Diethyl Disulfide Research Articles

Hydrogen sulfide production during yeast fermentation causes the accumulation of ethanethiol, S-ethyl thioacetate and diethyl disulfide

Hydrogen sulfide (H2S) is produced by yeast during winemaking and possesses off-flavors reminiscent of rotten eggs. The production of H2S during fermentation has also been associated in the finished wine with the rise of additional volatile sulfur compounds (VSCs) with strong aromas of cooked onions and vegetables. To characterize these more complex VSCs produced from H2S, we performed fermentations in synthetic grape juice. H2S production was manipulated experimentally by feeding increasing concentrations of sulfate to mutant strains that are unable to incorporate H2S efficiently as part of the sulfur assimilation pathway. In finished wines from these mutants, three VSCs – ethanethiol, S-ethyl thioacetate and diethyl disulfide – increased proportionally to H2S. 34S-labeled sulfate fed to the MET17-deleted strain was incorporated into same three VSCs, demonstrating that they are formed directly from H2S.

In Situ Measurements of Boundary Film Formation Pathways and Kinetics: Dimethyl and Diethyl Disulfide on Copper

The reaction pathways and shear-induced kinetics of methyl thiolate and ethyl thiolate species on copper are measured using in situ and ex situ techniques in ultrahigh vacuum. The in situ techniques consist of measuring the gas-phase products using a mass spectrometer placed in-line-of-sight of the rubbing interface while monitoring the variation in friction coefficient of an alkyl thiolate-covered surface as a function of the number of times it is rubbed (referred to in the paper as “number of scans”). The rubbed surfaces are analyzed using Auger spectroscopy as a function of the number of scans. The experiments are carried out for a tungsten carbide ball covered by a copper transfer film on copper surface at a normal load of 0.44 N and a sliding speed of 4 mm/s. The shear-induced reaction occurs as RS(ads) → S(ads) → S(subsurface), where RS(ads) is an adsorbed alkyl thiolate species, S(ads) is adsorbed atomic sulfur, and S(subsurface) is subsurface sulfur formed by shear-induced surface-to-bulk transport. The rate constants for the sequential reaction steps are found by fitting an analytical kinetic model to the yield of gas-phase products and Auger signals as a function of the number of scans over the surface. The validity of the kinetic parameters is confirmed by comparison with the variation in friction coefficient as a function of the number of scans. The analysis reveals that both ethyl and methyl thiolate species decompose under shear at approximately the same rate and that the rate of surface-to-bulk transport is higher than for thiolate decomposition.

Identification of complex septic odorants in Huangpu River source water by combining the data from gas chromatography-olfactometry and comprehensive two-dimensional gas chromatography using retention indices

Identification of the trace odorants causing the septic odors in source waters with complex matrixes has long been a big challenge. The Huangpu (HP) River, an important source water for Shanghai, has long been suffering from septic and musty odors, although major odorants have not been identified. In this study, combining the data from gas chromatography-olfactometry with mass spectrometry (GC-O/MS) and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) using retention indices (RIs) was used for the identification of odorants in HP source water. Olfactometry peaks detected in water extracts by GC-O/MS were combined with the chromatography peaks detected by GC×GC-TOFMS based on the RIs determined using the retention times (RTs) of alkanes C7–C30. A total of thirteen olfactometry peaks were obtained though GC-O/MS analysis, and potential odorants corresponding to each of the olfactometry peaks were screened based on the odor characteristics and match similarity using GC×GC-TOFMS. Finally, fourteen odorants (one odorant was detected in GC×GC-TOFMS without an olfactometry peak), including three septic odorants (bis(2-chloroisopropyl) ether, diethyl disulfide and dimethyl disulfide) and two musty ones (geosmin and 2-MIB), were confirmed by using authentic standards. The septic and musty odorants in six source water samples taken over a period of six months were quantified. Bis(2-chloroisopropyl) ether, with an odor activity value (OAV) of 1.84–3.2, was found to be a major septic odorant in HP source water, followed by diethyl disulfide (OAV 1.56–1.96) and dimethyl disulfide (OAV 0.37–2.42), while geosmin (OAV 4.37–11.44) was the major musty odorant, followed by 2-MIB (OAV 1.13–1.89). This is the first comprehensive study focusing on the identification of odorants in a complex source water. The integrated approach used in this study could be applied for the identification of odorants in other complex source waters suffering similar odor problems.

