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Statement of Problem: Bonding to fluorotic dentin is weaker than to sound dentin, but methods to improve bonding have not been well addressed., Purpose: The purpose of this in vitro study was to investigate the effects of dimethyl sulfoxide (DMSO) pretreatment on the bond strength and resin-dentin surface of fluorotic dentin of different severity., Material and Methods: Phosphoric acid-etched dentin specimens exhibiting mild fluorosis (ML-F), moderate fluorosis (MD-F), and severe fluorosis (SE-F) were randomly bonded with Single Bond 2 (SB2) pretreated with 50% DMSO (experimental groups) or deionized water (control groups). The bonded teeth were sectioned for microshear bond strength (μSBS) testing immediately or after aging, for micromorphology observation of the bonding interface under a scanning electron microscope, and for resin tags and microleakage evaluation under a confocal laser scanning microscope. The degree of conversion of the adhesive resin was calculated by Fourier transform infrared spectroscopy. According to varying bonding steps, the mineralized dentin powders of ML-F, MD-F, and SE-F were randomly divided into 4 subgroups (blank, PA, PA+SB2, and PA+DMSO+SB2) and incubated in artificial saliva to examine the level of enzymatic degradation product of type I collagen. Data were analyzed by using ANOVA and the Tukey test (α=.05)., Results: Dental fluorosis and thermocycling had negative effects on μSBS (P<.001), while DMSO pretreatment preserved or even improved μSBS (P<.001). DMSO had no influence on the degree of conversion (P=.618). Significant effects were found for bonding steps (P<.001), but not that of dental fluorosis (P=.131) on the enzymatic degradation product of type I collagen. Images showed sparser and more expanded collagen fibril meshwork, deeper resin penetration, and less microleakage in the experimental groups., Conclusions: DMSO pretreatment provided increased and durable dentin bonding to fluorotic dentin probably by dispersing collagen fibrils into a sparser network and inhibiting the degradation of type I collagen., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Because of the widespread application of anesthetic drugs in the fields of animal breeding and transportation, demand for the rapid, sensitive detection of anesthetic drugs in animal meat is increasing. The complex animal meat matrix contains various interfering substances, such as proteins, fats, and phospholipids, along with anesthetic drug residues at very low concentrations. Therefore, adopting appropriate pretreatment methods is necessary to improve the sensitivity of detection. In this study, a rapid, accurate analytical method based on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and solid phase extraction (SPE) was established to determine the contents of 18 caines in animal meat. The MS parameters, such as the collision energies of 18 caines, were optimized. Furthermore, the chromatographic separation conditions and response intensities of the caine in different mobile phases were compared. The effects of different pretreatment conditions on the extraction efficiencies of the 18 caines in meat samples and those of different purification conditions, such as extraction solvent, SPE column, and dimethylsulfoxide (DMSO) dosage, on their recoveries were investigated. Combined with the external standard method, the 18 caines in meat were successfully quantified. Sample pretreatment is a three-step process. First, in ultrasound-assisted extraction, 2.0 g samples were added to 2.0 mL water and extracted using 10 mL 0.1% (v/v) formic acid in acetonitrile under ultrasound conditions for 10 min. SPE was then performed using an Oasis PRIME HLB column. Finally, DMSO-assisted concentration was employed: the organic layer was collected and dried at 40 ℃ under a stream of N 2 gas with the addition of 100 μL DMSO. Acetonitrile-water (1∶9, v/v) was added to the residue to yield a final volume of 1.0 mL for use in UPLC-MS/MS. The 18 caines were separated using an HSS T 3 (100 mm×2.1 mm, 1.8 μm) column with 0.1% (v/v) formic acid in water (containing 0.02 mmol/L ammonium acetate) and methanol as mobile phases. Samples were detected using an electrospray ion source (ESI) in the positive ion and multiple reaction monitoring (MRM) modes during UPLC-MS/MS. Under the optimized conditions, the 18 target caine anesthetics displayed good linearities in the range of 1.00-50.0 μg/L, and the correlation coefficients ( R 2 ) were >0.999. The respective limits of detection (LODs) and quantification (LOQs) were 0.2-0.5 μg/kg, and 0.6-1.5 μg/kg. In pork, beef, and mutton samples, the recoveries obtained at three spiked levels were 83.4%-100.4% with relative standard deviations (RSDs) of 3.1%-8.5%. This simple, rapid, sensitive method may be applied in the detection of 18 caine anesthetics in animal meat and may provide technical support to the food safety department in China in monitoring the residues of caine anesthetics in animal meat.

The applications of optical fibers are impeded in implantable medical diagnostics due to incompatibility with biological tissues, and immune reaction in vivo. The utilization of biocompatible materials to construct a photonic sensing platform can reduce the immune response in in vivo medical diagnostics. Here, we developed real-time optical fiber sensors to determine the volumetric modulation of stimuli-responsive polymers. Asymmetric microlens structures were replicated on stimuli-sensitive hydrogels as stand-alone sensors and were chemically attached to the tips of silica and biocompatible optical fibers. Quantitative measurements were carried out using a smartphone to demonstrate the ease, simplicity, and practicality of the readout methodology. To demonstrate the utility in real-time sensing, the fiber probe was investigated in various concentrations of ethanol, propan-2-ol, and dimethyl sulfoxide. Also, the fiber probe showed a rapid response to pH in the acidic region with a sensitivity of 40 nW pH-1. To develop biocompatible probes for physiological applications, a microlens array-imprinted polymer was attached to the tip of a hydrogel optical fiber. The optical fiber probe in the refection configuration showed a sensitivity of 7 nW pH-1. The developed hydrogel fiber probes may have application in point-of-care diagnostics, continuous biomarker monitoring, and critical care sensing devices.

Cocrystallization is an attractive and promising technology that can improve the physical properties of formulations of active pharmaceutical ingredients (APIs). We have developed a "nano-spot method" that can evaluate the crystalline form on the nanogram scale. In this study, the following studies were performed to obtain versatile and comprehensive improvements to the nano-spot method: modification of the sample solution, application of solvent vapor exposure to attempt the precipitation of various states of crystals, and adoption of low-frequency Raman spectroscopy. Carbamazepine was used as a model API and cocrystallization screening was examined with 12 cocrystal formers (coformers). In the case of combinations that are already known to form cocrystals, spectra similar to those of previously reported cocrystals or new spectra were obtained. It was considered that the reported cocrystals or new polymorphs were obtained. In contrast, in the case of the combination which has been reported not to form a cocrystal, the spectra were consistent with that for the physical mixture of API and coformer, suggesting that a cocrystal also did not form in this screening. In addition, the newly adopted low-frequency Raman spectroscopy enabled the high-sensitive detection of the crystalline form., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Cryomedium toxicity is a major safety concern when transplanting cryopreserved organs. Therefore, thorough removal of potentially toxic cryoprotective agents (CPAs) is required before transplantation. CPAs such as dimethyl-sulfoxide (DMSO), propylene glycol (PG), and formamide (FMD), routinely employed in ice-free cryopreservation (IFC), have advantages in long-term preservation of tissue structures compared with conventional cryopreservation employing lower CPA concentrations. This study evaluated the impact of potential residual CPAs on human cardiac valves. Raman microspectroscopy and Raman imaging were established as nondestructive marker-independent techniques for in situ quantitative assessment of CPA residues in IFC valve tissues. In detail, IFC valve leaflets and supernatants of the washing solutions were analyzed to determine the washing efficiency. A calibration model was developed according to the CPA's characteristic Raman signals to quantify DMSO, PG and FMD concentrations in the supernatants. Single point Raman measurements were performed on the intact tissues to analyze penetration properties. In addition, Raman imaging was utilized to visualize potential CPA residues. Our data showed that washing decreased the CPA concentration in the final washing solution by 99%, and no residues could be detected in the washed tissues, validating the multistep CPA removal protocol routinely used for IFC valves. Raman analysis of unwashed tissues showed different permeation characteristics depending on each CPA and their concentration. Our results demonstrate a great potential of Raman microspectroscopy and Raman imaging as marker-independent in situ tissue quality control tools with the ability to assess the presence and concentration of different chemical agents or drugs in preimplantation tissues.

