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1.
Proc Natl Acad Sci U S A ; 116(39): 19311-19317, 2019 09 24.
Artículo en Inglés | MEDLINE | ID: mdl-31501321

RESUMEN

Dimethylsulfide (DMS), a gas produced by marine microbial food webs, promotes aerosol formation in pristine atmospheres, altering cloud radiative forcing and precipitation. Recent studies suggest that DMS controls aerosol formation in the summertime Arctic atmosphere and call for an assessment of pan-Arctic DMS emission (EDMS) in a context of dramatic ecosystem changes. Using a remote sensing algorithm, we show that summertime EDMS from ice-free waters increased at a mean rate of 13.3 ± 6.7 Gg S decade-1 (∼33% decade-1) north of 70°N between 1998 and 2016. This trend, mostly explained by the reduction in sea-ice extent, is consistent with independent atmospheric measurements showing an increasing trend of methane sulfonic acid, a DMS oxidation product. Extrapolation to an ice-free Arctic summer could imply a 2.4-fold (±1.2) increase in EDMS compared to present emission. However, unexpected regime shifts in Arctic geo- and ecosystems could result in future EDMS departure from the predicted range. Superimposed on the positive trend, EDMS shows substantial interannual changes and nonmonotonic multiyear trends, reflecting the interplay between physical forcing, ice retreat patterns, and phytoplankton productivity. Our results provide key constraints to determine whether increasing marine sulfur emissions, and resulting aerosol-cloud interactions, will moderate or accelerate Arctic warming in the context of sea-ice retreat and increasing low-level cloud cover.


Asunto(s)
Aerosoles/análisis , Atmósfera/análisis , Agua de Mar/análisis , Sulfuros/análisis , Regiones Árticas , Clima , Ecosistema , Cubierta de Hielo , Mesilatos/análisis , Mesilatos/metabolismo , Océanos y Mares , Fitoplancton/metabolismo , Estaciones del Año , Sulfuros/metabolismo
2.
J Sep Sci ; 40(17): 3414-3421, 2017 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-28675589

RESUMEN

Methanesulfonic acid is routinely used in pharmaceuticals but can contain potentially genotoxic impurities such as methyl methanesulfonate and ethyl methanesulfonate. The aim of this study was to develop a simple high-performance liquid chromatography with ultraviolet detection method for determining methyl methanesulfonate and ethyl methanesulfonate in methanesulfonic acid. Samples (250 mg) in water/acetonitrile (200 µL) were first combined with 10.0 mol/L sodium hydroxide solution (270 µL). Then they were mixed with 2.0 mg/mL N,N-diethyldithiocarbamate (500 µL), diluted to 5 mL with N,N-dimethylacetamide and allowed to react at 80°C for 1 h. The derivatives were analyzed using gradient high-performance liquid chromatography with ultraviolet detection (277 nm) and structurally elucidated by liquid chromatography with mass spectrometry. With acetonitrile/5 mmol/L ammonium acetate solution as the eluent and 1 mL/min as the flow rate on a C18 column, the derivatives were eluted at 10.6 and 14.8 min. Good linearity (correlation coefficients > 0.999) and low limits of quantitation (0.6 ppm) were obtained. The recoveries were in the range of 80-115% with relative standard deviation < 5.0%. Finally, the established method was successfully used for the determination of methyl methanesulfonate and ethyl methanesulfonate in methanesulfonic acid.


Asunto(s)
Cromatografía Líquida de Alta Presión , Metanosulfonato de Etilo/análisis , Mesilatos/análisis , Metilmetanosulfonato/análisis , Contaminación de Medicamentos
3.
J Sep Sci ; 39(18): 3638-46, 2016 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-27440123

