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PubMed1976

Fluorescence of tryptophan-containing peptides on paper or silica gel after treatment with formaldehyde, formaldehyde-ozone or formaldehyde-hydrochloric acid.

Sensitive and specific procedures for the chromatographic detection of tryptophan and tryptophan-containing peptides are described. Formaldehyde gas induces strong and characteristic fluorescence from tryptophan and peptides with NH2-terminal tryptophan residues on silica gel. On filter-paper, the detection of small amounts of these compounds requires the additional use of an oxidant, such as ozone. Treatment with formaldehyde-hydrochloric acid was used as a method for inducing fluorescence from tryptophan-containing peptides regardless of the position of the tryptophan residue in the peptide molecule. This reaction is useful for the chromatographic demonstration of small amounts of such peptides on both paper and silica gel. The spectral properties of the fluorophores of such tryptophan-containing peptides are distinctive and serve to distinguish them from all other known biogenic compounds that are capable of giving fluorescence with formaldehyde.

Chromatography, Gel↗

PubMed1990

The movement of blood formaldehyde in methanol intoxication. II. The movement of blood formaldehyde and its metabolism in the rabbit.

The movement of blood formaldehyde in rabbits that were intoxicated with methanol has been investigated by simple headspace gas chromatography-mass spectrometry for the microdetermination of formaldehyde in the blood. When methanol alone was administered to rabbits orally, formaldehyde could not be detected in the blood. Further, in an experiment on the metabolism of methanol in vitro, formaldehyde was not detected in specimen samples but formate was. In contrast, when methanol was orally administered to rabbits that had been pretreated with diethyldithiocarbamate (DDC), an aldehyde dehydrogenase (ALDH) inhibitor, 17 to 33 microM of formaldehyde were detected in the blood 4 hours later. However, formaldehyde was not detected in the blood when methanol was orally administered to rabbits that had been pretreated with pyrazole, an alcohol dehydrogenase (ADH) inhibitor. After rabbits were given an intravenous administration of formaldehyde, and on the addition of formaldehyde to a rabbit liver homogenate and blood, the formaldehyde in both instances was metabolized rapidly. Formaldehyde that was not metabolized within 10 to 15 minutes, however, bound to the tissue proteins. Therefore, according to the results of this study, formaldehyde was seen to be rapidly metabolized to formate without accumulating in the blood or binding to the tissue proteins. Formaldehyde thus appears to have little influence on the symptoms of methanol poisoning.

Animals↗

PubMed1992

Allergic contact dermatitis from formaldehyde. A case study focussing on sources of formaldehyde exposure.

Formaldehyde is a common contact allergen. The prognosis of formaldehyde-sensitive patients is generally considered to be bad because of widespread exposure to formaldehyde. 11 patients with eczema and a positive patch test to formaldehyde were interviewed by a dermatologist and a toxicologist/chemist and instructed to fill in a questionnaire on exposure to chemical products. The content of formaldehyde and formaldehyde releasers in such products was examined using the database of the Danish Product Register (PROBAS) and by supplemental inquiries of manufacturers or importers. All the patients used one or more products containing formaldehyde or formaldehyde releasers. Sources of exposure were cosmetics and personal care products, dishwashing liquids, water-based paints, photographic products, etc. Patients were advised to use alternatives to those products containing formaldehyde or formaldehyde releasers. The status of 10 out of the 11 patients' eczema at follow-up was about 1/3 healed, 1/3 improved and in 1/3 no change. When the relevance of positive patch test reactions to formaldehyde was based on information obtained on exposure, a very high rate of current relevance was found. Computerized data on product composition allows the screening of products for contact allergens and also generates lists of contact allergens indicated for patch testing, based on the patients' own products.

Adult↗

PubMed1991

Demonstration of formaldehyde dehydrogenase activity in formaldehyde-resistant Enterobacteriaceae.

