Oxidation of branched chain amino acids by HOCl: Kinetics and mechanism.

The kinetics of the chlorination of leucine, isoleucine, and valine (BCAAs) was studied in excess HOCl by stopped-flow and spectrophotometric methods (25 ◦C, I = 1.0 M NaClO4). The intermediates and products were identified and monitored by 1H NMR spectroscopy. It was established that these reactions are fully analogous and proceed according to distinct mechanisms under alkaline and neutral conditions. At high pH, the formation and subsequent rate determining decomposition of N-monochloroamino acid control the process. The decomposition occurs via competing pH-independent and OH--assisted reaction paths and the sequence of chlorination, dichlorination and decarboxylation steps leads to the formation of N-chloroimines and their carbanionic forms, which are in fast acid - base equilibria. The dechlorination of the carbanions yields nitriles as the main products. The hydration of the N-chloro imines produces chloramine and aldehydes which are involved in further oxidation reactions with HOCl. The formation of chloroform and chloroacetaldehyde was confirmed in each system. At pH 7.0, the N-chloro derivatives of BCAAs form immediately and are converted into the corresponding N,N-dichloro species within a few seconds after mixing the reactants. In this reaction, the reactive form of the oxidant is Cl2O. The first-order decomposition of the dichloroamino acids occurs on stopped-flow timescale (k = 0.5 - 0.7 s-1) and yields N-chloroimines which slowly decompose with a characteristic first-order rate constant on the order of a few times 10-5 s-1. The main products are the corresponding nitriles that account for about 80% and 60% of the original amounts of amino acids under neutral and alkaline (cOH- = 5.00 × 10-2 M) conditions, respectively. Aldehydes, carboxylic acids, chloroform and NCl3 were also identified as by-products. The results unequivocally confirm that harmful chlorinated species may form from amino acids long after the chlorination step in water treatment technologies that deteriorates the quality of the finished water. ENVIRONMENTAL IMPLICATION: In source waters, amino acids account for about 75% of the total dissolved nitrogen. Therefore, it is an essential issue how the reactions of these compounds with hypochlorite ion can be controlled to avoid the formation of toxic compounds. The compounds formed from BCAAs are considered to be harmful both under alkaline and neutral conditions (chloroacetaldehyde, chloroform, nitriles). However, some of the intermediates have extended lifetime in these systems and they may also react with other components of raw water during water treatment processes.

The chlorination of glycine and α-alanine at excess HOCl: Kinetics and mechanism.

The chlorination of the two simplest amino acids at HOCl excess was studied by stopped-flow, conventional spectrophotometric and time resolved 1H NMR kinetic methods at 25 °C. These reactions show distinct characteristics under neutral and alkaline conditions. At high pH, the common feature of the two systems is that the N-dichloroamino carboxylate ion does not form and the overall process is controlled by the initial decomposition of the N-monochloro derivative. Under such conditions, carbanions form in equilibrium acid - base processes and open alternative reaction paths, resulting in enhanced complexity of the corresponding mechanisms. In the case of α-alanine, the formation of acetonitrile and N-chloro acetamide as main products; acetate ion, acetaldehyde, chloroacetaldehyde, chloroform as byproducts; acetamide and N-chloro ethanimine as intermediates was confirmed. In the case of glycine, the final products are formamide and OCN-. Under neutral conditions, monochloroamino acid forms immediately upon mixing the reactants, and subsequently it is converted into dichloroamino acid by Cl2O in a fast process. In considerably slower further reaction steps, acetonitrile and acetate ion form as final products in the α-alanine system, while the chlorination of glycine proceeds to full mineralization. The detailed mechanisms suggested for these reactions postulate the formation of various imines and N-chloro imines which are involved in decarboxylation, dechlorination, hydration and hydrolytic reaction steps.

The Chlorination of N-Methyl Amino Acids with Hypochlorous Acid: Kinetics and Mechanisms.

