Potential use of Methylibium sp. as a biodegradation tool in organosilicon and volatile compounds removal for biogas upgrading.

Organosilicon compounds are the most undesirable compounds for the energy recovery of biogas. These compounds are still resistant to biodegradation when biotechnologies are considered for biogas purification. Herein we isolated 52 bacterial species from anaerobic batch enrichment cultures (BEC) saturated with D4 and from an anaerobic lab-scale biotrickling filter (BTF) fed with a gas flow containing D4 as unique carbon source. Among those Methylibium sp. and Pseudomonas aeruginosa showed the highest capacity to remove D4 (53.04% ±â€¯0.03 and 24.42% ±â€¯0.02, respectively). Contrarily, co-culture evaluation treatment for the biodegradation of siloxanes together with volatile organic compounds removed a lower concentration of D4 compared to toluene and limonene, which were completely removed. Remarkably, the siloxane D5 proved to be more biodegradable than D4. Substrates removal values achieved by Methylibium sp. suggested that this bacterial isolate could be used in biological removal technologies of siloxanes.

Extraction and quantitative analysis of water by GC/MS for trace-level dimethylsilanediol (DMSD).

Dimethylsilanediol (DMSD) is related to the most important bifunctional building block for silicone oligomers and polymers, although DMSD itself is not used in any commercial applications. The environmental release of DMSD is linked to the hydrolytic degradation of other silicone materials in soil and water as DMSD is usually one of the major products. Most common extraction and quantification methods are not suitable for the analysis of trace- and ultratrace-levels of DMSD in water. This is because DMSD is highly water soluble and can readily undergo self-condensation when concentrated. In addition, DMSD may also coexist with DMSD precusors such methylsiloxanes in water. In the present study, solid-phase extraction (SPE) in combination with gas chromatography-mass spectrometry (GC/MS) without pre-column derivatization was tested for analyzing water samples for DMSD. It was found that direct analysis by GC/MS can be used for a wide range of concentrations if DMSD was extracted into a dry organic solvent. Isolute® ENV + may be used for such extraction at higher DMSD concentrations, while Supelclean™ ENVI-Carb™ Plus was found to be better for trace and ultratrace analysis. Increased salt content in water can increase its DMSD extraction efficiency, while polarity of the eluting solvents is a determining factor for eluting efficiency. Moisture in the final extract is a detrimental factor for direct GC/MS analysis. With a proper moisture removal procedure and a suitable internal standard, coupling of SPE and direct GC/MS analysis reduces the method detection limits for DMSD to lower ppb levels. Based on field sample analysis, solvent and instrumental background, not instrumental sensitivity, was found to be the limiting factor in lowering the detection limits for this analysis.

Analysis of loxoprofen in tablets, patches, and equine urine as tert-butyldimethylsilyl derivative by gas chromatography-mass spectrometry.

Loxoprofen is a non-steroidal anti-inflammatory drug of the 2-arylpropionic acid type, which has used to treat musculoskeletal disorders in the horse racing industry. However, it has also used illicitly to mask clinical signs of inflammation and pain in racehorses. Thus, its accurate analysis has become an important issue in horse doping laboratories. In this study, an analytical method of loxoprofen was developed as tert-butyldimethylsilyl (TBDMS) derivative by gas chromatography-mass spectrometry (GC-MS). Characteristic fragment ions of [M-15], [M-57], and [M-139] permitted the accurate and selective detection of loxoprofen. Under optimal conditions, this method showed good linearity (r ≥ 0.999) in the range of 10-500 ng/mL, repeatability (% relative standard deviation = 5.6-8.5), and accuracy (% relative error = - 0.3-0.9) with a detection limit of 1.0 ng. When applied to the analysis of loxoprofen in tablet and patch products, loxoprofen was positively identified as TBDMS derivative by GC-MS. The present method provided rapid and accurate determination of loxoprofen in patch and tablet products. Levels of loxoprofen were highest in equine urine at 0.5 and 1 h after oral administration with single dose (3 mg/kg) to three horses, and then rapidly reduced to below the lower limit of quantification at 24 h. Therefore, the present method will be useful for the pharmacokinetic study and doping tests for loxoprofen and other similar acidic drugs in horses.

