Macromolecules, properties

The best-known solute effects on membrane and macromolecule properties are those of the inorganic salts. Hofmeister (2) showed that... 

In metal-containing macromolecules or macromolecular metal complexes (MMC) (article in the previous edition of the Handbook see [1]) suitable compounds are combined to materials with new unusual properties organic or inorganic macromolecules with metal ions, complexes, chelates or also metal clusters. These combinations result in new materials with high activities and specific selectivities in dilferent functions. This article concentrates on synthetic aspects of artificial metal-containing macromolecules. Properties are shortly mentioned, and one has to look for more details in the cited literatures. In order to understand what kind of properties are realized in metal-containing macromolecules, in a first view functions of comparable natural systems (a short overview is given below) has to be considered ... 

Originally it was stated that the influence of ions on macromolecules properties was connected with structuring or breaking of bulk water structure. However recent studies have demonstrated that either direct ion-macromolecule interactions or interactions with water molecules in the first hydration shell of the macromolecules govern the Hofmeister effect as well as phase separation in ATP systems (Zhang Cremer, 2006). Thus, in ATPS... 

Abd-El-Aziz AS, Agatemor C, Etldn N (2014) Sandwich complex-containing macromolecules property tunability through versatile synthesis. Macromol Rapid Commtm 35 513-559... 

Materials have many properties that are important, scientifically and teclmologically, that do not depend on the details of long-range stnicture. For example, consider a solution of globular macromolecules in a solvent... 

Luengo G ef a/1997 Thin film rheology and tribology of oonfined polymer melts oontrasts with bulk properties Macromolecules 30 2482-94... 

Among the main theoretical methods of investigation of the dynamic properties of macromolecules are molecular dynamics (MD) simulations and harmonic analysis. MD simulation is a technique in which the classical equation of motion for all atoms of a molecule is integrated over a finite period of time. Harmonic analysis is a direct way of analyzing vibrational motions. Harmonicity of the potential function is a basic assumption in the normal mode approximation used in harmonic analysis. This is known to be inadequate in the case of biological macromolecules, such as proteins, because anharmonic effects, which MD has shown to be important in protein motion, are neglected [1, 2, 3]. 

A polymer is a macromolecule that is constructed by chemically linking together a sequent of molecular fragments. In simple synthetic polymers such as polyethylene or polystyrer all of the molecular fragments comprise the same basic unit (or monomer). Other poly me contain mixtures of monomers. Proteins, for example, are polypeptide chains in which eac unit is one of the twenty amino acids. Cross-linking between different chains gives rise to j-further variations in the constitution and structure of a polymer. All of these features me affect the overall properties of the molecule, sometimes in a dramatic way. Moreover, or... 

The final class of methods that we shall consider for calculating the electrostatic compone of the solvation free energy are based upon the Poisson or the Poisson-Boltzmann equatior Ihese methods have been particularly useful for investigating the electrostatic properties biological macromolecules such as proteins and DNA. The solute is treated as a body of co stant low dielectric (usually between 2 and 4), and the solvent is modelled as a continuum high dielectric. The Poisson equation relates the variation in the potential (f> within a mediu of uniform dielectric constant e to the charge density p ... 

There are two problems to consider when calculating 3D pharmacophores. First, unless the molecules are all completely rigid, one must take account of their conformational properties The second problem is to determine which combinations of pharmacophoric groups are common to the molecules and can be positioned in a similar orientation in space. More than one pharmacophore may be possible indeed, some algorithms can generate hundreds of possible pharmacophores, which must then be evaluated to determine which best fits the data. It is important to realise that all of these approaches to finding 3D pharmacophores assume that all of the molecules bind in a common manner to the macromolecule. 

Example The distance between two ends of a large, flexible molecule can provide information about its structural properties or its interaction with solvent. Analysis of an angle can reveal a hinged motion in a macromolecule. 

Morawitz, H., Macromolecules in Solution, Interscience, New York, 1965. Richards, E. G., An Introduction to the Physical Properties of Large Molecules in Solution, Cambridge University Press, Cambridge, 1980. 