Catalytic reaction of diethyl disulfide with methanol

Diethyl disulfide reacted with methanol in the presence of solid acid catalysts at 250–350°C to give dimethyl, ethyl methyl, and diethyl sulfides. The most active catalysts were those containing simultaneously moderate basic sites, strong Lewis acid sites, and some amount of strong protonic acid sites. These catalysts ensured a total selectivity of 99% for dialkyl sulfides.

A newly isolated Pseudomonas putida S-1 strain for batch-mode-propanethiol degradation and continuous treatment of propanethiol-containing waste gas

Pseudomonas putida S-1 was isolated from activated sludge. This novel strain was capable of degrading malodorous 1-propanethiol (PT). PT degradation commenced with no lag phase by cells pre-grown in nutrition-rich media, such as Luria–Bertani (LB), and PT-contained mineral medium at specific growth rates of 0.10–0.19h−1; this phenomenon indicated the operability of a large-scale cell culture. A possible PT degradation pathway was proposed on the basis of the detected metabolites, including dipropyl disulfide, 3-hexanone, 2-hexanone, 3-hexanol, 2-hexanol, S0, SO42−, and CO2. P. putida S-1 could degrade mixed pollutants containing PT, diethyl disulfide, isopropyl alcohol, and acetaldehyde, and LB-pre-cultured cells underwent diauxic growth. Waste gas contaminated with 200–400mg/m3 PT was continuously treated by P. putida S-1 pre-cultured in LB medium in a completely stirred tank reactor. The removal efficiencies exceeded 88% when PT stream was mixed with 200mg/m3 isopropanol; by contrast, the removal efficiencies decreased to 60% as the empty bed residence time was shortened from 40s to 20s.

The Search for a Volatile Human Specific Marker in the Decomposition Process.

In this study, a validated method using a thermal desorber combined with a gas chromatograph coupled to mass spectrometry was used to identify the volatile organic compounds released during decomposition of 6 human and 26 animal remains in a laboratory environment during a period of 6 months. 452 compounds were identified. Among them a human specific marker was sought using principle component analysis. We found a combination of 8 compounds (ethyl propionate, propyl propionate, propyl butyrate, ethyl pentanoate, pyridine, diethyl disulfide, methyl(methylthio)ethyl disulfide and 3-methylthio-1-propanol) that led to the distinction of human and pig remains from other animal remains. Furthermore, it was possible to separate the pig remains from human remains based on 5 esters (3-methylbutyl pentanoate, 3-methylbutyl 3-methylbutyrate, 3-methylbutyl 2-methylbutyrate, butyl pentanoate and propyl hexanoate). Further research in the field with full bodies has to corroborate these results and search for one or more human specific markers. These markers would allow a more efficiently training of cadaver dogs or portable detection devices could be developed.

Impact of Storage Conditions on the Stability of Volatile Sulfur Compounds in Sampling Bags.

