Chain-like

The features created by crustal movements may be mountain chains, like the Himalayas, where collision of continents causes extensive compression. Conversely, the depressions of the Red Sea and East African Rift Basin are formed by extensional plate movements. Both type of movements form large scale depressions into which sediments from the surrounding elevated areas ( highs ) are transported. These depressions are termed sedimentary basins (Fig. 2.3). The basin fill can attain a thickness of several kilometres. 

The sequence of amino acids in a peptide can be written using the three-letter code shown in Figure 45.3 or a one-letter code, both in common use. For example, the tripeptide, ala.ala.phe, could be abbreviated further to AAF Although peptides and proteins have chain-like structures, they seldom produce a simple linear system rather, the chains fold and wrap around each other to give complex shapes. The chemical nature of the various amino acid side groups dictates the way in which the chains fold to arrive at a thermodynamically most-favored state. 

The highly conductive class of soHds based on TTF—TCNQ have less than complete charge transfer (- 0.6 electrons/unit for TTF—TCNQ) and display metallic behavior above a certain temperature. However, these soHds undergo a metal-to-insulator transition and behave as organic semiconductors at lower temperatures. The change from a metallic to semiconducting state in these chain-like one-dimensional (ID) systems is a result of a Peieds instabihty. Although for tme one-dimensional systems this transition should take place at 0 Kelvin, interchain interactions lead to effective non-ID behavior and inhibit the onset of the transition (6). 

It is usual to think that plastics are a relatively recent development but in fact, as part of the larger family called polymers, they are a basic ingredient of animal and plant life. Polymers are different from metals in the sense that their structure consists of very long chain-like molecules. Natural materials such as silk, shellac, bitumen, rubber and cellulose have this type of structure. However, it was not until the 19th century that attempts were made to develop a synthetic... 

The words polymers and plastics are often taken as synonymous but in fact there is a distinction. The polymer is the pure material which results from the process of polymerisation and is usually taken as the family name for materials which have long chain-like molecules (and this includes rubbers). Pure polymers are seldom used on their own and it is when additives are present that the term plastic is applied. Polymers contain additives for a number of reasons. The following list outlines the purpose of the main additives used in plastics. 

In a thermoplastic material the very long chain-like molecules are held together by relatively weak Van der Waals forces. A useful image of the structure is a mass of randomly distributed long strands of sticky wool. When the material is heated the intermolecular forces are weakened so that it becomes soft and flexible and eventually, at high temperatures, it is a viscous melt. 

Conventional rubbers are members of the polymer family in that they consist of long chain-like molecules. These chains are coiled and twisted in a random... 

Compounds containing a heteroatom in the / -position of the side-chain, like 2-(propynyloxymethyl)pyrimidines (R = H, SiMej) and 5-phenyl-2-[2-(l-pro-2-ynyl)pyrolidin-2-yl)]pyrimidine react smoothly at 140 °C to give 5,7-dihydrofuro[3,4-h]pyridine (89T5151) and 3-phenylpyrido[3,2-c]pyrroli-zine, respectively (Scheme 38) (92JOC3000). 

Polymerization is a reaction in which chain-like macromolecules are formed hy comhining small molecules (monomers). 

The molecules join together to form a long chain-like molecule which may contain many thousands of ethylene units. Such a molecule is referred to as a polymer, in this case polyethylene, whilst in this context ethylene is referred to as a monomer. Styrene, propylene, vinyl chloride, vinyl acetate and methyl methacrylate are other examples of monomers which can polymerise in this way. Sometimes two monomers may be reacted together so that residues of both are to be found in the same chain. Such materials are known as copolymers and are exemplified by ethylene-vinyl acetate copolymers and styrene-acrylonitrile copolymers. 

Compounds that contain only hydrogen and carbon are called hydrocarbons. The hydrocarbons that have only single bonds all have similar chemistry and they are called, as a family, the saturated hydrocarbons. If there are carbon-carbon double bonds, the reactivity is much enhanced. Hence hydrocarbons containing one or more double bonds are named as a distinct family, unsaturated hydrocarbons. Both saturated and unsaturated hydrocarbons can occur in chain-like structures or in cyclic structures. Each of these families will be considered. 