RESUMEN

Analytical methods based on multiplug filtration cleanup coupled with pulse glow discharge-ion mobility spectrometry and liquid chromatography tandem mass spectrometry were developed for the analysis of tricaine mesylate residue in fish and fish-raising water samples. A silica fiber holder and an appropriate new interface were designed to make the direct introduction of the fiber into the pulse glow discharge-ion mobility spectrometry introduction mechanism. The multiplug filtration cleanup method with adsorption mixtures was optimized for the determination of tricaine mesylate in fish samples. Good linear relationships were obtained by the two methods. For fish samples, limits of detection were 6 and 0.6 µg/kg by ion mobility spectrometry and liquid chromatography with tandem mass spectrometry, respectively. The matrix effect of the established liquid chromatography tandem mass spectrometry method was negligible for fish samples but that of the ion mobility spectrometry method was not. The two methods were compared. The ion mobility spectrometry system could be used a rapid screening tool on site with the advantage of rapidity, simplicity, and portability, and the liquid chromatography tandem mass spectrometry system could be used for validation in laboratory conditions with the advantage of lower limit of detection, stability, and precision.


Asunto(s)
Aminobenzoatos/análisis , Cromatografía Liquida/métodos , Filtración/métodos , Espectrometría de Movilidad Iónica/métodos , Mesilatos/análisis , Residuos de Plaguicidas/análisis , Espectrometría de Masas en Tándem/métodos , Contaminantes Químicos del Agua/análisis , Aminobenzoatos/aislamiento & purificación , Animales , Peces , Límite de Detección , Mesilatos/aislamiento & purificación , Alimentos Marinos/análisis , Contaminantes Químicos del Agua/aislamiento & purificación
4.
Environ Sci Technol ; 49(24): 13964-72, 2015 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-26529541

RESUMEN

A number of field observations employing aerosol mass spectrometers (AMS) have demonstrated that organic matter rich in monocarboxylic acids and aliphatic carbonyls originating from cooking activities (the COA factor) contributes significantly to ambient organic matter (OM) in urban environments. Little is known about the contribution and nature of COA in rural localities. We studied the correlation of COA with chemical tracers at a rural site in the Po Valley, Italy. Our statistical approach, based on positive matrix factorization (PMF) shows that the COA factor was clearly linked to local emissions of chloride and methanesulfonic acid (MSA), chemical tracers not associated with cooking emissions, or with combustion sources. While the association with Cl is not understood at this stage, the emission of reduced sulfur compounds, aliphatic carbonyls and monocarboxylic acids is consistent with several agricultural practices (e.g., manure storage) and waste disposal systems (e.g., landfills) which characterize the suburban and rural areas of the Po Valley and of other many populated environments. It is concluded that the nature and origins of the AMS COA factor measured at a rural site are complex and include far more than the emissions from food cooking.


Asunto(s)
Aerosoles/análisis , Contaminantes Atmosféricos/análisis , Espectrometría de Masas/métodos , Agricultura , Contaminantes Atmosféricos/química , Culinaria , Italia , Estiércol , Mesilatos/análisis , Eliminación de Residuos , Población Rural , Compuestos de Azufre/análisis , Instalaciones de Eliminación de Residuos
5.
Anal Chem ; 84(11): 5066-73, 2012 Jun 05.
Artículo en Inglés | MEDLINE | ID: mdl-22530732

RESUMEN

Isothermal titration calorimetry (ITC) is a powerful classical method that enables researchers in many fields to study the thermodynamics of molecular interactions. Primary ITC data comprise the temporal evolution of differential power reporting the heat of reaction during a series of injections of aliquots of a reactant into a sample cell. By integration of each injection peak, an isotherm can be constructed of total changes in enthalpy as a function of changes in solution composition, which is rich in thermodynamic information on the reaction. However, the signals from the injection peaks are superimposed by the stochastically varying time-course of the instrumental baseline power, limiting the precision of ITC isotherms. Here, we describe a method for automated peak assignment based on peak-shape analysis via singular value decomposition in combination with detailed least-squares modeling of local pre- and postinjection baselines. This approach can effectively filter out contributions of short-term noise and adventitious events in the power trace. This method also provides, for the first time, statistical error estimates for the individual isotherm data points. In turn, this results in improved detection limits for high-affinity or low-enthalpy binding reactions and significantly higher precision of the derived thermodynamic parameters.


Asunto(s)
Calorimetría/métodos , Análisis de Inyección de Flujo/estadística & datos numéricos , Animales , Automatización de Laboratorios , Anhidrasa Carbónica II/análisis , Bovinos , Calor , Análisis de los Mínimos Cuadrados , Mesilatos/análisis , Termodinámica
6.
Nature ; 440(7083): 491-6, 2006 Mar 23.
Artículo en Inglés | MEDLINE | ID: mdl-16554810

RESUMEN

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.


