Acid stabilization

Proteins are biopolymers formed by one or more continuous chains of covalently linked amino acids. Hydrogen bonds between non-adjacent amino acids stabilize the so-called elements of secondary structure, a-helices and / —sheets. A number of secondary structure elements then assemble to form a compact unit with a specific fold, a so-called domain. Experience has shown that a number of folds seem to be preferred, maybe because they are especially suited to perform biological protein function. A complete protein may consist of one or more domains. 

Howardt describes a model system used to test the molecular weight distribution of a condensation polymer The polymer sample was an acetic acid-stabilized equilibrium nylon-6,6. Analysis showed it to have the following end group composition (in equivalents per 10 g) acetyl = 28.9,... 

The routine compositional and functional testing done on the adhesives includes gas chromatographic testing for purity, potentiometric titrations for acid stabilizer concentrations, accelerated thermal stabiUty tests for shelf life, fixture time cure speed tests, and assorted ASTM tests for tensile shear strengths, peel and impact strengths, and hot strengths. 

When chlorine is employed for outdoor swimming pool sanitation, it is relatively rapidly decomposed by sunlight. Isocyanuric acid stabilizes chlorine by formation of photostable chloroisocyanurates (12). By contrast, bromine is not stabilized by isocyanuric acid. 

Properties. Cyanamide [420-04-2] also called carbamodiimide or carbamic acid nitrile, crystallises from a variety of solvents as somewhat unstable, colorless, orthorhombic, dehquescent crystals (2). Dimerization is prevented by traces of acidic stabilizers such as monosodium phosphate and by storage at low temperature. 

Under certain conditions hydrogen cyanide can polymerize to black soHd compounds, eg, hydrogen cyanide homopolymer [26746-21-4] (1) and hydrogen cyanide tetramer [27027-02-2], C H N (2). There is usually an incubation period before rapid onset of polymer formation. Temperature has an inverse logarithmic effect on the incubation time. Acid stabilizers such as sulfuric and phosphoric acids prevent polymerization. The presence of water reduces the incubation period. 

Under acidic conditions the degradation process becomes more complex. The substituent on the 6-position has an important effect on the rate of degradation. Thus, acid stability has been found to increase as follows 6-APA > ampicillin, cyclacillin>... 

Oxepin, 4-ethoxycarbonyl-2,3,6,7-tetrahydro-synthesis, 7, 578 Oxepin, 2-methyl-enthalpy of isomerization, 7, 555 Oxepin, 2,3,4,5-tetrahydro-reduction, 7, 563 synthesis, 7, 578 Oxepin, 2,3,4,7-tetrahydro-synthesis, 7, 578 Oxepin, 2,3,6,7-tetrahydro-oxidation, 7, 563 reduction, 7, 563 Oxepin-2,6-dicarboxylic acid stability, 7, 565 Oxepinium ions synthesis, 7, 559 Oxepins, 7, 547-592 antiaromaticity, 4, 535 applications, 7, 590-591 aromatization, 7, 566 bond lengths and angles, 7, 550, 551 cycloaddition reactions, 7, 27, 569 deoxygenation, 7, 570 dipole moment, 7, 553 disubstituted synthesis, 7, 584... 

Claisen ester condensation, 6, 279 Thiazolecarboxylic acid chlorides reactions, 6, 279-280 Thiazolecarboxylic acid hydrazides synthesis, 6, 280 Thiazolecarboxylic acids acidity, 6, 279 decarboxylation, 6, 279 reactions, S, 92 6, 274 Thiazole-2-carboxylic acids decarboxylation, S, 92 Thiazole-4-carboxylic acids stability, S, 92 Thiazole-5-carboxylic acids decarboxylation, S, 92 Thiazole-4,5-dicarboxylic acid, 2-amino-diethyl ester reduction, 6, 279 Thiazole-4,5-dicarboxylic acids diethyl ester saponification, 6, 279 Thiazolediones diazo coupling, 5, 59 Thiazoles, 6, 235-331 ab initio calculations, 6, 236 acidity, S, 49 acylation, 6, 256 alkylation, S, 58, 73 6, 253, 256 analytical uses, 6, 328 antifogging agents... 

Trimethylsilyl ethers are quite susceptible to acid hydrolysis, but acid stability is quite dependent on the local steric environment. For example, the 17o -TMS ether of a steroid is quite difficult to hydrolyze. 

