Sulfide

硫化物
  • 文章类型: Journal Article
    含铁金属在硫酸盐还原条件下的腐蚀是经济上重要的问题。在许多基础研究中,现在称为普通脱硫弧菌的微生物菌株用作模型微生物,这些基础研究开发了在硫酸盐还原条件下含铁金属腐蚀的现有模型。提出的普通D.的腐蚀机理包括:(1)消耗H2以加速Fe0的氧化,并将质子还原为H2;(2)与亚铁结合形成促进H2产生的硫化铁涂层的硫化物的产生;(3)垂死的细胞释放氢化酶,催化Fe0氧化并产生H2;(4)从Fe0到细胞的直接电子转移;(5)黄素作为电子在Fecells和电子之间转移电子0。对金属表面上生长的细胞进行转录组学和蛋白质组学分析的证明可能性表明,对普通D.vulgaris腐蚀生物膜的类似研究可以帮助鉴定在腐蚀中起重要作用的蛋白质。在普通D.中进行靶向基因缺失的工具可用于功能遗传研究。这些方法,加上用于检测低浓度H2的仪器,以及用于评估假定的电子穿梭功能的成熟技术,预计将有可能确定哪种拟议的寻常D.vulgaris腐蚀机理是最重要的。
    Corrosion of iron-containing metals under sulfate-reducing conditions is an economically important problem. Microbial strains now known as Desulfovibrio vulgaris served as the model microbes in many of the foundational studies that developed existing models for the corrosion of iron-containing metals under sulfate-reducing conditions. Proposed mechanisms for corrosion by D. vulgaris include: (1) H2 consumption to accelerate the oxidation of Fe0 coupled to the reduction of protons to H2; (2) production of sulfide that combines with ferrous iron to form iron sulfide coatings that promote H2 production; (3) moribund cells release hydrogenases that catalyze Fe0 oxidation with the production of H2; (4) direct electron transfer from Fe0 to cells; and (5) flavins serving as an electron shuttle for electron transfer between Fe0 and cells. The demonstrated possibility of conducting transcriptomic and proteomic analysis of cells growing on metal surfaces suggests that similar studies on D. vulgaris corrosion biofilms can aid in identifying proteins that play an important role in corrosion. Tools for making targeted gene deletions in D. vulgaris are available for functional genetic studies. These approaches, coupled with instrumentation for the detection of low concentrations of H2, and proven techniques for evaluating putative electron shuttle function, are expected to make it possible to determine which of the proposed mechanisms for D. vulgaris corrosion are most important.
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  • 文章类型: Journal Article
    我们对某些具有通式I2-II-IV-VI4的类金刚石材料的整体不稳定性指数(G)值的计算表明,该结构可能不稳定或确定不正确。要计算给定化合物的G值,必须首先使用晶体结构计算键合价和(BVS)。具有高G值的化合物的两个例子,根据文献中的数据,是Wurtz-锡矿型双铜镉硅四硫化物(Cu2CdSiS4)和锡矿型双铜汞四硫化物(Cu2HgSnS4),分别于1967年和1965年首次报道。在本研究中,Cu2CdSiS4和Cu2HgSnS4在1000和900°C下通过固态合成制备,分别。通过粉末X射线衍射评估相纯度。光学漫反射UV/Vis/NIR光谱分别用于估计Cu2CdSiS4和Cu2HgSnS4的2.52和0.83eV的光学带隙。使用单晶X射线衍射数据对结构进行解析和细化。证实了Cu2CdSiS4的构造类型,其中Cd2+,Si4和三个晶体学上独特的S2-离子中的两个位于镜平面上。同时验证了Cu2HgSnS4的结构类型,所有离子都位于特殊位置。S2-离子位于镜像平面上,Cu+离子位于四重旋转反转轴上,Hg2+和Sn4+离子位于四重旋转反转轴的交点上,一个镜像平面和一个双旋转轴。利用这里解析和细化的晶体结构,重新评估G值,发现G值在表明稳定晶体结构的合理应变的范围内。这项工作,以及从文献中收集的一些例子,表明,在现代仪器上收集的准确数据应用于可靠地计算BVSs和G值。
    Our calculations of the global instability index (G) values for some diamond-like materials with the general formula I2-II-IV-VI4 have indicated that the structures may be unstable or incorrectly determined. To compute the G value of a given compound, the bond valence sums (BVSs) must first be calculated using a crystal structure. Two examples of compounds with high G values, based on data from the literature, are the wurtz-stannite-type dicopper cadmium silicon tetrasulfide (Cu2CdSiS4) and the