Specific functional groups

Alternatively, spacer arms can be introduced into a macromolecule to extend a reactive group away from its surface. The extra length of a spacer can provide less steric hindrance to conjugation and often yields more active complexes. 

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In order for the transferability of parameters to be a good description of the molecule, force fields use atom types. This means that a sp carbon will be described by different parameters than a. sp - carbon, and so on. Usually, atoms in aromatic rings are treated differently from sp atoms. Some force fields even parameterize atoms for specific functional groups. For example, the carbonyl oxygen in a carboxylic acid may be described by different parameters than the carbonyl oxygen in a ketone. 

Both the Clemmensen and the Wolff-Kishner reductions are designed to carry out a specific functional group transformation the reduction of an aldehyde or ketone carbonyl to a methylene group Neither one will reduce the carbonyl group of a carboxylic acid nor... 

Some of the analytical methods utilize highly selective and sensitive detection techniques for specific functional groups of atoms in compounds, whereas others respond in a more universal manner, i.e., to the number of carbon atoms present in the organic molecule.- ... 

An example of how information from fragmentation patterns can be used to solve structural problems is given in Worked Example 12.1. This example is a simple one, but the principles used are broadly applicable for organic structure determination by mass spectrometry. We ll see in the next section and in later chapters that specific functional groups, such as alcohols, ketones, aldehydes, and amines, show specific kinds of mass spectral fragmentations that can be interpreted to provide structural information. 

All IR spectra have many absorptions, but those useful for identifying specific functional groups are usually found in the region from 1500 cm-1 to 3300 cm-1. Pay particular attention to the carbonyl region (1670-1780 cm-1), the aromatic region... 

Common chemistries include tannins and lignins but also more modem polyacrylates and derivatives, which often act as carriers for specific functional groups and provide novel chemistry molecules. The polyacrylates may also be copolymerized, perhaps with maleates [maleic anhydride, cis-butenedioic anhydride (OCOCHrCHCO) is the usual starting point material], styrene (vinylbenzene, phenylethylene,... 

For the most part, it is the provision of specific functional groups into certain positions on a backbone molecule, and its subsequent polymerization to form chains of particular molecular weight ranges, that gives the novel chemistry co- and terpolymers their beneficial and sometimes unique properties. Polyacrylates are commonly employed as backbone molecules. 

Proteins derive their powerful and diverse capacity for molecular recognition and catalysis from their ability to fold into defined secondary and tertiary structures and display specific functional groups at precise locations in space. Functional protein domains are typically 50-200 residues in length and utilize a specific sequence of side chains to encode folded structures that have a compact hydrophobic core and a hydrophilic surface. Mimicry of protein structure and function by non-natural ohgomers such as peptoids wiU not only require the synthesis of >50mers with a variety of side chains, but wiU also require these non-natural sequences to adopt, in water, tertiary structures that are rich in secondary structure. 

Suitable reagents for derivatizing specific functional groups are summarized in Table 8.21. Many of the reactions and reagents are the familiar ones used in qualitative analysis for the characterization of organic compounds by physical means. Alcohols are converted to esters by reaction with an acid chloride in the presence of a base catalyst (e.g., pyridine, tertiary amine, etc). If the alcohol is to be recovered after the separation, then a derivative which is fairly easy to hydrolyze, such as p-nltrophenylcarbonate, is convenient. If the sample contains labile groups, phenylurethane derivatives can be prepared under very mild reaction conditions. Alcohols in aqueous solution can be derivatized with 3,5-dinitrobenzoyl chloride. 

Chemical separations may first be accomplished by partitioning on the basis of polarity into a series of solvents from non-polar hexane to very polar compounds like methanol. Compounds may also be separated by molecular size, charge, or adsorptive characteristics, etc. Various chromatography methods are utilized, including columns, thin layer (TLC) gas-liquid (GLC), and more recently, high pressure liquid (HPLC) systems. HPLC has proven particularly useful for separations of water soluble compounds from relatively crude plant extracts. Previously, the major effort toward compound identification involved chemical tests to detect specific functional groups, whereas characterization is now usually accomplished by using a... 

The latter could be obtained, if particular donor substituents (e.g. specific functional groups) facing corresponding acceptor groups of the guest molecule are added to the host and vice versa, thus using specific host-guest interactions of polar... 

These enzymes catalyse the non-hydrolytic cleavage of bonds in a substrate to remove specific functional groups. Examples include decarboxylases, which remove carboxylic acid groups as carbon dioxide, dehydrases, which remove water, and aldolases. The decarboxylation of pyruvic acid (10.60) to form acetaldehyde (10.61) takes place in the presence of pyruvic decarboxylase (Scheme 10.13), which requires the presence of thiamine pyrophosphate and magnesium ions for activity. 

More potentially useful rhena-/8-ketoimine complexes have been prepared in which the rhena-/6-ketoimine group is attached to a molecular fragment that reacts with specific functional groups. In Eq. (5), the... 

The reactivity of organic compounds toward eh varies systematically (Hart and Anbar, 1970), the variation often attributable to electron density of a specific functional group. Other generalizations are the following ... 

Fourier transform infrared (FTIR) spectroscopy, 13C nuclear magnetic resonance (NMR) spectroscopy, ultraviolet-visible (UV-VIS) and fluorescence spectroscopy can be integrated with chromatographic techniques especially in the study of ageing and degradation of terpenic materials. They can be used to study the transformation, depletion or formation of specific functional groups in the course of ageing. 

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