Background: Solvate ionic liquids (SILs) are a new class of ionic liquids that are equimolar solutions of lithium bistrifluoromethanesulfonimide in either triglyme or tetraglyme, referred to as G3LiTFSA and G4LiTFSA, respectively. SILs play a role in energy storage lithium batteries, and have been proposed as potential alternatives to traditional organic solvents such as DMSO. G3TFSA and G4TFSA have been shown to exhibit no toxicity in vivo up to 0.5% (v/v), and solubilize small compounds (N,N-diethylaminobenzaldehyde) with full penetrance, similar to DMSO delivered DEAB. Herein, we compare the effects of storage (either at room temperature or - 20 °C) on DEAB solubilized in either DMSO, G3TFSA or G4TFSA to investigate compound degradation and efficacy., Results: The findings show that DEAB stored at room temperature (RT) for 4 months solubilized in either G3TFSA, G4TFSA or DMSO displayed no loss of penetrance. The same was observed with stock solutions stored at - 20 °C for 4 months; however G4TFSA remained in a liquid state compared to both G3TFSA and DMSO. Moreover, we examined the ability of G3TFSA and G4TFSA to solubilize another small molecular therapeutic, the FGFR antagonist SU5402. G4TFSA, unlike G3TFSA solubilized SU5402 and displayed similar phenotypic characteristics and reduced dlx2a expression as reported and shown with SU5402 in DMSO; albeit more penetrative., Conclusion: This study validates the use of these ionic liquids as a potential replacement for DMSO in vivo as organic solubilizing agents.

The influence of abiotic and biotic variables on the concentration of dimethyl sulfide (DMS), dimethylsulfoniopropionate (DMSP), and dimethylsulfoxide (DMSO), were investigated during an annual cycle in 2016 in the Belgian Coastal Zone (BCZ, North Sea). We reported strong seasonal variations in the concentration of these compounds linked to the phytoplankton succession with high DMS(P,O) producers (mainly Phaeocystis globosa) occurring in spring and low DMS(P,O) producers (various diatoms species) occurring in early spring and autumn. Spatial gradients of DMS and DMSP were related to those of phytoplankton biomass itself related to the inputs of nutrients from the Scheldt estuary. However, the use of a relationship with Chlorophyll-a (Chl-a) concentration is not sufficient to predict DMSP. Accounting for the phytoplankton composition, two different DMSP versus Chl-a correlations could be established, one for diatoms and another one for Phaeocystis colonies. We also reported high nearshore DMSO concentrations uncoupled to Chl-a and DMSP concentrations but linked to high suspended particulate matter (SPM) presumably coming from the Scheldt estuary as indicated by the positive relationship between annual average SPM and salinity., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Dimethylsulphide (DMS) photo-oxidation and dimethylsulphoxide (DMSO) photoproduction were estimated in 26 laboratory irradiations of coastal samples from NE England (Tyne estuary) and W Scotland (Loch Linnhe and River Nant at Taynuilt). Pseudo-first order rate constants of DMS photo-oxidation (0.038 h -1 to 0.345 h -1 ) and DMSO photo-production (0.017 h -1 to 0.283 h -1 ) varied by one order of magnitude and were lowest in the coastal North Sea. Estuarine samples (salinity S < 30) had a mean DMSO yield of 96 ± 16% (n = 14), consistent with 1:1 M conversion via photosensitised oxidation by singlet oxygen. Photochemical rate constants were strongly correlated with coloured dissolved organic matter (CDOM) absorption coefficients at 350 nm, a 350 . Variations in a 350 explained 61% (R 2  = 0.61, n = 26) and 73% (R 2  = 0.73, n = 17) of the variability in DMS photo-oxidation and DMSO production, respectively. However, CDOM normalised photochemical rate constants increased strongly towards coastal waters exhibiting lowest CDOM absorbance, indicating water samples of marine character (S > 30) to be most reactive with respect to DMS photo-oxidation. Estimates of water column averaged DMS photo-oxidation rate constants, obtained by scaling to mean daily irradiance (July, NE England) and mid-UV underwater irradiance, were 0.012 d -1 , 0.019 d -1 , and 0.017 d -1 for upper estuary (S < 20), lower estuary (20 < S < 30) and coastal waters (S > 30), at the lower end of previous observations. Comparing our water column averaged DMS photo-oxidation rate constants with estimated DMS losses via air-sea gas exchange and previously reported biological consumption implies that DMS photochemical removal is of only minor importance in our study area., (Copyright © 2017. Published by Elsevier Ltd.)

A quantitative nuclear magnetic resonance (qNMR) method to measure the content of Orlistat in tablets was studied and found to be efficient, accurate, reliable, and simple. In this paper, phloroglucinolanhydrous and dimethylsulfoxide- d ₆ (DMSO- d ₆) served as the internal standard and solvent, respectively. The qNMR methodology, including the linearity, range, the limit of detection (LOD) and quantification (LOQ), stability, precision, and accuracy, was validated seriatim, and the results were very favorable. The content determination results of three batches of Orlistat in tablets were almost identical upon comparing the qNMR method and the high-performance liquid chromatography (HPLC) method. The recommended method authentically compensated the deficiencies of the current HPLC method for determining Orlistat content, and proved to be a method complementary to traditional analysis for the purity measurement of Orlistat in some pharmaceutical preparations., Competing Interests: The authors declare that they have no conflict of interest.