GC-MS/MS survey of collision-induced dissociation of tert-butyldimethylsilyl-derivatized amino acids and its application to (13)C-metabolic flux analysis of Escherichia coli central metabolism.

Stable isotope labeling experiments using mass spectrometry have been employed to investigate carbon flow levels (metabolic flux) in mammalian, plant, and microbial cells. To achieve a more precise (13)C-metabolic flux analysis ((13)C-MFA), novel fragmentations of tert-butyldimethylsilyl (TBDMS)-amino acids were investigated by gas chromatography-tandem mass spectrometry (GC-MS/MS). The product ion scan analyses of 15 TBDMS-amino acids revealed 24 novel fragment ions. The amino acid-derived carbons included in the five fragment ions were identified by the analyses of (13)C-labeled authentic standards. The identification of the fragment ion at m/z 170 indicated that the isotopic abundance of S-methyl carbon in methionine could be determined from the cleavage of C5 in the precursor of [M-159](+) (m/z 218). It was also confirmed that the precision of (13)C-MFA in Escherichia coli central carbon metabolism could be improved by introducing (13)C-labeling data derived from novel fragmentations. Graphical Abstract Novel collision-induced dissociation fragmentations of tert-butyldimethylsilyl amino acids were investigated and identified by GC-MS/MS.

Preliminary study on application of urine amino acids profiling for monitoring of renal tubular injury using GLC-MS.

BACKGROUND: The early diagnosis of the nephrotoxic effect of xenobiotics and drugs is still an unsolved problem. Recent studies suggest a correlation between the nephrotoxic activity of xenobiotics and increased concentration of amino acids in urine. The presented study was focused on the application of GLC-MS method for amino acids profiling in human urine as a noninvasive method for monitoring of kidney condition and tubular injury level. MATERIAL AND METHODS: The analytic method is based on the conversion of the amino acids present in the sample to tert-butyldimethylsilyl (TBDMS) derivatives and their analysis by gas-liquid chromatography-mass spectrometry (GLC-MS). The procedure of urine sample preparation for chromatographic analysis was optimized. RESULTS: The presence of 12 amino acids in most of the tested healthy human urine samples was detected. The significant differences in the levels of particular amino acids between patients with tubular injury and healthy controls were found, especially for lysine, valine, serine, alanine and leucine (on average 30.0, 7.5, 3.6, 2.9 and 0.5 fold respectively). CONCLUSIONS: We found that this approach based on GLC-MS detection can be used in nephrotoxicity studies for urine amino acids monitoring in exposure to xenobiotics and drugs.

29Si-1H IMPACT HMBC: a suitable tool for analyzing silylated derivatives.

A modified version of the IMPACT heteronuclear multiple bond correlation (HMBC) has allowed the characterization of an organosilane and a tetrasilylated yttrium complex. With the help of this sequence, an average gain in sensitivity close to 2 has been obtained compared with the standard HMBC experiment for disilanes as well as for yttrium complexes containing silylated ligands. This modified version of this long-range correlation experiment opens the way for following kinetics in the range of a fraction of a minute and to study by NMR low concentrated samples and low abundant nuclei.

Time-lapse fluorescence imaging and quantitative single cell and endosomal analysis of peritoneal macrophages using fluorescent organosilica nanoparticles.

