Hypothesis of mechanism

Analysis of graft copolymer fractions shows that they always contain PVC and BD-AN copolymer in sufficient quantity to eliminate the hypothesis of mechanical coprecipitation (for a mixture we find ca. 95% homopolymer). The amount of PVC in the first fraction is higher (ca. 70-80%) than in the last. 

This presentation is less general than that of de Groot and Mazur, which involves the magnetic field. In Haase s study, the hypothesis of mechanical equihbrium id jdt = 0) comes into play in the form of a zero pressure gradient, which is equivalent if we neglect the influence of the magnetic field in the Lorentz force and if electrical neutrality is verified. 

The hypothesis of mechanical contamination from the pneumatic transfer system was eliminated by placing the sample manually into the irradiation position (194). It was also shown (195) that the difference between the results with nitrogen as a carrier gas and those with chemical etching after the irradiation is not due to oxygen in the atmosphere around the sample as a result of the transfer system not being air-tight. 

The results of Olah and his co-workers require, then, no special hypothesis regarding mechanism of nitration, in so far as they relate to... 

The notion of concurrent SnI and Sn2 reactions has been invoked to account for kinetic observations in the presence of an added nucleophile and for heat capacities of activation,but the hypothesis is not strongly supported. Interpretations of borderline reactions in terms of one mechanism rather than two have been more widely accepted. Winstein et al. have proposed a classification of mechanisms according to the covalent participation by the solvent in the transition state of the rate-determining step. If such covalent interaction occurs, the reaction is assigned to the nucleophilic (N) class if covalent interaction is absent, the reaction is in the limiting (Lim) class. At their extremes these categories become equivalent to Sn and Sn , respectively, but the dividing line between Sn and Sn does not coincide with that between N and Lim. For example, a mass-law effect, which is evidence of an intermediate and therefore of the SnI mechanism, can be observed for some isopropyl compounds, but these appear to be in the N class in aqueous media. 

One of the merits of the above treatment, which justifies its inclusion in this review, is that it allows a quantitative comparison of the selectivity of nucleophilic heteroaromatic substitution (expressed by the reaction constant) with that for the analogous reaction with nitro-activated systems. Values for the latter are in the range 3.6 to 6.0. The fact that in both cases high p-values of similar magnitude are found is consistent with the hypothesis of similar mechanisms for both classes of compounds. 

However, the linear bond cleavage hypothesis of the firefly bioluminescence was made invalid in 1977. It was clearly shown by Shimomura et al. (1977) that one O atom of the CO2 produced is derived from molecular oxygen, not from the solvent water, using the same 180-labeling technique as used by DeLuca and Dempsey. The result was verified by Wannlund et al. (1978). Thus it was confirmed that the firefly bioluminescence reaction involves the dioxetanone pathway. Incidentally, there is currently no known bioluminescence system that involves a splitting of CO2 by the linear bond cleavage mechanism. 

The original monoamine hypothesis of depression states that depressions are associated with a deficiency of catecholamines, particularly norepinephrine, at functionally important adrenergic receptor sites in the brain. Elation conversely may be associated with an excess of such amines. The hypothesis was articulated in 1966 only after the mechanism of action of the tricyclic antidepressant desipramine and of the psychostimulants... 

Usually, the molecular strands are coiled in the glassy polymer. They become stretched when a crack arrives and starts to build up the deformation zone. Presumably, strain softened polymer molecules from the bulk material are drawn into the deformation zone. This microscopic surface drawing mechanism may be considered to be analogous to that observed in lateral craze growth or in necking of thermoplastics. Chan, Donald and Kramer [87] observed by transmission electron microscopy how polymer chains were drawn into the fibrils at the craze-matrix-interface in PS films [92]. One explanation, the hypothesis of devitrification by Gent and Thomas [89] was set forth as early as 1972. 

In Section 8.3 the mechanism of heterolytic dediazoniation of arenediazonium ions was discussed, and it was shown that the hypothesis of Crossley et al. (1940) that the aryl cation is the characteristic metastable intermediate in those reactions was not consistent with some experimental facts found in 1952 by Lewis and Hinds. Nevertheless, these facts did not have significant influence on the scientific community, which continued to accept the original and apparently convincing hypothesis of the rate-limiting formation of an aryl cation as an intermediate as correct . The incom-patabilities of various mechanistic hypotheses with experimental facts were, however, discussed in some detail only two decades later (Zollinger, 1973 a). Another year passed before I performed a crucial experiment that refuted a number of hypotheses (Bergstrom et al., 1974, 1976). ... 

The free radical damage hypothesis of desiccation injury requires that these various protective mechanisms are unable to detoxify reactive species during dehydration and rehydration. There is evidence that free radicals increase with decreasing moisture content of seeds (Priestley et al., 1985), and, in plants subjected to episodic droughting, increased levels of malon-dialdehyde occur (Price Hendry, 1987). 