Asunto(s)
Ambiente , Hielo , Hierro , Calcio/análisis , Clima , Hierro/análisis , Biología Marina , Mesilatos/análisis , Océanos y Mares , Periodicidad , Sodio/análisis , América del Sur
7.
Molecules ; 17(5): 5319-38, 2012 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-22565482

RESUMEN

A solvent- and halogen-free synthesis of high purity triflate ionic liquids via direct alkylation of organic bases (amines, phosphines or heterocyclic compounds) with methyl and ethyl trifluoromethanesulfonate (methyl and ethyl triflate) has been developed. Cheap and non-toxic dimethyl and diethyl carbonate serve as source for the methyl and ethyl groups in the preparation of methyl and ethyl triflate by this invented process. The properties of ionic liquids containing the triflate anion are determined and discussed.


Asunto(s)
Líquidos Iónicos/síntesis química , Mesilatos/síntesis química , Alquilación , Aminas/química , Compuestos Heterocíclicos/química , Líquidos Iónicos/análisis , Espectroscopía de Resonancia Magnética , Mesilatos/análisis , Estructura Molecular , Fosfinas/química , Solventes/química , Temperatura
8.
Sensors (Basel) ; 11(6): 6425-34, 2011.
Artículo en Inglés | MEDLINE | ID: mdl-22163963

RESUMEN

A low-cost sensor array system for banana ripeness monitoring is presented. The sensors are constructed by employing a graphite line-patterning technique (LPT) to print interdigitated graphite electrodes on tracing paper and then coating the printed area with a thin film of polyaniline (PANI) by in-situ polymerization as the gas-sensitive layer. The PANI layers were used for the detection of volatile organic compounds (VOCs), including ethylene, emitted during ripening. The influence of the various acid dopants, hydrochloric acid (HCl), methanesulfonic acid (MSA), p-toluenesulfonic acid (TSA) and camphorsulfonic acid (CSA), on the electrical properties of the thin film of PANI adsorbed on the electrodes was also studied. The extent of doping of the films was investigated by UV-Vis absorption spectroscopy and tests showed that the type of dopant plays an important role in the performance of these low-cost sensors. The array of three sensors, without the PANI-HCl sensor, was able to produce a distinct pattern of signals, taken as a signature (fingerprint) that can be used to characterize bananas ripeness.


Asunto(s)
Grafito/análisis , Absorción , Compuestos de Anilina/análisis , Bencenosulfonatos/análisis , Alcanfor/análisis , Diseño de Equipo , Etilenos/análisis , Frutas , Gases , Mesilatos/análisis , Musa , Polímeros/química , Espectrofotometría Ultravioleta/métodos , Ácidos Sulfónicos/análisis
9.
J Chromatogr A ; 1642: 462048, 2021 Apr 12.
Artículo en Inglés | MEDLINE | ID: mdl-33744606

RESUMEN

The aim of this work was to expand the applicability range of UHPSFC to series of synthetic and commercialized peptides. Initially, a screening of different column chemistries available for UHPSFC analysis was performed, in combination with additives of either basic or acidic nature. The combination of an acidic additive (13 mM TFA) with a basic stationary phase (Torus DEA and 2-PIC) was found to be the best for a series of six synthetic peptides possessing either acidic, neutral or basic isoelectric points. Secondly, methanesulfonic acid (MSA) was evaluated as a potential replacement for TFA. Due to its stronger acidity, MSA gave better performance than TFA at the same concentration level. Furthermore, the use of reduced percentages of MSA, such as 8 mM, yielded similar results to those observed with 15 mM of MSA. The optimized UHPSFC method was, then, used to compare the performance of UHPSFC against RP-UHPLC for peptides with different pI and with increasing peptide chain length. UHPSFC was found to give a slightly better separation of the peptides according to their pI values, in few cases orthogonal to that observed in UHPLC. On the other hand, UHPSFC produced a much better separation of peptides with an increased amino acidic chain compared to UHPLC. Subsequently, UHPSFC-MS was systematically compared to UHPLC-MS using a set of linear and cyclic peptides commercially available. The optimized UHPSFC method was able to generate at least similar, and in some cases even better performance to UHPLC with the advantage of providing complementary information to that given by UHPLC analysis. Finally, the analytical UHPSFC method was transferred to a semipreparative scale using a proprietary cyclic peptide, demonstrating excellent purity and high yield in less than 15 min.