The hst which follows gives an outline of the properties of a Monte Carlo simulation used in the context of molecular modeling studies for sampling either multiple conformations of smaller, flexible stmctures or multiple local minima of larger macromolecules or polymers ... 

Coa.cerva.tlon, A phenomenon associated with coUoids wherein dispersed particles separate from solution to form a second Hquid phase is termed coacervation. Gelatin solutions form coacervates with the addition of salt such as sodium sulfate [7757-82-6] especially at pH below the isoionic point. In addition, gelatin solutions coacervate with solutions of oppositely charged polymers or macromolecules such as acacia. This property is useful for microencapsulation and photographic apphcations (56—61). 

Arsenic. Arsenic is under consideration for inclusion as an essential element. No clear role has been estabHshed, but aresenic, long thought to be a poison, may be involved in methylation of macromolecules and as an effector of methionine metaboHsm (158,160). Most research has focused on the toxicity or pharmaceutical properties of arsenic (158). 

The compositional distribution of ethylene copolymers represents relative contributions of macromolecules with different comonomer contents to a given resin. Compositional distributions of PE resins, however, are measured either by temperature-rising elution fractionation (tref) or, semiquantitatively, by differential scanning calorimetry (dsc). Table 2 shows some correlations between the commercially used PE characterization parameters and the stmctural properties of ethylene polymers used in polymer chemistry. 

Processes for HDPE with Broad MWD. Synthesis of HDPE with a relatively high molecular weight and a very broad MWD (broader than that of HDPE prepared with chromium oxide catalysts) can be achieved by two separate approaches. The first is to use mixed catalysts containing two types of active centers with widely different properties (50—55) the second is to employ two or more polymerization reactors in a series. In the second approach, polymerization conditions in each reactor are set drastically differendy in order to produce, within each polymer particle, an essential mixture of macromolecules with vasdy different molecular weights. Special plants, both slurry and gas-phase, can produce such resins (74,91—94). 

Synthetic polymers have become extremely important as materials over the past 50 years and have replaced other materials because they possess high strength-to-weight ratios, easy processabiUty, and other desirable features. Used in appHcations previously dominated by metals, ceramics, and natural fibers, polymers make up much of the sales in the automotive, durables, and clothing markets. In these appHcations, polymers possess desired attributes, often at a much lower cost than the materials they replace. The emphasis in research has shifted from developing new synthetic macromolecules toward preparation of cost-effective multicomponent systems (ie, copolymers, polymer blends, and composites) rather than preparation of new and frequendy more expensive homopolymers. These multicomponent systems can be "tuned" to achieve the desired properties (within limits, of course) much easier than through the total synthesis of new macromolecules. 

The advantages of this type of system are that the release rates are independent of the dmg properties, macromolecules and ionic species may be dehvered, fluxes may be high, and release rates are not dependent upon environmental conditions such as pH. The disadvantages are that the system is subject to dose-dumping if it is chewed. It is also more expensive to formulate than coating tablets, and there is a possibiUty of hole plugging. 

The spectroscopic techniques that have been most frequently used to investigate biomolecular dynamics are those that are commonly available in laboratories, such as nuclear magnetic resonance (NMR), fluorescence, and Mossbauer spectroscopy. In a later chapter the use of NMR, a powerful probe of local motions in macromolecules, is described. Here we examine scattering of X-ray and neutron radiation. Neutrons and X-rays share the property of being found in expensive sources not commonly available in the laboratory. Neutrons are produced by a nuclear reactor or spallation source. X-ray experiments are routinely performed using intense synclirotron radiation, although in favorable cases laboratory sources may also be used. 

Schnell, R., Stamm, M. and Creton, C, Mechanical properties of homopolymer interfaces transition from simple pullout to crazing with increasing interfacial width. Macromolecules, 32(10), 3420-3425 (1999). 

G. Faivre, J. L. Gardissat. Viscoelastic properties and molecular structure of amorphous selenium. Macromolecules 79 1988-1996, 1986. 

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