Polymer backbone, features

An elegant synthesis method which is specific to sulfone polymers containing phenyl—phenyl linkages (such as PPSF) is the nickel-catalysed coupling of aryl dihahdes. The scheme for this synthesis involves a two-step process. First, an aromatic dihaUde intermediate is formed which carries the backbone features of the desired polymer. This aromatic dihahde intermediate is then self-coupled in the presence of sero-valent nickel, triphenylphosphine, and excess sine to form the biphenyl- or terphenyl-containing polymer. AppHcation of this two-step scheme to PPSF can be depicted as follows ... 

The common feature of the p-phenylene group stiffens the polymer backbone so that the polymers have higher TgS than similar polymers which lack the aromatic group. As a consequence the aromatic polymers tend to have high heat deformation temperatures, are rigid at room temperature and frequently require high processing temperatures. 

Erdmann et al. (2000) report the fabrication of devices for the localized delivery of salicylic acid from the poly(anhydride-co-ester)s mentioned in Section II.C. A unique feature of this drug delivery system is that the drug compound is part of the polymer backbone. Devices were implanted intraorally and histopathology was reported (Erdmann et al., 2000). Chasin et al. (1990) review fabrication and testing of implantable formulations for other drugs including angiogenesis inhibitors for treatment of carcinomas and bethanechol for the treatment of Alzheimer s disease. 

Sealants obtained by curing polysulfide liquid polymers with aryl bis(nitrile oxides) possess stmctural feature of thiohydroximic acid ester. These materials exhibit poor thermal stability when heated at 60°C they soften within days and liquefy in 3 weeks. Products obtained with excess nitrile oxide degrade faster than those produced with equimolar amounts of reagents. Spectroscopic studies demonstrate that, after an initial rapid addition between nitrile oxide and thiol, a second slower reaction occurs which consumes additional nitrile oxide. Thiohydroximic acid derivatives have been shown to react with nitrile oxides at ambient temperature to form 1,2,4-oxadiazole 4-oxides and alkyl thiol. In the case of a polysulfide sealant, the rupture of a C-S bond to form the thiol involves cleavage of the polymer backbone. Continuation of the process leads to degradation of the sealant. These observations have been supported by thermal analysis studies on the poly sulfide sealants and model polymers (511). 

A striking feature of the stereoregular polyacetylenes is their simple NMR spectral patterns, which facilitates elucidation of the polymerization mechanism as well as the polymer structure. A co-polymer of phenylacetylene with partly G-labeled phenylacetylene (Ph G= GH) shows two doublet carbon signals with /i3c-i3C of 72 Hz, indicating the presence of G= G bond in the polymer backbone.This is a clear indication of the insertion mechanism instead of the metathesis pathway. 

Another noteworthy feature of the polymeric silane depicted in Fig. la is that the silane chains on the polymer backbone carry dialkoxy groups. In comparison with monomeric silanes which carry trialkoxy groups, these polymeric silanes are claimed to offer superior substrate reactivity and to provide further performance improvements [4, 5]. A probable explanation seems to be the difference in the number of siloxane bonds that can possibly be formed with the glass surface by the two types. 

A major development in this area was brought about by the invention of crosslinked polystyrene-supported 9-(/)-chlorobenzoy 1 )quinine ligands 17 [54] and 18 [55], The salient feature of this invention is the connection of the quinine unit to the polymer backbone through a sterically undemanding spacer. Thereby, the quinuclidine, which in catalysis coordinates to osmium, is free of steric interaction with the polymeric side chain. Dihydroxylation of trans-stilbene in the presence of 17 and NMO as co-oxidant gave stilbene diol with 87% ee. However, changing the terminal oxidant to K3[Fe(CN6)] led to full inhibition of the reaction. This result was explained by a possible collapse of the polymer in the required protic solvent, which prevented substrate penetration. 

Disaccharides can have similar utility to monosaccharides in DNA delivery polymers. Trehalose, a disaccharide composed of two glucose units linked via an a-(l—>1) glycosidic bond, has been shown to have cryo- and lyo-protective properties, attributed to an unusually large hydration volume [152]. As a function of these properties, trehalose has been shown to prevent aggregation and fusion of proteins and lipids [153]. Logically, incorporation of these features into a polymer backbone could afford similar characteristics to a DNA delivery system and may prevent aggregation of polyplexes in physiological serum concentrations and ionic... 

Glucose Sensors. Siloxane polymers are known to be extremely flexible. This flexibility will, of course, be sensitive to the amount of side-chain substitution present along the polymer backbone. For instance, in the homopolymer used in these studies (polymer A), the presence of a ferrocenylethyl moiety bound to each silicon subunit should provide an additional degree of steric hindrance, and thus a barrier to rotation about the siloxane backbone, in comparison with the copolymers, which have ferrocene relays attached to only a fraction of the Si atoms. Because these siloxane polymers are insoluble in water, their flexibility is an important factor in their ability to facilitate electron transfer from the reduced enzyme. Relays contained within more rigid redox polymers, such as poly(vinylferrocene), cannot achieve close contact with the enzyme s redox centers and are thus less effective as electron transfer mediators (25,34). The importance of this feature can be seen quite clearly by comparing the mediating ability of the homopolymer A with that of copolymers B-D, as shown in Figures 4 and 5. 

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