Formaldehyde release mechanisms

Base-catalyzed phenol-formaldehyde (PF) board, mechanisms of formaldehyde release, 87... 

Compounds that induce bronchoconstriction include tobacco smoke, formaldehyde, and diethyl ether. Several other compounds, such as acidic fumes (e.g., sulfuric acid) and gases, such as ozone and nitrogen dioxide, as well as isocyanates, can cause bronchoconstriction. Also, cellular damage in the airways induces bronchoconstriction because of the release of vasoactive compounds. Frequently, different mechanisms work at the same time, provoking bronchoconstriction and increased secretion of mucus, both of which interfere with respiration. 

The effect of various chemical modifications on the mechanical properties of reconstituted collagen and the diffusion rates of the steroid medroxyprogesterone was investigated (38). Formaldehyde-treated films, which are heavily crosslinked, have high moduli and low rates of drug release. Films treated with chrome quickly become hydrated in solution and have low moduli and very rapid drug release characteristics. 

Brononol (2-Bromo-2-nitropropane-1,3-diol) in combination with methyl and propyl paraben. The paper generated by the Danish group (ref. 5 Knoll BASF publication) shows that the mechanism of action of Bronopol is independent of formaldehyde formation. The inclusion of Tetrasodium EDTA at about 0.02% to remove ions in the water or extracts and carefully excluding any tertiary amines such as triethanolamine to counteract the fears of the marketers with reference to possible nitrosamine formation and release of formaldehyde. The pH used is usually at 6 and below. 

Astonishingly, the study of the mechanism of formaldehyde loss from anisole revealed two different pathways for this process, one involving a four- and one a five-membered cyclic transition state (Fig. 6.37). [129] The four-membered transition state conserves aromaticity in the ionic product, which therefore has the lower heat of formation. Prompted by the observation of a composite metastable peak, this rather unusual behavior could be uncovered by deconvolution of two different values of kinetic energy release with the help of metastable peak shape analysis (Chap. 2.8). 

Figure 13.6 (a) Mechanism for the hydroxy I ation of lysine N-methyl group leading to dehydroxylation and release of formaldehyde, succinate and CO2. 

Methenamine (Hiprex, Mandelamine, Urex) exerts antibacterial properties in a unique fashion. In an acidic environment, this drug decomposes into formaldehyde and ammonia. Formaldehyde is bactericidal to almost all bacteria, and bacteria do not develop resistance to this toxin. This mechanism enables methenamine to be especially useful in treating urinary tract infections, because the presence of this drug in acidic urine facilitates the release of formaldehyde at the site of infection (i.e., within the urinary tract). Use of methenamine is safe, although high doses are associated with gastrointestinal upset and problems with urination (bloody urine, pain while urinating). 

In ambient air, the primary removal mechanism for acrolein is predicted to be reaction with photochemically generated hydroxyl radicals (half-life 15-20 hours). Products of this reaction include carbon monoxide, formaldehyde, and glycolaldehyde. In the presence of nitrogen oxides, peroxynitrate and nitric acid are also formed. Small amounts of acrolein may also be removed from the atmosphere in precipitation. Insufficient data are available to predict the fate of acrolein in indoor air. In water, small amounts of acrolein may be removed by volatilization (half-life 23 hours from a model river 1 m deep), aerobic biodegradation, or reversible hydration to 0-hydroxypropionaldehyde, which subsequently biodegrades. Half-lives less than 1-3 days for small amounts of acrolein in surface water have been observed. When highly concentrated amounts of acrolein are released or spilled into water, this compound may polymerize by oxidation or hydration processes. In soil, acrolein is expected to be subject to the same removal processes as in water. 

The liydroxycarbene mechanism is supported mainly by observation of IR absorption bands suggesting enolic complexes of the type M=CH(OH) if CO/Hj is chemisorbed on iron catalysts [112. 162, 1631. Sorption measurements showed that chemisorbed CO/Hj mixtures are always released in a I 1 ratio, even when gas mixtures of a different composition were used for adsorption [164]. Based on mass spectrometry formaldehyde was shown to be the primary reaction product (16SJ. 

Apart from the environmental factors, chemical compounds also induce cross-linking of gelatin. Supporting this is the mechanism in Fig. 5, which highlights the role of external aldehydes. Among the low molecular weight aldehydes, formaldehyde is most important as it is released in dosage forms from plasticizers and preservatives, fats, and polyethylenated... 

Despite this practical progress, great uncertainty still exists as to the precise mechanism by which formaldehyde is held within a board and slowly released as a gas to the atmosphere. Historically, many have considered the emission potential of a board to be governed, particularly in a board s early life, by the board s so-called free formaldehyde content (9). 

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