stannite-type dicopper mercury tin tetrasulfide (Cu2HgSnS4), which were first reported in 1967 and 1965, respectively. In the present study, Cu2CdSiS4 and Cu2HgSnS4 were prepared by solid-state synthesis at 1000 and 900 °C, respectively. The phase purity was assessed by powder X-ray diffraction. Optical diffuse reflectance UV/Vis/NIR spectroscopy was used to estimate the optical bandgaps of 2.52 and 0.83 eV for Cu2CdSiS4 and Cu2HgSnS4, respectively. The structures were solved and refined using single-crystal X-ray diffraction data. The structure type of Cu2CdSiS4 was confirmed, where Cd2+, Si4+ and two of the three crystallographically unique S2- ions lie on a mirror plane. The structure type of Cu2HgSnS4 was also verified, where all ions lie on special positions. The S2- ion resides on a mirror plane, the Cu+ ion is situated on a fourfold rotary inversion axis and both the Hg2+ and the Sn4+ ions are located on the intersection of a fourfold rotary inversion axis, a mirror plane and a twofold rotation axis. Using the crystal structures solved and refined here, the G values were reassessed and found to be in the range that indicates reasonable strain for a stable crystal structure. This work, together with some examples gathered from the literature, shows that accurate data collected on modern instrumentation should be used to reliably calculate BVSs and G values.
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  • 文章类型: Journal Article
    在大多数先前的研究中,通过MIC方法研究了大肠杆菌外膜突变体对环丙沙星(CF)的敏感性。在目前的工作中,使用生理和生化方法以及电化学传感器研究了这些突变体对CF的早期反应。传感器的使用使得监测溶解氧成为可能,钾和细胞外硫化物连续直接在实时生长的培养物中。如果没有CF,在缺乏孔蛋白OmpF和脂多糖(LPS)的突变体与亲本之间没有发现显着差异。唯一的例外是与亲本和ompF相比,lpcA中的细胞外谷胱甘肽高5-6倍,细胞内谷胱甘肽低1.5-3倍。环丙沙星抑制生长,呼吸,膜电位和K+消耗,与亲本相比,这在两个突变体中都不太明显。这些参数的变化相互关联,但不是为了生存。在母体中3μgml-1CF时观察到硫化物水平的可逆增加,在ompF中为20μgml-1CF,在所有浓度的lpcA中均不存在。获得的数据表明,使用电化学传感器可以更完整地了解细菌对CF的早期反应。
    In most previous studies the sensitivity of Escherichia coli outer membrane mutants to ciprofloxacin (CF) was studied by MIC method. In the present work, the early response of these mutants to CF was studied using physiological and biochemical methods and electrochemical sensors. The use of sensors made it possible to monitor dissolved oxygen, potassium and extracellular sulfide continuously directly in growing cultures in real time. In the absence of CF, no significant differences were found between the mutants deficient in porin OmpF and lipopolysaccharide (LPS) and the parent. The only exception was 5-6 times higher extracellular glutathione and 1.5-3 times lower intracellular glutathione in the lpcA compared to the parent and the ompF. Ciprofloxacin inhibited growth, respiration, membrane potential and K+ consumption, which was less pronounced in both mutants compared to the parent. Changes in these parameters correlated with each other, but not with survival. A reversible increase in sulfide level was observed at 3 μg ml-1 CF in the parent, at 20 μg ml-1 CF in ompF and was absent in lpcA at all concentrations. The data obtained show that the use of electrochemical sensors can provide a more complete understanding of the early response of bacteria to CF.
