Poly variants

For a more detailed discussion it is best to subdivide the cases according to the variance of the system we shall consider first systems for which the variance is one or zero, and then the case of poly variant systems. 

We met these theorems in studying the properties of states of uniform composition (chap. XVIII, 6) we shall now examine them in a more general form as a property of all static indifferent states in a poly variant system. 

We have already seen that all the states of a mono variant system are indifferent states. On the other hand, if a poly variant system is in an indifferent state, then its properties are in many ways analogous to those of mono variant systems. 

In the same way, for an indifferent state of a closed poly variant system, the temperature is sufficient to determine p and the composition of the phases, but not the masses of the individual phases. Furthermore, as we have seen, the law governing the variations hp and hT along an indifferent line, are of just the same form as the law which relates Sp and ST along the equilibrium states of a monovariant system. However, a profound difference is apparent between monovariant systems, and indifferent states of a pol3rvariant system when we consider the possibility of a closed system moving along the line of indifference. A closed mono variant system can clearly traverse its indifferent line, for this is simply its equilibrium line on the other hand, for a polyvariant closed system the ability to move along the indifferent line is exceptional as we shall now proceed to show. 

Case 2 w>2. A poly variant closed system of the second category cannot in general achieve an indifferent state although it may reach an indifferent point if the initial masses instead of being taken at random, are chosen correctly. 

The use of a catalytic quantity of alkah equivalent to only a small fraction of the acetate has the advantage that contamination of the poly(vinyl alcohol) with salts, which are difficult to remove, is minimized. A variant of the process is the use of a mixture of alcohol with the acetate ester produced by the alcoholysis as the alcoholyzing agent. This provides a means of controlling the completeness of removal of the acetate groups from the poly(vinyl acetate) (111). 

The poly(vinyl ethers), whieh were first made available in Germany before 1940, are not of importance in the plastics industry but have applications in adhesives, surfaee coatings and rubber technology. Of the many vinyl ether polymers prepared, only those from the vinyl alkyl ethers and some halogenated variants are of interest. Two methods of monomer preparations may be used. 

Although the first two materials discussed in this chapter, the polyphenylenes and poly-p-xylylenes, have remained in the exotic category, most of the other materials have become important engineering materials. In many cases the basic patents have recently expired, leading to several manufacturers now producing a polymer where a few years ago there was only one supplier. Whilst such competition has led in some cases to overcapacity, it has also led to the introduction of new improved variants and materials more able to compete with older established plastics materials. 

The polymetallosiloxanes above may in fact be considered as variants of a series of polymetalloxanes which are akin to the silicones but which contain, for example, tin, germanium and titanium instead of silicon. Of the poly-organostannoxanes, dibutyl tin oxide finds use as a stabiliser for PVC and as a silicone cross-linking agent. Polyorganogermanoxanes have also been prepared (Figure 29.13). 

The specialty class of polyols includes poly(butadiene) and polycarbonate polyols. The poly(butadiene) polyols most commonly used in urethane adhesives have functionalities from 1.8 to 2.3 and contain the three isomers (x, y and z) shown in Table 2. Newer variants of poly(butadiene) polyols include a 90% 1,2 product, as well as hydrogenated versions, which produce a saturated hydrocarbon chain [28]. Poly(butadiene) polyols have an all-hydrocarbon backbone, producing a relatively low surface energy material, outstanding moisture resistance, and low vapor transmission values. Aromatic polycarbonate polyols are solids at room temperature. Aliphatic polycarbonate polyols are viscous liquids and are used to obtain adhesion to polar substrates, yet these polyols have better hydrolysis properties than do most polyesters. 

Another, simple form of elemental carbon would be chains formed from carbon atoms. As a prototype model a single>stranded chain is most suitable. If branching were to be considered, all intermediate forms up to and including the diamond and graphite like clusters would be included. For non branched chains, the two variants to choose from are a system of alternating singly and triply bonded carbon atoms (poly-ynes), and a system with all double bonds (cumulenes). Cumulene structures are assumed to be the preferred ones for odd membered chains, whereas the even ones may have some poly-yne character. Recent studies on linear Cg show that a cumulene-like structure is preferred, both at the SCF level and when correlation is accounted for(50). 

Regarding this proposal, it should be noted that while 1,1-eliminations on Si-Si-C units to generate silylenes are well known thermal processes (54) the photochemical variant seems not to have been described. The rearrangement of silylsilylenes (4) to disilenes is known to be rapid (55), and silyl radical addition at the least hindered site would produce the observed persistent radical. Preliminary evidence for the operation of 1,1-photoelimination processes in the polysilane high polymers has been obtained, in that the exhaustive irradiation at 248 nm of poly(cyclohexylmethylsilane) (PCHMS) produces —10-15% volatile products which contain trialkylsilyl terminal groups. For example, the following products were produced and identified by GC— MS (R=cyclohexyl,R = methyl) H(RR Si)2H (49%), H(RR Si)3H (19%), R2R SiH (2%), R 2RSiRR SiH (5%) and R2R SiRR SiH (7%). 

Posttranscrip-tional processing of hnRNA (pre-mRNA) None In nucleus 5 cap (7-MeG) 3 tail (poly-A sequence) Removal of introns from hnRNA Alternative splicing yields variants of protein product... 

One of the first attempts to extend polymer-assisted epoxidations to asymmetric variants were disclosed by Sherrington et al. The group employed chiral poly(tartrate ester) hgands in Sharpless epoxidations utilizing Ti(OiPr)4 and tBuOOH. However, yields and degree of stereoselection were only moderate [76]. In contrast to most concepts, Pu and coworkers applied chiral polymers, namely polymeric binaphthyl zinc to effect the asymmetric epoxidation of a,/9-unsaturated ketones in the presence of terPbutyl hydroperoxide (Scheme 4.11). 

Fig. 6. Post-translational modifications of core and linker histones. The sites of acetylation, phosphorylation, poly-ADP ribosylation, methylation, and ubiquitination are incficated by numbers that correspond to the amino acid position from the N-termini of the molecules. The nomenclature of histone HI variants is as in Fig. 3. The length of C- and N-terminal tails is in relative scale between core histones to illustrate primary structural differences between these proteins.

Yet another hypothesis considers the somatic variant Hle of histone HI, in its poly(ADP-ribosyl)ated isoform, as a nuclear traw -acting factor involved in maintaining the methylation pattern on DNA [161]. 

Enzyme levels and activities within the human population can vary considerably and many of the enzymes involved in the metabolism of xenobiotics are polymorphicaUy distributed in the human population. Genetic polymorphism (from Greek poly many , morph form ) is defined as the occurrence of at least two different alleles, with allele frequencies exceeding 1% at a particular locus. The allelic variants include point mutations as well as deletions and insertions and genetic polymorphism may cause an increase, a decrease, or no change in enzymatic activity. 

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