Contents 4 Covalent Structures

Artificial membranes are used to study the influence of drug structure and of membrane composition on drug-membrane interactions. Artificial membranes that simulate mammalian membranes can easily be prepared because of the readiness of phospholipids to form lipid bilayers spontaneously. They have a strong tendency to self-associate in water. The macroscopic structure of dispersions of phospholipids depends on the type of lipids and on the water content. The structure and properties of self-assembled phospholipids in excess water have been described [74], and the mechanism of vesicle (synonym for liposome) formation has been reviewed [75]. While the individual components of membranes, proteins and lipids, are made up of atoms and covalent bonds, their association with each other to produce membrane structures is governed largely by hydrophobic effects. The hydrophobic effect is derived from the structure of water and the interaction of other components with the water structure. Because of their enormous hydrogen-bonding capacity, water molecules adopt a structure in both the liquid and solid state. 

As has been described in Chapter 4, random copolymers of styrene (St) and 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) form a micelle-like microphase structure in aqueous solution [29]. The intramolecular hydrophobic aggregation of the St residues occurs when the St content in the copolymer is higher than ca. 50 mol%. When a small mole fraction of the phenanthrene (Phen) residues is covalently incorporated into such an amphiphilic polyelectrolyte, the Phen residues are hydrophobically encapsulated in the aggregate of the St residues. This kind of polymer system (poly(A/St/Phen), 29) can be prepared by free radical ter-polymerization of AMPS, St, and a small mole fraction of 9-vinylphenanthrene [119]. 

With increasing B content, the covalent component of the bonding in boride lattices increases owing to the appearance of direct B—B bonds and a decrease in the metallic bond character, e.g., in the structural series of the CUAI2 family ... 

We investigated the efficiency of NSC expansion on surfaces with EGF-His immobilized in the correct orientation. NSCs were obtained from neurosphere cultures prepared from fetal rat striatum harvested on embryonic day 16. NSCs were cultured for 5 days on EGF-His-immobilized substrates prepared with mixed SAMs of different COOH-thiol contents. Cells adhered and formed network structures at a density that increased with the COOH-thiol content of the surface. As a control, cells were seeded onto surfaces without immobilized EGF-His. This resulted in poor cell adhesion during the entire culture period. In addition, when EGF-His adsorbed to SAMs with 100% COOH-thiol or SAMs with NTA-derivatized COOH that lacked Ni2+ chelation, we observed poor initial cell adhesion, and the cells formed aggregates within 5 days. Interestingly, the substrate used to covalently immobilize EGF-His with the standard carbodiimide chemistry was not a suitable surface for cell adhesion and proliferation. The control experimental results contrasted markedly with results from EGF-His-chelated surfaces. 

Monomeric TNF is biologically inactive the active form is a homotrimer in which the three monomers associate non-covalently about a threefold axis of symmetry, forming a compact bellshaped structure. X-ray crystallographic studies reveal that each monomer is elongated and characterized by a large content of antiparallel P pleated sheet, which closely resembles subunit proteins of many viral caspids (Figure 9.4). 

The three major classes of biopolymers found in eukaryotic systems are nucleic acids, proteins, and polysaccharides. The latter class is the most complex with respect to structural and stereochemical diversity. Polysaccharides indeed possess a massive information content. Furthermore, polysaccharides are commonly found in nature covalently attached (conjugated) to other biomolecules such as proteins, isoprenoids, fatty acids, and lipids.1... 

Extended anionic partial structures of mercury occur in some high melting amalgams (MHg2 and related examples) with medium Hg content. Significant ionic bonding contributions between M and Hg in addition to covalent Hg-Hg contributions can be assumed to be responsible for the properties of these solids. 

Although the histone fold was first described from the structure of the histone octamer core of the nucleosome [17], the high a-helical content was predicted much earlier [43]. The core histones possess three functional domains (1) the histone fold domain, (2) an N-terminal tail domain, and (3) various accessory helices and less structured regions. The N-terminal tail domains of the core histones are currently the focus of intense research. Covalent modifications of residues in these unstructured domains appear to modify local chromatin structure, either directly or... 

The plasma membrane is a delicate, semipermeable, sheetlike covering for the entire cell. Forming an enclosure prevents gross loss of the intracellular contents the semipermeable character of the membrane permits the selective absorption of nutrients and the selective removal of metabolic waste products. In many plant and bacterial (but not animal) cells, a cell wall encompasses the plasma membrane. The cell wall is a more porous structure than the plasma membrane, but it is mechanically stronger because it is constructed of a covalently cross-linked, three-dimensional network. The cell wall maintains a cell s three-dimensional form when it is under stress. 

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