Odorous emissions from agricultural and waste management operations can cause annoyance to local populations. Volatile sulfur compounds (VSCs) are dominant odorants that are often lost during collection using sample bags. The degree of VSC losses depends on factors such as storage time, bag materials, temperature, sample relative humidity (RH), light exposure, and the presence of volatile organic compounds (VOCs). To assess the impact of those factors on the stability of 10 VSCs (hydrogen sulfide, methanethiol, ethanethiol, dimethyl sulfide, tert-butanethiol, ethyl methyl sulfide, 1-butanethiol, dimethyl disulfide, diethyl disulfide, and dimethyl trisulfide), laboratory-based experiments were conducted according to a factorial experimental design. Linear mixed-effects models were constructed for loss predictions. The estimated recovery of HS in Tedlar bag was 8 to 10% higher than in Mylar and Nalophan between 6 and 30 h. At ≤20°C and without being exposed to light, at least 75% relative recovery of the 10 VSCs in Tedlar bags can be achieved after 18 h, whereas, a maximum of 12 h of storage should not be exceeded to ensure a minimum of 74% relative recovery of the VSCs in Mylar and Nalophan bags.

Adsorption of odorous sulfur compounds onto activated carbons modified by gamma irradiation

A commercial activated carbon (AC) was modified by gamma irradiation and was tested as adsorbent for the removal of ethyl mercaptan, dimethyl disulfide and dimethyl disulfide in wet conditions. Modifications were carried out under five different conditions: irradiation in absence of water, in presence of ultrapure water, in ultrapure water at pH=1.0 and 1000mgL−1 Cl−, in ultrapure water at pH=7.5 and 1000mgL−1 Br−, and in ultrapure water at pH=12.5 and 1000mgL−1 NO3−. The chemical properties of each AC were characterized by elemental analysis, temperature programmed desorption and X-ray photoelectron spectroscopy. Outcomes show that a large number of oxygen functional groups were incorporated in the AC surface by gamma irradiation, especially in the AC irradiated in the presence of ultrapure water. The dynamic adsorption test results reveal that the incorporation of oxygen functional groups did not enhance the adsorption capacities for dimethyl sulfide and dimethyl disulfide. A significant improvement in the ethyl mercaptan adsorption capacity was correlated with the incorporation of phenolic groups in the AC surface. Moreover, diethyl disulfide was detected as by-product of ethyl mercaptan oxidation process under wet conditions and its formation depended on the chemical properties of ACs.

Synthesis of iron sulfide films through solid–gas reaction of iron with diethyl disulfide

Iron sulfide films were synthesized by the solid–gas reaction of diethyl disulfide on iron foils in the temperature range of 658–768 K using a microbalance, where the film growth kinetics followed Deal–Grove behavior. Analysis of the films by X-ray photoelectron and Raman spectroscopies as well as X-ray diffraction and scanning electron microscopy analysis revealed the formation of combined FeS/FeS2 (troilite/pyrite) films with a sheet-like morphology at low temperatures and only FeS (troilite) films with granular morphology at higher temperatures.

Determination of VOSCs in sewer headspace air using TD–GC–SCD

The management of odorous emissions from sewer networks has become an important issue for sewer operators resulting in the need to better understand the composition of volatile organic sulfur compounds (VOSCs). In order to characterise the composition of such malodorous emissions, a method based on thermal desorption (TD) and gas chromatography coupled to sulfur chemiluminescence detector (GC–SCD) has been developed to determine a broader range of VOSCs, hydrogen sulfide (H2S), methanethiol (MeSH), ethanethiol (EtSH), dimethyl sulfide (DMS), carbon disulfide (CS2), ethylmethyl sulfide (EMS), 1-butanethiol (1-BuSH), dimethyl disulfide (DMDS), diethyl disulfide (DEDS), and dimethyl trisulfide (DMTS). Parameters affecting the chromatographic behaviour of the target compounds were studied (e.g., temperature program, carrier gas velocity) as well as the experimental conditions affecting the adsorption/desorption process (temperature, flow and time). Optimised extraction of VOSCs samples was achieved under adsorption temperatures of less than −20°C, and a desorption flow rate of ~6ml/min. Active collection on the cold trap enabled a small gas volume of 50–100ml to be sampled for all analytes without breakthrough. Calibration curves were derived at different TD loading volumes with determined linearity ranging between 0.09ng and 60.1ng. The method detection limits (MDLs) were in the range of 0.10–5.26μg/m3 with TD recoveries higher than 66% and reproducibility (relative standard deviation values) between 1.8% and 6.1% being obtained for all compounds. The VOSCs characterisation at different sewerage collection sites in Sydney, Australia (for seasonal, weekly and diurnal) showed that six of the ten targeted compounds were consistently detected at all sample events. Diurnal patterns of VOSCs investigated were clearly observed with the highest concentration occurring after 12pm (noon) for H2S and MeSH. The consecutive 5 day analysis showed no significant difference in the targeted VOSCs concentrations and demonstrated the suitability of the method for routine sewer VOSCs emission measurements.