Fluorescent thiol-organosilica nanoparticles with 100 nm diameter (F-thiol-OS-100) were applied for time-lapse fluorescence imaging. The evaluation of F-thiol-OS-100 for quantitative analysis demonstrated great advantages as compared with quantum dots and organic fluorescent dye. Time-lapse fluorescence imaging of mouse peritoneal macrophages using F-thiol-OS-100 clearly demonstrated cellular uptake, and single cell analysis showed various patterns of uptake kinetics that could be quantitatively evaluated. We also performed quantitative analysis of endosomal uptake and movements in single cells. A correlation between morphologic findings and endosomal uptake and movement over time was also observed and analyzed quantitatively. The F-thiol-OS-100 showed high potential as a new fluorescence marker for time-lapse fluorescence imaging and quantitative single cell functional analysis for nanomedicine development. FROM THE CLINICAL EDITOR: In this study the authors report on 100 nm thiol-organosilica nanoparticles as time-lapse flurescent markers. F-thiol-OS-100 proved to be superior to quantum dots and organic flurescent dyes, and enabled quantitative single cell functional analysis.

One-step (18)F-labeling of peptides for positron emission tomography imaging using the SiFA methodology.

Here we present a procedure to label peptides with the positron-emitting radioisotope fluorine-18 ((18)F) using the silicon-fluoride acceptor (SiFA) labeling methodology. Positron emission tomography (PET) has gained high importance in noninvasive imaging of various diseases over the past decades, and thus new specific imaging probes for PET imaging, especially those labeled with (18)F, because of the advantageous properties of this nuclide, are highly sought after. N-terminally SiFA-modified peptides can be labeled with (18)F(-) in one step at room temperature (20-25 °C) or below without forming side products, thereby producing satisfactory radiochemical yields of 46 ± 1.5% (n = 10). The degree of chemoselectivity of the (18)F-introduction, which is based on simple isotopic exchange, allows for a facile cartridge-based purification fully devoid of HPLC implementation, thereby yielding peptides with specific activities between 44.4 and 62.9 GBq µmol(-1) (1,200-1,700 Ci mmol(-1)) within 25 min.

Acceptable levels for ingestion of dimethylsilanediol in water on the International Space Station.

INTRODUCTION: Water is recovered aboard the International Space Station (ISS) from humidity condensate and treated urine. The product water is monitored for total organic carbon (TOC). In 2010 the TOC readings indicated that a new contaminant had entered the potable water and was steadily increasing toward the TOC screening limit of 3 mg x L(-1). In a ground-based laboratory, chemists discovered that dimethylsilanediol (DMSD) was the principal new contaminant. As no standard existed for safe levels of DMSD in water, the Toxicology Office at Johnson Space Center was asked to set such a standard. METHODS: The Toxicology Office used methods developed over the past decade, in collaboration with the National Research Council Committee on Toxicology, for setting Spacecraft Water Exposure Guidelines (SWEGs). These methods require a thorough literature search and development of an acceptable concentration (AC) for each potential toxic effect, keeping in mind that the adverse effects that accompany spaceflight could increase toxicity for certain end points. Benchmark dose modeling was encouraged if sufficient data were available. The most sensitive AC becomes the driver for the SWEG. RESULTS: Hematotoxicity, hepatotoxicity, and possibly neurotoxicity were the most sensitive toxicological endpoints for DMSD. CONCLUSIONS: The SWEG for DMSD for 100 d of ingestion was set at 35 mg x L(-1), which is equivalent to 9 mg x L(-1) as TOC. This is well above the TOC SWEG of 3 mg x L(-1) and the peak DMSD level of processed water observed on orbit, which was 2.2 mg x L(-1) asTOC (8.5 mg x L(-10 of DMSD).

Para-hydrogen induced polarization of Si-29 NMR resonances as a potentially useful tool for analytical applications.

Para-hydrogen-induced polarization effects have been observed in the (29)Si NMR spectra of trimethylsilyl para-hydrogenated molecules. The high signal enhancements and the long T(1) values observed for the (29)Si hyperpolarized resonances point toward the possibility of using (29)Si for hyperpolarization applications. A method for the discrimination of multiple compounds and/or complex mixtures of hydroxylic compounds (such as steroids), consisting of the silylization of alcoholic functionalities with an unsaturated silylalkyl moiety and subsequent reaction with para-H(2), is proposed.

