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Volatile organic sulfur compounds (VOSCs) have been assigned environmental roles in global warming, acid precipitation, and cloud formation where two important members dimethyl sulfide (CH3)2 S, DMS, and methanethiol, CH3SH, MT, of VOSC group are involved.

The calculation and use of oxidation numbers in the study of metabolic reactions are discussed for normal oxidations (alcohol dehydrogenase and the NAD+/NADH couple, propanediol dehydratase) and for enzymatic reactions with a "hidden" redox component (transamination, the coupled conversion of ethylamine to ethanol, and the biomethylation of arsenic and selenium). (Contains 6 schemes.)

Tellurite exerts a deleterious effect on a number of small molecules containing sulfur moieties that have a recognized role in cellular oxidative stress. Because cysteine is involved in the biosynthesis of glutathione and other sulfur-containing compounds, we investigated the expression of Geobacillus stearothermophilus V cysteine-related genes cobA, cysK, and iscS and Escherichia coli cysteine regulon genes under conditions that included the addition of [K.sub.2]Te[O.sub.3] to the culture medium. Results showed that cell tolerance to tellurite correlates with the expression level of the cysteine metabolic genes and that these genes are up-regulated when tellurite is present in the growth medium.

A fast, simple and reliable chemical method based on the NaB[H.sub.4]-mediated reduction of Te[O.sub.3.sup.2-] followed by the spectrophotometric determination of elemental tellurium in solution is used for tellurite quantification. The method is found to be highly reproducible and is stable at different pH values and exhibits linearity over a broad range of tellurite concentrations.

The authors review the publications on selenium and tellurium biomethylation. The topics of interest include nutritional and medical considerations for tellurium and selenium, selenium metabolism in plants and tellurium reduction in microorganisms.

Background: Most semiconductor nanoparticles used in biomedical applications are made of heavy metals and involve synthetic methods that require organic solvents and high temperatures. This issue makes the development of water-soluble nanoparticles with lower toxicity a major topic of interest. In a previous work our group described a biomimetic method for the aqueous synthesis of CdTe-GSH Quantum Dots (QDs) using biomolecules present in cells as reducing and stabilizing agents. This protocol produces nanoparticles with good fluorescent properties and less toxicity than those synthesized by regular chemical methods. Nevertheless, biomimetic CdTe-GSH nanoparticles still display some toxicity, so it is important to know in detail the effects of these semiconductor nanoparticles on cells, their levels of toxicity and the strategies that cells develop to overcome it Results: In this work, the response of E. coli exposed to different sized-CdTe-GSH QDs synthesized by a biomimetic protocol was evaluated through transcriptomic, biochemical, microbiological and genetic approaches. It was determined that: i) red QDs (5 nm) display higher toxicity than green (3 nm), ii) QDs mainly induce expression of genes involved with Cd+2 stress (zntA and znuA) and tellurium does not contribute significantly to QDs-mediated toxicity since cells incorporate low levels of Te, iii) red QDs also induce genes related to oxidative stress response and membrane proteins, iv) Cd2+ release is higher in red QDs, and v) QDs render the cells more sensitive to polymyxin B. Conclusion: Based on the results obtained in this work, a general model of CdTe-GSH QDs toxicity in E. coli is proposed. Results indicate that bacterial toxicity of QDs is mainly associated with cadmium release, oxidative stress and loss of membrane integrity. The higher toxicity of red QDs is most probably due to higher cadmium content and release from the nanoparticle as compared to green QDs. Moreover, QDs-treated cells become more sensitive to polymyxin B making these biomimetic QDs candidates for adjuvant therapies against bacterial infections. [ABSTRACT FROM AUTHOR]

Abstract: The tellurium oxyanion, tellurite, is extremely noxious to most living organisms. Its toxicity has been mainly related to the generation of reactive oxygen species (ROS) as well as to an unbalancing of the thiol:redox buffering system. Nevertheless, a few bacteria are capable of thriving at high tellurite concentrations. One mechanism of resistance is the enzymatic and non-enzymatic reduction of tellurite to the less toxic elemental tellurium. This reduction generates nano- to micrometric tellurium crystals that display different shapes and sizes. To date, a very limited number of highly tellurite-resistant and tellurite-reducing bacterial species are available from international culture collections. In this work, we decided to look for tellurite-reducing bacteria from an extreme environment, Antarctica. This environment exhibits a combination of several extreme factors such as high UV-radiation and desiccation and freezing conditions that impact directly on the local biodiversity. Since, as does, all these factors induce ROS formation, we hypothesized that Antarctic bacteria could also exhibit tellurite-resistance. In this context, we isolated 123 tellurite-resistant bacteria, and characterized six new tellurite-resistant and tellurite-reducing bacterial strains from samples collected in Antarctica. These strains were identified according to their 16S rRNA gene sequence as Staphylococcus hameolyticus, Staphylococcus sciuri, Acinetobacter haemolyticus, Pseudomonas lini, and two strains of Psychrobacter immobilis. The isolates display tellurite-resistance about 35- to 500-fold higher than Escherichia coli (Te-sensitive organism), and a high level of tellurite reduction which might be interesting for an application in the field of bioremediation or nanoparticle biosynthesis. [Copyright &y& Elsevier]