The tendency of the halogens to form chain-like polyanions that are stabilized by delocalization of the negative charge [15,34] is a basic chemical principle. Donor-acceptor interactions between Lewis-acidic Br2 and halide anions, but also with polyhalides acting as Lewis bases, give rise to the formation of a variety of homo and heteroatomic adducts. The maximum number of atoms in these chains increases with the atomic weights... 

The maximum values of the percolation threshold are characteristic of matrix systems in which the filler does not form the chain-like structures till large concentrations are obtained. In practice, statistical or structurized systems are apparently preferable because they become conductive at considerably smaller concentrations of the filler. The deviation of the percolation threshold from the values of Cp to either side for a statistical system ( 0.15) can be used to judge the nature of filler distribution. 

Figure 7.2 Excess thermodynamic functions at 7= 298.15 K for. Y1C10H22 +. Y2C6H14, an example of a system where nonpolar chain-like molecules are mixed.

The importance of polydispersity is an interesting clue that it may be possible to tailor the weak interactions between polymer brushes by controlled polydispersity, that is, designed mixtures of molecular weight. A mixture of two chain lengths in a flat tethered layer can be analyzed via the Alexander model since the extra chain length in the longer chains, like free chains, will not penetrate the denser, shorter brush. This is one aspect of the vertical segregation phenomenon discussed in the next section. 

The alternation of double and single bonds means that each C atom has an unhybridized /7-orbital that can overlap with the /7-orbital on either side. This arrangement allows electrons to be delocalized along the entire chain like a onedimensional version of graphite. 

The analysis demonstrates the elegant use of a very specific type of column packing. As a result, there is no sample preparation, so after the serum has been filtered or centrifuged, which is a precautionary measure to protect the apparatus, 10 p.1 of serum is injected directly on to the column. The separation obtained is shown in figure 13. The stationary phase, as described by Supelco, was a silica based material with a polymeric surface containing dispersive areas surrounded by a polar network. Small molecules can penetrate the polar network and interact with the dispersive areas and be retained, whereas the larger molecules, such as proteins, cannot reach the interactive surface and are thus rapidly eluted from the column. The chemical nature of the material is not clear, but it can be assumed that the dispersive surface where interaction with the small molecules can take place probably contains hydrocarbon chains like a reversed phase. 

The relative stabilities of RSSR and R2S=S for R=OH and SH have been determined by Steudel and co-workers [23, 24]. At the MP2/6-311G //HF/ 6-311G +ZPE level of theory, (HO)2S=S (thiosulfurous acid) is just 13 kj mol less stable than the chain-like isomer HOSSOH (dihydroxydisul-fane) [23]. For R=SH, (HS)2S=S is less stable than the corresponding trisul-fane HSSSH by 132 kJ mor (MP2/6-31G -//HF/4-31G) [24]. 

It is well estabhshed that sulfur compounds as well as elemental sulfur have the tendency to form long chain molecules. All of these substances can be regarded as derivatives of the hydrogen polysulfanes (or polysulfanes) H2S . Polysulfanes form a long series of homologous chain-like molecules since the number n can assume any value. S-S and S-H bonds are frequently found in chemical and biological systems. Thus, polysulfanes have been the subject of numerous experimental and theoretical studies (for a recent review, see [15]). 

Using the first-principles molecular-dynamics simulation, Munejiri, Shimojo and Hoshino studied the structure of liquid sulfur at 400 K, below the polymerization temperature [79]. They found that some of the Ss ring molecules homolytically open up on excitation of one electron from the HOMO to the LUMO. The chain-like diradicals S " thus generated partly recombine intramolecularly with formation of a branched Sy=S species rather than cyclo-Ss- Furthermore, the authors showed that photo-induced polymerization occurs in liquid sulfur when the Ss chains or Sy=S species are close to each other at their end. The mechanism of polymerization of sulfur remains a challenging problem for further theoretical work. 

---