Asunto(s)
Cromatografía con Fluido Supercrítico/métodos , Mesilatos/análisis , Péptidos/análisis , Agua/química , Secuencia de Aminoácidos , Cromatografía Líquida de Alta Presión/métodos , Péptidos/química , Péptidos Cíclicos/análisis , Espectrofotometría Ultravioleta , Ácido Trifluoroacético/química
10.
Food Chem ; 313: 126132, 2020 May 30.
Artículo en Inglés | MEDLINE | ID: mdl-31927207

RESUMEN

Analytical method was developed for determining the total residue of ethofumesate (ET) herbicide using GC-MS/MS. The ET residues were analyzed as a sum of ET, 2-keto-ethofumesate (KET), and open-ring-2-keto-ethofumesate (OKET) and its conjugate. The extracted samples were partitioned with hexane and NaOH solution. For ET analysis, the hexane layer was cleaned up by a silica gel cartridge prior to GC-MS/MS analysis. For the analyses of the metabolites, the aqueous layer was heated with HCl to hydrolyze the conjugates, thereafter, heated in acetic anhydride to convert OKET to KET, and cleaned up by a silica gel cartridge prior to GC-MS/MS analysis. The method was validated for ET, KET, and OKET in garlic, onion, and sugar beet at 0.3 and 0.01 mg/kg. The recoveries were 94-113%, with relative standard deviations of <6%. The limits of detection were 0.0005 mg/kg for all analytes. The proposed method is suitable for regulatory analysis.


Asunto(s)
Benzofuranos/análisis , Cromatografía de Gases y Espectrometría de Masas , Mesilatos/análisis , Residuos de Plaguicidas/análisis , Cromatografía Líquida de Alta Presión , Ajo/química , Límite de Detección , Cebollas/química , Espectrometría de Masas en Tándem
11.
Electrophoresis ; 30(22): 3918-25, 2009 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-19885888

RESUMEN

A dicationic ion-pairing reagent, N,N'-dibutyl 1,1'-pentylenedipyrrolidinium, was used to form complexes with singly charged anions for their subsequent analysis by CE-ESI-MS in positive ion mode. This methodology offers the advantages of greater versatility and sensitivity relative to direct detection of the anions in negative ion mode, and it can be realized by a number of possible complexation strategies, including pre-column, on-column, and post-column modes. Four model anions, perfluorooctanoate, benzenesulfonate (BZSN), monochloroacetate (MCA), and trifluoromethanesulfonimide were amenable to complexation with the dicationic reagent, yielding singly charged cations with greater m/z. By optimizing various parameters, including the CE separation buffer composition and pH, the concentration of the dicationic reagent, the mode of complexation, the nebulizing gas pressure, and the sheath liquid composition, it was possible to develop a robust CE-ESI-MS method appropriate for the analysis of anions in a tap water sample. By this method, LODs were found to be 20.9 and 1.31 ng/mL for MCA and BZSN, respectively.


Asunto(s)
Acetatos/análisis , Aniones/análisis , Bencenosulfonatos/análisis , Caprilatos/análisis , Electroforesis Capilar/métodos , Fluorocarburos/análisis , Mesilatos/análisis , Pirroles/química , Compuestos de Amonio Cuaternario/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Imidas/análisis , Indicadores y Reactivos , Contaminantes Químicos del Agua/análisis , Abastecimiento de Agua/análisis
12.
J Chromatogr A ; 1591: 131-137, 2019 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-30679046

