Recovery of some common solvents from protective clothing breakthrough indicator pads by microwave-solvent extraction and gas chromatography

The efficiency of solvent adsorption using Permea-Tec general solvent pads, used for the detection of chemical breakthrough of protective clothing, was determined for methanol, acetone, ethyl methyl ketone, trichloroethylene (TriCE), tetrachloroethylene (TetCE), toluene, m-xylene, and D-limonene. Known volumes of single or mixed solvents were added to pads in the range 0.2-5.0 microliters (0.16-8.13 micrograms). After microwave-solvent extraction (ME) into hexan-1-ol, the samples (0.5-3.0 microliters) of the filtered and extracted solutions were analyzed by gas chromatography. All solvents exhibited > 97% adsorption on the pads at spiking levels of 0.48-0.98 microgram for each solvent. The solvent recovery for the system was calculated for each solvent, with solvents with boiling points below 110 degrees C showing recoveries of > 90%, and with solvents with boiling points above 110 degrees C showing recoveries from 80 to 90%. The recovery precision was good (RSD < or = 4%) for all solvents over the range 1.0-2.5 microliters of applied solvents to pads for ME and 1.0 microliter of extracted solutions for GC analysis.     

Development of a novel colorimetric indicator pad for detecting aldehydes

A colorimetric indicator was developed and a colorimetric indicator pad was fabricated for the rapid detection of aldehydes. The detection pad has two sides: an observation side on top and a barrier on the bottom. The top side contains a reagent which reacts directly with aldehydes to produce a color change, while the bottom side is coated with a double-sided plastic tape barrier to prevent the escape of chemicals. Sensitivity of the indicator pads was determined using the vapor sensitive ASTM F739 technique with the presence of the indicator. A significant indicator color change (yellow to red) occurred about 5 min before the infrared analyzer response of the ASTM method. The chemical principle and reaction characterization of the test are described. The stability and potential interferences of the indicator pad were also examined by directly spiking aldehydes and compounds with other functional groups, respectively, onto the indicator pads. The newly developed aldehyde indicator pad should find utility in detecting aldehydes in both liquid and vapor phases and in collecting aldehyde permeation through PPE for further study.     

Quantitative high-throughput determination of endogenous retinoids in human plasma using triple-stage liquid chromatography/tandem mass spectrometry

A high-throughput ultrasensitive analytical method based on liquid chromatography with positive ion atmospheric pressure chemical ionization (APCI) coupled to tandem mass spectrometric detection (LC/MS/MS) was developed for the determination of all-trans-4-oxo-retinoic acid (at4oxoRA), 13-cis-4-oxo-retinoic acid (13c4oxoRA), 13-cis-retinoic acid (13cRA), all-trans-retinoic acid (atRA) and all-trans-retinol (atROH) in human plasma. A stable isotope of atRA was used as internal standard (IS). The analytes and IS were isolated from 100 microL plasma by acetonitrile mono-phase extraction (MPE) performed in black 96-well microtiterplates. A 100 microL injection was focused on-column and chromatographed on an Agilent ZORBAX SB-C18 rapid-resolution high-throughput (RRHT) column with 1.8-microm particles (4.6 mmx50 mm) maintained at 60 degrees C. The initial mobile phase composition was acetonitrile/water/formic acid (10:90:0.1, v/v/v) delivered at 1.8 mL/min. Elution was accomplished by a fast gradient to acetonitrile/methanol/formic acid (90:10:0.1, v/v/v). The method had a chromatographic total run time of 7 min. An Applied Biosystems 4000 Q TRAP linear tandem mass spectrometer equipped with a heated nebulizer (APCI) ionization source was operated in multiple reaction monitoring (MRM) mode with the precursor-to-product ion transitions m/z 315.4-->297 (4-oxo-retinoic acids), 301.2-->205 (retinoic acids), 305.0-->209 (IS) and 269.2-->93 (retinol) used for quantification. The assay was fully validated and found to have acceptable accuracy, precision, linearity, sensitivity and selectivity. The mean extraction recoveries from spiked plasma samples were 80-105% for the various retinoids at three different levels. The intra-day accuracy of the assay was within 8% of nominal and intra-day precision was better than 8% coefficient of variance (CV) for retinoic acids. Inter-day precision results for quality control samples run over a 12-day period alongside clinical samples showed mean precision better than 12.5% CV. The limit of quantification was in the range of 0.1-0.2 ng/mL and the mass limit of detection (mLOD) was in the range 1-4 pg on column for the retinoic acids. The assay has been successfully applied to the analysis of 1700 plasma samples.     