The vast application of fluorescent semiconductor nanoparticles (NPs) or quantum dots (QDs) has prompted the development of new, cheap and safer methods that allow generating QDs with improved biocompatibility. In this context, green or biological QDs production represents a still unexplored area. This work reports the intracellular CdTe QDs biosynthesis in bacteria. Escherichia coli overexpressing the gshA gene, involved in glutathione (GSH) biosynthesis, was used to produce CdTe QDs. Cells exhibited higher reduced thiols, GSH and Cd/Te contents that allow generating fluorescent intracellular NP-like structures when exposed to CdCl2 and K2TeO3. Fluorescence microscopy revealed that QDs-producing cells accumulate defined structures of various colors, suggesting the production of differently-sized NPs. Purified fluorescent NPs exhibited structural and spectroscopic properties characteristic of CdTe QDs, as size and absorption/emission spectra. Elemental analysis confirmed that biosynthesized QDs were formed by Cd and Te with Cd/Te ratios expected for CdTe QDs. Finally, fluorescent properties of QDs-producing cells, such as color and intensity, were improved by temperature control and the use of reducing buffers. [ABSTRACT FROM AUTHOR]

Multiple applications of nanotechnology, especially those involving highly fluorescent nanoparticles (NPs) or quantum dots (QDs) have stimulated the research to develop simple, rapid and environmentally friendly protocols for synthesizing NPs exhibiting novel properties and increased biocompatibility. In this study, a simple protocol for the chemical synthesis of glutathione (GSH)-capped CdTe QDs (CdTe-GSH) resembling conditions found in biological systems is described. Using only CdCl2, K2TeO3 and GSH, highly fluorescent QDs were obtained under pH, temperature, buffer and oxygen conditions that allow microorganisms growth. These CdTe-GSH NPs displayed similar size, chemical composition, absorbance and fluorescence spectra and quantum yields as QDs synthesized using more complicated and expensive methods. CdTe QDs were not freely incorporated into eukaryotic cells thus favoring their biocompatibility and potential applications in biomedicine. In addition, NPs entry was facilitated by lipofectamine, resulting in intracellular fluorescence and a slight increase in cell death by necrosis. Toxicity of the as prepared CdTe QDs was lower than that observed with QDs produced by other chemical methods, probably as consequence of decreased levels of Cd+2 and higher amounts of GSH. We present here the simplest, fast and economical method for CdTe QDs synthesis described to date. Also, this biomimetic protocol favors NPs biocompatibility and helps to establish the basis for the development of new, "greener" methods to synthesize cadmium-containing QDs. [ABSTRACT FROM AUTHOR]

The selenocyanate anion, SeCN-, has been reported in wastewater from refineries whose petroleum comes from Se-rich marine shales. A metalloid-resistant bacterium was exposed to aqueous solutions of SeCN- to examine the relative toxicity of SeCN-, and the results were compared with the toxicity of selenate and selenite and another G16 metalloid oxyanion, tellurite. We also determined the volatile organo-selenium species produced by bacterial cultures amended with selenocyanate anion, and we investigated a solid phase preconcentration technique for collecting SeCN- from aqueous samples with different ionic strengths and subsequent detection using capillary electrophoresis. The relative toxicity of SeCN- is comparable to that of selenate and selenite using the metalloid-resistant bacterium LHVE as the test organism. Tellurite was more toxic at all concentrations examined than all three selenium-containing anions, SeO42-, SeO32-, SeCN-. Live cultures of LHVE amended with 1 mM NaSeCN produced volatile organo-sulphides and organo-selenides that could be collected in headspace using a solid phase microextraction fibre. The bioprocessing, i.e. the reduction and methylation of SeCN-, is similar to that of selenate and selenite by other metalloid-resistant bacteria. An aqueous 1.0 mM solution of SeCN- could be captured from solution on solid-phase extraction (SPE) cartridges using an aminopropyl-based stationary phase. Selenocyanate anions, slowly pumped into a wetted SPE cartridge, were trapped on the cartridge's solid phase and were subsequently eluted, thereby providing an increase in concentration above that of the original SeCN--containing solution. Preconcentration factors of 3.9 were achieved using a mixed sodium hydroxide/methanol elution solvent and by adding NaCl to aqueous SeCN- before loading on the SPE cartridge. [ABSTRACT FROM AUTHOR]