The development of an efficient sensor for the determination of the DMSO content in aqueous solution is highly desirable in a number of chemical industries. Presented herein is a ferrocene-conjugated iridium(III) complex, which exhibits remarkable capability to detect traces of DMSO (<1% v/v) in aqueous solution through a turn-on luminescence sensing mechanism. The extraordinary sensitivity and selectivity of this newly developed complex for DMSO renders it as one of the most powerful DMSO sensors known., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Preservation of honey bee (Apis mellifera L., Hymenoptera: Apidae) sperm, coupled with instrumental insemination, is an effective strategy to protect the species and their genetic diversity. Our overall objective is to develop a method of drone semen preservation; therefore, two experiments were conducted. Hypothesis 1 was that cryopreservation (-196 °C) of drone semen is more effective for long-term storage than at 16 °C. Our results show that after 1 yr of storage, frozen sperm viability was higher than at 16 °C, showing that cryopreservation is necessary to conserve semen. However, the cryoprotectant used for drone sperm freezing, dimethyl sulfoxide (DMSO), can harm the queen and reduce fertility after instrumental insemination. Hypothesis 2 was that centrifugation of cryopreserved semen to reduce DMSO prior to insemination optimize sperm quality. Our results indicate that centrifuging cryopreserved sperm to remove cryoprotectant does not affect queen survival, spermathecal sperm count, or sperm viability. Although these data do not indicate that centrifugation of frozen-thawed sperm improves queen health and fertility after instrumental insemination, we demonstrate that cryopreservation is achievable, and it is better for long-term sperm storage than above-freezing temperatures for duration of close to a year., (© The Authors 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Dimethylsulfoxide (DMSO) is a solvent which protects the structure of allografts during the cryopreservation and thawing process. However, several toxic effects of DMSO in patients after transplantation of cryopreserved allografts have been described. The aim of this study is to determine the residual DMSO in the cardiovascular allografts after thawing and preparation of cryopreserved allografts for clinical application following guidelines of the European Pharmacopoeia for DMSO detection. Four types of EHB allografts (aortic valve-AV, pulmonary valve-PV, descending thoracic aorta-DA, and femoral artery-FA) are cryopreserved using as cryoprotecting solution a 10% of DMSO in medium 199. Sampling is carried out after thawing, after DMSO dilution and after delay of 30 min from final dilution (estimated delay until allograft implantation). After progressive thawing in sterile water bath at 37-42 °C (duration of about 20 min), DMSO dilution is carried out by adding consecutively 33, 66 and 200 mL of saline. Finally, tissues are transferred into 200 mL of a new physiologic solution. Allograft samples are analysed for determination of the residual DSMO concentration using a validated Gas Chromatography analysis. Femoral arteries showed the most important DMSO reduction after the estimated delay: 92.97% of decrease in the cryoprotectant final amount while a final reduction of 72.30, 72.04 and 76.29% in DMSO content for AV, PV and DA, was found, respectively. The residual DMSO in the allografts at the moment of implantation represents a final dose of 1.95, 1.06, 1.74 and 0.26 mg kg -1 in AV, PV, DA and FA, respectively, for men, and 2.43, 1.33, 2.17 and 0.33 mg kg -1 for same tissues for women (average weight of 75 kg in men, and 60 kg in women). These results are seriously below the maximum recommended dose of 1 g DMSO kg -1 (Regan et al. in Transfusion 50:2670-2675, 2010) of weight of the patient guaranteeing the safety and quality of allografts.

A broadband sum frequency generation (BB-SFG) spectrometer with multimodal (MM) capabilities was constructed, which could be routinely reconfigured for tabletop experiments in reflection, transmission, and total internal reflection (TIR) geometries, as well as microscopic imaging. The system was constructed using a Ti:sapphire amplifier (800 nm, pulse width = 85 fs, repetition rate = 2 kHz), an optical parameter amplification (OPA) system for production of broadband IR pulses tunable between 1000 and 4000 cm(-1), and two Fabry-Pérot etalons arranged in series for production of narrowband 800 nm pulses. The key feature allowing the MM operation was the nearly collinear alignment of the visible (fixed, 800 nm) and infrared (tunable, 1000-4000 cm(-1)) pulses which were spatially separated. Physical insights discussed in this paper include the comparison of spectral bandwidth produced with 40 and 85 fs pump beams, the improvement of spectral resolution using etalons, the SFG probe volume in bulk analysis, the normalization of SFG signals, the stitching of multiple spectral segments, and the operation in different modes for air/liquid and adsorbate/solid interfaces, bulk samples, as well as spectral imaging combined with principle component analysis (PCA). The SFG spectral features obtained with the MM-BB-SFG system were compared with those obtained with picosecond-scanning-SFG system and high-resolution BB-SFG system (HR-BB-SFG) for dimethyl sulfoxide, α-pinene, and various samples containing cellulose (purified commercial products, Cladophora cell wall, cotton and flax fibers, and onion epidermis cell wall).

The chemosensor 2,3-bis((E)-((2-hydroxynaphthalen-1-yl)methylene)amino)maleonitrile (1) has been synthesized using 2-hydroxy-1-napthaldehyde and 2,3-diaminomaleonitrile and characterized. Sensor 1 exhibits selective binding with CN(-) in dimethyl sulfoxide (DMSO)/H2O (7:3 v/v) and DMSO/aqueous Tris (Tris(hydroxymethyl)aminomethane) buffer (7:3 v/v, 10 mM, pH 7.2) media with significant changes in its UV-visible and fluorescence spectra. Titration of 1-Zn(II) complex with CN(-) ion in DMSO/aqueous Tris buffer (7:3 v/v, 10 mM, pH 7.2) regenerates the free sensor 1, as supported by UV-visible spectra. (1)H NMR titration of 1 with CN(‒) in (CD3)2SO confirms the hydrogen-bonding interaction between the two OH groups of the former and the latter in bidentate manner. Sensor 1 impregnated on silica gel thin layer chromatography (TLC) strip followed by dipping in anion solutions in DMSO/H2O (7:3 v/v) generates yellow to red spectacular colour change with CN(-) ion selectively which can be exploited as potential tool for ready-made detection of toxic CN(-) ion in environmental and analytical chemistry. Similar visual change in colour for 1 is observed selectively with CN(-) also when both of them are taken in DMSO/H2O (7:3 v/v) solution. Sensor 1 is used as an imaging reagent for detection of the cellular uptake of CN(-) ion in Baby Hamster Kidney (BHK-21) cells., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this study, the target compound is dimethyl sulfoxide (DMSO), which is used as a photoresist stripping solvent in the semiconductor and thin-film transistor liquid crystal display (TFT-LCD) manufacturing processes. The effects of the operating parameters (pH, Fe(2+) and H2O2 concentrations) on the degradation of DMSO in the fluidized-bed Fenton process were examined. This study used the Box-Behnken design (BBD) to investigate the optimum conditions of DMSO degradation. The highest DMSO removal was 98 % for pH 3, when the H2O2 to Fe(2+) molar ratio was 12. At pH 2 and 4, the highest DMSO removal was 82 %, when the H2O2 to Fe(2+) molar ratio was 6.5. The correlation of DMSO removal showed that the effect of the parameters on DMSO removal followed the order Fe(2+) > H2O2 > pH. From the BBD prediction, the optimum conditions were pH 3, 5 mM of Fe(2+), and 60 mM of H2O2. The difference between the experimental value (98 %) and the predicted value (96 %) was not significant. The removal efficiencies of DMSO, chemical oxygen demand (COD), total organic carbon (TOC), and iron in the fluidized-bed Fenton process were higher than those in the traditional Fenton process.

Imidazolium trans-[tetrachloridodimethylsulfoxideimidazoleruthenate(III)], NAMI-A, is a promising antimetastatic prodrug with high specificity for metastatic cancer cells. Limited activity of NAMI-A against primary tumor suggests that its use in combination with other anticancer drug(s) might present a more desirable therapeutic outcome. The mechanism of activation and action of this prodrug is still largely unknown. The biological targets, as well, have not yet been delineated. The kinetics and mechanism of interaction of NAMI-A with 2-mercaptoethane sulfonate, MESNA, a chemoprotectant, have been studied spectrophotometrically under pseudo-first order conditions of excess MESNA. The reaction is characterized by initial reduction of NAMI-A and formation of dimeric MESNA as evidenced by electospray ionization mass spectrometry. A first order dependence on both NAMI-A and MESNA was obtained and a bimolecular rate constant of 0.71 ± 0.06 M(-1) s(-1) was deduced. Activation parameters determined (ΔS(≠) = -178.12 ± 0.28 J K(-1) mol(-1), ΔH(≠) = 20.64 ± 0.082 kJ mol(-1) and ΔG(≠) = 75.89 ± 1.76 kJ mol(-1) at 37 ± 0.1 °C and pH 7.4) are indicative of formation of an associative intermediate prior to product formation and subsequent hydrolysis of the reduced complex. Our results suggest that MESNA might be able to activate the prodrug while still protecting against toxicity when given in a regimen involving NAMI-A and chemotherapy drug(s) that induce bladder and kidney toxicities.

