Host factors in occupational diisocyanate asthma: a Swiss longitudinal study

Objective: To investigate the usefulness of surrogates for individual susceptibility to organic diisocyanates in occupational asthma. Subjects: All new cases declared to the Swiss National Accident Insurance Company (SUVA) for establishment of a case for compensable occupational disease during 1993. Sixty-nine persons, of whom three were women, were suspected of having occupational asthma due to isocyanates. Of these, 47 subjects fulfilled the criteria to be accepted as an occupational disease case. Methods: All subjects were studied clinically and gave a blood sample for the phenotyping of their alpha-antitrypsin status and for immunological studies. The subjects were also given a peroral dose of caffeine for the determination of their N-acetylation capacity. Finally, those with an occupational disease were subjected to the methacholine provocation test. Results: Forty-four persons with occupational disease, out of 47, were heterozygous antitrypsin carriers and/or slow acetylators of primary amines. In the bronchial provocation with methacholine, 12 of these subjects had an unaltered response and seven had a mild reaction, 13 a moderate one and 15 a severe reaction. Interpretation: The study confirms the finding that slow N-acetylators are susceptible to asthma from exposure to common diisocyanate monomers at work. The same applies to heterozygous antitrypsin-phenotype carriers. Thus, the use of these markers may reinforce the diagnostic procedure, but they cannot completely replace the immunological tests. [Authors]

Controlled dynamic generation of standard 1,6-hexamethylene diisocyanate aerosols

A procedure for the dynamic generation of 1,6-hexamethylene diisocyanate (HDI) aerosol atmospheres of 70 micrograms m-3 (0.01 ppm) to 1.75 mg m-3 (0.25 ppm), based on the precise control of the evaporation of pure liquid HDI and subsequent dilution with air, was developed. The apparatus consisted of a home-made glass nebulizer coupled with a separation stage to exclude non-respirable droplets (greater than 10 microns). The aerosol concentrations were achieved by passing air through the nebulizer at 1.5-4.5 l. min-1 to generate dynamically 0.01-0.25 ppm of diisocyanate in an experimental chamber of 8.55 m3. The distribution of the liquid aerosol was established with an optical counter and the diisocyanate concentration was determined from samples collected in impingers by a high-pressure liquid chromatographic method. The atmospheres generated were suitable for the evaluation both of sampling procedures full scale, and of analytical methods: at 140 micrograms m-3 (0.02 ppm) they remained stable for 15-min provocation tests in clinical asthma, as verified by breath-zone sampling of exposed patients.

Urinary hexane diamine to assess respiratory exposure to hexamethylene diisocyanate aerosol: a human inhalation study

The use of urinary hexane diamine (HDA) as a biomarker to assess human respiratory exposure to hexamethylene diisocyanate (HDI) aerosol was evaluated. Twenty-three auto body shop workers were exposed to HDI biuret aerosol for two hours using a closed exposure apparatus. HDI exposures were quantified using both a direct-reading instrument and a treated-filter method. Urine samples collected at baseline, immediately post exposure, and every four to five hours for up to 20 hours were analyzed for HDA using gas chromatography and mass spectrometry. Mean urinary HDA (microg/g creatinine) sharply increased from the baseline value of 0.7 to 18.1 immediately post exposure and decreased rapidly to 4.7, 1.9 and 1.1, respectively, at 4, 9, and 18 hours post exposure. Considerable individual variability was found. Urinary HDA can assess acute respiratory exposure to HDI aerosol, but may have limited use as a biomarker of exposure in the workplace. [Authors]

Toluene permeabilization differentially affects F- and P-type ATPase activities present in the plasma membrane of Streptococcus mutans

