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Similarity transformation probability

The authors then ask the following question Do there exist deterministic dynamical systems that are, in a precise sense, equivalent to a monotonous Markov process The question can be reformulated in a more operational way as follows Does there exist a similarity transformation A which, when applied to a distribution function p, solution of the Liouville equation, transforms the latter into a function p that can also be interpreted as a distribution function (probability density) and whose evolution is governed by a monotonous Markov process An affirmative answer to this question requires the following conditions on A (MFC) ... [Pg.32]

In a quest for a more environment-friendly process it has been found that reaction 8.4 can be catalyzed by Pd(II) complexes of various nitrogen-donor ligands (Scheme 8.1) under not too harsh conditions (100 °C, air) without the need of copper chlorides [10,11]. Of the investigated ligands, sulfonated batophenanthroline proved to be the best. Higher olefins, such as 1-hexene or cyclooctene were similarly transformed by this catalyst. Very importantly, there was no isomerization to internal olefins and 2-hexanone was formed with higher than 99 % selectivity. This outstanding selectivity is probably due to the absence of acid and Cu-chlorides. [Pg.212]

What is the nature of the insoluble forms of the prion protein They are hard to study because of the extreme insolubility, but the conversion of a helix to (3 sheet seems to be fundamental to the process and has been confirmed for the yeast prion by X-ray diffraction.11 It has been known since the 1950s that many soluble a-helix-rich proteins can be transformed easily into a fibrillar form in which the polypeptide chains are thought to form a P sheet. The chains are probably folded into hairpin loops that form an antiparallel P sheet (see Fig. 2-ll).ii-11 For example, by heating at pH 2 insulin can be converted to fibrils, whose polarized infrared spectrum (Fig. 23-3A) indicates a cross-P structure with strands lying perpendicular to the fibril axis >mm Many other proteins are also able to undergo similar transformation. Most biophysical evidence is consistent with the cross-P structure for the fibrils, which typically have diameters of 7-12 rnn."-11 These may be formed by association of thinner 2 to 5 nm fibrils.00 However, P-helical structures have been proposed for some amyloid fibrils 3 and polyproline II helices for others. 1 11... [Pg.1719]

A similar transformation of 2-furylcarbamates (e.g. 42) to A-carboxy-5-hydro-xypyrrolin-2-ones has been reported (78H1603, 80H1073). This type of oxidative rearrangement probably also accounts for the failure to isolate the 2-aminofurans 71 formed from 3-benzylidene-2,4-pentanediones and alkyl isocyanides (Scheme 14) (97MC697, 04TL1413). [Pg.22]

Subsequently, the same authors found that the structiual analogue bieyeUe azetidine derivative 166, having a silylated alcohol on the lateral ehain, showed increased reactivity in a similar transformation, albeit with low enantioselec-tivity (ee-value up to 26%), indicating that azabicyclo[3.2.0]heptane is more nucleophilic than azabicyclo[3.3.0]octane since the same MBH reaction with catalyst 163 was significantly slower (Scheme 2.81). This enhancement in catalytic activity can probably be attributed to increased pyramidalization of the nitrogen atom imposed by the four-membered ring. ... [Pg.117]

Triphosgene reacts with hydrazine ester 194 to give an activated intermediate 195, probably the carbamoyl chloride, which was not isolated but rapidly coupled to the amino terminus of a peptide to give the desired aza-peptide motif. Coupling of HCI, H-Pro-NH-iPr resulted in the aza-dipeptide 196, which was transformed into the AzAsn derivatives by the action of ammonia or methylamine. A similar transformation has been observed for Boc-Me hydrazine. [Pg.83]

In Escherichia coli. Salmonella typhimurium and Aerobacter aerogenes two soluble multi-activity enzymes or enzyme complexes function in the utilisation of chorismate (14) for L-phenyl-alanine and L-tyrosine synthesis An enzyme or enzyme complex (P-protein) containing chorismate mutase and prephenate dehydratase activities has been isolated and partially purified from Escherichia coli. Salmonella typhimurium and Aerobacter aerogenes. The enzyme complex catalyses the transformation of chorismate (14) to phenylpyruvate (32) and both enzymic activities are retained in physical association after chromatography on DEAE cellulose. Kinetic analysis indicated that in isolated enzyme systems direct synthesis of phenylpyruvate (32) from chorismate (14) does not occur. Prephenate (31) once formed dissociates from the enzyme surface and accumulates in the reaction medium. After a lag period it is converted to phenylpyruvate (32). Schmit, Artz and Zalkin also obtained evidence to show that functionally distinct sites (catalytic and regulatory) exist on the P-protein from Salmonella typhimurium for chorismate mutase and prephenate dehydratase activities. The P-protein was obtained from Escherichia coli K-12 by Davidson, Blackburn and Dopheide who showed that it existed in solution mainly as a dimer of similar (and probably identical) sub-units of... [Pg.22]

Hence, we use the trajectory that was obtained by numerical means to estimate the accuracy of the solution. Of course, the smaller the time step is, the smaller is the variance, and the probability distribution of errors becomes narrower and concentrates around zero. Note also that the Jacobian of transformation from e to must be such that log[J] is independent of X at the limit of e — 0. Similarly to the discussion on the Brownian particle we consider the Ito Calculus [10-12] by a specific choice of the discrete time... [Pg.269]

From their structures, it appears that the hydrolytic stability of macrocyclic lactones must necessarily be inferior to macrocyclic polyethers. Ease of synthesis of the cyclic esters is therefore one of the aspects which commend them to interest. It is probably for this reason that such lactones have not been made more often by the interesting approach of Kdgel and Schroder . These workers report the ozonolysis of dibenzo-18-crown-6 in a mixture of methanol and dichloromethane at —20°. Reduction of the ozon-ide at —75° using dimethylsulfide followed by warming and addition of acetone led to formation of 6 in 14% yield. The bis-oxalate had mp 164—165° from acetone, very similar to that of the starting crown. The transformation is illustrated below in Eq. (5.9). [Pg.225]


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See also in sourсe #XX -- [ Pg.263 ]




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