The effect of oxidative irradiation on mechanical properties on the foams of E-plastomers has been investigated. In this study, stress relaxation and dynamic rheological experiments are used to probe the effects of oxidative irradiation on the stmcture and final properties of these polymeric foams. Experiments conducted on irradiated E-plastomer (octene comonomer) foams of two different densities reveal significantly different behavior. Gamma irradiation of the lighter foam causes stmctural degradation due to chain scission reactions. This is manifested in faster stress-relaxation rates and lower values of elastic modulus and gel fraction in the irradiated samples. The incorporation of O2 into the polymer backbone, verified by IR analysis, conftrms the hypothesis of... 

The function of a sensory system is to select suitable modalities from the multitude presented by the environment, and translate them into corresponding modalities of sensory information that are then projected and processed into the various parts and finally submitted to the central processing-unit, the brain. A working hypothesis of the mechanism by which the taste system senses chemical compounds is that macromolecules that are... 

Fig. 4.4 Simplified hypothesis of the mechanism of gpI20-induced dorsal root gangUon (DRG) neurotoxicity. CXCR4 binding on Schwann cells by SDF-Ia or gpI20 results in the release of RANTES, which induces tumor necrosis factor (TNF)-a production by DRG neurons, and subsequent TNFRl-mediated neurotoxicity in an autocrine/paracrine fashion. Reproduced with permission of John Wiley Sons, Inc. (Keswani et al. 2003b)...

However, not all effects of NRTls on mitochondria can be explained by the DNA polymerase y hypothesis. Other mechanisms, either secondary to or independent of inhibition of DNA polymerase y are involved in NRTI toxicity (Moyle 2000a, 2000b Lewis et al. 2003). AZT is a potent inhibitor of mitochondrial DNA polymerase y but does not cause neuropathy in HIV patients (Dalakas 2001). Keswani and colleagues showed that NRTls caused direct mitochondrial toxicity through... 

The hypothesis of dissociative activation in Co(III) reactions stands the available tests well. It is therefore profitable to attempt to distinguish the D from the /j pathways. Fig. 7 summarizes the two pathways consistent with d activation, and the general methods for establishing the stoichiometric mechanism 1 are illustrated by the example of Co(NH3)50H2 ". ... 

The hypothesis of the participation of those cholesterol transporters (NPCILI and ABCAl) in the carotenoid transport remains to be confirmed, especially at the in vivo human scale. If the mechanism by which carotenoids are transported through the intestinal epithelial membrane seems better understood, the mechanism of intracellular carotenoid transport is yet to be elucidated. The fatty acid binding protein (FABP) responsible for the intracellular transport of fatty acids was proposed earlier as a potential transporter for carotenoids. FABP would transport carotenoids from the epithelial cell membrane to the intracellular organelles such as the Golgi apparatus where CMs are formed and assembled, but no data have illustrated this hypothesis yet. 

Among MC lattice models of the double layer, it is also worth mentioning the work of Nazmutdinov et al. (1988), who used a lattice model involving two mono-layers of water molecules on the surface of an electrode, forming a hexagonal close-packed array. The interaction of each water molecule in contact with the metal surface (assumed to be Hg) was taken from quantum-mechanical calculations. Information was obtained concerning the relative numbers of molecules with different numbers of hydrogen bonds, and it was concluded that the hypothesis of an icelike state of water in a monolayer on Hg is rather unlikely. 

Until recently no enzymes able to produce olivetol-like compounds have been isolated. In an article by Puna et al., polyketide III enzymes were responsible for the formation of phenohc lipid compound [34], a natural product group that ohvetol belongs to. Although the biosynthesized compounds contained a longer chain, which increased over time, the study supported the hypothesis of olivetohc acid production by a polyketide III synthase. Further studies on the genetic and protein level are essential to elucidate the mode of mechanism by which olivetohc acid is formed in C. sativa. 

Nickel(O) reacts with the olefin to form a nickel(0)-olefin complex, which can also coordinate the alkyl aluminum compound via a multicenter bond between the nickel, the aluminum and the a carbon atom of the trialkylaluminum. In a concerted reaction the aluminum and the hydride are transferred to the olefin. In this mechanistic hypothesis the nickel thus mostly serves as a template to bring the olefin and the aluminum compound into close proximity. No free Al-H or Ni-H species is ever formed in the course of the reaction. The adduct of an amine-stabihzed dimethylaluminum hydride and (cyclododecatriene)nickel, whose structure was determined by X-ray crystallography, was considered to serve as a model for this type of mechanism since it shows the hydride bridging the aluminum and alkene-coordinated nickel center [31]. 

Following the hypothesis of electron spin by Uhlenbeck and Goudsmit, P. A. M. Dirac (1928) developed a quantum mechanics based on the theory of relativity rather than on Newtonian mechanics and applied it to the electron. He found that the spin angular momentum and the spin magnetic moment of the electron are obtained automatically from the solution of his relativistic wave equation without any further postulates. Thus, spin angular momentum is an intrinsic property of an electron (and of other elementary particles as well) just as are the charge and rest mass. 

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