Functional Group Control

Bacterial cell walls contain different types of negatively charged (proton-active) functional groups, such as carboxyl, hydroxyl and phosphoryl that can adsorb metal cations, and retain them by mineral nucleation. Reversed titration studies on live, inactive Shewanella putrefaciens indicate that the pH-buffering properties of these bacteria arise from the equilibrium ionization of three discrete populations of carboxyl (pKa = 5.16 0.04), phosphoryl (oKa = 7.22 0.15), and amine (/ Ka = 10.04 0.67) groups (Haas et al. 2001). These functional groups control the sorption and binding of toxic metals on bacterial cell surfaces. 

A new convenient polymer modification for the conversion of the Si—H to Si—OH by the selective oxidation of the Si—H bond by dimethyldioxirane has been described. The oxyfunctionalization of the silane precursor polymers proceeded rapidly and quantitatively and can be applied to the synthesis of a wide variety of novel silanol polymers with specific properties from the corresponding precursor polymers containing Si—H functional groups. Control over the properties of these silanol polymers, such as reactivity and self-association of silanols, was realized through the placement of different substitute groups bonded directly to the silicon atom and by the variation of silanol composition in a copolymer. These novel silanol polymers with a... 

The mobility of the alkylchain,4,11 as well as the accessibility of the functional group control the separation efficiency. Gilpin12 found no difference in chromatographic performance in comparing a bidentate alkylsilane modified silica to its monodentate analogue. This indicates that chain mobility only has a minor influence on performance, for n-alkyl ligands. 

Scheme 19.58 Functional-group-controlled site-selective alkylation.

Until now, we have considered the disconnection of C-C bonds by participation of one functional group. In this chapter, we discuss examples where two functional groups control selection of the preferred C-C bond for disconnection by their electronic effects. Most heteroatoms (O, N S, Hal) in organic molecules are more electronegative, whereas P, Si and aU metals are more electropositive than carbon. The polarization C-heteroatom bond dictates the direction of the imaginative flow of the electrons in the disconnected C-C bond at a distance from the functional group. 

The condensation conditions must be as mild as possible, because we want to get only the most stable of the three possible enols (from the aldehyde). Though you could not haye predicted the exact conditions either for the double bond. cleayage or for the condensation, you should haye seen that control was possible as in each case the two functional groups are different enough. ( J. Amer. Chem. Soc.. 1960, 636 J. Org. Chem.. 1964, 29, 3740 ... 

Chlorination is carried out m a manner similar to brommation and provides a ready route to chlorobenzene and related aryl chlorides Fluormation and lodmation of benzene and other arenes are rarely performed Fluorine is so reactive that its reaction with ben zene is difficult to control lodmation is very slow and has an unfavorable equilibrium constant Syntheses of aryl fluorides and aryl iodides are normally carried out by way of functional group transformations of arylammes these reactions will be described m Chapter 22... 

Function 5 provides thermoset reactivity via functional groups such as methacrylates and amines. Function 6 permits the presence of two or three pendent organic groups. This allows all functionality to be controlled to the first-, second-, or third-degree levels. 

Carbon Cha.in Backbone Polymers. These polymers may be represented by (4) and considered derivatives of polyethylene, where n is the degree of polymeriza tion and R is (an alkyl group or) a functional group hydrogen (polyethylene), methyl (polypropylene), carboxyl (poly(acryhc acid)), chlorine (poly(vinyl chloride)), phenyl (polystyrene) hydroxyl (poly(vinyl alcohol)), ester (poly(vinyl acetate)), nitrile (polyacrylonitrile), vinyl (polybutadiene), etc. The functional groups and the molecular weight of the polymers, control thek properties which vary in hydrophobicity, solubiUty characteristics, glass-transition temperature, and crystallinity. 

Surface properties are generally considered to be controlled by the outermost 0.5—1.0 nm at a polymer film (344). A logical solution, therefore, is to use self-assembled monolayers (SAMs) as model polymer surfaces. To understand fully the breadth of surface interactions, a portfoHo of chemical functionahties is needed. SAMs are especially suited for the studies of interfacial phenomena owing to the fine control of surface functional group concentration. 

The living polymerization process offers enormous flexibiUty in the design of polymers (40). It is possible to control terminal functional groups, pendant groups, monomer sequencing along the main chain (including the order of addition and blockiness), steric stmcture, and spatial shape. 

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