Linear polymers, defined

All enzymes are proteins, with the exception of the recently discovered ribozymes. Ribozymes are special ribonucleic acids performing catalytic functions in the processing of RNA which will not be considered here. Proteins are polar macromolecules with molecular mass in the range 104-106. They are linear polymers, defined by the sequence of amino acids, which are linked by peptide bonds ... 

For example, a polypeptide is synthesized as a linear polymer derived from the 20 natural amino acids by translation of a nucleotide sequence present in a messenger RNA (mRNA). The mature protein exists as a weU-defined three-dimensional stmcture. The information necessary to specify the final (tertiary) stmcture of the protein is present in the molecule itself, in the form of the specific sequence of amino acids that form the protein (57). This information is used in the form of myriad noncovalent interactions (such as those in Table 1) that first form relatively simple local stmctural motifs (helix... 

At yet higher temperatures (>1.4T ) the secondary bonds melt completely and even the entanglement points slip. This is the regime in which thermoplastics are moulded linear polymers become viscous liquids. The viscosity is always defined (and usually measured) in shear if a shear stress o produces a rate of shear 7 then the viscosity (Chapter 19) is... 

Although polyethylene is virtually defined by its very name as a polymer of ethylene produced by addition polymerisation, linear polymers with the formula (CH2), have also been prepared by condensation reactions. For example in 1898 von Pechmann produced a white substance from an ethereal solution of... 

Among the physical characteristics of these nonlinear condensation polymerizations, the occurrence of a sharp gel point is of foremost significance. At the gel point, which occurs at a well-defined stage in the course of the polymerization, the condensate transforms suddenly from a viscous liquid to an elastic gel. Prior to the gel point, all of the polymer is soluble in suitable solvents, and it is fusible also. Beyond the gel point, it is no longer fusible to a liquid nor is it entirely soluble in solvents. Linear polymers, on the other hand, remain soluble in suitable solvents and fusible to liquids as well (unless the melting point is above the temperature of thermal decomposition), regardless of the extent of condensation. 

Several assumptions were made in using the broad MWD standard approach for calibration. With some justification a two parameter equation was used for calibration however the method did not correct or necessarily account for peak speading and viscosity effects. Also, a uniform chain structure was assumed whereas in reality the polymer may be a mixture of branched and linear chains. To accurately evaluate the MWD the polymer chain structure should be defined and hydrolysis effects must be totally eliminated. Work is currently underway in our laboratory to fractionate a low conversion polydlchlorophosphazene to obtain linear polymer standards. The standards will be used in polymer solution and structure studies and for SEC calibration. Finally, the universal calibration theory will be tested and then applied to estimate the extent of branching in other polydlchlorophosphazenes. 

The simplest, from the viewpoint of topological structure, are the linear polymers. Depending on the number m of the types of monomeric units they differentiate homopolymers (m=1) and copolymers (m>2). In the most trivial case molecules in a homopolymer are merely identified by the number l of monomeric units involved, whereas the composition of a copolymer macromolecule is defined by vector 1 with components equal to the numbers of mono-... 

Carbosilanes, defined this narrowly, as a class, monomers, cyclic and polycyclic oligomers and linear polymers, with emphasis on the cyclic and polycyclic systems, have been discussed in detail in an excellent recent book by Fritz and Matern [2]. 

In their seminal work in 1949, Zimm and Stockmayer [69] defined the ratio of the mean square radii of gyration of a branched and a linear polymer of equal molecular weight as the parameter g and is related to the parameter g, which is the ratio of the intrinsic viscosities of a branched and a linear polymer [65-69]. 

The present interest in linear polymers of defined structure can be traced back to... 

A second, and potentially more useful feature is the stability of these unimolecu-lar initiators to a wide variety of reaction and polymerization conditions which is in sharp contrast to traditional initiators for anionic procedures, such as n-butyl lithium. This allows the initiators to be fully characterized, purified and handled by normal techniques, thus simplifying the polymerization process. It also permits a variety of chemical transformations to be performed on the initiator prior to polymerization, which greatly facilitates the preparation of chain end functionalized macromolecules. For example, the chloromethyl functionalized al-koxyamine, 18, can be readily converted in high yield to the corresponding aminomethyl derivative, 19, followed by polymerization to give well-defined linear polymers, 20, with a single primary amine at the chain end (Scheme 12). 

Other dilute solution properties depend also on LCB. For example, the second virial coefficient (A2) is reduced due to LCB. However, near the Flory 0 temperature, where A2 = 0 for linear polymers, branched polymers are observed to have apparent positive values of A2 [35]. This is now understood to be due to a more important contribution of the third virial coefficient near the 0 point in branched than in linear polymers. As a consequence, the experimental 0 temperature, defined as the temperature where A2 = 0 is lower in branched than in linear polymers [36, 37]. Branched polymers have also been found to have a wider miscibility range than linear polymers [38], As a consequence, high MW highly branched polymers will tend to coprecipitate with lower MW more lightly branched or linear polymers in solvent/non-solvent fractionation experiments. This makes fractionation according to the extent of branching less effective. 

As was described earlier, the internal SDD of dendrimers is remarkably high compared to traditional polymers and is well defined by a narrow transition zone at the outside. When linear polymers are forced together by increasing their concentration in a solvent, they freely interpenetrate each other due to their open structure. Dendrimers, on the other hand, appear to represent a different case, due to their compact size and architectural features. 

Molecular catalysts, often in the form of metal ions complexed to a suitable ligand, can also be attached to dendrimer surfaces [3,9,10,93,94,96,148,149]. Such materials are generally structurally better defined than catalysts bounded to linear polymers, but like random-polymer catalysts they can be easily separated from reaction products. Note, however, that this approach results in a synthetic dead-end as far as further manipulation of the terminal groups is concerned, and thus some of the advantages of using dendrimers, such as solubility modulation, are lost. 

One of the possible alternative to micelles are spherical dendrimers of diameter generally ranging between 5 and 10 nm. These are highly structured three-dimensional globular macromolecules composed of branched polymers covalently bonded to a central core [214]. Therefore, dendrimers are topologically similar to micelles, with the difference that the strnctnre of micelles is dynamic whereas that of dendrimers is static. Thus, unlike micelles, dendrimers are stable nnder a variety of experimental conditions. In addition, dendrimers have a defined nnmber of fnnctional end gronps that can be functionalized to prodnce psendostationary phases with different properties. Other psendostationary phases employed to address the limitations associated with the micellar phases mentioned above and to modnlate selectivity include water-soluble linear polymers, polymeric surfactants, and gemini snrfactant polymers. 

Highly structured, 3-D nanoparticle-polymer nanocomposites possess unique magnetic, electronic, and optical properties that differ from individual entities, providing new systems for the creation of nanodevices and biosensors (Murray et al. 2000 Shipway et al. 2000). The choice of assembly interactions is a key issue in order to obtain complete control over the thermodynamics of the assembled system. The introduction of reversible hydrogen bonding and flexible linear polymers into the bricks and mortar concept gave rise to system formation in near-equilibrium conditions, providing well-defined stmctures. 

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