Clinical isolates of different Enterobacteriaceae strains and genetically modified variants which were resistant to the disinfectant formaldehyde were investigated. In cell-free extracts of all formaldehyde-resistant strains a glutathione-dependent formaldehyde dehydrogenase activity was demonstrated. In contrast cell extracts from formaldehyde sensitive strains did not show any formaldehyde dehydrogenase activity. The enzymatic degradation of formaldehyde seems to play an important role in formaldehyde resistance.

Aldehyde Oxidoreductases↗

PubMed1989

Proallergens of formaldehyde applied in patch testing of formaldehyde contact allergy.

The ability of the nonliquid, nonvolatile proallergen of formaldehyde, N-hydroxymethylsuccinimide, to test for contact allergy to formaldehyde has been investigated by in vitro penetration studies in human epidermis. Compared with the standard test, 1% formaldehyde in water, N-hydroxymethylsuccinimide equal to 0.8 mg formaldehyde gave a similar penetration profile. This is explained by cleavage of N-hydroxymethylsuccinimide into formaldehyde and carrier (succinimide) by transepidermal water on the surface of the skin. Results were confirmed by a guinea pig maximazation test on animals sensitized to formaldehyde and in a preliminary clinical study on nine patients with known allergy to formaldehyde.

Administration, Cutaneous↗

PubMedDate not supplied

Formaldehyde content of milk in goats fed formaldehyde-treated soybean oil-meal.

Formaldehyde is used in ruminant feeding for different purposes including the protection of dietary proteins from ruminal degradation. The formaldehyde content of milk of goats fed various levels of formaldehyde-treated soybean oil-meal has been determined by using a sensitive HPLC method. Results showed a significant linear correlation between ingested formaldehyde and formaldehyde concentration in milk. About 0.02% of ingested formaldehyde was excreted in milk, as free formaldehyde.

Animal Feed↗

PubMedDate not supplied

Release of formaldehyde and melamine from tableware made of melamine-formaldehyde resin.

The relationship between the concentrations of formaldehyde and melamine released into 4% acetic acid from dishes and bowls made of melamine-formaldehyde resin was determined. The average concentrations in the migration solution after the sample had been treated at 60, 80, and 95 degrees C for 30 min with 4% acetic acid were 0.0 +/- 0.1, 0.5 +/- 0.4 and 3.0 +/- 2.2 ppm, respectively for formaldehyde and 0.04 +/- 0.07, 0.21 +/- 0.20 and 1.19 +/- 1.18 ppm, respectively for melamine. The correlation between the concentrations of formaldehyde and melamine released at 95 degrees C was y=0.4858x-0.2728 (r=0.8860), where y is melamine concentration (ppm), x is formaldehyde concentration (ppm) and r is the correlation coefficient. The molar concentration ratios of formaldehyde to melamine (F/M ratio) were 15.4 +/- 11.6 at 80 degrees C and 14.9 +/- 10.1 at 95 degrees C. Hence the release of both migrants was affected by temperature but the F/M ratio was not affected. The release of both compounds was was increased on repetition of the migration test at 95 degrees C but their concentrations remained constant after the tenth and seventeenth repetitions of the treatment. During this period, the F/M ratio decreased according to the equation 1n y=-1.4344 1n x+3.7814 (r=-0.9984) for a sample before the tenth repetition of the treatment and remained between 1.7 and 1.9 after the twelfth repetition, where y is the F/M ratio and x is the number of repetitions of the treatment.

Acetates↗

PubMed1989

The sodium cycle in methanogenesis. CO2 reduction to the formaldehyde level in methanogenic bacteria is driven by a primary electrochemical potential of Na+ generated by formaldehyde reduction to CH4.

