated into M1 and M2 macrophages. Cells were treated with vortioxetine before or after differentiation, and their responsiveness was evaluated. This included oxy-radical and TNFα production, TNFα and PPARγ gene expression and NF-κB translocation. KEY RESULTS Vortioxetine significantly reduced the PMA-induced oxidative burst in monocytes and in macrophages (M1 and M2), causing a concomitant shift of macrophages from the M1 to the M2 phenotype, demonstrated by a significant decrease in the expression of the surface marker CD86 and an increase in CD206. Moreover, treatment of monocytes with vortioxetine rendered macrophages derived from this population less sensitive to PMA, as it reduced the oxidative burst, NF-kB translocation, TNFα release and expression while inducing PPARγ gene expression. FACS analysis showed a significant decrease in the CD14+ /CD16+ /CD86+ M1 population. CONCLUSIONS AND IMPLICATIONS These results demonstrate that in human monocytes/macrophages, vortioxetine has antioxidant activity and anti-inflammatory effects driving the polarization of macrophages towards their alternative phenotype. These findings suggest that vortioxetine, alongside its antidepressive effect, may have immunomodulatory properties.
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6.
Final products and kinetics of biochemical and chemical sulfide oxidation under microaerobic conditions.
Pokorna-Krayzelova, L, Vejmelková, D, Selan, L, Jenicek, P, Volcke, EIP, Bartacek, J
Water science and technology : a journal of the International Association on Water Pollution Research. 2018;(9):1916-1924
Abstract
Hydrogen sulfide is a toxic and usually undesirable by-product of the anaerobic treatment of sulfate-containing wastewater. It can be removed through microaeration, a simple and cost-effective method involving the application of oxygen-limiting conditions (i.e., dissolved oxygen below 0.1 mg L-1). However, the exact transformation pathways of sulfide under microaerobic conditions are still unclear. In this paper, batch experiments were performed to study biochemical and chemical sulfide oxidation under microaerobic conditions. The biochemical experiments were conducted using a strain of Sulfuricurvum kujiense. Under microaerobic conditions, the biochemical sulfide oxidation rate (in mg S L-1 d-1) was approximately 2.5 times faster than the chemical sulfide oxidation rate. Elemental sulfur was the major end-product of both biochemical and chemical sulfide oxidation. During biochemical sulfide oxidation elemental sulfur was in the form of white flakes, while during chemical sulfide oxidation elemental sulfur created a white suspension. Moreover, a mathematical model describing biochemical and chemical sulfide oxidation was developed and calibrated by the experimental results.
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7.
Tungsten disulfide (WS2) nanosheet-based photoelectrochemical aptasensing of chloramphenicol.
Zhou, Y, Sui, C, Yin, H, Wang, Y, Wang, M, Ai, S
Mikrochimica acta. 2018;(10):453
Abstract
A method is described for photoelectrochemical determination of chloramphenicol (CLOA). It is based on the use of (a) aptamers protected with photoactive WS2 nanosheets, and (b) DNase I-assisted target recycling. The DNA aptamer without label was employed for recognition of CLOA. In the absence of CLOA, the aptamer is adsorbed on the surface of WS2. This leads to a decrease of photocurrent due to the steric-hindrance effect of aptamer DNA. The adsorption of WS2 also protects the aptamer from digestion by DNase. In the presence of CLOA, the aptamer will be desorbed from the WS2 surface due to formation of an aptamer/CLOA conjugate. This results in an increased photocurrent due to a decreased amount of aptamer DNA on the electrode surface. The increase of photocurrent can be further improved by applying DNase triggered catalytic recycling of CLOA. Under optimal experimental conditions, the response is linear 10 pM - 10 nM CLOA concentration range, with a 3.6 pM lower detection limit (at 3σ). This method is acceptably selective, accurate and stable. It was applied to the determination of CLOA in spiked milk samples and gave satisfactory results. Graphical abstract A simple and sensitive photoelectrochemical apta-biosensor was fabricated for chloramphenicol detection. In this work, WS2 nanosheets were employed as photoactive material, and DNase I catalytic chloramphenicol recycling strategy was adopted to amplify the detection signal.
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8.
The effects of vortioxetine on cognitive dysfunction in patients with inadequate response to current antidepressants in major depressive disorder: A short-term, randomized, double-blind, exploratory study versus escitalopram.