Determination of organo-zinc based fungicides in timber treatments employing gas chromatographic analysis with mass selective detection and/or inductively coupled plasma atomic emission spectroscopy

A method for the determination of zinc octoate (zinc 2-ethylhexanoate) and acypetacs zinc in occupational hygiene samples and wood treatments formulations is described. The zinc carboxylates are liquid-liquid partitioned between toluene and 1 M HCl, with the liberated acids being extracted into the toluene and zinc (chloride) into the acid. The carboxylic acids are then methylated using trimethylsilyldiazomethane-methanol and the resultant methyl esters are selectively and sensitively analysed by gas chromatography with mass selective detection (GC-MS). Alternatively, the zinc content of the acid extract can be analysed by inductively coupled plasma atomic emission spectroscopy (ICP-AES). GC-MS is the preferred method of analysis for zinc octoate, where a single analyte (methyl-2-ethylhexanoate) is produced for analysis. Because acypetacs zinc contains a complex mixture of carboxylates, quantitative GC-MS analysis of the methyl esters produced is impractical and ICP-AES is the preferred method for quantitation. In this case, GC-MS can be used to confirm the identity of the product used. The analysis of occupational hygiene samples (cotton pads, gloves and socks as well as Tenax tubes and GF/A filters) spiked with metal carboxylates is demonstrated. Recoveries around 70-90% and reproducibilities of 5-23% (n=6-8) were typically achieved for the determination of tin octoate (a surrogate for zinc octoate) at spiking levels ranging from 4 to 190 microg per sampling device. Recoveries around 102-106% and reproducibilities of 10-12% (n=5-6) were typically achieved for acypetacs zinc at spiking levels ranging from 100 mg per sampling device. Reaction yields for the octoate methylation reaction were in the region of 85-87%. The method was used to monitor for occupational exposure to zinc octoate and acypetacs zinc during the application of wood treatments to fences.     

Enantiomeric separation of chiral phenoxy acid herbicides by electrokinetic chromatography. Application to the determination of analyte-selector apparent binding constants for enantiomers

The enantiomeric resolution of chiral phenoxy acid herbicides was performed by electrokinetic chromatography using a cyclodextrin as chiral pseudophase (CD-EKC). A systematic evaluation of several neutral and charged cyclodextrins was made. Among the cyclodextrins tested, (2-hydroxy)propyl beta-cyclodextrin (HP-beta-CD) was found to be the most appropriate for the enantioseparation of phenoxy acids. The influence of some experimental conditions, such as nature and pH of the background electrolyte, chiral selector concentration, and temperature, on the enantiomeric separation of phenoxy acids was also studied. The use of a 50 mM electrolyte solution in ammonium formate at pH 5 and a temperature of 40 degrees C enabled the enantiomeric resolution of four of the six phenoxy acids investigated (2-phenoxypropionic acid, 2(3-chlorophenoxy)propionic acid, 2-(4-chlorophenoxy)propionic acid, and 2-(2,4-dichlorophenoxy)propionic acid) obtaining migration times ranging from 9 to 15 min. Mixtures of the two phenoxy acids not enantiomerically resolved (2-(4-chlorophenoxy)-2-methylpropionic acid and 2-(2,4,5-trichlorophenoxy)propionic acid) and up to three of the phenoxy acids enantiomerically resolved were separated in about 15 min. Finally, the apparent binding constants for each enantiomer-HP-beta-CD pair were calculated at two temperature values (20 and 40 degrees C).     