CH4 formation from CO2 and H2 rather than from formaldehyde and H2 in methanogenic bacteria is inhibited by uncouplers, indicating that CO2 reduction to the formaldehyde level is energy-driven. We report here that in Methanosarcina barkeri the driving force is a primary electrochemical sodium potential (delta mu Na+) generated by formaldehyde reduction to CH4. This is concluded from the following findings. 1. CO2 reduction to CH4 was insensitive towards protonophores, when the Na+/H+ antiporter was inhibited; under these conditions delta mu Na+ was 120 mV (inside negative), whereas both delta mu H+ and the cellular ATP content were low. 2. CO2 reduction to CH4, rather than formaldehyde reduction, was sensitive towards Na+ ionophores, which dissipated delta mu Na+. 3. CO2 reduction to CH4, in the presence of protonophores and Na+/H+ antiport inhibitors, was coupled with the extrusion of 1-2 mol Na+/mol CH4, and formaldehyde reduction to CH4 was coupled with the extrusion of 3-4 mol Na+/mol CH4. Thus during CO2 reduction to the formaldehyde level 2-3 mol Na+ were consumed.

Amiloride↗

PubMed1979

[Effects of ventilation with defined formaldehyde concentrations on lung function and lung structures. Animal experiments on the noxiousness of formaldehyde residues after disinfection in the aseptor (author's transl)].

Having seen the development of fatal pneumonias in ventilated patients, the cause of which was assumed to be the presence of residual traces of formaldehyde in the air in the respirator Kilian and Haug showed in 1973 initial formaldehyde concentrations up to 0.2 ppm in the ventilatory air of respirators correctly disinfected in the Aseptor. To study the effects of formaldehyde on lung function and lung structures, 23 young pigs were automatically ventilated with defined formaldehyde concentrations during 6 hours. The concentrations used were 0.02 ppm, 0.2 ppm and 2.0 ppm (double of the maximum permissible concentration). We found no differences in lung function, as shown by compliance measurements and arterial blood gas analysis. No radiological differences were in the thorax. Histologically, there were only slight alterations in lung structure in the group ventilated with double the maximum permissible concentration of formaldehyde. We conclude that the disinfection of respirators using formaldehyde in the Aseptor will remain the method of choice.

Animals↗

PubMed1986

Evaluation of the Du Pont Pro-Tek Formaldehyde Badge and the 3M Formaldehyde Monitor.

The 3M Formaldehyde Monitor and the DuPont Pro-Tek Formaldehyde Badge were evaluated for performance and reliability. This evaluation revealed that the 3M monitor results were variable and lower than reference concentrations determined independently. When the monitors were humidified before use and then exposed in humid (ca. 80% RH) formaldehyde-containing atmosphere, the monitors did give accurate results. Results of additional experiments led to the conclusion that quantitative reaction between formaldehyde generated in our chamber and the absorbent pad in the 3M monitor required the presence of a minimum level of absorbed water. The DuPont badges gave good agreement with the reference concentrations determined independently under the following conditions: sampling period of 1 to 12 hr with a minimum integrated sample loading of 4 ppm-hr; at least 3 m/min (10 ft/min) face velocity; correction for blank badges; and correction for loss of reagent from the samples. The evaluation indicated that the DuPont badge was not well suited to short term sampling and was subject to evaporation of liquid from the absorbing liquid blister. Blank values also were found to be variable, necessitating the analysis of several blanks to be used for blank correction with each set of samples. This blank variability also contributed to high variability found when short term measurements were made. The badge also had a negative interference from phenol at high phenol-to-formaldehyde ratios. Some of the major problems observed with both passive monitors were found only after devices which had been aged under storage conditions were analyzed and these results interpreted. If all testing had been done with fresh sampling devices, many of the problems would not have been noticed. Based on the results of this study, this factor of diffusive monitor aging needs to be addressed in any further work on passive monitor evaluation.

Air Pollutants, Occupational↗

PubMed1979

Measurement of formaldehyde concentrations in a subatmospheric steam-formaldehyde autoclave.

A method has been developed for measuring formaldehyde concentrations in a subatmospheric steam-formaldehyde autoclave. Data obtained using this method indicate that the concentration of formaldehyde in the chamber atmosphere is not homogeneous and that it decreases rapidly with time. The penetration of formaldehyde vapour into narrow tubes has also been investigated and was shown to be dependent on the length-to-bore ratio of the tubes. The formaldehyde concentration within the tubes could be increased by using a lower vacuum in the air removal stage at the beginning of the cycle.