RESUMEN

The selective and sensitive determination of potential genotoxic methanesulfonate impurities in drug substances is highly challenging. A new method is reported for testing of methyl methanesulfonate (MMS), ethyl methanesulfonate (EMS) and isopropyl methanesulfonate (IPMS) in active pharmaceutical ingredients (APIs). Headspace single drop microextraction (HS-SDME) with room-temperature ionic liquid (RTIL) as extractant was employed to preconcentrate analytes and eliminate the drug matrix simultaneously. In order to increase volatilities for HS extraction and to improve their reactivity of the further derivatization at the same time, sodium iodide (NaI) was added to the sample to derivatize methanesulfonates to the corresponding iodoalkanes. The iodoalkanes in the extract were derivatized with N, N-diethyldithiocarbamate (DDTC) after HS-SDME, followed by separation and detection with high-performance liquid chromatography with ultraviolet detection (HPLC-UV). Several important parameters, including reaction temperature, reaction time and concentration of NaI, sample volume, microdrop volume, stirring rate, salt addition, extraction time, concentration, reaction time and reaction temperature of DDTC were investigated. Under the optimal conditions, LODs and LOQs of all methanesulfonates were 15 ng mL-1 and 40 ng mL-1, respectively. Linearity (correlation coefficient values r > 0.999) and precision (the relative standard deviations were 1.0-4.6%) of six repeated injections were obtained. The recoveries at three spiked concentration levels were all in the range of 86.2-107.5% with the relative standard deviations <3.5%. The method reported here avoids interference of drug substances efficiently and detects methanesulfonate impurities in high sensitivity by HPLC-UV in Imatinib Mesylate and Levofloxacin Mesylate.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Microextracción en Fase Líquida/métodos , Mesilatos/análisis , Ditiocarba/química , Límite de Detección , Reproducibilidad de los Resultados , Yoduro de Sodio/química , Temperatura , Factores de Tiempo
13.
Astrobiology ; 19(4): 506-516, 2019 04.
Artículo en Inglés | MEDLINE | ID: mdl-30615473

RESUMEN

While formaldehyde (HCHO) was likely generated in Earth's prebiotic atmosphere by ultraviolet light, electrical discharge, and/or volcano-created lightning, HCHO could not have accumulated in substantial amounts in prebiotic environments, including those needed for prebiotic processes that generate nucleosidic carbohydrates. HCHO at high concentrations in alkaline solutions self-reacts in the Cannizzaro reaction to give methanol and formate, neither having prebiotic value. Here, we explore the possibility that volcanic sulfur dioxide (SO2) might have generated a reservoir for Hadean HCHO by a reversible reaction with HCHO to give hydroxymethanesulfonate (HMS). We show that salts of HMS are stable as solids at 90°C and do not react with themselves in solution, even at high (>8 M) concentrations. This makes them effective stores of HCHO, since the reverse reaction slowly delivers HCHO back into an environment where it can participate in prebiotically useful reactions. Specifically, we show that in alkaline borate solutions, HCHO derived from HMS allows formation of borate-stabilized carbohydrates as effectively as free HCHO, without losing material to Cannizzaro products. Further, we show that SO2 can perform similar roles for glycolaldehyde and glyceraldehyde, two intrinsically unstable carbohydrates that are needed by various models as precursors for RNA building blocks. Zircons from the Hadean show that the Hadean mantle likely provided volcanic SO2 at rates at least as great as the rates of atmospheric HCHO generation, making the formation of Hadean HMS essentially unavoidable. Thus, hydroxymethylsulfonate adducts of formaldehyde, glycolaldehyde, and glyceraldehyde, including the less soluble barium, strontium, and calcium salts, are likely candidates for prebiotically useful organic minerals on early Earth.


Asunto(s)
Carbohidratos/análisis , Formaldehído/análisis , Mesilatos/análisis , Origen de la Vida , Dióxido de Azufre/análisis , Erupciones Volcánicas , Espectroscopía de Resonancia Magnética con Carbono-13 , Dihidroxiacetona/química , Formaldehído/química , Minerales , Espectroscopía de Protones por Resonancia Magnética , Solubilidad , Sulfitos/análisis
14.
Environ Sci Process Impacts ; 21(11): 1899-1907, 2019 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-31641706