Breath gas analysis in humans proved successful in identifying disease states and assessing metabolic functions in a non-invasive way. While many studies report diagnostic capability using volatile organic compounds (VOC) in breath, the inter-individual variability even in healthy human cohorts is rather large and not completely understood in its biochemical origin. Laboratory mice are the predominant animal model system for human disorders and are analysed under highly standardized and controlled conditions. We established a novel setup to monitor VOCs as biomarkers for disease in the breath gas of non-anesthetized, non-restrained mice using a proton transfer reaction mass spectrometer with time of flight detection. In this study, we implemented breath gas analysis in a dietary intervention study in C57BL/6J mice with the aim to assess the variability in VOC signatures due to a change in the diet matrix. Mice were fed a standard laboratory chow and then exposed to four semi-purified low- or high-fat diets for four weeks. Random forest (RF++) was used to identify VOCs that specifically respond to the diet matrix change. Interestingly, we found that the change from a chow diet to semi-purified diets resulted in a considerable drop of several VOC levels. Our results suggest that the diet matrix impacts VOC signatures and the underlying metabolic functions and may be one source of variability in exhaled volatiles.

Synergistic evolution of fluorescent Au(I)@(Ag2/Ag3)-thiolate core-shell particles has been made possible under the Sun in presence of the respective precursor coinage metal compounds and glutathione (GSH). The green chemically synthesized fluorescent clusters are giant (∼600 nm) in size and robust. Among all the common water miscible solvents, exclusively DMSO exhibits selective fluorescence quenching (Turn Off) because of the removal of GSH from the giant cluster. Again, only Pb(II) ion brings back the lost fluorescence (Turn On) leaving aside all other metal ions. This happens owing to the strong affinity of the sulfur donor of DMSO for Pb(II). Thus, employing the aqueous solution containing the giant cluster, we can detect DMSO contamination in water bodies at trace level. Besides, a selective sensing platform has emerged out for Pb(II) ion with a detection limit of 14 × 10(-8) M. Pb(II) induced fluorescence recovery is again vanished by I(-) implying a promising route to sense I(-) ion.

A direct injection gas chromatography method was developed for the determination of triethylamine and dimethyl sulfoxide (DMSO) in a drug substance (ML-189). Matrix effects were found to result in the overestimation of DMSO when methanol was used as diluent. Multiple approaches to eliminate matrix effects were unsuccessful; these included changes in sample size, split ratio, injector temperature and injector liner (e.g., deactivated liner). Ultimately, matrix effects were eliminated after the diluent was changed from methanol to acetone. A mechanism was proposed and discussed.

The behavior of dithizone (DTZ), an easily available dye has been studied for the first time in chromogenic sensing of CN(-) as an anionic species and for Co(2+) as a cationic species in DMSO/H2O media. So employing DTZ an efficient colorimetric chemosensor was afforded with a chromogenic selectivity for Co(2+) over other cations with detection limit of 0.04 μmol L(-1). The complex of Co(2+) with DTZ also displayed ability to detect up to 0.43 μmol L(-1) CN(-) (K(+) salts) among other competing anions through a fast response time of less than 30s which is much lower than most recently reported chromogenic probes. The linear dynamic ranges for the determination of Co(2+) and CN(-) were 0.3-4.4 and 3.3-58.6 μmol L(-1) respectively. This method could have potential application in a variety of cases requiring rapid and accurate analysis of Co(2+) and CN(-) for human serum and water samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Instrumental methods based on gas chromatography coupled to mass spectrometry (GC-MS) have been developed and compared using two different MS ionisation modes, electron impact (EI) and electron capture negative ionisation (ECNI), for the fast, quantitative and simultaneous determination of polychlorinated biphenyls (PCBs) and their main metabolites (hydroxylated PCBs, OH-PCBs, and methyl sulfone PCBs, MeSO2-PCBs). Parameters affecting chromatographic separation and MS detection were evaluated in order to achieve the highest selectivity and sensitivity for both operation modes. The analytical characteristics of the developed methods were studied and compared in terms of linear range, limits of detection (LODs), limits of quantification (LOQs), and instrumental precision (repeatability and intermediate precision). Both ionisation methods showed similar precision, being relative standard deviations (RSD, %) lower than 9% and 14% for repeatability and intermediate precision, respectively. However, better LODs (from 0.01 to 0.14 pg injected for the three families of congeners studied) were achieved using ECNI-MS as ionisation mode. The suitability of the developed method was demonstrated through their application to fish liver oil samples., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The success of allotransplants is critically dependent on both tissue viability and efficient removal of potentially toxic cryopreservants. In this study we analysed the dimethyl sulphoxide (Me2SO) content of cardiovascular tissue samples stored in tissue banks and optimized a washing protocol to be used before surgical implant. We compared the Me2SO content of heart valves, arteries and veins and quantitatively determined by HPLC the washing kinetics of each group of tissue samples under strictly controlled conditions using an industrial washing medium (BASE). Our results showed that heart valves and arteries have significantly slower Me2SO release kinetics than veins. Approximately 20 % of the initial content of cryopreservant could still be detected in the valves and arterial tissue after 15 min of continuous washing. Conversely, veins were almost completely cleared of the cryoprotectant under the same conditions. We propose a washing protocol consisting of two sequential washing with BASE for a total of 25 min for valves and arteries and 15 min for veins. In our hands, this protocol reliably ensures the removal of more than 95 % of the initial Me2SO content.

A multidisciplinary approach has been adopted to investigate and identify the source of malodour in washing machines and the potential for cross-contamination of laundry. Four washing machines were olfactively graded, and the number of colony-forming units (CFUs) bacteria was determined in four specific locations. Then, samples of terry-towel and fleece were washed, without the use of detergent, in the machines, and the occurrence of malodour over a 52-h period was assessed. Analysis of the scrapings from the four locations in the two malodorous machines identified a plethora of volatile organic compounds (VOCs) by either olfactory detection or mass spectral identification post-gas chromatographic separation. In addition, microbiological analysis from the swabs from the four locations within all four washing machines was carried out. Quantitative analysis of VOCs from 66 microbiological isolates from either the washing machines or fabrics was carried out. In total, 10 VOCs were identified: dimethyl disulfide, 3-methyl-1-butanol, 2,4-dithiapentane, dimethyl trisulfide, 2-tridecanone, indole, 2-phenylethanol, isovaleric acid, isobutyric acid and 1-undecene., (© 2013 The Society for Applied Microbiology.)