Degradation of ethyl mercaptan and its major intermediate diethyl disulfide by Pseudomonas sp. strain WL2

A Pseudomonas sp. strain WL2 that is able to efficiently metabolize ethyl mercaptan (EM) into diethyl disulfide (DEDS) through enzymatic oxidation was isolated from the activated sludge of a pharmaceutical wastewater plant. One hundred percent removal of 113.5 mg L(-1) EM and 110.3 mg L(-1) DEDS were obtained within 14 and 32 h, respectively. A putative EM degradation pathway that involved the catabolism via DEDS was proposed, which indicated DEDS were further mineralized into carbon dioxide (CO2), bacterial cells, and sulfate (SO4 (2-)) through the transformation of element sulfur and ethyl aldehyde. Degradation kinetics for EM and DEDS with different initial concentrations by strain WL2 were evaluated using Haldane-Andrews model with maximum specific degradation rates of 3.13 and 1.33 g g(-1) h(-1), respectively, and maximum degradation rate constants of 0.522 and 0.175 h(-1) using pseudo-first-order kinetic model were obtained. Results obtained that aerobic degradation of EM by strain WL2 was more efficient than those from previous studies. Substrate range studies of strain WL2 demonstrated its ability to degrade several mercaptans, disulfides, aldehydes, and methanol. All the results obtained highlight the potential of strain WL2 for the use in the biodegradation of volatile organic sulfur compounds (VOSCs).

Independent association between homocysteine plasma level and metabolic syndrome and synergistic effect on cardiovascular damage in essential hypertension

Gold electrodes modified with cationic self-assembled monolayers (SAMs) of 2,2′-dithiobisethaneamine (CYST) and 6,6′-dithiobishexaneamine (DTH) were used for the simultaneous determination of dopamine (DA) and ascorbate (AA). The cationic SAM modified electrodes have several advantages over the bare electrode for the oxidation of AA. A very large (∼450 mV) decrease in the overpotential for the oxidation of AA when compared with the bare electrode has been observed at the cationic monolayer-modified electrode. The electrostatic interaction of negatively charged AA with the monolayer shift the oxidation peak potential of AA to less positive potential and enhances the peak current. On the other hand, the positively charged DA is repelled from the monolayer and the oxidation potential shifts to more positive potential when compared to the bare electrode. The electrochemical oxidation of AA at the mixed monolayer of CYST and diethyl disulfide (DEDS) supports the influence of cationic terminal group of the monolayer on the oxidation of AA. Since the oxidation of AA occurs well before the oxidation potential of DA is reached, the homogeneous catalytic oxidation of AA by the oxidized DA has been advantageously eliminated at the monolayer-modified electrode. The cationic self-assembled monolayers successfully detect DA in the presence of high concentration of AA. The sensitivity of the electrode modified with CYST monolayer was found to be 0.036 and 0.021 μA/μM towards AA and DA, respectively.