RESUMEN

In the present study analytical methodologies were developed for two newly emerging polar perfluorinated alkyl substances (PFAS), namely F3-MSA, and HFPO-DA, in order to assess the occurrence and levels of these PFAS in Dutch and Belgian waters. Two separate methods were needed for analysing F3-MSA and HFPO-DA. A mixed-mode and a reversed phase C18 method were developed for F3-MSA and HFPO-DA, respectively, using a high resolution Orbitrap Fusion mass spectrometer for detection, yielding satisfactory LOD and LOQ results for both analytes. A sample campaign was performed collecting single grab samples from various locations and different stages of the drinking water production chain. Whereas both PFAS were absent in groundwaters, they were found to be present in surface waters, river bank and dune infiltrates, process water, and drinking water, demonstrating the persistence and mobility of both compounds. Based on provisional health-based guideline values (0.15 µg L-1 for HFPO-DA, 11.9 mg L-1 for F3-MSA), the current levels in drinking water from the suppliers involved in this study do not pose a health risk for the human population. Common removal processes used in drinking water production appeared to remove these polar compounds at most partially. At locations close to potential sources of these chemicals (e.g. fluoropolymer production sites), the quality of surface water or river bank filtrate abstracted for production of drinking water must therefore be monitored.


Asunto(s)
Agua Potable/análisis , Monitoreo del Ambiente/métodos , Fluorocarburos/análisis , Mesilatos/análisis , Contaminantes Químicos del Agua/análisis , Abastecimiento de Agua/normas , Agua Subterránea/química , Humanos , Ríos/química
15.
Food Chem ; 259: 213-218, 2018 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-29680046

RESUMEN

An Electrochemical nonenzymatic sensor was fabricated based on cetyltrimethylammonium bromide (CTAB), chitosan (Chit) and carbon nanotube (CNT) nanocomposite modified glassy carbon electrode. Scanning electron microscopy morphology showed that CNT well dispersed in Chit, while CTAB micelles assembled on the surface of the CNT. Due to the synergetic effect of the three components, excellent electrocatalytic activity towards the oxidation of hydroxymethanesulfinate (HMS) in the presence of both fixed and varying concentrations of sulfite was achieved. An enhanced peak current and expanded peak-to-peak separation between HMS and sulfite was observed. Differential pulse voltammetry was applied to quantify HMS and the calibration curve was linear in the range of 30-800 µM with a detection limit of 9.6 µM. The method was applied in the determination of HMS in food samples collected from local markets, and the results have no remarkable difference with the reference HPLC method.


Asunto(s)
Compuestos de Cetrimonio/química , Quitosano/química , Técnicas Electroquímicas , Mesilatos/análisis , Nanotubos de Carbono/química , Sulfitos/química , Carbono/química , Cetrimonio , Electrodos , Análisis de los Alimentos , Concentración de Iones de Hidrógeno , Límite de Detección , Microscopía Electrónica de Rastreo
16.
J Gen Physiol ; 127(5): 539-55, 2006 May.
Artículo en Inglés | MEDLINE | ID: mdl-16636203

RESUMEN

Voltage clamp fluorometry (VCF) combines conventional two-electrode voltage clamp with fluorescence measurements to detect protein conformational changes, as sensed by a fluorophore covalently attached to the protein. We have applied VCF to a type IIb Na+-coupled phosphate cotransporter (NaPi-IIb), in which a novel cysteine was introduced in the putative third extracellular loop and expressed in Xenopus oocytes. Labeling this cysteine (S448C) with methanethiosulfonate (MTS) reagents blocked cotransport function, however previous electrophysiological studies (Lambert G., I.C. Forster, G. Stange, J. Biber, and H. Murer. 1999. J. Gen. Physiol. 114:637-651) suggest that substrate interactions with the protein can still occur, thus permitting study of a limited subset of states. After labeling S448C with the fluorophore tetramethylrhodamine MTS, we detected voltage- and substrate-dependent changes in fluorescence (DeltaF), which suggested that this site lies in an environment that is affected by conformational change in the protein. DeltaF was substrate dependent (no DeltaF was detectable in 0 mM Na+) and showed little correlation with presteady-state charge movements, indicating that the two signals provide insight into different underlying physical processes. Interpretation of ion substitution experiments indicated that the substrate binding order differs from our previous model (Forster, I., N. Hernando, J. Biber, and H. Murer. 1998. J. Gen. Physiol. 112:1-18). In the new model, two (rather than one) Na+ ions precede Pi binding, and only the second Na+ binding transition is voltage dependent. Moreover, we show that Li+, which does not drive cotransport, interacts with the first Na+ binding transition. The results were incorporated in a new model of the transport cycle of type II Na+/Pi cotransporters, the validity of which is supported by simulations that successfully predict the voltage and substrate dependency of the experimentally determined fluorescence changes.