Reaction of 2,3-Dihalopropionic Acids and Their Derivatives with P- and N-Nucleophiles

3-(Triphenylphosphoniochlorido)acrylic and 2,3-dichloropropionic acids react with triphenylphosphine to form 1,2-bis(triphenylphosphoniochlorido)ethane. Under analogous conditions, 2,3-dibromopropionic acid undergoes debromination followed by triphenylphosphine addition to give, after water treatment, 3-(triphenylphosphoniobromido)propionic acid. 2,3-Dihalopropionitriles react similarly, providing 3-(triphenylphosphoniohalido) propionitriles. The reaction of 2,3-dibromopropionamide with triphenylphosphine was performed to show that E-(triphenylphosphoniobromido)acrylic acid is capable, by contrast to what was reported previously, of reacting with triphenylphosphine. Pyridine forms with 2,3-dihalopropionic acids vinylpyridinium halides, while the reactions with aliphatic amines gives rise to dehydrohalogenation products.     

Polyfunctional pyrazoles. 4. Synthesis of 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]acrylic and-propionic acids

3-(3-Aryl-4-formyl-1-pyrazolyl)propionic acids are converted by Knoevenagel condensation under conditions of microwave activation into 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]acrylic acids. Reduction of the latter with hydrazine hydrate in the presence of Raney nickel gives 3-[3-aryl-1-(2-ethoxycarbonyl)-4-pyrazolyl]propionic acids. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 686–690, May, 2006.     

Synthesis of some 7-substituted 3-chloro-3,4-dihydro-1-hydroxycarbostyrils by the reduction cyclization of α-chloro-β-(4-substituted-2-nitrophenyl)propionic acids

A new method was developed for the synthesis of some 7-substituted 3-chloro-3,4-dihydro-l-hydroxycarbostyrils 3c-g in which α-chloro-β-(4-substituted-2-nitrophenyl)propionic acids 2c-g were reductively cyclized by catalytic hydrogenation over platinum-on-carbon sulfided catalyst. In particular, this method was applied to α-chloro-β-(2-nitrophenyl)propionic acids bearing 4-methyl 2c , 4-ethyl 2d , 4-ethoxy 2e , 4-(n-butyl 2f and 4-phenyl 2g substituents to afford good yields of the corresponding 7-methyl 3c , 7-ethyl 3d , 7-ethoxy 3e , 7-(n-butyl) 3f , and 7-phenyl 3g substituted 3-chloro-3,4-dihydro-l-hydroxycarbostyrils. The various 4-substituted α-chloro-β-(2-nitrophenyl)propionic acids 2c-q were synthesized by reacting the in situ diazotized salts of the appropriate 4-substituted-2-nitroanilines in aqueous acetone with acrylic acid in the presence of cuprous chloride and hydrochloric acid. All compounds prepared in this study were characterized by microanalytical and ir and nmr spectral data.     

Synthesis of Derivatives of (4-Methyl-2-Quinolylthio)acetic and (4-Methyl-2-Quinolylthio)propionic Acids

An efficient synthesis has been developed for derivatives of (4-methyl-2-quinolylthio)acetic and (4-methyl-2-quinolylthio)propionic acids by the reaction of 4-methyl-2-thioxoquinoline with methyl methacrylate, the amide of methacrylic acid, acrylonitrile, ethyl bromoacetate, and ethyl acrylate. The hydrolysis of the resultant intermediates by (quinolylthio)acetic and (quinolylthio)propionic acids gave the corresponding acid products, which are also formed in the reaction of 4-methyl-2-thioxoquinoline with chloroacetic and acrylic acids. The reaction of 4-methyl-2-thioxoquinoline with allyl bromide was studied. The potassium permanganate oxidation of the resultant 2-allylthio-4-methylquinoline led to (4-methyl-2-quinolylthio)acetic acid.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 403–406, April, 2005.     