Formaldehyde↗

PubMed1989

The movement of blood formaldehyde in methanol intoxication. I. A simple headspace gas chromatography-mass spectrometry for determining the amount of formaldehyde in the blood.

A gas chromatographic-mass spectrometric method for determining the amount of formaldehyde in the blood has been investigated. This method is based on the formation of diethoxymethane, which results from the reaction of formaldehyde with ethanol while in an acid state. The calibration curve in blood specimens showed a good linearity in the range of 20 to 100 microM formaldehyde with a correlation coefficient of 0.996. The minimum detectable amount of formaldehyde in the blood was found to be 10 microM and this analytic method was deemed useful for microanalysis of formaldehyde in blood.

Formaldehyde↗

PubMed1991

Kinetics and mechanism of methanol and formaldehyde interconversion and formaldehyde oxidation catalyzed by liver alcohol dehydrogenase.

It has been shown that the hydrophobic interaction in the active-site plays a fundamental role in substrate binding. Proper molecular orientation is required for hydride transfer (Dalziel and Dickinson, 1967). For methanol, the binding is unfavored due to the lack of a hydrophobic chain. In the enzyme-coenzyme-substrate complex, the small methyl group of the substrate is not held in a fixed position, resulting in a low hydride transfer rate. The binding of NAD+ to the enzyme does not exhibit a significant effect on the binding of methanol, nor does methanol affect NAD+ binding. In the presence of LADH, methanol is oxidized by NAD+ to formaldehyde, while formaldehyde can be oxidized by NAD+ to formate ion or reduced by NADH to methanol. These reactions follow a rapid equilibrium random mechanism. Among these three reactions, the reduction of formaldehyde is the most rapid. The rate of formaldehyde oxidation is faster than the oxidation of methanol. Our study with these non-hydrophobic substrates provides an important bridge between the bioinorganic activation of zinc-bound water and the bioorganic oxidation of ethanol. Furthermore, it furnishes some insight into an enzymatic system that is so highly sensitive to small changes in substrate chain length that it can magnify the consequence of a modest change in substrate hydrophobicity.

Alcohol Dehydrogenase↗

PubMed1976

Protection against toxic effects of formaldehyde in vitro, and of methanol or formaldehyde in vivo, by subsequent administration of SH reagents.

Rapid and progressive inactivation in vitro of both alcohol dehydrogenase and aldehyde dehydrogenase by low concentrations of acetaldehyde or formaldehyde is illustrated. This inactivation can be prevented or reversed by glutathione or other SH reagents. Those effects led to investigations in vivo. Rats and mice were injected with concentrations that would result in death in approximately 10 h (methanol) and approximately 4 h (formaldehyde). When 2,3-dimercaptopropanol (BAL), cysteine, or mercaptoethanol was injected (10 min to 3 h) after administration of methanol or formaldehyde, approximately 70% of the animals survived indefinitely; the remaining 30% showed substantial increase in survival time. The findings indicate the possibility of using reagents such as BAL for human therapy and suggest that the toxicity of methanol and formaldehyde is due in part to effects other than acidosis.

Alcohol Oxidoreductases↗

PubMed1989

Disinfection with gaseous formaldehyde. Second Part: Influence of test materials on formaldehyde residues and the bactericidal and sporicidal effectiveness.