The effect of the pretreatment of water hyacinth with ionic liquid and co-solvent on the lignocellulosic composition, structural change and biogas production was evaluated in this study. The results from regenerated water hyacinth indicate that, the content of the lignocellulosic composition was changed, the crystallinity of the structure was decreased, and the surface became more porous. After the pretreatment with 1-N-butyl-3-methyimidazolium chloride ([Bmim]Cl)/dimethyl sulfoxide (DMSO) under 120°C for 120min, the cellulose content of regenerated water hyacinth was increased by 27.9%, 49.2% of the lignin was removed, and the biogas yield was increased by 97.6% as compared with unpretreated water hyacinth. The ionic liquids and co-solvents were successfully recovered by forming aqueous biphasic systems with K3PO4., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Spectroscopic imaging has been an increasingly critical approach for unveiling specific molecules in biological environments. Toward this goal, we demonstrate hyperspectral stimulated Raman loss (SRL) imaging by intrapulse spectral scanning through a femtosecond pulse shaper. The hyperspectral stack of SRL images is further analyzed by a multivariate curve resolution (MCR) method to reconstruct quantitative concentration images for each individual component and retrieve the corresponding vibrational Raman spectra. Using these methods, we demonstrate quantitative mapping of dimethyl sulfoxide concentration in aqueous solutions and in fat tissue. Moreover, MCR is performed on SRL images of breast cancer cells to generate maps of principal chemical components along with their respective vibrational spectra. These results show the great capability and potential of hyperspectral SRL microscopy for quantitative imaging of complicated biomolecule mixtures through resolving overlapped Raman bands.

The horizontal distributions and diurnal variations of particulate and dissolved dimethylsulfoxide (DMSOp, DMSOd) were studied in the surface water of the Yellow Sea and the Bohai Sea in June, 2011. The determination of DMSO was based on the DMS produced by NaBH4 reduction, which was analyzed using the purge-and-trap technique coupled with gas chromatographic separation and flame photometric detection. The concentrations of DMSOp and DMSOd ranged from 5.43 to 18.35 nmol x L(-1) and from 4.75 to 43.80 nmol x L(-1), respectively, with average values of (11.47 +/- 0.25) nmol x L(-1) and (13.42 +/- 0.58) nmol x L(-1). The results showed that no relationship was found between DMSOp and environmental factors such as chlorophyll a (Chl-a), temperature and salinity, whereas a positive correlation was observed between DMSOp/Chl-a and salinity, indicating that intracellular DMSO could act as a cryo-osmoregulator. A significant relationship was also found between DMSOd and dimethylsulfide (DMS), whereas there was no relationship between DMSOd and DMSOp or DMSOd and bacteria, implying that DMSOd in the surface water was produced mainly through the photochemical oxidation of DMS. In addition, both the DMSOp and DMSOd concentrations exhibited obvious diurnal variations with the higher values in the day time.

A new passive dosing method was developed to determine aqueous solubility of hydrophobic chemicals. In the passive dosing method, chemical crystals were loaded to a polydimethylsiloxane (PDMS) phase to maintain the maximum chemical activity and to prevent direct contact of chemical crystals with the aqueous solution. Eight polycyclic aromatic hydrocarbons (PAHs) were chosen covering their literature aqueous solubility from 0.001 to 30 mg L(-1). Values of the aqueous solubility for less hydrophobic PAHs (naphthalene, 2-methylnaphthalene, and fluorene) were measured by an Organization for Economic Co-ordination and Development (OECD)-recommended generator column method and those for more hydrophobic PAHs (anthracene, chrysene, and benzo(a)pyrene) were measured by the passive dosing method. For phenanthrene and pyrene, both methods were used for comparison. The results obtained by the passive dosing method were very close to those obtained by the generator column method. Aqueous solubilities in deionized water for more hydrophobic PAHs obtained using the passive dosing method agreed very well with values reported in the literature, suggesting the utility of the passive dosing method for the determination of aqueous solubility for highly hydrophobic chemicals. Because hydrophobic chemicals are often introduced in aqueous solutions by using a cosolvent, the solubility enhancement for PAHs at low cosolvent volume fractions was also evaluated. Three cosolvents (dimethyl sulfoxide, ethanol, and acetone) were chosen and their volume fractions in water were between 0.2% and 2%. The enhancement of the aqueous solubility could be well explained quantitatively by using a log-linear cosolvency model. The measured values of cosolvency power at the range of volume fraction investigated (σ(0.02)) correlated very well with log K(ow) of the PAHs. The combination of the log-linear model and semiempirical relationships between σ(0.02) and log K(ow) would be useful for the prediction of the solubility enhancement of hydrophobic chemicals.

Unlabelled: Cartilage cryopreservation requires optimal loading of protective solutes, most commonly dimethyl sulfoxide (DMSO), to maximize chondrocyte survival. Previously, diffusion models have been used to predict the distribution of solutes in tissue samples, but the accuracy of spatiotemporal predictions of these models have not been validated with empirical studies and remains unknown., Objective: In this study, magnetic resonance spectroscopic imaging was used to measure the spatial and temporal changes in DMSO and water concentrations in porcine articular cartilage plugs, throughout 1 h of solute loading., Design: A custom NMR spectroscopic imaging pulse sequence provided water and DMSO concentration images with an in-plane spatial resolution of 135 μm and a temporal resolution of 150 s, repeated for 60 min throughout DMSO loading. Delayed gadolinium-enhanced magnetic resonance of cartilage (d-GEMRIC) imaging provided fixed charge density and spin-density imaging provided water density images prior to DMSO loading., Results: The measured spatial and temporal distribution of DMSO in three different samples was compared to independent predictions of Fick's law and the modified triphasic biomechanical model by Abazari et al. (2011) with the empirical data more closely agreeing with the triphasic model., Conclusion: Dynamic NMR spectroscopic imaging can measure spatial and temporal changes in water and cryoprotectant concentrations in articular cartilage. The modified triphasic model predictions for the interstitial distribution of DMSO were confirmed and its advantage over the predictions by Fick's law model, which is commonly used in the literature of cryobiology, was demonstrated., (Copyright © 2012 Osteoarthritis Research Society International. Published by Elsevier Ltd. All rights reserved.)

Dimethyl sulfoxide (DMSO) is a chemical of industrial significance with many important applications. DMSO is used as an industrial solvent, in drug delivery and healthcare applications, among others. Analysis of DMSO in water typically involves extensive sample preparation, enrichment, and derivatization to improve solute detectability. A novel gas chromatographic procedure has been developed for the direct measurement of trace levels of DMSO in an aqueous matrix, such as potable water. The technology utilizes stacked injection techniques for in-column solute enrichment, a precolumn to enhance solute focusing effects, and sulfur chemiluminescence detection for matrix suppression and sensitivity. A detection limit of 2 parts per billion (ppb) (v/v) of DMSO in water was attained. Relative precision of less than 7% at the concentration of 10 ppb (v/v) of DMSO was demonstrated. A correlation coefficient of 0.9988 was obtained over a range of 2 ppb (v/v) to 100 ppb (v/v). No detectable carry-over was found at the 5 ppb (v/v) level whereas less than 4% carry-over was observed at the 100 ppb (v/v) level. Various sample storage media including glass, polyethylene, and polycarbonate were also studied to minimize solute loss. Recoveries greater than 84% were achieved with all storage media tested. The method was found to be reliable and simple to implement., (© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Sodium benzoate is used in oral liquid pharmaceutical products for its anti-microbial properties. The benzoate salts present in liquid pharmaceutical products can potentially generate residual levels of free benzene during manufacturing of the drug product and or during the shelf-life of the product under its storage conditions. To ensure the safety and quality of the pharmaceutical products (containing benzoate in the formulation), a selective and sensitive analytical method is required to monitor residual benzene in oral liquid pharmaceutical products. In this paper, we report the development and validation of a general static-headspace gas chromatographic (SH-GC) method to determine residual benzene in oral liquid pharmaceutical products. The liquid pharmaceutical drug product sample is dissolved in dimethylsulfoxide (DMSO) in a GC headspace vial. A DB-624 capillary column (30 m x 0.32 mm I.D. and 1.8 μm film thickness) was used under isothermal conditions with a flame ionization detection (FID). The benzene peak was well separated from all other volatile compounds that are present in the formulation of a number of liquid drug products. This method was successfully validated using a representative oral liquid pharmaceutical drug product. The limit of detection of the method for benzene is 0.5 ppm which met the 2 ppm limit of current ICH guideline for residual benzene in pharmaceutical products., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The potent odorant dimethyl sulfide (1), showing a low odor threshold of 0.12 microg/L in water, is known to contribute to the aromas of various foods. Its cabbage-like odor plays an important role, particularly, in cooked vegetables, such as cabbage, celery, or asparagus. On the other hand, in fruit juices or beer, 1 may generate off-flavors. S-Methylmethionine (2) has previously been characterized as precursor of 1 during thermal processing, and several methods for its quantitation have been proposed. Using deuterium-labeled 2 as the internal standard, a stable isotope dilution assay (SIDA) using LC-MS/MS was developed for the fast quantitation of 2 in vegetables and malt. Application of the method to different foods revealed amounts between 2.8 mg (fresh tomatoes) and 176 mg (celery) of 2 per kilogram. To correlate the amount of 1 formed upon processing with the amounts of 2 present in the raw material, 1 was quantified before and after a thermal treatment of the same raw materials by a SIDA. Concentrations between 1.1 mg/kg (fresh tomatoes) and 26 mg/kg (celery) were determined in the processed samples. The quantitation of 2 during steeping, germination, and malting of barley, and a correlation of the data with the amounts of 1 formed after thermal treatment of the malt, resulted in yields between 24 and 27 mol % calculated on the basis of the amounts of 2. The results suggested that the extent of the formation of 1 can be predicted, for example, in plant materials, from the amount of 2 present in the raw foods.

