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Model studies on the influence of matrix type and storage environment on the stability of a model aroma mixture during storage.

The objective of this study was to investigate the effect of oxygen in the storage atmosphere on the degradation of model compounds when present in water or a medium chain triglyceride (MCT) matrix. A model aroma compound mixture was prepared in oil (MCT) or water, and it was then stored under either an ambient air or argon atmosphere containing respectively ca. 20% and <0.5% residual oxygen. Samples were analyzed by SPME-GC/MS to determine the relative stability over time of different classes of aroma compounds. The low-oxygen atmosphere appeared to have a significant protective effect on sulfur compounds, aldehydes, and ketones in oil but a detrimental influence on pyrroles. Data showed little influence of the atmosphere for these compounds in water. In addition, the type of matrix had a significant effect (P < 0.05) on the stability of aldehydic, ester, and pyrrole compounds. These compounds were more stable in MCT than in water.

Drug Stability↗

Rapid screening of organosulfur agents for potential chemopreventive activity using the murine NA assay.

The chemopreventive efficacy of 11 organosulfur compounds was assessed using the murine nuclear aberration (NA) assay in C57BL/6J mice. The sulfur compounds were introduced by stomach gavage. Benzo[a]pyrene (BP), which is a carcinogen known to a) undergo biotransformation by pathways mediated by P-450 and b) induce NA in the intestine, was used as the challenge. All animals were killed 48 hours after BP injection, and NA per crypt were scored. The results indicated that several agents were active in inhibiting BP nucleotoxicity to the colon, most notably, allyl mercaptan, benzyl mercaptan, and phenylethyl mercaptan. The NA assay was useful in effectively prescreening certain compounds for potential interactions with chemical carcinogens, thus serving as one indicator of chemopreventive activity.

Animals↗

Microbial desulfurization of gasoline in a Mycobacterium goodii X7B immobilized-cell system.

Mycobacterium goodii X7B, which had been primarily isolated as a bacterial strain capable of desulfurizing dibenzothiophene to produce 2-hydroxybiphenyl via the 4S pathway, was also found to desulfurize benzothiophene. The desulfurization product was identified as o-hydroxystyrene by gas chromatography (GC)-mass spectrometry analysis. This strain appeared to have the ability to remove organic sulfur from a broad range of sulfur species in gasoline. When Dushanzi straight-run gasoline (DSRG227) containing various organic sulfur compounds was treated with immobilized cells of strain X7B for 24 h, the total sulfur content significantly decreased, from 227 to 71 ppm at 40 degrees C. GC flame ionization detection and GC atomic emission detection analysis were used to qualitatively evaluate the effects of M. goodii X7B treatment on the contents of gasoline. In addition, when immobilized cells were incubated at 40 degrees C with DSRG275, the sulfur content decreased from 275 to 54 ppm in two consecutive reactions. With this excellent efficiency, strain X7B is considered a good potential candidate for industrial applications for the biodesulfurization of gasoline.

Biodegradation, Environmental↗

Biodegradation of sediment-bound PAHs in field-contaminated sediment.

The biodegradation of polycyclic aromatic hydrocarbons (PAHs) has been reported to occur under aerobic, sulfate reducing, and denitrifying conditions. PAHs present in contaminated sites, however, are known for their persistence. Most published studies were conducted in systems where PAHs were freshly spiked, and biodegradation was often tested using pure cultures or enrichments. This paper investigated the degradation potentials of PAHs that were present in aged contaminated sediment by indigenous bacteria, where the limited bioavailability of PAHs due to aging played an important role. The sediment and the overlaying water were collected from a contaminated site to prepare sediment-water slurries, and the sediment served as both the media containing PAH substrates and the habitat for the indigenous microorganisms. Reduced sulfur compounds present in the sediment caused rapid oxygen depletion due to extensive activities of sulfur-oxidizing bacteria and could result in a dramatic pH drop. Once oxygen depletion and acidification problems were avoided, substantial removals of two-, three-, four-, and five-ring PAHs were achieved aerobically, though the extent of degradations was smaller than what was reported for freshly spiked PAHs. The amendment of inorganic N and P, co-substrates, or surfactant Triton X-100 did not enhance the level of degradations appreciably. Under denitrifying conditions, no distinct PAH degradation was observed, while the complete denitrification of nitrate to nitrogen occurred stoichiometrically with a concomitant increase in sulfate concentration, indicating the dominance of autotrophic denitrifiers. The addition of ethanol or acetic acid did not stimulate PAH degradation. Substantial PAH degradation attributed to sulfate reduction was only observed for phenanthrene, the low-ring PAH existing in a highest initial concentration. Addition of ethanol or acetic acid did not change this finding. This is the first study to our knowledge that revealed the importance of indigenous bacteria involved in natural sulfur cycling in determining degradation behavior of PAHs.