Streptococcus mutans membrane-bound P- and F-type ATPases are responsible for H+ extrusion from the cytoplasm thus keeping intracellular pH appropriate for cell metabolism. Toluene-permeabilized bacterial cells have long been used to study total membrane-bound ATPase activity, and to compare the properties of ATPase in situ with those in membrane-rich fractions. The aim of the present research was to determine if toluene permeabilization can significantly modify the activity of membrane-bound ATPase of both F-type and P-type. ATPase activity was assayed discontinuously by measuring phosphate release from ATP as substrate. Treatment of S. mutans membrane fractions with toluene reduced total ATPase activity by approximately 80% and did not allow differentiation between F- and P-type ATPase activities by use of the standard inhibitors vanadate (3 µM) and oligomycin (4 µg/mL). Transmission electron microscopy shows that, after S. mutans cells permeabilization with toluene, bacterial cell wall and plasma membrane are severely injured, causing cytoplasmic leakage. As a consequence, loss of cell viability and disruption of H+ extrusion were observed. These data suggest that treatment of S. mutans with toluene is an efficient method for cell disruption, but care should be taken in the interpretation of ATPase activity when toluene-permeabilized cells are used, because results may not reflect the real P- and F-type ATPase activities present in intact cell membranes. The mild conditions used for the preparation of membrane fractions may be more suitable to study specific ATPase activity in the presence of biological agents, since this method preserves ATPase selectivity for standard inhibitors.

A study of the thermal decomposition of allyl t-butyl peroxide and 3-hydroperoxy-1-propene (allyl hydroperoxide) in toluene /|nby Krishnankutty Nair V. G. -- 260 St. Catharines [Ont. : s. n.],

Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.

Experimental investigation of optical limiting and thermal lensing in toluene solutions of C70

Optical limiting and thermal lensing studies are carried out in C70–toluene solutions. The measurements are performed using 9-ns pulses generated from a frequencydoubled Nd:YAG laser at 532 nm. Optical limiting studies in fullerene molecules lead to the conclusion that reverse saturable absorption is the major mechanism for limiting. Analysis of thermal lensing measurements showed a quadratic dependence of thermal lens signal on incident laser energy, which also supports the view that optical limiting in C70 arises due to sequential two-photon absorption via excited triplet state (reverse saturable absorption).

Pulsed photoacoustic technique to study nonlinear processes in liquids: Results in toluene

Pulsed photoacoustic measurements have been carried out in toluene at 532 nm wavelength using a Q-switched frequency doubled Nd:YAG laser. The variation of photoacoustic signal amplitude with incident laser power indicates that at lower laser powers one photon absorption takes place at this wavelength while a clear two photon absorption occurs in this liquid at higher laser powers. The studies made here demonstrate that pulsed photoacoustic technique is simple and effective for the investigation of multiphoton processes in liquids.

Photoacoustic signal saturation and optical limiting in C70-toluene solution

Pulsed photoacoustic studies in solutions of C70 in toluene are made using the 532-nm radiation from a frequency-doubled Nd:YAG laser. It is found that contrary to expectation, there is no photoacoustic (PA) signal enhancement in the power-limiting range of laser fluences. Instead, the PA signal tends to saturate during optical power-limiting phenomenon. This could be due to the enhanced optical absorption from the photoexcited state and hence the depletion of the ground-state population. PA measurements also ruled out the possibility of multiphoton absorption in the C70 solution. We demonstrate that the nonlinear absorption leading to optical limiting is mainly due to reverse saturable absorption.

A Study of Photoacoustic Effects and Optical Limiting in the Solution of C60 in Toluene

Pulsed photoacoustic studies in solution of C60 in toluene have been made using the 532 nm radiation from a frequency doubled Nd:YAG laser. Though C60 is found to exhibit the phenomenon of optical limiting, the results on photoacoustic measurements do not give any indication of multiphoton transitions as suggested in some of the earlier works. Results of photoacoustic measurements show that excited state absorption is the dominant process responsible for optical limiting while phenomena like nonlinear scattering may contribute to a lesser extent.

Studies on polyurethane elastomers based on liquid natural rubber

In the present study, the photochemical depolymerisation of NR in toluene, in presence of H202 and a homogenizing solvent (Methanol/Tetrahydro— furan) so as to get hydroxyl terminated liquid natural rubber (HTNR) has been carried out. The copolymeri— sation of this product with butane 1,4 diol and toluene 2,4 diisocyanate in presence of a catalyst, dibutyl tin dilaurate, to produce polyurethanes with HTNR soft segments is also reported. The preparation of block copolymers based on poly(ethylene oxide) with varying molecular weights and HTNR are also discussed along with a detailed study on their thermal and mechanical properties

Micellar catalysis for partial oxidation of toluene to benzoic acid in supercritical CO2: effects of fluorinated surfactants

One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reponed for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO2 using the principle of micellar catalysis. [CF3(CF2)(8)COO](2)Co.xH(2)O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co2+ cations in scCO(2)) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water-CO2 mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 degreesC. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF3(CF2)(8)COO](2)Mg.yH(2)O/Co(II) acetate is as effective as the [CF3(CF2)(8)COO](2)Co.xH(2)O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO(2) can be easily separated via CO2 depressurisation and be reused without noticeable deactivation. (C) 2003 Elsevier B.V. All rights reserved.