The pararosaniline method for the determination of formaldehyde residues on test surfaces after exposure to gaseous formaldehyde was standardized as well as the methods of collection, preparation and desorption from the samples. The analysis of residues on plates of 5 different materials yielded the following amounts of residues after 60 minutes exposure to 3.2 mg HCHO1-1 air at 45 degrees C and a relative humidity (RH) of about 90%; silicon rubber 287.2 micrograms, lacquered polyurethane foam 109.6 micrograms, lacquered aluminium 30.3 micrograms, plexiglass 13 micrograms and stainless steel 4 micrograms HCHO 100 cm-2. The residues of formaldehyde on lacquered aluminum after an HCHO exposition with condensing layer at 20 and 30 degrees C were 10(3)-fold higher than after an exposition to gaseous formaldehyde without a condensing layer at a relative humidity of about 90% and a temperature of 40 degrees C. The inactivations of S. aureus and Bacillus subtilis spores on carriers of 5 different materials were determined under the same conditions (60 min, 3.2 mg HCHO 1-1 air, 45 degrees C and a RH of about 90%). The decimal reductions showed that Staphylococcus aureus ATCC 6538 was more readily inactivated on non porous plexiglass with a D-value of 0.7 min or stainless steel D = 1.1 min than on porous silicon rubber D = 3 min. For spores of Bacillus subtilis var. niger DSM 675, D-values of 1.6 min for plexiglass, 2.3 min for stainless steel, 2.7 min for lacquered aluminium, 3.2 min for lacquered polyurethane foam and 4.1 min for silicon rubber were registered.

Bacillus subtilis↗

PubMed1989

Disinfection with gaseous formaldehyde. Fourth Part: Influence of aeration on the level of formaldehyde residues.

After a formaldehyde exposition of 100 cm2 aluminium plates covered with a structured lacquer during 60 min at 40 degrees C and relative humidity of about 90% in a model chamber formaldehyde residues of 9.5, 21.9 and 57 micrograms HCHO 100 cm-2 were recorded for plates exposed respectively to 0.75, 1.5 and 3.2 mg HCHO l-1 air. In the model chamber tempered at 40 degrees C the reduction of the HCHO residues after an additional 60 min ventilation with an internal air circulation was 63%. After a passive aeration for 60 min in a room at ambient temperature (24 +/- 3 degrees C) without ventilation the formaldehyde residues decreased by 70-74%. In a heating cabinet tempered at 40 degrees C after an internal active aeration of 60 minutes the residual formaldehyde diminished by 76-82%.

Disinfection↗

PubMed1987

Generation of formaldehyde by N-demethylation of antipyrine. Detection of formaldehyde in bile by 13C-NMR spectroscopy.

The importance of NMR spectroscopy as a tool to investigate metabolic events in vitro and in vivo becomes more and more evident. Particularly 13C-NMR spectroscopy is able to deliver a wide range of information regarding the chemistry of xenobiotics in vivo. We studied the N-demethylation of N-methyl-13C-labelled antipyrine using an isolated perfused rat liver with a fluorocarbon suspension (FC 43) as oxygen carrier. Bile was collected in different fractions during the experiment. On the vascular side metabolite formation was monitored by continuous flow NMR spectroscopy. In bile the metabolic events were detected by standard NMR techniques. The bile spectra exhibit, among others, a signal at 84.2 ppm, indicating formaldehyde hydrate derived from the N-methyl group of antipyrine by an oxidative metabolic pathway. Neither formaldehyde hydrate nor other oxidation products could be detected in the vascular perfusate. The biliary excretion of considerable amounts of formaldehyde during the N-demethylation of antipyrine might have toxicological consequences for the intra- and extrahepatic bile ducts.

Animals↗

PubMed1986

Residual formaldehyde in steam-formaldehyde sterilized materials.

The amounts of residual formaldehyde and paraformaldehyde present in polymeric materials after steam-formaldehyde sterilization in a commercial sterilizer were determined. Appreciable amounts of residue were detected in ethylene-vinyl alcohol copolymer (EVOH), polyamide-6 (PA-6) and natural rubber (NR). These polymers all have a relatively low contact angle with water which indicated that the wettability of a material is an important parameter in determining amount of residue. The residue present in EVOH and in PA-6,6 filter material appeared to be toxic in the HFL-test (a screening test for acute toxicity). This indicated that a more thorough investigation into the possible toxicological consequences of the use of some steam-formaldehyde sterilized materials is necessary.

Biocompatible Materials↗