Aerobiosis↗

Sulfur assimilation and the role of sulfur in plant metabolism: a survey.

Sulfur occurs in two major amino-acids, cysteine (Cys) and methionine (Met), essential for the primary and secondary metabolism of the plant. Cys, as the first carbon/nitrogen-reduced sulfur product resulting from the sulfate assimilation pathway, serves as a sulfur donor for Met, glutathione, vitamins, co-factors, and sulfur compounds that play a major role in the growth and development of plant cells. This sulfur imprinting occurs in a myriad of fundamental processes, from photosynthesis to carbon and nitrogen metabolism. Cys and Met occur in proteins, with the former playing a wide range of functions in proteins catalysis. In addition, the sulfur atom in proteins forms part of a redox buffer, as for glutathione, through specific detoxification/protection mechanisms. In this review, a survey of sulfur assimilation from sulfate to Cys, Met and glutathione is presented with highlights on open questions on their respective biosynthetic pathways and regulations that derived from recent findings. These are addressed at the biochemical and molecular levels with respect to the fate of Cys and Met throughout the plant-cell metabolism.

Journal Article↗

Emissions of chemical compounds and bioaerosols during the secondary treatment of paper mill effluents.

This study identified and quantified the main chemical compounds--the substances responsible for the disagreeable odors--and the bioaerosols emitted during the biological treatment of paper mill effluents. It also identified the characteristics of the process that effects the generation or diffusion of these substances. All treatment stages were evaluated. Measuring sites were located as closely as possible to the potential emission sources. Measurements were taken in the summer in 11 paper mills during a 2- to 3-day period in each mill. Chemical compounds were evaluated by direct-reading instruments; bioaerosols were sampled by impaction and counted. Sulfur compounds, emitted into the air when the effluent or the sludge is stirred, had the highest concentrations; their presence was attributable to such things as kraft-type paper pulp. Next in concentration were the carbon and nitrogen oxides, ammonia, and some organic acids, produced by the action of microorganisms. These acids are found mainly in the sludge environment. Terpenes, which come from wood, are present at various locations in paper mills. Odor perception thresholds for most of these substances are much lower than those established to protect the health of workers. Significant concentrations of total bacteria, total molds, and endotoxins were measured at several sites. Gram-negative bacteria were high at only one site, whereas the mold Aspergillus fumigatus was occasionally present at low concentration. No actinomycetes bacteria were detected. The highest concentrations were measured where there was water or dust aerosolization. Emissions are therefore controlled by controlling the operations that lead to the dispersion of water and particles into the air.

Air Pollutants, Occupational↗

Determination of volatile components in fresh, frozen, and freeze-dried Padrón-type peppers by gas chromatography-mass spectrometry using dynamic headspace sampling and microwave desorption.

"Padrón-type" peppers are a small variety of Capsicum annuum cultivated mainly in Galicia, Spain. To compare the effects of freezing and freeze-drying on the volatile components of Padrón-type peppers, preserved samples are analyzed by means of dynamic headspace sampling on an adsorbent followed by microwave desorption into a gas chromatograph equipped with a mass spectrometric detector. Sixty-five compounds are identified, including hydrocarbons, terpenes, alcohols, phenols, ethers, aldehydes, ketones, esters, pyrroles, pyrazines, and sulfurous compounds. Fresh whole, homogenized, and freeze-dried peppers have characteristic volatile-component profiles, whereas frozen peppers have a highly variable volatile-component profile.

