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Even if a polymer is synthesized free from contaminants and impurities, it is still not a pure substance in the usually accepted sense Polymers, in their purest form, are mixtures of molecules of different molecular weight The reason for the polydispersity of polymers lies in the statistical variations present in the polymerization processes When one discusses the molecular weight of a polymer, one is actually involved with its average molecular weight Both the average molecular weight and the exact distribution of different molecular weights within a polymer are required in order to fully characterize it The control of molecular weight and molecular weight distribution (MWD) is often used to obtain and improve certain desired physical properties in a polymer product Various methods based on solution properties are used to determine the average molecular weight of a polymer sample.



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These include methods based on colligative properties, light scattering, and viscosity [Heimenz, 1984; Morawetz, 1975; Slade, 1998; Sperling, 2001] The various methods do not yield the same average molecular weight Different average molecular weights are obtained because the properties being measured are biased differently toward the different-sized polymer molecules in a polymer sample Some methods are biased toward the larger-sized polymer molecules, while other methods are biased toward the smaller-sized molecules The result is that the average molecular weights obtained are correspondingly biased toward the larger- or smaller-sized molecules The following average molecular weights are determined: 1 The number-average molecular weight M n is determined by experimental methods that count the number of polymer molecules in a sample of the polymer.

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The methods for measuring M n are those that measure the colligative properties of solutions vapor pressure lowering (vapor pressure osmometry), freezing point depression (cryoscopy), boiling point elevation (ebulliometry), and osmotic pressure (membrane osmometry) The colligative properties are the same for small and large molecules when comparing solutions at the same molal (or mole fraction) concentration For example, a 1-molal solution of a polymer of molecular weight 105 has the same vapor pressure, freezing point, boiling point, and osmotic.

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MISCELLANEOUS TOPICS Enzymatic Polymerizations In Vivo (within Living Cells)

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Plants and animals synthesize a number of polymers (e.g., polysaccharides, proteins, nucleic acids) by reactions that almost always require a catalyst. The catalysts present in living systems are usually proteins and are called enzymes. Reactions catalyzed by enzymes are called enzymatic reactions; polymerizations catalyzed by enzymes are enzymatic polymerizations. Humans bene t from naturally occurring polymers in many ways. Our plant and animal foodstuffs consist of these polymers as well as nonpolymeric materials (e.g., sugar, vitamins, minerals). We use the polysaccharide cellulose (wood) to build homes and other structures and to produce paper. Various microorganisms, such as yeast and bacteria, have been used in industrial bioreactors to produce a host of important products, including alcoholic beverages, penicillin, and carbohydrates (including polysaccharides such as starch). More recently, proteins have been produced for therapeutic purposes by recombinant DNA technology [Blei and Odian, 2000]. Diabetics who lack insulin have until now taken insulin derived from other animals such as pigs and beef. Pig and beef insulins are close to but not exactly the same in structure as human insulin. The bacterium Escherichia coli has been used to produce human insulin by recombinant DNA technology. The bacterial DNA is altered in the laboratory to contain the gene for human insulin and then inserted into the organism by various techniques

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(chemical or thermal shock, viral vectors, microinjection) The E coli are fooled into using the altered DNA to produce the desired human protein The protein is then harvested by breaking the bacterial cell walls and using an appropriate separation technique This approach offers much potential for producing a host of therapeutic proteins There has been an effort to use microorganisms to produce commodity polymers for use as plastics, elastomers, and bers as a supplement to the polymers produced by the traditional methods such as those described throughout this chapter Some species of bacteria produce poly(hydroxyalkanoate) (PHA) storage (reserve) polymers when growth is restricted by some nutrient other that their carbon-containing food source [Jung et al, 2000; Shah et al, 2000] (This is analogous to the storage in higher animals of carbohydrates and lipids as glycogen and triacylglycerols, respectively [Blei and Odian, 2000].

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