The formation and decomposition kinetics of N-chloro-N-methyl amino acids were studied to predict the fate and impact of these compounds in water treatment technologies and biological systems. These compounds form in fast second-order reactions between N-methyl amino acids and hypochlorous acid. The comparison of the activation parameters for the reactions of N-methyl substituted and nonsubstituted branched-chain amino acids reveals the transition-state features less organized structure and stronger bonds between the reactants in the reactions with the N-methyl derivatives. This is due to a combined positive inductive effect of the N-methyl group and the alkyl side chain as well as to the steric effects of the substituents. N-Methyl-N-chloro amino acids decompose much faster than the nonsubstituted compounds. The reaction rates do not depend on the pH, and the same final product is formed in the entire pH range. N-Chlorosarcosine is an exception, as it decomposes via competing paths, kdobs = kd + kdOH[OH-], yielding different final products. This feature is most likely due to the lack of an alkyl substituent on the α-carbon atom. Under physiological pH, aldehydes and methylamine form in these reactions, which are not particularly toxic.

The decomposition of N-chloro amino acids of essential branched-chain amino acids: Kinetics and mechanism.

The formation of N-chloro-amino acids is of outmost importance in water treatment technologies and also in vivo processes. These compounds are considered as secondary disinfectants and play important role in the defense mechanism against invading pathogens in biological systems. Adversary effects, such as apoptosis or necrosis are also associated with these compounds and the intermediates and final products formed during their decomposition. In the present study, the decomposition kinetics of the N-chloro derivatives of branched chain amino acids (BCAAs) - leucine, isoleucine, valine - were studied. On the basis of spectrophotometric measurements, it was confirmed that the decomposition proceeds via a spontaneous and an OH- assisted path in each case: kobs = k + kOH[OH-]. 1H, 13C NMR and MS experiments were also performed to identify the products and to monitor the progress of the reactions. It was established that the pH independent and the [OH-] dependent paths lead to the formation of the same aldehyde in each system (isovaleraldehyde, 2-methyl-butyraldehyde, and isobutyraldehyde) as a primary product. Under alkaline conditions, a portion of the aldehydes are converted into the corresponding Schiff-bases by the excess amino acid in a reversible process. A common mechanism was proposed for these reactions which postulates the formation of imines and hemiaminals as reactive intermediates.

The formation of N-chloramines with proteinogenic amino acids.

In this study, the formation of 17 N-chloramines from proteinogenic amino acids and HOCl was studied by direct kinetic method in the pH = 3-13 range. Thus, the uncertainties associated with the indirect methods used in some of the previous studies were eliminated. Each reaction proceeds according to an overall second order kinetics: v = - k [HOCl][R-NH2] and the rate constants are several times 107 M-1s-1. A very slight correlation was found between the lgk and the pKAA of the amino acids. The results make possible to predict the reactivity order of the amino acids toward HOCl under various conditions. A comparison of the parameters of activation indicates that the presence of a bulky substituent on the side chain close to the α-carbon atom decreases the strength of bonding between the reactants and make the structure more diffuse in the transition state. The chlorination of histidine proceeds via two pH dependent paths presumably leading to the formation of N-chloramine and a side chain chlorinated product. The latter compound may be involved in fast subsequent trans-chlorination reactions. The results presented here resolve earlier discrepancies in the literature and are relevant in chlorination water treatment technologies as well as in the interpretation of in vivo processes involving the formation of N-chloro amino acids in a wide pH range.

pH controlled byproduct formation in aqueous decomposition of N-chloro-α-alanine.

N-chloro-amino acids are readily formed in chlorination water treatment technologies. These reactions are also important in biological systems where HOCl plays an important role in the defense mechanism against invading pathogens. The intermediates and the products formed are of primary concern because they may have significant biological activities. In order to clarify intimate details and resolve discrepancies in the literature, the decomposition kinetics of N-chloro-α-alanine (MCA) was studied in the neutral - alkaline pH range by UV-vis spectrophotometry and 1H-NMR method. In contrast to earlier reports, the decomposition reaction proceeds via two distinct reaction paths: kobs1 = kOH[OH-] + k, where kOH = (1.38 ± 0.02) × 10-2 M-1s-1 and k = (2.95 ± 0.09) × 10-4 s-1. In slightly alkaline solution, the sole product is acetaldehyde. Under alkaline conditions, the main product is pyruvate ion, however, N-acetyl-α-alanine is also formed in a subsequent reaction sequence. A detailed kinetic model is postulated which involves the rate determining dissociation of MCA into Cl- and ethanimine which produces acetaldehyde in further reaction steps. Via the OH- assisted path, first a carbanion is formed which undergoes dechlorination and produces iminopropionate ion. This species is transformed into pyruvate ion through hydration and deamination steps.