Capsicum↗

[The role of deiodase and iodase in disturbed iodination processes in the thyroid].

Together with A. Costa of Turin, we have found adequate iodine in the food along the Northern slopes of the Alpine range in Valais, Switzerland, which has been known as a goitrous zone from time immemorial. In various statistical reports it has been pointed out that ostensibly the morbidity of goiter only regresses after the iodine added to the cooking salt is increased from 5 mg to 10 mg per kg. We see a regression of juvenile goiter only, because after puberty, 50 per cent of the Swiss population over the age of 50 have already developed goiter. We have found a goiter in rabbits and other experimental animals after feeding them cabbage and after the application of organic and inorganic sulfur compounds. After cabbage, a pre-Basedow type of goiter developed, after the application of sulfur the goiter was of a degenerative type, since in the latter case the iodase is first blocked by the thyroid and later destroyed.

Adolescent↗

Fluorocarbons: properties and syntheses.

The paper discusses custom syntheses of fluorocarbons for potential use as artificial blood substitutes. The term "fluorocarbon" designates a perfluorinated carbon compound which does not contain another halogen or hydrogen. Prominent requirements of an artificial blood substitute are: 1) efficient oxygen/carbon dioxide transport, 2) biological inertness, 3) low vapor pressure, 4) dispersibility to form emulsion. Fluorocarbons are superior to other liquids in dissolving oxygen and carbon dioxide. The most biologically inert halogenated alkanes are fully fluorinated. Introduction of another halogen or unsaturation decreases biological inertness. Boiling points of fluoroalkanes can be estimated from the Kinney equation. The most common method of fluorination, namely electrofluorination, is briefly described and applied to several types of organic compounds. Hydrocarbons give low yields of perfluoroalkanes. Alternatively, perfluoroalkanes may be prepared through reaction of functionalized substrates. Innert perfluorocyclic ethers are obtained from substrate ethers or acid fluorides. All types of amines perfluorinate but only perfluorotertiary amines are inert. Divalent organo-sulfur compounds afford inert perfluorinated products with sulfur in the hexavalent state. Sulfonyl fluorides give perfluorosulfonyl fluorides which can be pyrolytically coupled producing perfluoroalkanes. The Schoniger combustion method and neutron activation are described as analytical means for determining fluorine content.

Animals↗

An overview of polylactides as packaging materials.

Polylactide polymers have gained enormous attention as a replacement for conventional synthetic packaging materials in the last decade. By being truly biodegradable, derived from renewable resources and by providing consumers with extra end-use benefits such as avoiding paying the "green tax" in Germany or meeting environmental regulations in Japan, polylactides (PLAs) are a growing alternative as a packaging material for demanding markets. The aim of this paper is to review the production techniques for PLAs, summarize the main properties of PLA and to delineate the main advantages and disadvantages of PLA as a polymeric packaging material. PLA films have better ultraviolet light barrier properties than low density polyethylene (LDPE), but they are slightly worse than those of cellophane, polystyrene (PS) and poly(ethylene terephthalate) (PET). PLA films have mechanical properties comparable to those of PET and better than those of PS. PLA also has lower melting and glass transition temperatures than PET and PS. The glass transition temperature of PLA changes with time. Humidity between 10 and 95% and storage temperatures of 5 to 40 degrees C do not have an effect on the transition temperature of PLA, which can be explained by its low water sorption values (i.e. <100 ppm at Aw = 1). PLA seals well at temperatures below the melting temperature but an appreciable shrinking of the films has been noted when the material is sealed near its melting temperature. Solubility parameter predictions indicate that PLA will interact with nitrogen compounds, anhydrides and some alcohols and that it will not interact with aromatic hydrocarbons, ketones, esters, sulfur compounds or water. The CO2, O2 and water permeability coefficients of PLA are lower than those of PS and higher than those of PET. Its barrier to ethyl acetate and D-limonene is comparable to PET. The amount of lactic acid and its derivatives that migrate to food simulant solutions from PLA is much lower than any of the current average dietary lactic acid intake values allowed by several governmental agencies. Thus, PLA is safe for use in fabricating articles for contact with food.