Effects of fluorescent light, riboflavin, ascorbic acid, sodium azide, and butylated hydroxyanisole (BHA) on the volatiles in milk at 4 degrees C were determined using a combination of headspace-solid phase microextraction (HS-SPME), gas chromatography (GC), and mass spectrometry (MS). Pentanal, hexanal, heptanal, and dimethyl disulfide were formed only in the milk stored under light and increased significantly as the duration of light exposure increased from 0 to 8 h and the concentration of added riboflavin increased from 5 to 50 ppm (P < 0.05). As fat content in milk increased, peak areas of pentanal, hexanal, and heptanal increased significantly (P < 0.05) while those of dimethyl disulfide did not change significantly (P > 0.05). Sodium azide prevented the formation of dimethyl disulfide in milk, implying that dimethyl disulfide can be formed through singlet oxygen oxidation (type II pathway). Addition of ascorbic acid and BHA reduced the formation of hexanal, heptanal, and dimethyl disulfide significantly (P < 0.05). Generation mechanisms of pentanal seem to be different from those of hexanal and heptanal in milk. Both singlet oxygen oxidation (type II pathway) and free radicals (type I pathway) play important roles in the formation of light-induced volatiles in milk.

Dimethylsulfoxide (DMSO) is a cryoprotective substance often used to allow long term storage of stem cells or tissue grafts. However, a high frequency of adverse events is associated with the infusion of thawed cells. These events are in part due to DMSO, leading many cell therapy facilities to introduce a washing step before the delivery of the grafts. The lack of method for evaluating the residual quantities of this substance in the reinfused cells led us to develop a technique, based on capillary zone electrophoresis for assaying DMSO. The cryoprotectant was measured in 55 hematopoietic stem cell grafts, 6 parathyroids and 5 blood vessels immediately after thawing and after washing or bathing in a saline solution. The results showed that DMSO reduction in stem cell grafts reached more than 90% after the washing procedure. Furthermore, this study has shown that 2 washing steps significantly improved DMSO elimination as compared to 1 washing step. For parathyroids and blood vessels, bathing the tissues after thawing in a saline solution allowed more than 95% DMSO reduction. This study demonstrated that the technique of DMSO measurement used here, is simple and feasible on complex matrices such as protein samples after dilution. It is an appropriate method for residual quantification of the cryoprotectant before graft.

Objective: Long-term storage of articular cartilage (AC) remains challenging due to poor post-thaw viability. An initial step towards addressing this issue is characterizing cryoprotectant (CPA) transport, since ensuring adequate CPA equilibration throughout the tissue offers protection during cooling. This study takes a systematic approach in determining CPA transport rates through bovine AC and uses that information in mathematical models to determine CPA equilibration times., Design: Diffusion of high concentration single (6.9 M dimethyl sulfoxide (DMSO)) and multi-component CPA solutions (VS55, 3.1 M DMSO+2.2 M 1,2-propanediol (PD)+3.1 M formamide (FM)) was measured through AC using (1)H nuclear magnetic resonance (NMR) imaging and localized spectroscopy, respectively. Using experimentally calculated effective diffusivities, diffusion models describing CPA transport through the tissue matrix and across chondrocyte membranes were combined to design a CPA addition and removal scheme for a cartilage plug of clinically relevant dimensions., Results: (1)H NMR imaging and localized spectroscopy experiments suggested that the permeation of CPAs through AC (5 mm diameter, 5-10 mm in thickness) took on the order of 4 h for full equilibration at 22 degrees C. Imaging clearly showed the permeation of DMSO into cartilage over time and localized spectroscopy was able to distinguish the permeation rates of the individual VS55 components and water. Experimentally measured diffusivity values were used in CPA addition/removal simulations with a cartilage plug of clinically relevant dimensions (5 mm diameter, 2 mm in thickness). Results suggested a multi-step approach for adding and removing high concentration CPAs, with the addition and removal each taking approximately 2 h to complete., Conclusions: This study provides a foundation for designing CPA addition and removal protocols for effective long-term storage of cartilage tissue using a novel approach to measure CPA permeation.

Residual solvents (RS) are volatile organic chemicals that are used or produced during the manufacturing process of drug substances or excipients. The European Pharmacopoeia (Ph. Eur.) limits the amount of RS in pharmaceuticals, considering the International Conference on Harmonization (ICH) of Technical Requirements for Registration of Pharmaceuticals for Human Use guidelines for RS. According to the Ph. Eur. general method, water insoluble samples may be analyzed using DMF as dilution solvent at high equilibration temperatures such as 105 degrees C. This could be problematic in the case of antibiotics, many of which are water insoluble and temperature sensitive. Moreover, antibiotics are complex in nature and beside RS, one can expect several other volatile impurity peaks in the chromatogram. In this study, the Ph. Eur. method for RS analysis was evaluated for selected groups of antibiotics. An alternative dilution medium was proposed (DMSO-water), which offers optimum sensitivity while working at lower equilibration temperatures such as 80 degrees C. The optimized method was investigated for precision, accuracy, linearity and detection limits.

A fully automated protein precipitation technique for biological sample preparation has been developed for the quantitation of drugs in various biological matrixes. All liquid handling during sample preparation was automated using a Hamilton MicroLab Star Robotic workstation, which included the preparation of standards and controls from a Watson laboratory information management system generated work list, shaking of 96-well plates, and vacuum application. Processing time is less than 30 s per sample or approximately 45 min per 96-well plate, which is then immediately ready for injection onto an LC-MS/MS system. An overview of the process workflow is discussed, including the software development. Validation data are also provided, including specific liquid class data as well as comparative data of automated vs manual preparation using both quality controls and actual sample data. The efficiencies gained from this automated approach are described.