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  • 文章类型: Journal Article
    深海热液烟囱的生物活动是由化学营养微生物驱动的,这些微生物从排出的高温流体中代谢化学物质。了解这种环境中的分类学和微生物微观结构是微古生物学和古生态学研究的必要条件。这项研究检查了最近来自罗马遗址热液喷口的黑人吸烟者的化石微生物和相关的微观结构,巴布亚新几内亚近海的东马努斯盆地。尽管所检查的硫化物烟囱的中心由高温矿物学(黄铜矿和树枝状闪锌矿)主导,丝状和球形生物形态发生在外部,热液和海水混合的暖区,这表明它们在重晶石-黄铁矿共沉淀物的胶体和肉毒黄铁矿中的存在。根据在高温栖息地中的存在,两种形态类型都可以解释为嗜热微生物。它们单独(非共生)的发生暗示了对微环境条件的敏感性,这是预期的高温,pH值,和深海热液烟囱壁上的氧化还原梯度。虽然两种形态都经历了温和的热套印,存在分类差异:(i)丝状化石中细胞留下的空间主要由二氧化硅填充,Whereasinter/externalfeatures(crosswalls/septaeandoutershiaths)arepyrized;(ii)coccoidalfossilesshowbothsilica-andydromite-invilledinteriors,和一般更好的保存细胞壁。这些不同的表现可能与微环境因素和生物因素之间的相互作用有关,潜在的对比代谢,以及不同细菌和/或古细菌的细胞壁化学差异。进一步的假设是,球形特征代表生物膜形成生物,其有机物衍生物有助于形成紧密相关的波浪状和皱纹碳质层状结构,这些层状结构至少可以与周围黄铁矿的质地区分开。因此,所提供的数据提供了证据,表明来自热液系统的微生物群的微观结构对于古生物学研究与来自沉积环境的微生物群具有相似的意义。
    Biological activity at deep-sea hydrothermal chimneys is driven by chemotrophic microorganisms that metabolize chemicals from the venting high-temperature fluids. Understanding taphonomy and microbial microtextures in such environments is a necessity for micropaleontological and palaeoecological research. This study examines fossilized microorganisms and related microtextures in a recent black smoker from the Roman Ruins hydrothermal vent site, Eastern Manus Basin offshore of Papua New Guinea. Whereas the center of the examined sulfide chimney is dominated by high-temperature mineralogy (chalcopyrite and dendritic sphalerite), filamentous and coccoidal biomorphs occur in an outer, warm zone of mixing between hydrothermal fluids and seawater, which is indicated by their occurrence within colloform and botryoidal pyrite of barite-pyrite coprecipitates. Both morphotypes can be interpreted as thermophilic microorganisms based on their occurrence in a high-temperature habitat. Their separate (non-commensal) occurrence hints at sensitivities to microenvironmental conditions, which is expectable for strong temperature, pH, and redox gradients at the walls of deep-sea hydrothermal chimneys. Whereas both morphotypes experienced mild thermal overprint, taphonomic differences exist: (i) spaces left by cells in filamentous fossils are predominately filled by silica, whereas inter/extracellular features (crosswalls/septae and outer sheaths) are pyritized; (ii) coccoidal fossils show both silica- and pyrite-infilled interiors, and generally better preservation of cell walls. These different manifestations presumably relate to an interplay between microenvironmental and biological factors, potentially contrasting metabolisms, and differences in cell wall chemistries of distinct bacteria and/or archaea. A further hypothesis is that the coccoidal features represent biofilm-forming organisms, whose organic matter derivates contributed to the formation of intimately associated wavy and wrinkly carbonaceous laminations that are at least locally distinguishable from the texture of the surrounding pyrite. Hence, the presented data provide evidence that microtextures of microbiota from hydrothermal systems can have a similar significance for palaeobiological research as those from sedimentary environments.
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  • 文章类型: Journal Article
    中国南部的天宝水库(被桉树人工林包围)是居民的饮用水来源。然而,水库水经历黑水(BW),其原因尚不清楚。在这项研究中,进行了现场观察和模拟实验室实验,以了解BW的原因。薄膜(DGT)器件中的扩散梯度监测了铁(Fe2)浓度的空间变化,锰(Mn2+),硫化物(S2-),和在SWI处溶解的有机碳(DOC)。平面光电(PO)表明缺氧对高正流Fe2有很大贡献,Mn2+,和S2-测量,其在SWI处共沉淀形成黑色材料(FeS和MnS)。Fe-S和Mn-S之间的共沉淀具有显着的正相关性(Fe-S:r>0.05,p<0.05,Mn-S:r>0.2,p<0.05)。从11月(强热分层)到12月(弱热分层)单宁浓度显着降低(p<0.05)表明,由于分层较弱,Fe2和单宁在12月的水库水混合过程中发生了反应。模拟实验证实,新鲜桉树叶在缺氧过程中产生大量(p<0.05)单宁,并与Fe2反应产生黑水。Fe2和DOC之间的高度正相关(r>0.8)表明Fe2和DOC结合并有助于水库水变黑。该研究有助于更好地了解桉树人工林对水质的影响,为我国南方水库流域科学种植桉树人工林,保证饮用水安全提供指导。
    Tianbao reservoir in southern China (surrounded by Eucalyptus plantation) serves as a source of drinking water for the inhabitants. However, the reservoir water experiences black water (BW) of which the cause remains unclear. In this study, field observation and simulated laboratory experiment were conducted to understand the cause of the BW. The diffusive gradient in thin-film (DGT) device monitored the spatial changes in concentration of iron (Fe2+), manganese (Mn2+), sulfide (S2-), and dissolved organic carbon (DOC) at the SWI. The planar optode (PO) showed that hypoxia contributed immensely to the high positive fluxes Fe2+, Mn2+, and S2- measured, which co-precipitated to form black materials (FeS and MnS) at the SWI. The co-precipitation between Fe-S and Mn-S was supported by their significant positive correlation (Fe-S: r > 0.05, p < 0.05, Mn-S: r > 0.2, p < 0.05). Significant reduction (p < 0.05) in tannins concentration from November (strong thermal stratification) to December (weak thermal stratification) indicated that Fe2+ and tannins reacted during the mixing of reservoir water in December due to weak stratification. The simulated experiment confirmed that fresh Eucalyptus leaves produces a significant (p < 0.05) amount of tannins during hypoxia and reacts with Fe2+ to produce black water. A high positive correlation (r > 0.8) between Fe2+ and DOC demonstrated that Fe2+ and DOC combined and contributed to the reservoir water blackening. The study provides a better understanding on the impact of Eucalyptus plantation on water quality and provide guidance for scientific planting of Eucalyptus plantation in reservoir basins in southern China to ensure safe drinking water.
