Amino acid decomposition

Armesto, X. L., Canie L, M., Losada, M., Santaballa, J. A. Concerted Grob Fragmentation in W-Halo-a-amino Acid Decomposition. J. Org. Chem. 1994, 59, 4659-4664. 

Ethylamine has been reported to occur in various fresh fruits and vegetables, grains, coffee, various cheeses, and fish. Ethylamine also occurs in the environment as a result of amino acid decomposition. 

The various decomposition reactions outlined in the preceeding section would remove amino acid from the buffered solutions, and if these reactions were significant compared with the k values, Equation 9 would have to be modified. Since the racemization was studied under anaerobic conditions, the decarboxylation and deamination reactions are the only important amino acid decomposition reactions. With the exception of the deamination of aspartic acid, the decomposition rates of the other amino acids studied were negligible compared with the racemization rate of the amino acid. Integration of Equation 9 yields... 

The TVD curves of selected amino acids were determined by Contarini and Wendlandt (121). A comparison of the TVD and DSC peak temperature is shown in Table 11.8. The TVD peak temperatures are somewhat higher than those obtained by DSC. Obviously, the kinetics of the electrodedecomposition produces) reaction are different from those of the decomposition reaction. These electrode reactions probably involve one or more diffusion steps between the electrode surface and the amino acid or amino acid decomposition produces), which would be different from the decomposition kinetics themselves. The leading edge of the TVD curve peaks is reproducible to within +1-2%. However, after the peak maximum temperature is attained, the reproducibility falls to within +20% in some cases. This is related to the electrode-amino acid decomposition products interface, which, due to the nature of the reaction, would not be expected to be reproducible. The trailing edge portion of the curve also consists of several shoulder peaks that may be related to the consecutive and/or concurrent reactions previously described in the DSC curves. These reactions could produce decomposition products that would react with the aluminum metal electrode surface. 

The most important reactions which provide volatile carbonyl compounds were presented in sections 3.7.2.1.9 (lipid peroxidation), 4.2.4.3.3 (caramelization) and 4.2.4.4.T (amino acid decomposition by the Strecker degradation mechanism). 

Snpplementation with essential oils that have antimicrobial activity enables to consider them as natnral feed snpplements fnlfilling these expectations, whose mechanism of action will be directly associated with the influence on bacteria specialized in ammonia production and indirectly with the influence on amino acid decomposition. 

Table 3.3. Amino acids decomposition into functionai groups...

The amino-acids are colourless, crystalline substances which melt with decomposition. They are mostly soluble in water and insoluble in alcohol. 

The melting points of the derivatives of a number of amino acids are collected in Table 111,132. Most a-amino acids decompose on heating so that the melting points would be more accurately described as decomposition points the latter vary somewhat with the rate of heating and the figures given are those obtained upon rapid heating. 

The deterruination of amino acids in proteins requires pretreatment by either acid or alkaline hydrolysis. However, L-tryptophan is decomposed by acid, and the racemi2ation of several amino acids takes place during alkaline hydrolysis. Moreover, it is very difficult to confirm the presence of cysteine in either case. The use of methanesulfonic acid (18) and mercaptoethanesulfonic acid (19) as the protein hydroly2ing reagent to prevent decomposition of L-tryptophan and L-cysteine is recommended. En2ymatic hydrolysis of proteins has been studied (20). 

The principal pathway for the decomposition of aspartame begins with the cleavage of the ester bond, which may or may not be accompanied by cyclization (Eig. 2). The resultant diketopipera2ine and/or dipeptide can be further hydroly2ed into individual amino acids (qv). 

Fig. 2. Decomposition of aspartame to diketopipera2ine and/or aspartyl-phenylalanine and then to the amino acids aspartic acid and phenylalanine (22).

A significant difference between pseudoirreversible inhibitors and mechanism-based inactivators is the reversibiUty of the inactivation. A complete evaluation of the mechanism involved would require evidence not only for the covalent enzyme-inhibitor complex, but also for its decomposition products and its rate of reactivation. It is often difficult to identify the active site amino acid residue covalently linked to the inhibitor because of the instabiUty of the complex. 

Amino acids have high melting or decomposition points and are best examined for purity by paper or thin layer chromatography. The spots are developed with ninhydrin. Customary methods for the purification of small quantities of amino acids obtained from natural sources (i.e. l-5g) are ion-exchange chromatography (see Chapter 1). For general treatment of amino acids see Greenstein and Winitz [The Amino Acids, Vols 1-3, J.Wiley Sons, New York 1961] and individual amino acids in Chapters 4 and 6. 