How the disulfide conformation determines the disulfide/thiol redox potential

Protein disulfides can adopt a wide variety of conformations, each having different energies. Limited experimental data suggest that disulfides adopting a high energy have an enhanced likelihood for reduction, but the exact nature of this relation is not clear. Using a computational approach, we give insight on the conformational dependence of the redox behavior of the disulfide bond, which relates structure to reactivity. The relative energy of different conformations of the diethyl disulfide model system correlates with the disulfide/thiol redox potential E°. Insight in the calculated redox potentials is obtained via quantitative molecular orbital theory, and via the decomposition of E° into a vertical electron affinity and a subsequent reorganization term. We have identified the determinants of the disulfide conformational energies and characterized the barrier to rotation around the disulfide bond. Our findings on the diethyl disulfide model system can be transferred to examples from the Protein Data Base. In conclusion, strained disulfide conformations with a high conformational energy have a large tendency to be reduced. Upon reduction, unfavorable interactions are released. This explains why reorganization effects and not a higher tendency to accept electrons account for the high reduction potential of high-energy disulfides.

Disulfide Oil Hazard Assessment Using Categorical Analysis and a Mode of Action Determination

Diethyl and diphenyl disulfides, naphtha sweetening (Chemical Abstracts Service [CAS] # 68955-96-4), are primarily composed of low-molecular-weight dialkyl disulfides extracted from C4 to C5 light hydrocarbon streams during the refining of crude oil. The substance, commonly known as disulfide oil (DSO), can be composed of up to 17 different disulfides and trisulfides with monoalkyl chain lengths no greater than C4. The disulfides in DSO constitute a homologous series of chemical constituents that are perfectly suited for a hazard evaluation using a read-across/worst-case approach. The DSO constituents exhibit a common mode of action that is operable at all trophic levels. The observed oxidative stress response is mediated by reactive oxygen species and free radical intermediates generated after disulfide bond cleavage and subsequent redox cycling of the resulting mercaptan. Evidence indicates that the lowest series member, dimethyl disulfide (DMDS), can operate as a worst-case surrogate for other members of the series, since it displays the highest toxicity. Increasing the alkyl chain length or degree of substitution has been shown to serially reduce disulfide toxicity through resonance stabilization of the radical intermediate or steric inhibition of the initial enzymatic step. The following case study examines the mode of action for dialkyl disulfide toxicity and documents the use of read-across information from DMDS to assess the hazards of DSO. The results indicate that DSO possesses high aquatic toxicity, moderate environmental persistence, low to moderate acute toxicity, high repeated dose toxicity, and a low potential for genotoxicity, carcinogenicity, and reproductive/developmental effects.

Stability of Volatile Sulfur Compounds (VSCs) in sampling bags – impact of temperature

Volatile sulfur compounds (VSCs) are a major component of odorous emissions that can cause annoyance to local populations surrounding wastewater, waste management and agricultural practices. Odour collection and storage using sample bags can result in VSC losses due to sorption and leakage. Stability within 72 hour storage of VSC samples in three sampling bag materials (Tedlar, Mylar, Nalophan) was studied at three temperatures: 5, 20, and 30 °C. The VSC samples consisted of hydrogen sulfide (H2S), methanethiol (MeSH), ethanethiol (EtSH), dimethyl sulfide (DMS), tert-butanethiol (t-BuSH), ethylmethyl sulfide (EMS), 1-butanethiol (1-BuSH), dimethyl disulfide (DMDS), diethyl disulfide (DEDS), and dimethyl trisulfide (DMTS). The results for H2S showed that higher loss trend was clearly observed (46-50% at 24 hours) at 30 °C compared to the loss at 5 °C or 20 °C (of up to 27% at 24 hours) in all three bag materials. The same phenomenon was obtained for other thiols with the relative recoveries after a 24 hour period of 76-78% at 30 °C and 80-93% at 5 and 20 °C for MeSH; 77-80% at 30 °C and 79-95% at 5 and 20 °C for EtSH; 87-89% at 30 °C and 82-98% at 5 and 20 °C for t-BuSH; 61-73% at 30 °C and 76-98% at 5 and 20 °C for 1-BuSH. Results for other sulfides and disulfides (DMS, EMS, DMDS, DEDS) indicated stable relative recoveries with little dependency on temperature (83-103% after 24 hours). DMTS had clear loss trends (with relative recoveries of 74-87% in the three bag types after 24 hours) but showed minor differences in relative recoveries at 5, 20, and 30 °C.

