Condensation hypothesis

This widespread conformity to the Gurvitsch rule constitutes powerful support for the capillary condensation hypothesis in relation to Type IV isotherms. It is perhaps hardly necessary to stress that in order to test data for conformity to the rule it is essential that the stage which corresponds to the complete filling of the pores shall be clearly identifiable—as in the... 

Anderson, C. F., and Record, M. T. Jr. (1980). The relationship between the Poisson-Boltzmann model and the condensation hypothesis An analysis based on the low salt form of the Donnan coefficient. Biophys. Chem. 11, 353—360. 

C. F. Anderson and M. T. Record, Jr., Biophys. Chem., 11, 353 (1980). The Relationshijp between the Poisson-Boltzmann Model and the Condensation Hypothesis An Analysis Based on the Low Salt Form of the Donnan Coefficient. 

In formulating an explanation of this enhanced adsorption, there are several features to be accounted for the increase in adsorption occurs without hysteresis the amount of adsorbate involved is relatively small the Kelvin r -values are also small (e.g. for nitrogen, less than 17 A) and the effect is found in a region of relative pressures where, according to the simple tensile strength hypothesis, capillary condensate should be incapable of existence. 

The mechanism of chemical adhesion is probably best studied and demonstrated by the use of silanes as adhesion promoters. However, it must be emphasized that the formation of chemical bonds may not be the sole mechanism leading to adhesion. Details of the chemical bonding theory along with other more complex theories that particularly apply to silanes have been reviewed [48,63]. These are the Deformable Layer Hypothesis where the interfacial region allows stress relaxation to occur, the Restrained Layer Hypothesis in which an interphase of intermediate modulus is required for stress transfer, the Reversible Hydrolytic Bonding mechanism which combines the chemical bonding concept with stress relaxation through reversible hydrolysis and condensation reactions. 

The second line of circumstantial evidence quoted in support of this hypothesis is the ready formation of l,2,3,4-tetrahydro-/3-carboline derivatives under pseudo-physiological conditions of temperature, pH, and concentration. Tryptamine and aldehydes, trypt-amine and a-keto acids, and tryptophan and aldehydes condense at room temperature in a Pictet-Spengler type intramolecular Mannich reaction in the pH range 5.2-8.0 (cf. Section III, A, 1, a). It was argued that experiments of this type serve as models for biochemical reactions and may be used in evidence. 

Available information on the mechanism of cyclocondensation is rather contradictory. According to one hypothesis, both the condensation of aryl halides with copper acetylides and the cyclization occur in the same copper complex (63JOC2163 63JOC3313). An alternative two-stage reaction route has also been considered condensation followed by cyclization (66JOC4071 69JA6464). However, there is no clear evidence for this assumption in the literature and information on the reaction of acetylenyl-substituted acids in conditions of acetylide synthesis is absent. 

The acetate labeling results clearly demonstrated a polyketide origin for the naphthoate fragment. This resulted in the hypothesis that the first enzyme-free intermediate in azinomycin biosynthesis would be naphthoate 102, with condensation to fonn a polyketone chain, reduction, cyclization, and dehydration/aromati-... 

To accommodate this new finding and the previous results, we considered a new pathway (Scheme 3), in which acetate or its derivative condenses with arginine followed by decarboxylation. Such Claisen-type condensation on alpha-amino acid has some precedent in biochemical systems (6). To prove this hypothesis, we synthesized [2- C, 2-arginine and ornithine and fed to A, flos-aquae (5). 

Three other portions of the molecule which do not fit the polyketide combination pattern (Scheme 7B a,f,n) can be also explained by assuming they are derived from a dicarboxylic acid such as 3-hydroxy-3-methylglutaric acid (Scheme 8b). If that is the case, brevetoxins are a new type of mbced polyketides which are formed by condensation on both ends of dicarboxylic acids (Scheme 8c). In order to prove further the hypothesis, feeding experiments with such putative precursors as succinate, acetoacetate, and propionate are in progress. 

This alternative hypothesis may explain the observational differences between different workers. Brune Smith (1982), unlike Wilson et al. (1972), found Si distributed throughout the cement but were uncertain whether it was due to Si in the matrix or the degradation of fine particles to silica gel. But Brune Smith (1982) used a normal glass powder while Wilson et al. (1972) removed fine particles to improve resolution. These differing observations are reconciled if the silicic acid which is formed migrates slightly before condensing to silica gel. 

The earlier assumption that Luna was a body which had been captured by the Earth can now be regarded as relatively unlikely. The same is true for the double planet hypothesis , according to which Luna and the Earth were formed at the same time from condensing primordial matter (Taylor, 1994). There are, however, still disagreements on the point in time at which the collision occurred and on the masses and the physical states of the heavenly bodies involved (Halliday and Drake, 1999). 

The co-condensation reactions described above have led to the formation of interesting new compounds and sometimes very unexpected products. The nature of the products formed for example in the osmium atom experiments indicate high degrees of specificity can be achieved. However, the detailed mechanisms of the co-condensation reactions are not known. It seems most likely that in all cases the initial products formed at the co-condensation temperature are simple ligand-addition products and that the insertion of the metal into the carbon-hydrogen bond occurs at some point during the warming up process. In support of this hypothesis we note the virtual absence of any... 

L-tryptophan is compulsory, the biosynthetic machinery displays wide latitude in its ability to condense a second auxiliary amino acid—L-alanine in the case of (+)-ll,ll -dideoxyverticillin A (1)—to afford a tryptophan-derived diketopiperazine intermediate 13. Mirroring Woodward and Robinson s biogenetic hypothesis for the calycanthaceous alkaloids, single-electron oxidation of the electron-rich tryptophan residue would likely initiate an oxidative dimerization of the diketopiperazine precursor with concomitant cyclization to yield the octacyclic intermediate 17. Subsequent A-methylation of the amides would then yield an unembellished skeletal core of the dimeric epipolythiodiketopiperazine alkaloids. The first step en route... 

A third hypothesis (C) involves the supposition that the reaction is effected through an aldol condensation between ethyl acetoacetate and the carbonyl form of the sugar.18... 

The third hypothesis (C) is that reaction takes place through an aldol condensation between the ethyl acetoacetate and the carbonyl form of the sugar. There is some precedent indicating that it is possible for /3-ketonic esters to undergo aldol condensation. These compounds react mole to mole with the aliphatic aldehydes and afford unsaturated substances, which could be formed via an aldol condensation with subsequent dehydration. 

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