Chain-elongation

The natural tendency of a chain segment, comprised of nitrogen bonds, is to retract, at a given temperature for such a chain segment, the equation of elasticity is derived from 

N is the number of skeletal bonds in one chain and k is the Boltzmann constant while b is the mean skeletal bond. The mean square end-to-end distance, Nb2, is also referred to as the square of the Gaussian correlation length between the chain ends, o(N) it reflects the effect of linkage of chemical units. The previous relationship between the force f and the extension r is extended to any real chain submitted to a small elongation provided the correlation length, o(N), includes the stiffness property of the polymer o(N)2= A.KNb2 XK is referred to as a persistence length. The related reduction of entropy is expressed as  

AS = -3k----7. The longer the stretching vector, r, the higher the reduction of entropy. 

Mx is the quantum operator associated with the transverse magnetisation. With regard to the proton magnetic relaxation, the probe determined by the end-to-end vector r, is substituted for any chemical unit attached to the chain segment. The observation is thus delocalised over the space scale defined by the distance r = 5 nm. From the spectroscopy point of view, HD represents a dispersion of non-coherent broadening frequencies and 

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Historically, many attempts have been made to systematize the arrangement of fatty acids in the glyceride molecule. The even (34), random (35), restricted random (36), and 1,3-random (37) hypotheses were developed to explain the methods nature utilized to arrange fatty acids in fats. Invariably, exceptions to these theories were encountered. Plants and animals were found to biosynthesize fats and oils very differently. This realization has led to closer examination of biosynthetic pathways, such as chain elongation and desaturation, in individual genera and species. 

The synthetic scheme typically involves chain-extending addition of protected mononucleotides to a nucleoside bound covalentiy at the 3 -hydroxyl to an inert siUca-based soHd support, such as controlled pore glass (Fig. 11). The initial base-protected 5 -O-dimethoxytrityl (DMT) deoxynucleoside is linked to the soHd support via the reaction of a siUca-bound amino-silane and the -nitrophenylester of the 3 -succinylated nucleoside, yielding a 3 -terminal nucleoside attached to the soHd support (1) (Fig. 11). Chain elongation requites the removal of the 5 -DMT protecting group. 

FIGURE 25.13 Double bonds are introduced into the growing fatty acid chain in E. coli by specific dehydrases. Palmitoleoyl-ACP is synthesized by a sequence of reactions involving four rounds of chain elongation, followed by double bond insertion by /3-hydroxydecanoyl thioester dehydrase and three additional elongation steps. Another elongation cycle produces cA-vaccenic acid. 

Chain elongation of carboxylic acids by one methylene group... 

Reduction of the double bond yields the saturated, chain-elongated butyryl ACP. 

Further chain elongation of palmitic acid occurs by reactions similar to those just described, but CoA rather than ACP is the carrier group, ancl separate enzymes are needed for each step rather than a multienzyme synthase complex. 

Of great importance for porphyrin chemistry is the introduction of carbon substituents by Vilsmeier formylation100 or Friedel-Crafts acylation.100 The introduced substituents allow further carbon-chain elongations and other transformations so that interesting porphyrin derivatives can be synthesized. The Vilsmeier formylation of copper octaethylporphyrin (5) takes place at themethine position. The copper can then be easily removed by treatment with acid.105... 

The reagent ( )-l-(diisopropylaminocarbonyloxy)-2-butenyltitanium was also successfully applied for the chain elongation of the chiral aldehyde 9 in the total synthesis of 22,23-dihydroaver-mectin B]b. Starting from ent-9, the products ent-11 and ent-10 are formed in the same ratio110. 

CHAIN ELONGATION OF ALKENES via gem-DIHALOCYCLOPROPANES l,l-DIPHENYL-2-BROMO-3-ACETOXY-l-PROPENE... 

Such aldolase-catalyzed bidirectional chain elongation ( tandem aldolization) of simple, readily available dialdehydes has been developed into an efficient method for the generation of higher carbon sugars (e.g. (87)/(89)) by simple one-pot operations (Figure 10.32) [126,156]. The choice offuranoid (87) or pyranoid (89) nature of the products can be determined by a suitable hydroxyl substitution pattern in a corresponding cycloolefinic precursor (86) versus (88)). The overall specific substitution... 

Dias N., Dheur S., Nielsen P.E., Gryaznov S., Van Aerschot A., Herde-wijN P., Helene G., Saison-Behmoaras T. E. Antisense PNA tridecamers targeted to the coding region of Ha-ras mRNA arrest polypeptide chain elongation. J. Mol. Biol. 1999 294 403-416. 

The stereochemistry of the first step was ascertained by an X-ray analysis [8] of an isolated oxazaphospholidine 3 (R = Ph). The overall sequence from oxi-rane to aziridine takes place with an excellent retention of chiral integrity. As the stereochemistry of the oxirane esters is determined by the chiral inductor during the Sharpless epoxidation, both enantiomers of aziridine esters can be readily obtained by choosing the desired antipodal tartrate inductor during the epoxidation reaction. It is relevant to note that the required starting allylic alcohols are conveniently prepared by chain elongation of propargyl alcohol as a C3 synthon followed by an appropriate reduction of the triple bond, e. g., with lithium aluminum hydride [6b]. 

Figure 21-S. Microsomal elongase system for fatty acid chain elongation. NADH is also used by the reductases, but NADPH is preferred.

Certain long-chain unsaturated fatty acids of metabolic significance in mammals are shown in Figure 23-1. Other C20, C22, and C24 polyenoic fatty acids may be derived from oleic, linoleic, and a-flnolenic acids by chain elongation. Palmitoleic and oleic acids are not essential in the diet because the tissues can introduce a double bond at the position of a saturated fatty acid. 

Figure 23-3. Biosynthesis of the co9, co6,and co3 families of polyunsaturated fatty acids. Each step is catalyzed by the microsomal chain elongation or desaturase system 1,elongase 2,A desaturase 3,A desaturase 4,A desaturase. ( .Inhibition.)...

A number of different DNA polymerase molecules engage in DNA replication. These share three important properties (1) chain elongation, (2) processivity, and (3) proofreading. Chain elongation accounts for the rate (in nucleotides per second) at which polymerization occurs. Processivity is an expression of the number of nucleotides added to the nascent chain before the polymerase disengages from the template. The proofreading function identifies copying errors and corrects them. In E coli, polymerase III (pol III) functions at the... 

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