Shape-Programmed Nanofabrication: Understanding the Reactivity of Dichalcogenide Precursors

Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallyl<dibenzyl<di-tert-butyl<diisopropyl<diethyl<dimethyl<diphenyl. The dissociation energy of chalcogen-chalcogen (E-E) bonds remains relatively constant across the series. The only exceptions are diphenyl dichalcogenides, which have a much lower E-E bond dissociation energy. An increase in C-E bond dissociation energy results in a decrease in R-E-E-R precursor reactivity, leading to progressively slower nucleation and higher selectivity for anisotropic growth, all the way from dots to pods to tetrapods. Under identical experimental conditions, we obtain CdS and CdSe nanocrystals with spherical, elongated, or tetrapodal morphology by simply varying the identity and reactivity of the dichalcogenide precursor. Interestingly, we find that precursors with strong C-E and weak E-E bond dissociation energies such as Ph-S-S-Ph serve as a ready source of thiol radicals that appear to stabilize small CdE nuclei, facilitating anisotropic growth. These CdS and CdSe nanocrystals have been characterized using structural and spectroscopic methods. An intimate understanding of how molecular structure affects the chemical reactivity of molecular precursors enables highly predictable and reproducible synthesis of colloidal nanocrystals with specific sizes, shapes, and optoelectronic properties for customized applications.

Sulfides: chemical ionization induced fragmentation studied with Proton Transfer Reaction‐Mass Spectrometry and density functional calculations

We report the energy-dependent fragmentation patterns upon protonation of eight sulfides (organosulfur compounds) in Proton Transfer Reaction-Mass Spectrometry (PTR-MS). Studies were carried out, both, experimentally with PTR-MS, and with theoretical quantum-chemical methods. Charge retention usually occurred at the sulfur-containing fragment for short chain sulfides. An exception to this is found in the unsaturated monosulfide allylmethyl sulfide (AMS), which preferentially fragmented to a carbo-cation at m/z 41, C3H5(+). Quantum chemical calculations (DFT with the M062X functional 6-31G(d,p) basis sets) for the fragmentation reaction pathways of AMS indicated that the most stable protonated AMS cation at m/z 89 is a protonated (cyclic) thiirane, and that the fragmentation reaction pathways of AMS in the drift tube are kinetically controlled. The protonated parent ion MH(+) is the predominant product in PTR-MS, except for diethyl disulfide at high collisional energies. The saturated monosulfides R-S-R' (with R<R') have little or no fragmentation, at the same time the most abundant fragment ion is the smaller R-S(+) fragment. The saturated disulfides R-S-S-R display more fragmentation than the saturated monosulfides, the most common fragments are disulfide containing fragments or long-chain carbo-cations. The results rationalize fragmentation data for saturated monosulfides and disulfides and represent a detailed analysis of the fragmentation of an unsaturated sulfide. Apart from the theoretical interest, the results are in support of the quantitative analysis of sulfides with PTR-MS, all the more so as PTR-MS is one of a few techniques that allow for ultra-low quantitative analysis of sulfides.