Asunto(s)
Fluorometría/métodos , Técnicas de Placa-Clamp/métodos , Proteínas Cotransportadoras de Sodio-Fosfato de Tipo II/química , Proteínas Cotransportadoras de Sodio-Fosfato de Tipo II/fisiología , Animales , Transporte Biológico/efectos de los fármacos , Transporte Biológico/fisiología , Cisteína/análisis , Electrofisiología , Femenino , Lenguado , Litio/metabolismo , Mesilatos/análisis , Mesilatos/farmacología , Modelos Biológicos , Oocitos/química , Oocitos/citología , Oocitos/fisiología , Fosfatos/metabolismo , Unión Proteica , Conformación Proteica , Sodio/metabolismo , Proteínas Cotransportadoras de Sodio-Fosfato de Tipo II/efectos de los fármacos , Especificidad por Sustrato , Xenopus laevis
17.
Chemosphere ; 67(9): S22-7, 2007 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-17215020

RESUMEN

In the present investigation, eleven human adipose tissue samples, two seal blubber samples and two pelican muscles samples were analyzed with regard to their concentrations of PCB parent compounds as well as to the respective chiral methylsulfonyl metabolites 3-MeSO2-CB 91, 4-MeSO2-CB 91, 3-MeSO2-CB 95, 4-MeSO2-CB 95, 3-MeSO2-CB 149, 4-MeSO2-CB 149, 3-MeSO2-CB 132, 4-MeSO2-CB 132, 3-MeSO2-CB 174, and 4-MeSO2-CB 174 and the achiral metabolites 3-MeSO2-CB 49, 4-MeSO2-CB 49, 3-MeSO2-CB 101, 4-MeSO2-CB 101, 3-MeSO2-CB 110, 4-MeSO2-CB 110 and 3-MeSO2-DDE. In order to verify enantioselective transformation processes and to compare the different enzymatic transformation pathways in birds and mammals, the enantioselective excesses of the chiral PCB-metabolites were determined by enantioselective gas chromatography with electron capture and mass spectrometric detection using modified cyclodextrin phases, including heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/OV1701 (1:1) for the parent PCBs and heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/SE52 (1:4) for the metabolites, respectively.


Asunto(s)
Tejido Adiposo/química , Diclorodifenil Dicloroetileno/metabolismo , Contaminantes Ambientales/metabolismo , Mesilatos/metabolismo , Músculos/química , Bifenilos Policlorados/metabolismo , Animales , Ciclodextrinas/metabolismo , Diclorodifenil Dicloroetileno/análisis , Contaminantes Ambientales/análisis , Cromatografía de Gases y Espectrometría de Masas , Humanos , Mesilatos/análisis , Bifenilos Policlorados/análisis , Phocidae , Estereoisomerismo
18.
J AOAC Int ; 100(4): 1029-1037, 2017 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-28150570

RESUMEN

The characterization of process-related impurities and degradation products of safinamide mesilate (SAFM) in bulk drug and a stability-indicating HPLC method for the separation and quantification of all the impurities were investigated. Four process-related impurities (Imp-B, Imp-C, Imp-D, and Imp-E) were found in the SAFM bulk drug. Five degradation products (Imp-A, Imp-C, Imp-D, Imp-E, and Imp-F) were observed in SAFM under oxidative conditions. Imp-C, Imp-D, and Imp-E were also degradation products and process-related impurities. Remarkably, one new compound, identified as (S)-2-[4-(3-fluoro-benzyloxy) benzamido] propanamide (i.e., Imp-D), is being reported here as an impurity for the first time. Furthermore, the structures of the aforementioned impurities were characterized and confirmed via IR, NMR, and MS techniques, and the most probable formation mechanisms of all impurities proposed according to the synthesis route. Optimum separation was achieved on an Inertsil ODS-3 column (250 × 4.6 mm, 5 µm), using 0.1% formic acid in water (pH adjusted to 5.0) and acetonitrile as the mobile phase in gradient mode. The proposed method was found to be stability-indicating, precise, linear, accurate, sensitive, and robust for the quantitation of SAFM and its process-related substances, including its degradation products.