Determination of volatile fatty acids in landfill leachates by ion-exclusion chromatography

An ion-exclusion chromatographic method with on-line desalinization for the determination of volatile fatty acids in landfill leachates is described. Highly sensitive conductivity detection of the organic acids was achieved by using dilute p-hydroxybenzoic acid solution as an eluent. Interference with mineral acids was reduced by treatment with barium chloride solution prior to desalinization. A silver-loaded cation-exchange guard column for the desalinization was installed in series with the analytical column to avoid the contamination of organic acids. This method features detection limits of 0.01 mg L(-1) formic acid, 0.02 mg L(-1) acetic acid, 0.05 mg L(-1) propionic acid, and 0.1 mg L(-1) butyric acid, respectively, with an injection of 20 microL sample. Application of the on-line desalinization LC method is illustrated for leachate samples from a Japanese sanitary landfill.     

Quantitative leak test for microholes and microtears in whole gloves and glove pieces

The current leak tests for gloves are qualitative. The developed quantitative leak test uses vacuum pressure to draw measured volumes of water to detect microholes/tears in whole gloves and glove pieces. A modified plastic vacuum desiccator interfaced with a Frazier air permeability tester allowed exposure of disposable unsupported/unlined/powderless Kimtech Blue nitrile to 50 mL of water for glove pieces or to 600 mL within a whole glove at vacua of 8–9 in. (20–23 cm) and 11–12 in. (28–30 cm) water gauge, respectively. Punctures of known dimensions were made before testing in specific glove areas using 21-, 22-, 26-, 30-, and 33-gauge needles (outer/inner diameters in micrometres of 873/514, 794/413, 635/311, 476/127, 318/159 and 238/133, respectively). The length of the punctures varied from 0.13 ± 0.01 to 0.80 ± 0.11 mm. Flow rates of water through the holes/tears ranged from 2.5 ± 0.4 to 106 ± 7 mL/min for glove pieces. For whole gloves, the ranges were from 31 ± 9 to 543 ± 110 mL/min in the palm area; and 0.23 ± 0.06 to 82 ± 18 mL/min in the finger/fingertip area. The method quantified tear lengths as short as 0.13 ± 0.01 mm.     

Development of a static headspace gas chromatographic procedure for the routine analysis of volatile fatty acids in wastewaters

An optimised procedure has been developed for the routine analysis of volatile fatty acids in wastewater matrices, using static headspace gas chromatography with flame ionisation detection. Factors such as sample volume, sample pre-treatment and the time and temperature of sample equilibration have been included in an optimisation model designed to provide maximum detector response for acetic, propionic, iso- and n-butyric and iso- and n-valeric acids in the concentration range 0-1000 mg/l. Optimal headspace conditions were observed when equilibrating at 85 degrees C for 30 min, using a 2.0 ml sample volume with the addition of 1.0 ml of NaHSO4 (62%, w/v) into standard 22.3 ml vials. 2-Ethylbutyric acid was used as an internal standard. The suitability of ordinary least squares regression and weighted least squares regression models for the purposes of calibration and quantification were investigated. A weighted least squares linear regression model applied to the heteroscedastic data provided lower detection limits, e.g. 3.7 and 3.3 mg/l for acetic and propionic acids.     

Reactions of dithiocarbamic acids derived from alkaloids, morpholine, and piperidine with acrylic acid and its derivatices

-(Thiocarbamoylthio)propionic acids derived from alkaloids, morpholine, and piperidine and their esters, amides, and nitriles were prepared by reactions of the corresponding dithiocarbamic acids with acrylic acid and its derivatives. Some of the compounds were tested for insecticidal activity.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1336–1339.Original Russian Text Copyright © 2004 by Zhivotova, Gazaliev, Ibraev, Fazylov, Kasenov.     