Fluence rate-dependent photobleaching of intratumorally administered Pc 4 does not predict tumor growth delay.

We examined effects of fluence rate on the photobleaching of the photosensitizer Pc 4 during photodynamic therapy (PDT) and the relationship between photobleaching and tumor response to PDT. BALB/c mice with intradermal EMT6 tumors were given 0.03 mg kg(-1) Pc 4 by intratumor injection and irradiated at 667 nm with an irradiance of 50 or 150 mW cm(-2) to a fluence of 100 J cm(-2). While no cures were attained, significant tumor growth delay was demonstrated at both irradiances compared with drug-only controls. There was no significant difference in tumor responses to these two irradiances (P = 0.857). Fluorescence spectroscopy was used to monitor the bleaching of Pc 4 during irradiation, with more rapid bleaching with respect to fluence shown at the higher irradiance. No significant correlation was found between fluorescence photobleaching and tumor regrowth for the data interpreted as a whole. Within each treatment group, weak associations between photobleaching and outcome were observed. In the 50 mW cm(-2) group, enhanced photobleaching was associated with prolonged growth delay (P = 0.188), while at 150 mW cm(-2) this trend was reversed (P = 0.308). Thus, it appears that Pc 4 photobleaching is not a strong predictor of individual tumor response to Pc 4-PDT under these treatment conditions.

Absorption and fluorescence spectroscopic properties of 1- and 1,4-silyl-substituted naphthalene derivatives.

Silyl-substituted naphthalene derivatives at the 1- and 1,4-positions were synthesized and their UV absorption, fluorescence spectroscopic properties, and fluorescence lifetimes were determined. Analysis of the results shows that the introduction of silyl groups at these positions of the naphthalene chromophore/fluorophore causes shifts of the absorption maxima to longer wavelengths and increases in fluorescence intensities. Bathochromic shifts of the absorption maxima and increases in fluorescence intensities are also promoted by the introduction of methoxy and cyano groups at the naphthalene 4- and 5-positions. In addition, the fluorescence of 9,10-dicyanoanthracene is efficiently quenched by these naphthalene derivatives with Stern-Volmer plot calculated rate constants that depend on the steric bulk of the silyl groups.

Raphidiophrys heterophryoidea sp. nov. (Centrohelida: Raphidiophryidae), the first heliozoan species with a combination of siliceous and organic skeletal elements.

Centrohelid heliozoans form a monophyletic group with uncertain affinities to other groups of protists. Except for a number of naked species, they have either siliceous scales or organic spicules covering the cell. According to the phylogenetic analysis of the 18S rDNA gene, it is hypothesized that scales are the ancestral form of cell coverings, while spicules are derived structures. The present paper describes a new species of centrohelids, Raphidiophrys heterophryoidea, isolated from the inner lakes of Valamo Island (North-Western Russia). This species has tangential scales, consisting of two plates, connected with radial, sometimes branched septa. Raphidiophrys heterophryoidea also has radially oriented spindle-shaped spicules. The organic nature of spicules and the siliceous nature of scales were verified by energy-dispersive X-ray microanalysis. Such a combination of organic and siliceous skeletal elements in one heliozoan is novel for any heliozoan species. The complex bipartite structure of scales suggested placing this new species in the genus Raphidiophrys. Consequently, the diagnoses of the genus Raphidiophrys and the family Raphidiophryidae were amended taking into account the optional presence of spicules. Raphidiophrys heterophryoidea presumably represents a stage of shift from scales to spicules, which, according to the molecular phylogenetic data, occurred at least twice in centrohelid evolution.

Facile C-S coupling reaction of aryl iodide and thiophenol catalyzed by Cu-grafted furfural functionalized mesoporous organosilica.