Asunto(s)
Alanina/análogos & derivados , Bencilaminas/análisis , Cromatografía Líquida de Alta Presión , Contaminación de Medicamentos , Mesilatos/análisis , Alanina/análisis , Estabilidad de Medicamentos
19.
Environ Sci Pollut Res Int ; 24(1): 644-658, 2017 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-27743329

RESUMEN

The aim of this study was to monitor the sediment, soil and surface water contamination with selected popular triketone herbicides (mesotrione (MES) and sulcotrione(SUL)), atrazine (ATR) classified as a possible carcinogen and endocrine disrupting chemical, as well as their degradation products, in Silesia (Poland). Seventeen sediment samples, 24 soil samples, and 64 surface water samples collected in 2014 were studied. After solid-liquid extraction (SLE) and solid phase extraction (SPE), analytes were determined by high-performance liquid chromatography (HPLC) with diode array detection (DAD). Ten years after the withdrawal from the use, ATR was not detected in any of the collected samples; however, its degradation products are still present in 41 % of sediment, 71 % of soil, and 8 % of surface water samples. SUL was determined in 85 % of soil samples; its degradation product (2-chloro-4-(methylosulfonyl) benzoic acid (CMBA)) was present in 43 % of soil samples. In 17 % of sediment samples, CMBA was detected. Triketones were detected occasionally in surface water samples. The chemometric analysis (clustering analysis (CA), single-factor analysis of variance (ANOVA), N-Way ANOVA) was applied to find relations between selected soil and sediment parameters and herbicides concentration. In neither of the studied cases a statistically significant relationship between the concentrations of examined herbicides, their degradation products and soil parameters (organic carbon (OC), pH) was observed.


Asunto(s)
Sedimentos Geológicos/análisis , Herbicidas/análisis , Contaminantes del Suelo/análisis , Contaminantes Químicos del Agua/análisis , Atrazina/análisis , Cromatografía Líquida de Alta Presión , Ciclohexanonas/análisis , Mesilatos/análisis , Polonia , Extracción en Fase Sólida
20.
J Hazard Mater ; 325: 136-156, 2017 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-27930998

RESUMEN

Triketones, derived chemically from a natural phytotoxin (leptospermone), are a good example of allelochemicals as lead molecules for the development of new herbicides. Targeting a new and key enzyme involved in carotenoid biosynthesis, these latest-generation herbicides (sulcotrione, mesotrione and tembotrione) were designed to be eco-friendly and commercialized fifteen-twenty years ago. The mechanisms controlling their fate in different ecological niches as well as their toxicity and impact on different organisms or ecosystems are still under investigation. This review combines an overview of the results published in the literature on ß-triketones and more specifically, on the commercially-available herbicides and includes new results obtained in our interdisciplinary study aiming to understand all the processes involved (i) in their transfer from the soil to the connected aquatic compartments, (ii) in their transformation by photochemical and biological mechanisms but also to evaluate (iii) the impacts of the parent molecules and their transformation products on various target and non-target organisms (aquatic microorganisms, plants, soil microbial communities). Analysis of all the data on the fate and impact of these molecules, used pure, as formulation or in cocktails, give an overall guide for the assessment of their environmental risks.


Asunto(s)
Herbicidas/análisis , Herbicidas/química , Cetonas/análisis , Cetonas/química , Ciclohexanonas/análisis , Ecosistema , Ecotoxicología , Ambiente , Concentración de Iones de Hidrógeno , Mesilatos/análisis , Fotoquímica , Plantas/efectos de los fármacos , Medición de Riesgo , Suelo , Microbiología del Suelo , Sulfonas/análisis , Temperatura , Agua , Contaminantes Químicos del Agua/química
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