Analysis of isomeric long-chain hydroxy fatty acids by tandem mass spectrometry: application to the diagnosis of long-chain 3-hydroxyacyl CoA dehydrogenase deficiency

Acetyl trimethylaminoethyl ester iodide derivatives have been used to selectively analyze isomeric long-chain hydroxy fatty acids by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The binary derivatives of 2-, 3-, 12- and 16-hydroxypalmitic acids afford remarkably different product ion spectra. Further discrimination between isomers is possible by acylating with pivaloyl chloride. 2- and omega-Hydroxy long-chain fatty acids form pivaloyl esters in quantitative yield whereas other secondary alcohols only partially react. Cotton-based filter paper used for blood collection contains substantial amounts of esterified long-chain hydroxy fatty acids. From the product ion spectra of the acetyl trimethylaminoethyl esters the hydroxydocosanoic and -tetracosanoic acids are >90% omega-hydroxy. All remaining saturated and unsaturated hydroxy acids are >90% 2-hydroxy acids. A method for the quantification of free 3-hydroxypalmitic acid in plasma by ESI-MS/MS for the diagnosis of long-chain 3-hydroxyacyl CoA dehydrogenase deficiency (LCHAD) is described. Median plasma concentrations of 0.43 micromol/L (control, n = 22) and 12.2 micromol/L (LCHAD, n = 3) were obtained from 5 microL plasma samples.     

Comparison of permeation resistance of protective gloves to organic solvents with ISO, ASTM and EN standard methods

In this study, the permeation resistance of nitrile and neoprene gloves to benzene and 1,2-dichloroethane was investigated using two permeation cells according to the ISO 6529, ASTM F739, and EN 374-3 standard test methods. The permeability coefficients were found to significantly increase with the flow rate of the collection medium. The appropriate flow rate of nitrogen collection should be higher than 75 and 150 mL/min for the ISO 6529 and ASTM F739 cells, respectively. For an open-loop system, the permeability coefficient of the ISO 6529 cell was obviously greater than that of the ASTM F739 cell, and the difference between these two cells was statistically significant. On the other hand, the breakthrough time was about 20–30 min for either the ISO 6529 or ASTM F739 cell at different flow rates of nitrogen collection. Fick's diffusion coefficient and solubility of permeant in the polymer glove can be specified as alternative test results for standard methods.     

Research on imidazo[1,2-a]benzimidazole derivatives. 25. Reaction of 2,9-disubstituted imidazo[1,2-a]benzimidazoles with acrylic acids and their derivatives

The substitutive addition of acrylic acids and their esters, amides, and nitriles to 2,9-disubstituted imidazo[1,2-a]benzimidazoles, which leads to 3-(imidazo[1,2-a]benzimidazol-3-yl)propionic acids and their derivatives, was studied. The rate of addition depends on the structure of the unsaturated compound, the nature of the substituent in the 2 position, the magnitude of the charge on the carbon atom in the 3 position of the heteroring, and the reaction conditions. The addition proceeds most smoothly in polyphosphoric acid (PPA). In the case of acrylonitrile imidazo[1,2-a]benzimidazol-3-ylpropionic acid amides were isolated in PPA. In the reaction of - or -substituted acrylic acids with 2-phenylimidazo[1,2-a]benzimidazoles in PPA, in addition to the corresponding imidazo[1,2-a]benzimidazol-3-ylpropionic acids, products of their intramolecular cyclodehydration at the ortho position of the phenyl substituent are formed.See [1] for Communication 24.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1496–1502, November, 1987.     