Strong nucleophiles such as Grignard reagents. In general, ortho esters are difficult to prepare directly from acids and are therefore more often prepared from the nitrile. Simple ortho esters derived from normal alcohols are the least stable in terms of acid stability and stability toward Grignard reagents, but as the ortho ester becomes more constrained its stability increases. 

Oxygen ortho esters are readily cleaved by mild aqueous acid (TsOH Pyr, H20 NaHS04, 5 1 DME, H2O, 0°, 20 min ) to form esters that are then hydrolyzed with aqueous base to give the acid. Note that a trimethyl ortho ester is readily hydrolyzed in the presence of an acid-sensitive ethoxyethyl acetal. The order of acid stability is... 

Some advantages of the Fmoc protective group are that it has excellent acid stability thus BOC and benzyl-based groups can be removed in its presence. It is readily cleaved, nonhydrolytically, by simple amines, and the protected amine is liberated as its free base. The Fmoc group is generally considered to be stable to hydrogenation conditions, but it has been shown that under some circumstances it can be cleaved with H2/Pd-C, AcOH, MeOH, (t /2 = 3-33 h). ... 

Benzyl carbamates substituted with one or more halogens are much more stable to acidic hydrolysis than are the unsubstituted benzyl carbamates.For example, the 2,4-dichlorobenzyl carbamate is 80 times more stable to acid than is the simple benzyl derivative. Halobenzyl carbamates can also be cleaved by hydrogenolysis with Pd-C. The following halobeni yl carbamates have been found to be useful when increased acid stability is required. 

MV Botuyan, A Toy-Palmer, J Chung, RC Blake II, P Beroza, DA Case. NMR solution structure of Cu(I) rusticyanm from Thiobacillus feiTooxidans Structural basis of the extreme acid stability and redox potential. J Mol Biol 263 752-767, 1996. 

In the immediate future it is unlikely that any of these polymers will attain commercial significance. Hopes that polyhaloaldehydes such as polychloral might be of some use because of their good acid stability have not been realised. This is because polymers prepared to date have poor alkali and thermal resistance, decomposing without melting. Chloral-dichloracetaldehyde copolymers have also proved similarly disappointing. 

Neoprene latex 115 contains a copolymer of chloroprene and methacrylic acid, stabilized with polyvinyl alcohol [15], With respect to other polychloroprene latices, this latex has two major advantages (1) excellent colloidal stability, which gives high resistance to shear and a broad tolerance to several materials ... 

To prevent premature polymerization, a strong protic or a Lewis acid is added to the distilled monomer and to adhesive formulations. A wide variety of materials have been utilized as acidic stabilizers in the alkyl cyanoacrylate monomers. A list of some of these materials is shown in Table 1 [2,11-14]. 

Alkyl cyanoacrylate monomers have been copolymerized with a variety of monomers, both by radical and anionic initiation. The radical-initiated copolymerization with acrylic monomers was performed with a sufficient amount of an acid stabilizer present to suppress polymerization by anionic means [19]. This investigation has been covered extensively elsewhere. 

The 3-chloro derivative was developed to impart greater acid stability to the azi-dobenzyl ether. It is much more stable to BF3 -Et20, but is cleaved in neat TFA. Conditions used to cleave the azidobenzyl ether also cleave the 4-azido-3-chlorobenzyl ether. ... 

The electron-withdrawing chlorine atoms confer greater acid stability to this group than that conferred on the usual benzyl group. It is cleaved by hydrogen-olysis (Pd/C-H2). ... 

The Dmab group was developed for glutamic acid protection during Fmoc/r-Bu based peptide synthesis. The group shows excellent acid stability and stability toward 20% piperidine in DMF. It is formed from the alcohol using the DCC protocol for ester formation and is cleaved with 2% hydrazine in DMF at rt. ... 

Q The enzyme active site contains an aspartic acid, a histidine, and a serine. First, histidine acts as a base to deprotonate the -OH group of serine, with the negatively charged carboxylate of aspartic acid stabilizing the nearby histidine cation that results. Serine then adds to the carbonyl group of the triacylglycerol, yielding a tetrahedral intermediate. 

TABLE 6 Acid Stability of Some Alkyl Ether Carboxylic Acids... 

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