Biocompatible Materials↗

An environmental nuisance: odor concentrated and transported by dust.

Intensive swine production generates odorous emissions which flow from the buildings housing the animals. High ventilation rates bring in fresh air, remove heat and moisture and enhance pork productivity. Numerous compounds contribute to the uniquely offensive odors from swine facilities, including fatty acids, amines, aromatics and sulfur compounds. Dust particles, which originate predominantly from feces and feed, can adsorb and concentrate odorants in swine facilities. In addition, organic particles can decay and generate odorous compounds. Odorants can exist in much higher concentrations in the dust particles than in equivalent volumes of air. Thus, inhalation of odorous dust and deposition of the dust particles in the mucus overlying the olfactory mucosa are likely responsible for some odor-related complaints by swine farm neighbors. Accurate prediction of odor transport and dispersion downwind from swine farms may require models of dust dispersion and correlation between dust and odorant levels. Unfortunately, many approaches to estimating odor impact currently incorporate filtering of air to remove particulate matter before sensing by humans or electronic sensors. Accelerated progress in understanding this and other 'real world' odor control problems will require methodological innovations that allow quantification of odor in response to air streams containing vapor and particulate phases.

Air↗

Comparative aspects of sulfur mineralization in sediments of a eutrophic lake basin.

The net mineralization of organic sulfur compounds in surface sediments of Wintergreen Lake was estimated from a mass-balance budget of sulfur inputs and sediment sulfur concentrations. The net mineralization of organic sulfur inputs is <50% complete, which is consistent with the dominance of organic sulfur (>80% of total sulfur) in sediment. Although sediment sulfur is predominantly organic, sulfate reduction is the most significant process in terms of the quantities of sulfur transformed in surface sediments. Rates of sulfate reduction in these sediments average 7 mmol/m per day. On an annual basis, this rate is 19-fold greater than net rates of organic sulfur mineralization and 65-fold greater than sulfate ester hydrolysis.

Journal Article↗

Desulfurization of dibenzothiophene by Corynebacterium sp. strain SY1.

Strain SY1, identified as a Corynebacterium sp., was isolated on the basis of the ability to utilize dibenzothiophene (DBT) as a sole source of sulfur. Strain SY1 could utilize a wide range of organic and inorganic sulfur compounds, such as DBT sulfone, dimethyl sulfide, dimethyl sulfoxide, dimethyl sulfone, CS2, FeS2, and even elemental sulfur. Strain SY1 metabolized DBT to dibenzothiophene-5-oxide, DBT sulfone, and 2-hydroxybiphenyl, which was subsequently nitrated to produce at least two different hydroxynitrobiphenyls during cultivation. These metabolites were separated by silica gel column chromatography and identified by nuclear magnetic resonance, UV, and mass spectral techniques. Resting cells of SY1 desulfurized toluenesulfonic acid and released sulfite anion. On the basis of these results, a new DBT degradation pathway is proposed.

Biodegradation, Environmental↗

Applications and limitations of ADM 1 in municipal wastewater solids treatment.

The ADM 1 model has been implemented in a steady-state whole wastewater plant simulator. The ADM 1 model has been in use with good success for approximately 2 years on a wide range of wastewater treatment facilities. However, a number of modifications were necessary to allow it to be used in the context of municipal wastewater treatment. It was found that the model's use was greatly simplified if used in conjunction with a larger plant simulator to assist in the feed fractionation. It was also found that a better fit to actual operating data was achieved if some of the slowly biodegradable particulate fraction was partitioned into ADM particulate fractions other than the composite fraction. Another significant limitation of the model is in the absence of phosphorus modeling. The ADM model needs to have phosphorus handling for all the relevant fractions, and needs to include the handling of inorganic reactions such as struvite precipitation and metal phosphate/metal hydroxide precipitation. Activity effects on chemical equilibria are significant when considering phosphorus. Also of importance in wastewater treatment is the fate of sulfur compounds. This includes the generation of H2S in the digester gas and the fate of the sulfur species in the digested sludge (as a predictor of odour-generating potential).