Volatile organic sulfur compounds (VOSCs) play a major role in the global sulfur cycle. Two components, dimethyl sulfide (DMS) and methanethiol (MT) are formed in large amounts by living systems (e.g. algae, bacteria, plants), particularly in marine environments. A major route to DMS is by action of a lyase enzyme on dimethylsulfoniopropionate (DMSP). DMSP has other roles, for instance as an osmoprotectant and cryoprotectant. Demethiolation of DMSP and other materials leads to MT. A major transport process is release of DMS from the oceans to the atmosphere. Oxidation of DMS in the atmosphere by hydroxyl and nitrate radicals produces many degradation products including CO2, COS, dimethyl sulfoxide, dimethyl sulfone, organic oxyacids of sulfur, and sulfate. These materials also have roles in biotic processes and there are complex metabolic interrelationships between some of them. This review emphasizes the chemical reactions of the organic sulfur cycle. For biotic reactions, details of relevant enzymes are provided when possible. [Copyright &y& Elsevier]

Presents a study which examined microbial methylation of arsenic, antimony and bismuth. List of natural products discovered during the 19th century which contain methyl groups attached to nitrogen atoms; Discussion on the function of anaerobic microorganisms; Enzymology of biomethylation.

Reports on the metabolism of selenate and selenite by Rhodobacter sphaeroides. Comparison of selenium bioconversion by R. sphaeroides in selenium-amended cultures versus selenite-amended cultures; Chemical forms of selenium in the microbial cells; Accumulation of selenium in the microbial cells by volatilization.

Presents the different methods used to teach schematic relationships in complex chemical instrumentation. Use of the World Wide Web for Chemistry-based animation.

The increasing importance of tellurium in organic synthesis, in industrial applications, and as a possible component in pesticides means that its introduction into the environment will probably increase in the future. A knowledge of the relative toxicity and the mode of toxic action of tellurium-containing chemicals is therefore important. The work presented here, using growth-rate inhibition effects on Pseudomonas fluorescens of two model compounds, telluranthrene and tetrachlorodiphenyl ditelluride, suggests that these compounds are at least as toxic as the relatively well-known selenium oxyanions, selenate andselenite. Experiments with human promyelocytic (line HL-60) cells indicate that both the above organotellurium compounds induce a form ofcell death called apoptosis, or programmed cell death. The inductionof apoptosis occurred in both a time- and dose-dependent manner, as assayed by three different analytical methods: fluorescence microscopy, flow cytometry, and gel electrophoresis. The results indicate thatorganotellurium compounds may find applicability in the fields of chemoprevention and cancer therapy, similar to organoselenium compounds. [ABSTRACT FROM AUTHOR]

The tellurium oxyanion tellurite is harmful for most microorganisms. Since its toxicity occurs chiefly once the toxicant reaches the intracellular compartment, unveiling the toxicant uptake process is crucial for understanding the whole phenomenon of tellurium toxicity. While the PitA phosphate transporter is thought to be one of the main paths responsible for toxicant entry into Escherichia coli , genetic and physiological evidence have identified the ActP acetate carrier as the main tellurite importer in Rhodobacter capsulatus . In this work, new background on the role of these transporters in tellurite uptake by E. coli is presented. It was found that, similar to what occurs in R. capsulatus , ActP is able to mediate toxicant entry to this bacterium. Lower reactive oxygen species levels were observed in E. coli lacking the actP gene. Antioxidant enzyme catalase and fumarase C activity was almost unchanged after short exposure of E. coli Δ actP to sublethal tellurite concentrations, suggesting a low antioxidant response. In this strain, tellurite uptake decreased significantly during the first 5 min of exposure and inductively coupled plasma optical emission spectroscopy assays using an actP -overexpressing strain confirmed that this carrier mediates toxicant uptake. Relative gene expression experiments by qPCR showed that actP expression is enhanced at short times of tellurite exposure, while pitA and pitB genes are induced later. Summarizing, the results show that ActP is involved in tellurite entry to E. coli and that its participation occurs mainly at early stages of toxicant exposure. [ABSTRACT FROM AUTHOR]

Several transporters suspected to be involved in tellurite uptake in Escherichia coli were analyzed. Results showed that the PitA phosphate transporter was related to tellurite uptake. Escherichia coli ΔpitA was approximately four-fold more tolerant to tellurite, and cell viability remained almost unchanged during prolonged exposure to the toxicant as compared with wild type or ΔpitB cells. Notably, reduced thiols (toxicant targets) as well as superoxide dismutase, catalase, and fumarase C activities did not change when exposing the ΔpitA strain to tellurite, suggesting that tellurite-triggered oxidative damage is attenuated in the absence of PitA. After toxicant exposure, remaining extracellular tellurite was higher in E. coli ΔpitA than in control cells. Whereas inductively coupled plasma atomic emission spectrometric studies confirmed that E. coli ΔpitA accumulates ∼50% less tellurite than the other strains under study, tellurite strongly inhibited (32)P(i) uptake suggesting that the PitA transporter is one of the main responsible for tellurite uptake in this bacterium.