Vieta, E, Sluth, LB, Olsen, CK
Journal of affective disorders. 2018;:803-809
Abstract
BACKGROUND Major Depressive Disorder (MDD) is a heterogeneous disease characterized by emotional, physical and cognitive symptoms. This study explored the effects of vortioxetine versus escitalopram on outcomes of cognition, functioning and mood symptoms in depressed patients with inadequate response to current antidepressant treatment. METHODS In this parallel-group, active-comparator study, adult patients (18-65 years, N = 101) with MDD, with inadequate response to current antidepressant monotherapy, were randomized 1:1 to 8 weeks' double-blind treatment with flexible doses (10-20mg/day) of either vortioxetine or escitalopram. Primary and key secondary efficacy measures were the Digit Symbol Substitution Test (DSST), analyzed using a mixed model for repeated measurements, and the University of San Diego Performance-based Skills Assessment - Brief (UPSA-B), analyzed using analysis of covariance (last observation carried forward method). RESULTS At week 8, DSST and UPSA-B performance had improved in both treatment groups, with no statistically significant treatment differences. Numerical improvements across measures of cognition, functioning and mood symptoms generally favored vortioxetine. Most adverse events were mild or moderate, with nausea being the most common adverse event. LIMITATIONS This was an exploratory study with small sample sizes implying limited statistical power. CONCLUSION Although this explorative study did not meet primary endpoints, the results confirm vortioxetine in doses of 10-20mg/day as an efficacious and well-tolerated antidepressant switch treatment. The overall direction of numerical effect sizes across cognition endpoints support previous findings that vortioxetine specifically benefits cognitive function in MDD.
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9.
Surface-Chemistry-Mediated Control of Individual Magnetic Helical Microswimmers in a Swarm.
Wang, X, Hu, C, Schurz, L, De Marco, C, Chen, X, Pané, S, Nelson, BJ
ACS nano. 2018;(6):6210-6217
Abstract
Magnetic helical microswimmers, also known as artificial bacterial flagella (ABFs), perform 3D navigation in various liquids under low-strength rotating magnetic fields by converting rotational motion to translational motion. ABFs have been widely studied as carriers for targeted delivery and release of drugs and cells. For in vivo/ in vitro therapeutic applications, control over individual groups of swimmers within a swarm is necessary for several biomedical applications such as drug delivery or small-scale surgery. In this work, we present the selective control of individual swimmers in a swarm of geometrically and magnetically identical ABFs by modifying their surface chemistry. We confirm experimentally and analytically that the forward/rotational velocity ratio of ABFs is independent of their surface coatings when the swimmers are operated below their step-out frequency (the frequency requiring the entire available magnetic torque to maintain synchronous rotation). We also show that ABFs with hydrophobic surfaces exhibit larger step-out frequencies and higher maximum forward velocities compared to their hydrophilic counterparts. Thus, selective control of a group of swimmers within a swarm of ABFs can be achieved by operating the selected ABFs at a frequency that is below their step-out frequencies but higher than the step-out frequencies of unselected ABFs. The feasibility of this method is investigated in water and in biologically relevant solutions. Selective control is also demonstrated inside a Y-shaped microfluidic channel. Our results present a systematic approach for realizing selective control within a swarm of magnetic helical microswimmers.
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10.
Polysulfides and products of H2S/S-nitrosoglutathione in comparison to H2S, glutathione and antioxidant Trolox are potent scavengers of superoxide anion radical and produce hydroxyl radical by decomposition of H2O2.
Misak, A, Grman, M, Bacova, Z, Rezuchova, I, Hudecova, S, Ondriasova, E, Krizanova, O, Brezova, V, Chovanec, M, Ondrias, K
Nitric oxide : biology and chemistry. 2018;:136-151
Abstract
Exogenous and endogenously produced sulfide derivatives, such as H2S/HS-/S2-, polysulfides and products of the H2S/S-nitrosoglutathione interaction (S/GSNO), affect numerous biological processes in which superoxide anion (O2-) and hydroxyl (OH) radicals play an important role. Their cytoprotective-antioxidant and contrasting pro-oxidant-toxic effects have been reported. Therefore, the aim of our work was to contribute to resolving this apparent inconsistency by studying sulfide derivatives/free radical interactions and their consequent biological effects compared to the antioxidants glutathione (GSH) and Trolox. Using the electron paramagnetic resonance (EPR) spin trapping technique and O2-, we found that a polysulfide (Na2S4) and S/GSNO were potent scavengers of O2- and cPTIO radicals compared to H2S (Na2S), GSH and Trolox, and S/GSNO scavenged the DEPMPO-OH radical. As detected by the EPR spectra of DEPMPO-OH, the formation of OH in physiological solution by S/GSNO was suggested. All the studied sulfide derivatives, but not Trolox or GSH, had a bell-shaped potency to decompose H2O2 and produced OH in the following order: S/GSNO > Na2S4 ≥ Na2S > GSH = Trolox = 0, but they scavenged OH at higher concentrations. In studies of the biological consequences of these sulfide derivatives/H2O2 properties, we found the following: (i) S/GSNO alone and all sulfide derivatives in the presence of H2O2 cleaved plasmid DNA; (ii) S/GSNO interfered with viral replication and consequently decreased the infectivity of viruses; (iii) the sulfide derivatives induced apoptosis in A2780 cells but inhibited apoptosis induced by H2O2; and (iv) Na2S4 modulated intracellular calcium in A87MG cells, which depended on the order of Na2S4/H2O2 application. We suggest that the apparent inconsistency of the cytoprotective-antioxidant and contrasting pro-oxidant-toxic biological effects of sulfide derivatives results from their time- and concentration-dependent radical production/scavenging properties and their interactions with O2-, OH and H2O2. The results imply a direct involvement of sulfide derivatives in O2- and H2O2/OH free radical pathways modulating antioxidant/toxic biological processes.