Internal solvation

Additional bands were observed at 520 nm (and 395 nm) and at 456 nm (and 330 nm) and were ascribed to the cation solvated internally by the neighboring aromatic ring or by monomer. 

Chen W, Gordon MS. The effective fragment model for solvation internal rotation in formamide. J Chem Phys 1996 105 11081-11090. 

Chen, W., Gordon, M. S. (1996]. The Effective Fragment Model for Solvation Internal Rotation In Formamide,/. Chem. Phys., 105,11081-11090. 

To enable an atomic interpretation of the AFM experiments, we have developed a molecular dynamics technique to simulate these experiments [49], Prom such force simulations rupture models at atomic resolution were derived and checked by comparisons of the computed rupture forces with the experimental ones. In order to facilitate such checks, the simulations have been set up to resemble the AFM experiment in as many details as possible (Fig. 4, bottom) the protein-ligand complex was simulated in atomic detail starting from the crystal structure, water solvent was included within the simulation system to account for solvation effects, the protein was held in place by keeping its center of mass fixed (so that internal motions were not hindered), the cantilever was simulated by use of a harmonic spring potential and, finally, the simulated cantilever was connected to the particular atom of the ligand, to which in the AFM experiment the linker molecule was connected. 

Solvation—Desolvation Equilibrium. From the observation of migration of plasticizer from plasticized polymers it is clear that plasticizer molecules, or at least some of them, are not bound permanently to the polymer as iu an internally plasticized resia, but rather an exchange—equiHbrium mechanism is present. This implies that there is no stoichiometric relationship between polymer and plasticizer levels, although some quasi-stoichiometric relationships appear to exist (3,4). This idea is extended later ia the discussion of specific iateractions. 

In continuum boundary conditions the protein or other macromolecule is treated as a macroscopic body surrounded by a featureless continuum representing the solvent. The internal forces of the protein are described by using the standard force field including the Coulombic interactions in Eq. (6), whereas the forces due to the presence of the continuum solvent are described by solvation tenns derived from macroscopic electrostatics and fluid dynamics. 

In Raman spectroscopy the intensity of scattered radiation depends not only on the polarizability and concentration of the analyte molecules, but also on the optical properties of the sample and the adjustment of the instrument. Absolute Raman intensities are not, therefore, inherently a very accurate measure of concentration. These intensities are, of course, useful for quantification under well-defined experimental conditions and for well characterized samples otherwise relative intensities should be used instead. Raman bands of the major component, the solvent, or another component of known concentration can be used as internal standards. For isotropic phases, intensity ratios of Raman bands of the analyte and the reference compound depend linearly on the concentration ratio over a wide concentration range and are, therefore, very well-suited for quantification. Changes of temperature and the refractive index of the sample can, however, influence Raman intensities, and the band positions can be shifted by different solvation at higher concentrations or... 

A special case of the internal stabilization of a cationic chain end is the intramolecular solvation of the cationic centre. This can proceed with the assistance of suitable substituents at the polymeric backbone which possess donor ability (for instance methoxy groups 109)). This stabilization can lead to an increase in molecular weight and to a decrease in non-uniformity of the products. The two effects named above were obtained during the transition from vinyl ethers U0) to the cis-l,2-dimethoxy ethylene (DME)1U). An intramolecular stabilization is discussed for the case of vinyl ether polymerization by assuming a six-membered cyclic oxonium ion 2) as well as for the case of cationic polymerization of oxygen heterocycles112). Contrary to normal vinyl ethers, DME can form 5- and 7-membe red cyclic intermediates beside 6-membered ringsIl2). 

O Hara (134, 135). The total values of AH and AS are divided into internal (AHjnt. Sint) and external, i.e., solvation, (AHext, ASext) terms ... 

The use of computer simulations to study internal motions and thermodynamic properties is receiving increased attention. One important use of the method is to provide a more fundamental understanding of the molecular information contained in various kinds of experiments on these complex systems. In the first part of this paper we review recent work in our laboratory concerned with the use of computer simulations for the interpretation of experimental probes of molecular structure and dynamics of proteins and nucleic acids. The interplay between computer simulations and three experimental techniques is emphasized (1) nuclear magnetic resonance relaxation spectroscopy, (2) refinement of macro-molecular x-ray structures, and (3) vibrational spectroscopy. The treatment of solvent effects in biopolymer simulations is a difficult problem. It is not possible to study systematically the effect of solvent conditions, e.g. added salt concentration, on biopolymer properties by means of simulations alone. In the last part of the paper we review a more analytical approach we have developed to study polyelectrolyte properties of solvated biopolymers. The results are compared with computer simulations. 

As for the theoretical treatment, we could only try to include the eleetrostatie solute-solvent interaetions and, in faet, we corrected the electronic potential energies for the solvation effeets by simply adding as calculated according to the solvaton model [eq. (2)]. The resulting potential curves are to be seen as effective potentials at equilibrium, i.e. refleeting orientational equilibrium distributions of the solvent dipoles around the eharged atoms of the solute molecule. In principle, the use of potentials thus corrected involves the assumption that solvent equilibration is more rapid than internal rotation of the solute molecule. Fig. 4 points out the effects produced on the potential... 

Although cSFC shows relatively poor figures of merit (speed, sensitivity, detection dynamic range and sample capacity) as well as a limited application area, its applications tend to be unique. These include solutes that can be solvated with pure SCCO2 and quantified with FID. Linear density programs typical in cSFC are ideal for homologous series found in surfactants, many prepolymers, etc. Selectivity in cSFC, which can be achieved by mobile phase density and temperature programming, relies on selective interactions with the stationary phase. Quantitative analysis in cSFC may be rendered difficult by small injected volumes the use of internal standards is recommended. 

The primary method for demonstration of the existence of drug polymorphs, or solvate species, is that of powder x-ray diffraction (XRD). Such measurements represent a specification of the internal structure within a crystal, and an evaluation of its lattice type. Since dissolution and subsequent drying can sometimes yield an undesired structure, it is also important to confirm crystal structures at each formulation stage during the beginning of the development process. 

C. J. Cramer and D. G. Truhlar, Quantum chemical conformational analysis of 1,2-ethanediol Correlation and solvation effects on the tendency to form internal hydrogen bonds in the gas phase and aqueous solution, J. Am. Chem. Soc. 116 3892 (1994). 

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