A new functionalized mesoporous organosilica has been designed via Schiff-base condensation of furfural and 3-aminopropyltriethoxy-silane (APTES) followed by its hydrothermal co-condensation with tetraethylorthosilicate (TEOS) in the presence of a cationic surfactant CTAB. Subsequent reaction of this mesoporous organosilica with Cu(OAc)(2) in absolute ethanol leads to the formation of a new Cu(II)-grafted mesoporous organosilica catalyst 1. Powder XRD, HR TEM, FE SEM, N(2) sorption and FT IR spectroscopic tools are used to characterize the materials. This Cu-anchored mesoporous material acts as an efficient, reusable catalyst in the aryl-sulfur coupling reaction between aryl iodide and thiophenol for the synthesis of value added diarylsulfides.

Comparison of MTBSTFA and BSTFA in derivatization reactions of polar compounds prior to GC/MS analysis.

In this study, MTBSTFA and BSTFA, which are among the preferred derivatization reagents for silylation were both tested on derivatization of six different groups of polar chemicals to get information about usefulness in terms of sensitivity and specificity of both reagents. Tested compound groups were nitrophenols and methoxyphenols, sterols and sugars, dicarboxylic acids and hydroxylated polycyclic aromatic hydrocarbons. It was found that MTBSTFA-derivates produce characteristic fragmentation patterns presenting mainly the fragments [M](+), [M-57](+) and [M-131](+), of which [M-57](+) is generally dominant on the mass spectrogram. BSTFA-derivates mainly show the fragments [M](+), [M-15](+) and [M-89](+) whereof the molecular ion [M](+) is generally dominant. It was also found that steric hindrance and molecular mass play a very important role in the choice of the best suited derivatization reagent: compounds with sterically hindered sites derivatized with MTBSTFA produce very small analytical responses or no signal at all, and compounds with high molecular mass produce no characteristic fragmentation pattern when derivatization is performed with BSTFA. It was also found that MTBSTFA-derivatization facilitates separation of isomer analytes, suggesting its choice in combination to semi-polar columns, whilst BSTFA seems better for sterically hindered compounds. Findings were confirmed with applications of both reagents to biological and environmental matrices (urine and atmospheric aerosols).

Determination of descriptors for organosilicon compounds by gas chromatography and non-aqueous liquid-liquid partitioning.

Measurements of retention factors by gas chromatography on up to 10 complementary stationary phases at up to 5 temperatures for each stationary phase and liquid-liquid partition coefficients in three biphasic organic solvent systems (n-hexane-acetonitrile, n-heptane-N,N-dimethylformamide and n-heptane-2,2,2-trifluoroethanol) were used to estimate solute descriptors for 54 organosilicon compounds for use in the solvation parameter model. Many of the E descriptor values (electron lone pair interactions) are negative for simple siloxanes and silanes indicating that these compound bind electron lone pairs more tightly than n-alkanes. Silanes and siloxanes with alkyl groups have near zero dipolarity/polarizability (S descriptor). The S descriptor is only modest for simple phenylsilanes, silazanes, silanols, orthosilicates, and alkoxides. All organosilicon compounds with silicon-oxygen bonds are reasonably strong hydrogen-bond bases (B descriptor) but only the silanol group is a reasonably strong hydrogen-bond acid (A descriptor). Silanes (SiH) and silazanes (SiNHSi) are weak hydrogen-bond acids. Cavity formation and dispersion interactions (V or L descriptor) are often the main component of solvation models for siloxanes and silanes that have simple alkyl and aromatic substituents. A number of physicochemical properties (vapor pressure, aqueous solubility, biphasic partition coefficients, sorption coefficients, etc.) for linear and cyclic dimethylsiloxanes can be reliably predicted from their descriptors in established models for organic compounds.

Derivatization of organophosphorus nerve agent degradation products for gas chromatography with ICPMS and TOF-MS detection.