Anaerobiosis↗

Role of poly(ADP-ribose) polymerase (PARP) in DNA repair in sulfur mustard-exposed normal human epidermal keratinocytes (NHEK).

We previously reported that, in normal human epidermal keratinocytes (NHEK) cultures exposed to the alkylating compound sulfur mustard (bis-(2-chloroethyl) sulfide, HD, 0.3-1 mM), there is a rapid (< or =1 h) activation (100% above unexposed control) of the DNA repair enzyme DNA ligase I (130 kD) followed by a first-order decay (1-5 h). The DNA ligase activation is accompanied by a time-dependent (0.5-4 h) and significant DNA repair. Inhibition of another putative DNA repair enzyme, poly(ADP-ribose) polymerase (PARP), by using 3-amino benzamide does not affect DNA ligase activation following HD exposure, but increases the half-life of the activated enzyme threefold. To examine the role of PARP in HD-induced DNA ligase activation and subsequent DNA repair, we conducted studies using cultured keratinocytes in which the level of PARP had been selectively lowered (> or =85%) by the use of induced expression of antisense RNA. In these cells, there was no stimulation of DNA ligase up to 3 h, and a small stimulation (ca. 30% above unexposed control at 5-6 h after HD exposure. A time-course (0.5-6 h) study of DNA repair in HD-exposed PARP-deficient keratinocytes revealed a much slower rate of repair compared with HD-exposed NHEK. The results suggest an active role of PARP in DNA ligase activation and DNA repair in mammalian cells, and also indicate that modulation of PARP-mediated mechanisms may provide a useful approach in preventing HD toxicity.

Cell Culture Techniques↗

[Utilization of different sulfur sources by propionic acid bacteria].

The object of this work was to study the ability of propionic bacteria to utilize sulfur compounds having various degrees of oxidation. Propionibacterium shermanii was found to utilize sulfite, thiosulfate, sulfide and elemental sulfur, apart from sulfate, as a sulfur source. When the culture grew in a medium with elemental sulfur, sulfide was produced. The utilization of sulfate by P. shermanii had a peculiar character. In the process of the culture growth, the utilization of sulfate alternated with its release into the medium.

Culture Media↗

IST1 insertional inactivation of the resB gene: implications for phenotypic switching in Thiobacillus ferrooxidans.

Thiobacillus ferroxidans ATCC 19859 undergoes rapid phenotypic switching between a wild-type state characterized by the ability to oxidize ferrous iron (FeII) and reduced sulfur compounds and a mutant state where it has lost the capacity to oxidize FeII but retains the ability to oxidize sulfur. The mutant has also gained the capacity to swarm. It is proposed that loss of FeII oxidation is due to the reversible transposition of the insertion sequence IST1 into resB encoding a putative cytochrome c-type biogenesis protein. Downstream from resB and co-transcribed with it is resC, encoding another putative cytochrome biogenesis protein. IST1 insertional inactivation of resB could result in the loss of activity of its target c-type cytochrome(s). This putative target cytochrome(s) is proposed to be essential for FeII oxidation but not for sulfur oxidation. Curiously, resB and resC pertain to the proposed system II cytochrome biogenesis pathway whereas gamma Proteobacteria, of which T. ferrooxidans is a member, normally use system I. This could represent an example of lateral gene transfer.

Bacterial Proteins↗

Evidence for organic synthesis in high temperature aqueous media--facts and prognosis.

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to >400 degrees C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. Heterocyclic sulfur compounds have been identified in high temperature zones and hydrothermal petroleums of the Guaymas Basin vent systems. They can be interpreted as being synthesized from formaldehyde and sulfur or HS kappa- in the hydrothermal fluids. Other products from potential synthesis reactions have not yet been found in the natural systems but are expected based on known industrial processes and inferences from experimental simulation data. Various industrial processes have been reviewed and are of relevance to hydrothermal synthesis of organic compounds. The reactivity of organic compounds in hot water (200-350 degrees C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to >400 degrees C.

Amino Acids↗