The objective of this study was to investigate approaches to protect selected flavor compounds from deterioration when stored in an oil matrix. An aroma compound model mixture was prepared in a medium-chain triglyceride (MCT) or sunflower oil (SfO) matrix and stored under either an ambient air or argon atmosphere containing, respectively, ca. 20 and <0.5% residual oxygen as controls or containing a natural antioxidant, delta-tocopherol (0.01%). Samples were analyzed by static headspace GC/FID to determine the stability over time of the compounds in mixture. It was found that the type of oil had the greatest effect (P < 0.01) on overall compound stability. A low-oxygen atmosphere also had a significant (P < 0.05) protective effect on the aroma compounds in both oils. The addition of delta-tocopherol generally offered little additional protection. No significant relationship could be determined between the oxidation of the lipid matrix and the loss of oxidation-sensitive thiol compounds.

Introduction: Decellularized cryopreserved allograft vascular tissue may provide a nonimmunogenic scaffold that is suitable for repopulation by cells from a variety of sources, conferring the potential for growth and repair. Although dimethyl sulfoxide (Me(2)SO) is generally regarded as a safe cryoprotectant, even low levels may alter function of repopulating cells. We investigated the residual concentration of Me(2)SO in the aqueous compartment of cryopreserved ovine aortic valve conduits following decellularization., Materials and Methods: Aortic valve conduits from Suffolk sheep were cryopreserved in 1.1 M (7.5% vol/vol) Me(2)SO according to the protocol of our local tissue bank. Three aortic valve conduits were decellularized in a series of hypotonic and hypertonic Tris buffers. Tissue samples were taken at regular time intervals throughout the decellularization process and equilibrated in double distilled, deionized H(2)O for 28 days. Quantitative proton nuclear magnetic resonance spectroscopy was used to determine the residual Me(2)SO concentration in the equilibration solutions from which Me(2)SO tissue concentrations were calculated., Results: After thawing, the mean Me(2)SO concentration in the valve conduit was 0.302 +/- 0.081 M. The decellularization process resulted in a stepwise reduction in the Me(2)SO concentration to less than 8.56 x 10(-5) +/- 9 x 10(-5) M (P = 0.02). The diffusion coefficient was 2.5 x 10(-6) cm(2)/s., Conclusions: Our study demonstrates that Me(2)SO is effectively washed out of the aortic valve conduit during decellularization, resulting in a final concentration that is several orders of magnitude less than Me(2)SO concentrations reported to alter cell function.

Successful cryopreservation of articular cartilage (AC) could improve clinical results of osteochondral allografting and provide a useful treatment alternative for large cartilage defects. However, successful cartilage cryopreservation is limited by the time required for cryoprotective agent (CPA) permeation into the matrix and high CPA toxicity. This study describes a novel, practical method to examine the time-dependent permeation of CPAs [dimethyl sulfoxide (DMSO) and propylene glycol (PG)] into intact porcine AC. Dowels of porcine AC (10 mm diameter) were immersed in solutions containing high concentrations of each CPA for different times (0, 15, 30, 60 min, 3, 6, and 24 h) at three temperatures (4, 22, and 37 degrees C), with and without cartilage attachment to bone. The cartilage was isolated and the amount of cryoprotective agent within the matrix was determined. The results demonstrated a sharp rise in the CPA concentration within 15-30 min exposure to DMSO and PG. The concentration plateaued between 3 and 6 h of exposure at a concentration approximately 88-99% of the external concentration (6.8 M). This observation was temperature-dependent with slower permeation at lower temperatures. This study demonstrated the effectiveness of a novel technique to measure CPA permeation into intact AC, and describes permeation kinetics of two common CPAs into intact porcine AC.

Methylsulfonylmethane (MSM) is a sulfur-containing compound found in a wide range of human foods including fruits, vegetables, grains, and beverages. More recently, it has been marketed as a dietary supplement worldwide. The objective of this study was to evaluate the pharmacokinetic profile and distribution of radiolabeled MSM in rats. Male Sprague-Dawley rats were administered a single oral dose of [35S]MSM (500 mg/kg), and blood levels of radioactivity were determined at different time points for up to 48 h. Tissue levels of radioactivity at 48 and 120 h and urine and fecal radioactivity levels were measured at different time points for up to 120 h following [35S]MSM administration to rats. Oral [35S]MSM was rapidly and efficiently absorbed with a mean tmax of 2.1 h, Cmax of 622 microg equiv/mL, and AUC0-inf of 15124 h.microg equiv/mL. The t1/2 was 12.2 h. Soft tissue distribution of radioactivity indicated a fairly homogeneous distribution throughout the body with relatively lower concentrations in skin and bone. Approximately 85.8% of the dose was recovered in the urine after 120 h, whereas only 3% was found in the feces. No quantifiable levels of radioactivity were found in any tissues after 120 h, indicating complete elimination of [35S]MSM. The results of this study suggest that [35S]MSM is rapidly absorbed, well distributed, and completely excreted from the body.

A novel dimethyl sulfoxide (DMSO) sensor using DMSO reductase and film electrodes was constructed. The Au and Ag electrodes were fabricated on slide glass by vacuum deposition and the application of a photolithographic technique. The micro-chamber (4 x 50 x 1 mm, volume 200 microl) was fabricated on a poly(dimethylsiloxane) (PDMS) polymer. The Pt electrode was implanted in a PDMS polymer. DMSO reductase was immobilized on a Au film electrode with bovine serum albumin (BSA)-glutaraldehyde. This sensor could determine DMSO in an unpurged aqueous solution with glucose oxidase (GOD) and catalase (CAT) for oxygen removal. The DMSO sensor showed a linear response within 1 mM DMSO with a correlation coefficient of 0.999. The detection limit was 200 microM (3sigma), and the sensitivity was 23.8 mA M(-1) cm(-2). The relative standard deviations at each concentration were within 3.6%.

Odours caused by volatile organic sulphides (VOS) have a history spanning over 20 years for Philadelphia's Northeast Water Pollution Control Plant (NEWPCP). A "canned corn" type of odour has caused residential complaints. Traditional odour control approaches based on hydrogen sulphide failed. This study confirmed that dimethyl sulphoxide (DMSO) from a chemical facility was the dominant cause of the "canned corn" nuisance odour in the form of dimethyl sulphide (DMS). During a discharge, DMSO concentrations up to 12 mg/L were found in the influent of the NEWPCP. Each DMSO concentration peak induced a DMS peak. DMS concentrations increased from less than 50 microg/L to 6 mg/L with a corresponding decrease in DMSO. Approximately 79% of DMSO from the primary sedimentation influent was passed to the effluent, and to downstream processes, such as the aeration tanks where the DMS was volatilised by the aeration. The DMS partial pressure in ambient air of NEWPCP can be between 0.03 and 0.18 x 10(-3) atm during a DMSO discharge. From the above information, the potential of VOS production is estimated and a practical plan for remediation can be designed.

Volatile sulfur compounds have been reported to be responsible for the sulfurous off-flavors generated during the thermal processing of milk; however, their analysis has been a challenge due to their high reactivity, high volatility, and low sensory threshold. In this study, reactive thiols were stabilized and the volatile sulfur compounds in milk were extracted by headspace solid-phase microextraction, and analyzed by gas chromatography and pulsed-flame photometric detection. Calibration curves for 7 sulfur-containing compounds were constructed in milk by the standard addition technique. Raw, pasteurized, and UHT milk samples with various fat contents were analyzed. Compared with raw and pasteurized samples, UHT milk contained substantially higher concentrations of hydrogen sulfide, methanethiol, carbon disulfide, dimethyl trisulfide, and di-methyl sulfoxide. The high odor activity values calculated for methanethiol and dimethyl trisulfide suggested that these 2 compounds, in addition to di-methyl sulfide reported in a previous study, could be the most important contributors to the sulfurous note in UHT milk.