Separation and detection of seven V-type (venomous) and G-type (German) organophosphorus nerve agent degradation products by gas chromatography with inductively coupled plasma mass spectrometry (GC-ICPMS) is described. The nonvolatile alkyl phosphonic acid degradation products of interest included ethyl methylphosphonic acid (EMPA, VX acid), isopropyl methylphosphonic acid (IMPA, GB acid), ethyl hydrogen dimethylamidophosphate sodium salt (EDPA, GA acid), isobutyl hydrogen methylphosphonate (IBMPA, RVX acid), as well as pinacolyl methylphosphonic acid (PMPA), methylphosphonic acid (MPA), and cyclohexyl methylphosphonic acid (CMPA, GF acid). N-(tert-Butyldimethylsilyl)-N-methyltrifluroacetamide with 1% TBDMSCl was utilized to form the volatile TBDMS derivatives of the nerve agent degradation products for separation by GC. Exact mass confirmation of the formation of six of the TBDMS derivatives was obtained by GC-time of flight mass spectrometry (TOF-MS). The method developed here allowed for the separation and detection of all seven TBDMS derivatives as well as phosphate in less than ten minutes. Detection limits for the developed method were less than 5 pg with retention times and peak area precisions of less than 0.01 and 6%, respectively. This method was successfully applied to river water and soil matrices. To date this is the first work describing the analysis of chemical warfare agent (CWA) degradation products by GC-ICPMS.

Liquid-chromatographic separation and determination of process-related impurities, including a regio-specific isomer of celecoxib on reversed-phase C18 column dynamically coated with hexamethyldisilazane.

A simple and rapid reversed-phase high-performance liquid-chromatographic method for the separation and determination of process-related impurities of celecoxib (CXB) in bulk drugs and pharmaceuticals was developed. The separation of impurities viz., 4-methylacetophenone (I), 1-(4-methylphenyl)-4,4,4-trifluorobutane-1,3-dione (II), 4-hydrazinobenzene sulfonamide (III) and a regio-specific isomer [3-(4-methylphenyl)-5-trifluoromethyl-1H-pyrazole-1-yl]-benzenesulfonamide (IV), was accomplished on an Inertsil ODS-3 column dynamically coated with 0.1% hexamethyldisilazane (HMDS) in acetonitrile:water (55:45 v/v) as a mobile phase and detection at 242 nm using PDA at ambient temperature. The chromatographic conditions were optimized by studying the effects of HMDS, an organic modifier, time of silanization and column temperature. The method was validated and found to be suitable not only for monitoring the synthetic reactions, but also to evaluate the quality of CXB.

Investigation of thermodynamic properties of poly(methyl methacrylate-co-n-butylacrylate-co-cyclopentyl styryl-polyhedral oligomeric silsesquioxane) by inverse gas chromatography.

The thermodynamic properties of poly(methyl methacrylate-co-butyl acrylate-co-cyclo -pentylstyryl polyhedral oligomeric silsesquioxane) (poly(MMA-co-BA-co-styryl-POSS)) were investigated by means of inverse gas chromatography (IGC) using 20 different kinds of solvents as the probes. Some thermodynamic parameters, such as molar heats of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter, partial molar heats of mixing and solubility parameter were obtained to judge the interactions between POSS-contained polymers and solvents and the solubility of the polymers in these solvents. It was found that acetates, aromatic hydrocarbons and hydrocarbon halides were good solvents, n-hexane, ethanol, n-propanol, n-butanol and n-pentanol were moderate solvents, while n-heptane, n-octane, n-nonane, n-decane and methanol were poor solvents for all POSS-contained polymers within the experimental temperature range. Incorporation of POSS in polymer increased the solubility of polymers in solvents, and the more the POSS in polymer was, the better the solubility was and stronger the hydrogen bonding interaction was, but the POSS content in polymers seemed to have no obvious influence on the solubility parameter of polymers.