Cooperative process

We consider a finite space, which contains the NA sample and is in contact with a bath of water or water vapor. That allows one to maintain the r.h. in the experimental space at a constant level and change it when necessary. Such a scheme corresponds to the real experiments with wet NA samples. A NA molecule is simulated by a sequence of units of the same type. Thus, in the present study, we consider the case of a homogeneous NA or the case where averaging over the unit type is possible. Every unit can be found in the one of three conformational states unordered. A- or B- conformations. The units can reversibly change their conformational state. A unit corresponds to a nucleotide of a real NA. We assume that the NA strands do not diverge during conformational transitions in the wet NA samples [18]. The conformational transitions are considered as cooperative processes that are caused by the unfavorable appearance of an interface between the distinct conformations. 

In general, therefore, there are three processes, prior to the kind of capillary condensation associated with the hysteresis loop of a Type IV isotherm, which may occur in a porous body containing micropores along with mesoporesia primary process taking place in very narrow micropores a secondary, cooperative process, taking place in wider micropores, succeeded by a tertiary process governed by a modified Kelvin equation. 

The weakness of the adsorbent-adsorbate forces will cause the uptake at low relative pressures to be small but once a molecule has become adsorbed, the adsorbate-adsorbate forces will promote the adsorption of further molecules—a cooperative process—so that the isotherms will become convex to the pressure axis. 

E. F. Vainstein Department of Kinetics and Thermodynamics of Cooperative Processes, N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Moscow, Russia... 

For the quantitative description of the cooperative process in the macromolecule-low molecular weight ligand systems, Hill s equation is used. It expresses the dependence of the degree of macromolecule saturation with the ligand (Y) on the equilibrium concentration of the ligand in solution [67] ... 

Cooperative effects are of considerable interest for high capacity chromatography of BAS, since for practical purposes high-selectivity bonding is possible only in cooperative processes. This is very important for carrying out the sorption, separation and concentration of BAS. 

The presence of a critical St content in ASt-x can also be seen in fluorescence spectra [29], This copolymer in aqueous solution shows an excimer emission peaking at 325 nra. As shown in Fig. 8, the intensity of the excimer emission increases, while the monomer emission decreases, with increasing St content. Eventually the excimer dominates the monomer emission at an St content of 72 mol%. The excimer emission becomes apparent at an St content of about 50 mol%, which agrees with the critical St content estimated by viscometry and NMR spectroscopy. The existence of the critical St content suggests the hydro-phobic self-aggregation to be a cooperative process. 

Thermodynamic Aspects of the Triple Helix-Coil Transition 4.1 Cooperative Processes... 

In the case of cooperative processes, the formation of a nucleus, already discussed from the kinetical point of view, plays a crucial role. The steady state described by Eq. (1) depicts the formation of a triple helix as the simplest model by the formation of a nucleus Hx through fast pre-equilibria and subsequent propagation steps, Hx in this case is a triple-helical intermediate with x tripeptide units (that means x hydrogen bonds) in the helical state. The final product H3n 2 possesses two hydrogen bonds less than tripeptide units because the three single chains are staggered at one amino add residue each. 

For this kind of cooperative processes, it is characteristic that the formation of the nucleus is thermodynamically more difficult than for further propagation steps (positive cooperativity). This implies that the elementary transition step of an individual chain segment (tripeptide unit) is influenced by the state of adjacent segments through intramolecular interactions. 

The experimental data show that the magnitude of the heat capacity (or similarly of the specific heat) under adiabatic conditions decreases regularly with the increase of filler content. This phenomenon was explained by the fact that the macromolecules, appertaining to the mesophase layers, are totally or partly excluded to participate in the cooperative process, taking place in the glass-transition zone, due to their interactions with the surfaces of the solid inclusions. 

Theoretically, the problem has been attacked by various approaches and on different levels. Simple derivations are connected with the theory of extrathermodynamic relationships and consider a single and simple mechanism of interaction to be a sufficient condition (2, 120). Alternative simple derivations depend on a plurality of mechanisms (4, 121, 122) or a complex mechanism of so called cooperative processes (113), or a particular form of temperature dependence (123). Fundamental studies in the framework of statistical mechanics have been done by Riietschi (96), Ritchie and Sager (124), and Thorn (125). Theories of more limited range of application have been advanced for heterogeneous catalysis (4, 5, 46-48, 122) and for solution enthalpies and entropies (126). However, most theories are concerned with reactions in the condensed phase (6, 127) and assume the controlling factors to be solvent effects (13, 21, 56, 109, 116, 128-130), hydrogen bonding (131), steric (13, 116, 132) and electrostatic (37, 133) effects, and the tunnel effect (4,... 

Other particular theories are confined to diffusion-controlled reactions (109), to the so called cooperative processes (113), in which the reactivity depends on the previous state, or to resistance of semiconductors (102), while those operating with hydrogen bridges (131), steric factors (132), or electrostatic effects (133, 175) are capable of being generalized less or more. 

The case of isotactic polypropylene (iPP) presents some differences with respect to those just discussed. While both sPP and PET adopt in their mesophases disordered, extended, essentially non-helical conformations, iPP is characterized by a unique, relatively well ordered, stable chain structure with three-fold helical symmetry [18,19,36]. More accurately we can state that an iPP chain segment can exist in the mesophase either as a left handed or as the enantiomeric right-handed three-fold helix. The two are isoener-getic and will be able to interconvert only through a rather complex, cooperative process. From a morphological point of view Geil has reported that thin films of mesomorphic iPP quenched from the melt to 0 °C consist of... 

At the same time, as the concentration decreases the exchange of water molecules by cooperative processes becomes easier and so significant fluctuations in the coordination numbers are observed, which are estimated to be about 1. At even lower concentrations, ion-water correlation patterns will become obscured and then undetectable. As an extrapolation, dynamic processes might contribute more and more to the description of the solution. The strong interaction between Li+ and OH2 (dH. i = 34 kcal/mole in the vapor phase 130>) may cause the cation-water complexes to remain quite well-defined tetrahydrates, on the average, despite all dynamic effects. 

Of course from a molecular point of view this is no longer surprising - we know that dynamic dilution is a highly cooperative process. However the quantitative prediction of the dynamic moduli of Fig. 14 is clearly a very demanding task for a theory with essentially no free parameters We outHne here how the tube model calculation is done in this case for details see [56]. 

Structure. A-DNA, on the other hand, requires dehydrated conditions. The transition of B-A DNA is a reversible and cooperative process, in which the A-form is considered the high-energy state. The underlying factors for this instability have been addressed, with little snccess. ... 

Combining the above descriptions leads to a picture that describes the experimentally observed concentration dependence of the polymer diffusion coefficient. At low concentrations the decrease of the translational diffusion coefficient is due to hydrodynamic interactions that increase the friction coefficient and thereby slow down the motion of the polymer chain. At high concentrations the system becomes an entangled network. The cooperative diffusion of the chains becomes a cooperative process, and the diffusion of the chains increases with increasing polymer concentration. This description requires two different expressions in the two concentration regimes. A microscopic, hydrodynamic theory should be capable of explaining the observed behavior at all concentrations. 

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