Benzyioxycarbonyi chioride (Cbz-Ci, benzyi cbioroformate) [501-53-1] M 170.6, b 103 /20mm, d 1.195, n 1.5190. Commercial material is better than 95% pure and may contain some toluene, benzyl alcohol, benzyl chloride and HCl. After long storage (e.g. two years at 4 , Greenstein and Winitz [The Chemistry of the Amino Acids Voi 2 p. 890, J Wiley and Sons NY, 1961] recommended that the liquid should be flushed with a stream of dry air, filtered and stored over sodium sulfate to remove CO2 and HCl which are formed by decomposition. It may further be distilled from an oil bath at a temperature below 85 because Thiel and Dent [Annalen 301 257 1898] stated that benzyioxycarbonyi chloride decarboxylates to benzyl chloride slowly at 100 and vigorously at 155 . Redistillation at higher vac below 85 yields material which shows no other peaks than those of benzyioxycarbonyi chloride by NMR spectroscopy. LACHRYMATORY and TOXIC. 

The crude product is dissolved in five times its weight of water, and after clearing with a little Norite the solution is diluted with one and one-half volumes of 95 per cent alcohol. The product separates in well-formed, snow-white crystals, and after standing for several days in an ice chest is collected with suction on a Buchner funnel. The yield of purified histidine monohydrochloride is 75-80 g. (Note 5). The compound melts at 251-2520, with decomposition. The amino acid is not race-mized by the procedure employed, and shows the characteristic optical activity, [a]n6° = +8.00, in the presence of three moles of... 

Photodriven reactions of Fischer carbenes with alcohols produces esters, the expected product from nucleophilic addition to ketenes. Hydroxycarbene complexes, generated in situ by protonation of the corresponding ate complex, produced a-hydroxyesters in modest yield (Table 15) [103]. Ketals,presumably formed by thermal decomposition of the carbenes, were major by-products. The discovery that amides were readily converted to aminocarbene complexes [104] resulted in an efficient approach to a-amino acids by photodriven reaction of these aminocarbenes with alcohols (Table 16) [105,106]. a-Alkylation of the (methyl)(dibenzylamino)carbene complex followed by photolysis produced a range of racemic alanine derivatives (Eq. 26). With chiral oxazolidine carbene complexes optically active amino acid derivatives were available (Eq. 27). Since both enantiomers of the optically active chromium aminocarbene are equally available, both the natural S and unnatural R amino acid derivatives are equally... 

KINETICS AND MECHANISM OF DECOMPOSITION OF N-Br-AMINO ACIDS IN ALKALINE MEDIUM... 

More recently Hand et al. (ref. 9) have studied the decomposition reaction of N-chloro-a-amino acid anions in neutral aqueous solution, where the main reaction products are carbon dioxide, chloride ion and imines (which hydrolyze rapidly to amine and carbonyl products). They found that the reaction rate constant of decarboxylation was independent of pH, so they ruled out a proton assisted decarboxylation mechanism, and the one proposed consists of a concerted decarboxylation. For N-bromoamino acids decomposition in the pH interval 9-11 a similar concerted mechanism was proposed by Antelo et al. (ref. 10), where the formation of a nitrenium ion (ref. 11) can be ruled out because it is not consistent with the experimental results. Antelo et al. have also established that when the decomposition reaction takes place at pH < 9, the disproportionation reaction of the N-Br-amino acid becomes important, and the decomposition goes through the N,N-dibromoamino acid. This reaction is also important for N-chloroamino compounds but at more acidic pH values, because the disproportionation reaction... 

The decomposition kinetics of the N-Br-amino acids was studied spectro-photometrically by following the fall in absorbance at the wavelength of the absorbance maximum of the N-bromoamino acid, in a Milton Roy Spectronic 3000 Array or a Beckman DU65 single-beam spectrophotometer, both equipped with a cell carrier thermostated to within 0.1 °C by water flow. Kinetic experiments were initiated using a hand-driven HI-TECH SFA-12 Rapid Kinetics Accessory with a 1.00 cm flow cell. 

Order respect to N-Br-amino acid concentration. With the aim of establishing the reaction order with respect to the N-bromoalanine concentration, we have obtained the values of the initial rates for different N-bromoamino acid concentrations with a fixed OH" concentration of 0.23M. The logarithmic plot shows to be a straight line (Fig. 3) with a slope of 1.07 0.03. This means that the decomposition reaction of N-Br-alanine is first order with respect to the N-bromoalanine concentration. From the plot of initial rate against initial N-bromoalanine concentration (Table 1) we can obtain for the pseudofirst order rate constant for N-bromoalanine decomposition a value of 0.0160 0.(XX)4 s-f... 

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