A colorimetric whole-cell sensor for dimethyl sulfide (DMS) was constructed based on the in vivo conversion of intrinsic pigments in response to the analyte. In a marine bacterium, Rhodovulum sulfidophilum, carotenoids are synthesized via the spheroidene pathway. In this pathway, demethylspheroidene, a yellow carotenoid, is converted to spheroidene under catalysis of O-methyltransferase. Spheroidene monooxygenase (CrtA) catalyzes the terminal step of the pathway and converts spheroidene to spheroidenone, a red carotenoid. Here, the CrtA gene in R. sulfidophilum was removed and then reintroduced downstream of the DMS dehydrogenase gene promoter. Using this whole-cell sensor, 3 muM DMS or dimethyl sulfoxide can be detected without adding any color-forming reagent. The ratio of the red spheroidenone to total carotenoids increased, as the DMS concentration was raised to 0.3 mM. Comparison of the signal to the background color indicated a shift in the color coordinate from a yellow to a red hue. An intense signal was obtained with 1-day incubation at a high cell density when sensor cells at the exponential growth phase were used. These results show that the genetically engineered R. sulfidophilum cells can be used to monitor the quality of marine aquacultural environments by the naked eye.

Functional barriers are multilayer structures deemed to prevent migration of some chemicals released by food-contact materials into food. In the area of plastics packaging, different migration behaviours of mono- and multilayer structures are assessed in terms of lag time and of their influence of the solubility of the migrants in food simulants. Whereas barriers to oxygen or to aromas must prevent the diffusion of these compounds under conditions of use, a functional barrier must also be efficient under processing conditions, to prevent diffusion of substances when the polymer layers are in contact at high (processing) temperatures. Diffusion in melted polymers at high temperatures is much slower for glassy polymers, than in polymers that are rubbery at ambient temperature. To evaluate the behaviour of functional barriers under conditions of use, a set of reference diffusion coefficients in the 40-60 degrees C range were determined for 14 polymers. Conditions for accelerated migration tests are proposed based on worst-case activation energy in the 40-60 degrees C range. For simulation of migration, numerical models are available. The rules derived from the models can be used both by industry (to optimize a material in terms of migration) or by risk assessors. Differences in migration behaviour between mono- and multilayer materials are discussed.

An European Union (EU)-funded project QLK1-CT-2001-00930 (BIOSAFEPAPER) involves the development, validation and intercalibration of a short-term battery of toxicological tests for the safety assessment of food-contact paper and board. Dissemination of the results to industry, legislators (e.g. DG Consumer Protection, DG Enterprises, DG Research), standardization bodies such as CEN, and consumers will create an agreed risk evaluation procedure. The project involves pre-normative research in order to establish a set of in-vitro cytotoxicity and genotoxicity tests that will be easily adaptable to food-contact fibre-based materials and have endpoints relevant to consumer safety, including sub-lethal cellular events. These tests will be performed on samples representing actual migration conditions from food-contact paper and board with respect to different foodstuffs, and should form an experimental basis for scientifically sound recommendations for a harmonized system of risk evaluation and product testing.

The quality of a corporate compound collection can be significantly affected by a complex combination of storage and operational processing factors. Water content in DMSO solutions is one factor that is of great interest as it can affect solubility, degradation, and freeze-thaw cycle parameters. To the authors' knowledge, this is the first report of using near-infrared (NIR) spectroscopy to assess water content in DMSO compound stock solutions within the common storage vessel format of polypropylene microtubes. The precision and accuracy of the NIR technique was benchmarked against a Karl Fisher titration method, and a correlation coefficient was determined to be 0.985 over a range of 1% to 10% water in DMSO by weight. The advantages of the NIR technique include accuracy, precision, speed, nondestructiveness, and the capability of assessing compounds under in situ storage conditions within microtubes. In this report, the authors demonstrate the accuracy and precision of using NIR to assess water content in DMSO solutions and present a case study to demonstrate the utility of the technique to aid in assessing a pharmaceutical compound collection.

As part of an overall systems approach to generating highly accurate screening data across large numbers of compounds and biological targets, we have developed and implemented streamlined methods for purifying and quantitating compounds at various stages of the screening process, coupled with automated "traditional" storage methods (DMSO, -20 degrees C). Specifically, all of the compounds in our druglike library are purified by LC/MS/UV and are then controlled for identity and concentration in their respective DMSO stock solutions by chemiluminescent nitrogen detection (CLND)/evaporative light scattering detection (ELSD) and MS/UV. In addition, the compound-buffer solutions used in the various biological assays are quantitated by LC/UV/CLND to determine the concentration of compound actually present during screening. Our results show that LC/UV/CLND/ELSD/MS is a widely applicable method that can be used to purify, quantitate, and identify most small organic molecules from compound libraries. The LC/UV/CLND technique is a simple and sensitive method that can be easily and cost-effectively employed to rapidly determine the concentrations of even small amounts of any N-containing compound in aqueous solution. We present data to establish error limits for concentration determination that are well within the overall variability of the screening process. This study demonstrates that there is a significant difference between the predicted amount of soluble compound from stock DMSO solutions following dilution into assay buffer and the actual amount present in assay buffer solutions, even at the low concentrations employed for the assays. We also demonstrate that knowledge of the concentrations of compounds to which the biological target is exposed is critical for accurate potency determinations. Accurate potency values are in turn particularly important for drug discovery, for understanding structure-activity relationships, and for building useful empirical models of protein-ligand interactions. Our new understanding of relative solubility demonstrates that most, if not all, decisions that are made in early discovery are based upon missing or inaccurate information. Finally, we demonstrate that careful control of compound handling and concentration, coupled with accurate assay methods, allows the use of both positive and negative data in analyzing screening data sets for structure-activity relationships that determine potency and selectivity.

Imidazolium trans-imidazoledimethylsulphoxidetrachlororuthenate (NAMI-A) was tested in vitro on the pro-adhesive properties, evaluated as resistance to trypsin treatment, which is a bona fide measure of adhesion strength, of KB and HeLa carcinoma cell lines and on human polymorphonuclear neutrophils (HPMN). NAMI-A increased the pro-adhesive activity of KB cells at 0.001 mM concentration, after few minutes incubation and this effect was not influenced by the vehicle used for cell challenge, neither did it depend on NAMI-A concentration or on temperature. The same effect occurred on HeLa cells at 0.01 mM NAMI-A. This effect, detected at concentrations up to 100 times lower than those necessary to block cells at the G(2)-M premitotic phase of cell cycle, or to inhibit matrix metalloproteinase release or cell invasion, was not related to ruthenium uptake by tumour cells. HeLa cells and healthy HPMN, following short exposure to 0.1 mM NAMI-A, assumed a different shape, with the extrusion of filopodia (HeLa) and of large lamellopodia (HPMN), which increased their interactions with the substrate. This effect was attributed to stabilisation, altered turnover and sensitivity to cytochalasin D of actin filaments. Provided that adhesion is associated with cell motility and invasion, these data suggest that NAMI-A may exert antimetastatic properties at concentrations lower than those observed in the lungs at the end of a conventional intraperitoneal treatment in vivo.