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  • 文章类型: Journal Article
    Experimental evolution studies using cyanobacteria as model organisms are scarce despite the role of cyanobacteria in the evolution of photosynthesis. Three different experimental evolution approaches have been applied to shed light on the sulfide adaptation process, which played a key role in the evolution of this group. We used a Microcystis aeruginosa sulfide-sensitive strain, unable to grow above ~0.1 mM, and an Oscillatoria sp. strain, isolated from a sulfureous spa (~0.2 mM total sulfide). First, performing a fluctuation analysis design using the spa waters as selective agent, we proved that M. aeruginosa was able to adapt to this sulfide level by rare spontaneous mutations. Second, applying a ratchet protocol, we tested if the limit of adaptation to sulfide of the two taxa was dependent on their initial sulfide tolerance, finding that M. aeruginosa adapted to 0.4 mM sulfide, and Oscillatoria sp. to ~2 mM sulfide, twice it highest tolerance level. Third, using an evolutionary rescue approach, we observed that both speed of exposure to increasing sulfide concentrations (deterioration rate) and populations\' genetic variation determined the survival of M. aeruginosa at lethal sulfide levels, with a higher dependence on genetic diversity. In conclusion, sulfide adaptation of sensitive cyanobacterial strains is possible by rare spontaneous mutations and the adaptation limits depend on the sulfide level present in strain\'s original habitat. The high genetic diversity of a sulfide-sensitive strain, even at fast environmental deterioration rates, could increase its possibility of survival even to a severe sulfide stress.
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  • 文章类型: Journal Article
    In this study, we investigated the interaction between selenite and either Fe((II))aq or S((-II))aq in solution, and the results were used to investigate the interaction between Se((IV))aq and FeS in suspension. The reaction products were characterized by a combination of methods (SEM, XRD and XAS) and the reaction mechanisms were identified. In a first experiment, Se((IV))aq was reduced to Se((0)) by interaction with Fe((II))aq which was oxidized to Fe((III)), but the reaction was only partial. Subsequently, some Fe((III)) produced akaganeite (β-FeOOH) and the release of proton during that reaction decreased the pH. The pH decrease changed the Se speciation in solution which hindered further Se((IV)) reduction by Fe((II))aq. In a second experiment, Se((IV))aq was quantitatively reduced to Se((0)) by S((-II))aq and the reaction was fast. Two sulfide species were needed to reduce one Se((IV)), and the observed pH increase was due to a proton consumption. For both experiments, experimental results are consistent with expectations based on the oxidation reduction potential of the various species. Upon interaction with FeS, Se((IV))aq was reduced to Se((0)) and minute amounts of pyrite were detected, a consequence of partial mackinawite oxidation at surface sulfur sites. These results are of prime importance with respect to safe deep disposal of nuclear waste which contains the long-lived radionuclide (79)Se. This study shows that after release of (79)Se((IV)) upon nuclear waste matrix corrosion, selenite can be reduced in the near field to low soluble Se((0)) by interaction with Fe((II))aq and/or S((-II))aq species. Because the solubility of Se((0)) species is significantly lower than that of Se((IV)), selenium will become much less (bio)available and its migration out of deep HLW repositories may be drastically hindered.
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