Reduction of enantioselectivity in the kinetic disposition and metabolism of verapamil in rats exposed to toluene

Toluene and verapamil are subject to extensive oxidative metabolism mediated by CYP enzymes, and their interaction can be stereoselective. In the present study we investigated the influence of toluene inhalation on the enantioselective kinetic disposition of verapamil and its metabolite, norverapamil, in rats. Male Wistar rats (n = 6 per group) received a single dose of racemic verapamil (10 mg/kg) orally at the fifth day of nose-only toluene or air (control group) inhalation for 6 h/day (25, 50, and 100 ppm). Serial blood samples were collected from the tail up to 6 h after verapamil administration. The plasma concentrations of verapamil and norverapamil enantiomers were analyzed by LC-MS/MS by using a Chiralpak AD column. Toluene inhalation did not influence the kinetic disposition of verapamil or norverapamil enantiomers (p > 0.05, Kruskal-Wallis test) in rats. The pharmacokinetics of verapamil was enantioselective in the control group, with a higher plasma proportion of the S-verapamil (AUC 250.8 versus 120.4 ng.h.mL(-1); p <= 0.05, Wilcoxon test) and S-norverapamil (AUC 72.3 versus 52.3 ng.h.mL(-1); p <= 0.05, Wilcoxon test). Nose-only exposure to toluene at 25, 50, or 100 ppm resulted in a lack of enantioselectivity for both verapamil and norverapamil. The study demonstrates the importance of the application of enantioselective methods in studies on the interaction between solvents and chiral drugs.

Benzene, toluene and xylene biodegradation by Pseudomonas putida CCMI 852

Meio mineral líquido contendo benzeno (B) ou tolueno (T) ou xileno (X) a 100 mg L-1 e suas misturas de BT, BX e TX (50 + 50 mg L-1 cada mistura) e BTX (33,3 + 33,3 + 33,3 mg L-1 cada mistura) foram utilizados para avaliar a atividade de degradação de B, T e X por Pseudomonas putida CCMI 852 contendo um plasmídeo TOL. Após 18 a 24 horas de homogenização da mistura, o inoculo foi adicionado e o decréscimo da concentração dos solventes foi determinado entre 24 e 25 horas por GC. Pseudomonas putida CCMI 852 foi capaz de metabolizar T e X, mas não B. Na mistura BTX, B não foi metabolizado também e a velocidade de degradação de T e X decresceu cerca de 50% comparado com soluções contendo apenas T ou X.

Thermo-reversible sol-gel transition of TiO2 nanoparticles with surface modified by p-toluene sulfonic acid

In this paper an unprecedent thermo-reversible sol-gel transition for titania nanoparticles dispersed in a solution of p-toluene sulfonic acid (PTSH) in isopropanol is reported. The sol formed by the thermo-hydrolysis at 60 degrees C of titanium tetraisopropoxide (Ti((OPr)-Pr-i)(4)) reversibly changes into a turbid gel upon cooling to room temperature. Turbidimetric measurements performed for samples containing different nominal acidity ratios (A = [PTSH]/[Ti]) have evidenced that the gel transformation temperature increases from 20 to 35 degrees C as the [PTSH]/[Ti] ratio increases from 0.2 to 2.0. SAXS results indicate that the thermo-reversible gelation is associated to a reversible aggregation of a monodisperse set of titania nanoparticles with average gyration radius of approximate to 2 nm. From the different PTSH species evidenced by Raman spectroscopy and TG/DTA of dried gels we proposed that the then-no-reversible gelation in this systems is induced by the formation of a supramolecular network, in which the protonated surface of nanoparticles is interconnected through cooperative hydrogen bonds between -SO3 groups of p-toluene sulfonic acid. (C) 2009 Elsevier Ltd. All rights reserved.