Fragment, bonding between fragments

As indicated above, the observed effect of intermolecular coordination results in the formation of alternating copolymers having coordination bonds between fragments of the corresponding comonomers. ... 

The primary structure of a peptide is given by its ammo acid sequence plus any disulfide bonds between two cysteine residues The primary structure is determined by a systematic approach m which the protein is cleaved to smaller fragments even individual ammo acids The smaller fragments are sequenced and the mam sequence deduced by finding regions of overlap among the smaller peptides... 

Scheme 1. (a) Formation of a fragment with m/z = 247 from a covalent bond between y-GPS and DBA dimer, (b) Final structure of the cation with mjz = 247. Reproduced by permission of the American Chemical Society from Ref. [55]. 

One area where the concept of atomic charges is deeply rooted is force field methods (Chapter 2). A significant part of the non-bonded interaction between polar molecules is described in terms of electrostatic interactions between fragments having an internal asymmetry in the electron distribution. The fundamental interaction is between the Electrostatic Potential (ESP) generated by one molecule (or fraction of) and the charged particles of another. The electrostatic potential at position r is given as a sum of contributions from the nuclei and the electronic wave function. 

Carbonyl compounds can undergo various photochemical reactions among the most important are two types of reactions that are named after Norrish. The term Norrish type I fragmentation refers to a photochemical reaction of a carbonyl compound 1 where a bond between carbonyl group and an a-carbon is cleaved homolytically. The resulting radical species 2 and 3 can further react by decarbonylation, disproportionation or recombination, to yield a variety of products. 

In addition to fragmentation by the McLafferty rearrangement, aldehydes and ketones also undergo cleavage of the bond between the carbonyl group and the a carbon, a so-called a cleavage. Alpha cleavage yields a neutral radical and a resonance-stabilized acyl cation. 

Isothermal a—time curves for the decomposition of U02(CH3C02)2 in air (513—573 K) [1018] showed two approximately linear regions, 0.0 < a < 0.2 and 0.2 < a < 0.9, for which the values of E were 107 and 165 kJ mole-1, respectively. In nitrogen, the earlier portion of the curve was not linear and E = 151 kJ mole-1 for the later interval. The zero-order kinetic behaviour was explained by growth of nuclei in thin, plate-like crystals, which were shown by microscopic and surface area measurements to fragment when a > 0.85. The proposed initial step in the decomposition was fission of bonds between the U02+ and the (OCO CH3) species [1018]. 

The second structural type found for organometallic cobalt porphyrins contains an organic fragment bridged between the cobalt and one pyrrolic nitrogen. Cobalt complexes of N-alkyl- or N-arylporphyrins arc well established (but will not be specifically addressed here). The bridged complexes are derivatives of these where the N-alkyl group also forms a cr-bond to cobalt. They are also related to the axially... 

There are two main classes of proteolytic digestive enzymes (proteases), with different specificities for the amino acids forming the peptide bond to be hydrolyzed. Endopeptidases hydrolyze peptide bonds between specific amino acids throughout the molecule. They are the first enzymes to act, yielding a larger number of smaller fragments, eg, pepsin in the gastric juice and trypsin, chymotrypsin, and elastase secreted into the small intestine by the pancreas. Exopeptidases catalyze the hydrolysis of peptide bonds, one at a time, fi"om the ends of polypeptides. Carboxypeptidases, secreted in the pancreatic juice, release amino acids from rhe free carboxyl terminal, and aminopeptidases, secreted by the intestinal mucosal cells, release amino acids from the amino terminal. Dipeptides, which are not substrates for exopeptidases, are hydrolyzed in the brush border of intestinal mucosal cells by dipeptidases. 

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