Allergenic compounds on the inner and outer surfaces of natural latex gloves: MALDI mass spectrometry and imaging of proteinous allergens

Natural latex gloves are the cause of a severe health problem to an increasing number of healthcare workers or patients due to the presence of protein allergens as Hevein or Rubber Elongation Factor (REF). One of the most challenging problems is the in situ localization of theses allergens in, e.g. gloves, to estimate the allergenic potential of the latex material. A sample preparation protocol applying a binary matrix-assisted laser desorption/ionization(MALDI) matrix containing alpha-cyano-4-hydroxy cinnamic acid (CHCA) and 2,5-dihydroxy benzoic acid (DHB) on trifluoro acetic acid (TFA) etched latex glove surfaces allowed the direct determination (exact molecular weight) of Hevein, REF and a truncated form of REF (tREF) within nine different brands of natural latex gloves by means of MALDI-TOF-MS in the linear mode. MALDI mass spectrometry demonstrated that Hevein, tREF and REF were present on the inner surfaces (in direct contact with the skin) of many, but not all, investigated gloves without any prior extraction procedure. Additionally, different isoforms of the allergen Hevein were detected (exhibiting ragged C-termini). tREF and REF could always be detected beside each other, but were not observed on every latex glove sample, which contained Hevein. It was also demonstrated that there is a significant difference in terms of proteins and polymers between inner and outer surfaces of gloves, which helps to explain the different allergenic potential of these.MALDI imaging allowed for the first time the unambiguous localization of all three allergens in parallel and showed that Hevein was present on 36% of the investigated area of a latex glove with a certain localization, whereupon, tREF and REF were only found on 25% of the investigated material.     

Synthesis of (2-methylquinolin-4-ylsulfanyl)-substituted acetic and propionic acids and propionitriles

A procedure has been developed for the synthesis of (2-methylquinolin-4-ylsulfanyl)-substituted acetic and propionic acids and propionitriles having methyl, methoxy, or carboxy groups or halogen atom in position 6 or 8 of the quinoline ring via reactions of the corresponding substituted 2-methylquinoline-4-thiols with chloroacetic or acrylic acid and acrylonitrile.     

Development and validation of a capillary electrophoresis method for the measurement of short-chain organic acids in natural rubber latex

Short-chain organic acid contents in serum of natural latex are interesting to measure and capillary electrophoresis (CE) has proved to be a good tool for their study. In the present work a method has been developed to identify the short-chain organic acids present in sera of natural rubber latex (oxalic, formic, fumaric, aconitic, succinic, malic, glutaric, citric, acetic, glycollic, propionic and quinic acids), the separation was optimised and the quantification method validated. The separation was performed on a CE system with UV detection at 200 nm. The separation was carried out with an uncoated fused-silica capillary (57 cm x 50 microm I.D.) and was operated at -10 kV potential. The separation buffers were prepared with 0.5 M H3PO4, 0.5 mM cetyltrimethylammonium bromide and pH adjusted by adding NaOH to 6.25 except for propionic acid which was better measured at pH 7.00. Validation parameters are adequate and limits of detection range from 0.005 mM to 1.6 mM. Short-chain organic acids were measured with this method in sera of three different types of latex.     

Extraction and percolation of PAEs from chemical protective gloves

Phthalates (PAEs) have high solubility in polymers and are added as plasticisers to increase the flexibility and plasticity of polymeric materials. In this study, methanol, hexane, ethyl ether and acetone were used for the extraction of PAEs from chemical protective gloves at temperatures of 20–80 °C. DEHP (di-2-ethylhexyl phthalate) and DBP (di-n-butyl phthalate) were extracted from neoprene, nitrile and PVC glove samples using the above four solvents. The extraction level of DEHP from the glove samples was proportional to the Log K_ow values of the extraction solvents. This result implied that PAEs were more soluble in non-polar solvents and were likely to be extracted from the gloves. Increasing the extraction temperature resulted in a higher extraction of DBP and DEHP from the gloves. In the ASTM F739 permeation method, the aromatic solvents permeated through the glove samples and dissolved DEHP. If the permeant and DEHP had similar solubility parameters, DEHP was likely to be leached from the gloves. The modelling results indicated that the permeation behaviour of the organic solvent in the PVC glove was non-Fickian diffusion. It was speculated that the plasticiser increased the diffusion coefficients of the permeants in the PVC gloves. This study suggested that the potential dissolution and leaching of PAEs from chemical protective gloves should be a concern for workers who handle organic solvents.