Odor and Odorous Chemical Emissions from Animal Buildings: Part 6. Odor Activity Value

There is a growing concern with air and odor emissions from agricultural facilities. A supplementary research project was conducted to complement the U.S. National Air Emissions Monitoring Study (NAEMS). The overall goal of the project was to establish odor and chemical emission factors for animal feeding operations. The study was conducted over a 17-month period at two freestall dairies, one swine sow farm, and one swine finisher facility. Samples from a representative exhaust airstream at each barn were collected in 10 L Tedlar bags and analyzed by trained human panelists using dynamic triangular forced-choice olfactometry. Samples were simultaneously analyzed for 20 odorous compounds (acetic acid, propanoic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, guaiacol, phenol, 4-methylphenol, 4-ethylphenol, 2-aminoacetophenone, indole, skatole, dimethyl disulfide, diethyl disulfide, dimethyl trisulfide, hydrogen sulfide, and ammonia). In this article, which is part 6 of a six-part series summarizing results of the project, we investigate the correlations between odor concentrations and odor activity value (OAV), defined as the concentration of a single compound divided by the odor threshold for that compound. The specific objectives were to determine which compounds contributed most to the overall odor emanating from swine and dairy buildings, and develop equations for predicting odor concentration based on compound OAVs. Single-compound odor thresholds (SCOT) were statistically summarized and analyzed, and OAVs were calculated for all compounds. Odor concentrations were regressed against OAV values using multivariate regression techniques. Both swine sites had four common compounds with the highest OAVs (ranked high to low: hydrogen sulfide, 4-methylphenol, butyric acid, isovaleric acid). The dairy sites had these same four compounds in common in the top five, and in addition diethyl disulfide was ranked second at one dairy site, while ammonia was ranked third at the other dairy site. Summed OAVs were not a good predictor of odor concentration (R2 = 0.16 to 0.52), underestimating actual odor concentrations by 2 to 3 times. Based on the OAV and regression analyses, we conclude that hydrogen sulfide, 4-methylphenol, isovaleric acid, ammonia, and diethyl disulfide are the most likely contributors to swine odor, while hydrogen sulfide, 4-methyl phenol, butyric acid, and isovaleric acid are the most likely contributors to dairy odors.

Shear-induced boundary film formation from dialkyl sulfides on copper

The friction of a copper surface, which is exposed to diethyl disulfide (DEDS), dimethyl disulfide (DMDS) or dimethyl trisulfide (DMTS) while rubbing by a tungsten carbide pin, are explored in an ultrahigh vacuum tribometer to investigate the effect of the sulfur-to-carbon stoichiometry on gas-phase lubrication. Surface analyses by Auger spectroscopy of the wear scars after rubbing reveal that the amount of sulfur increases with sulfur content of the gas-phase lubricant, as anticipated. It is found that the friction reduction depends on the normal load, where the friction coefficient tends to decrease more at lower loads, and that the load at which the most friction-reducing tribofilm is formed depends on the stoichiometry of the gas-phase lubricant. DEDS (with a sulfur to carbon ratio of 0.5) only reduces the friction coefficient to a minimum value of ∼0.28 at a normal load of 0.25 N, for DMDS (S/C = 1.0) friction is reduced to ∼0.28 for loads below ∼0.7 N, and DMTS (S/C = 1.5) reduces friction to this value for all loads tested.

Preparation and properties of sandwiched trinuclear palladium(II) complexes with tridentate phosphine and phosphine sulfide ligands

The central phosphino group of tripodal tetradentate tris[2-(diphenylphosphino)ethyl]phosphine (pp 3) was selectively oxidized by the reaction with diethyl disulfide to give tridentate phosphine ligand pOp 3. The terminal phosphino groups were reacted with sulfur to give pOp 3 trisulfide (pOp 3S 3). Three palladium(II) ions were sandwiched in the two pOp 3 and pOp 3S 3 ligands to form the trinuclear complexes with three trans( P) and trans( S) PdX 2 (X = Cl, Br, I) moieties, respectively. The tripodal triphosphine, 1,1,1-tris(diphenylphosphinomethyl)ethane ( i-p 3), and its mono- and tri-sulfide, which have shorter carbon chains compared with pOp 3, form the mononuclear dichloro palladium(II) complexes with cis( P) and cis( S) geometries. Difference in the catalytic activity for the C–C coupling reaction was discussed in connection with the coordinated groups and geometries of the complexes.