Rotation, anomaly

Zimmerman LM, Laulinan H (1953) Intraabdominal hernias due to developmental and rotational anomalies. Ann Surg 138 82-91... 

Because of the rotation of the N—N bond, X-500 is considerably more flexible than the polyamides discussed above. A higher polymer volume fraction is required for an anisotropic phase to appear. In solution, the X-500 polymer is not anisotropic at rest but becomes so when sheared. The characteristic viscosity anomaly which occurs at the onset of Hquid crystal formation appears only at higher shear rates for X-500. The critical volume fraction ( ) shifts to lower polymer concentrations under conditions of greater shear (32). The mechanical orientation that is necessary for Hquid crystal formation must occur during the spinning process which enhances the alignment of the macromolecules. 

Red giant stars, both in the field and in globular clusters, present abundance anomalies that can not be explained by standard stellar evolution models. Some of these peculiarities, such as the decline of 12C/13C, and that of Li and 12C surface abundances for stars more luminous than the bump, clearly point towards the existence of extra-mixing processes at play inside the stars, the nature of which remains unclear. Rotation has often been invoked as a possible source for mixing inside Red Giant Branch (RGB) stars ([8], [1], [2]). In this framework, we present the first fully consistent computations of rotating low mass and low metallicity stars from the Zero Age Main Sequence (ZAMS) to the upper RGB. 

NMR studies on 28 and 29 indicate that both the thiophene and furan rings rotate freely at room temperature (vide infra) and therefore, anomalies in the UV spectra of 28 and 29 should be attributed to the through-bond interaction between the Si-Si cr bonds and aromatic 77 bonds. This was further confirmed by photoelectron spectral studies. As shown in Table II, the lift of HOMO for 12 relative to the model compound was 0.4 eV, but those for 28 and 29 were 0.7 and 0.6 eV, respectively. Apparently, more effective through-bond interaction occurs for 28 and 29 (21). 

First of all, quantum calculations allow one to predict basicity scales in agreement with experiment provided that the calculations are performed on the preferred conformation of the isolated molecule. If this is not done, a given term within a consistent series may jump from one rank to another as a function of the conformation used for the calculations. The determinant role of preferred conformation on any property (barrier to internal rotation and inversion, dipole moment, first adiabatic ionization potential, acidity and basicity in the gas phase, energy of complexation to BF3, etc.) was clearly demonstrated. We further show the importance of the role of preferred conformation in explaining some of the anomalies in Drago s systematics. 

The HCP case exhibits one additional signal of the onset of rapid change in vibrational resonance structure. This is the sudden onset of vibrational perturbations at (0, 32, 0) [5]. Local perturbations, where one rotational term curve crosses another, are manifest as level shifts, extra lines, and intensity anomalies [18]. Such perturbations are typically rare at low vib and... 

In several previous papers, the possible existence of thermal anomalies was suggested on the basis of such properties as the density of water, specific heat, viscosity, dielectric constant, transverse proton spin relaxation time, index of refraction, infrared absorption, and others. Furthermore, based on other published data, we have suggested the existence of kinks in the properties of many aqueous solutions of both electrolytes and nonelectrolytes. Thus, solubility anomalies have been demonstrated repeatedly as have anomalies in such diverse properties as partial molal volumes of the alkali halides, in specific optical rotation for a number of reducing sugars, and in some kinetic data. Anomalies have also been demonstrated in a surface and interfacial properties of aqueous systems ranging from the surface tension of pure water to interfacial tensions (such as between n-hexane or n-decane and water) and in the surface tension and surface potentials of aqueous solutions. Further, anomalies have been observed in solid-water interface properties, such as the zeta potential and other interfacial parameters. 

Gas-phase basicities of several substituted benzaldehydes (62 X = o-/m-/p-Me/F, o-j 77 -Cl) have been measured, relative to benzaldehyde or mesitylene as reference bases, over a range of temperatures.101 The tolualdehydes are more basic than benzaldehyde, the halobenzaldehydes less so, following classical aromatic substituent effects. The data also correlate well with solution-based linear-free-energy substituent constants, as well as with theoretical (MNDO) calculations. Some deviations are noteworthy (i) the o-halobenzaldehydes (especially chloro) have higher basicities than predicted, but calculations tend to rale out the hydrogen-bonded isomer (63), which is also contraindicated by a normal A,S value, inconsistent with the expected restriction of— hOH rotation in such a structure (ii) anomalies in the high-temperature behaviour of m-fluorobenzaldehyde in the presence of mesitylene reference base are consistent with a specific catalysed isomerization to the ortho- or para-isomer. 

The effects of a number of substituent groups on the fluorescence of aromatic compounds are listed in Table 2.3. There are exceptions to this table since a number of other factors must be considered. For example, molecules which are able to rotate, bend or twist have a tendency to lose energy from the excited state through molecular collision and other vibrational processes. It is not possible to compile a complete set of rules for determining whether a molecule will fluoresce, as there are many anomalies. 

Anomalous behaviour of the molar rotation depending upon the generation can basically be indicative of the existence of chiral substructures in the dendrimer branches. In many cases such anomalies merely occur as a result of constitutional differences between the chiral building blocks which are exposed to different local environments in the different parts of the dendrimer. CD-spectro-scopic studies can often provide more detailed information about the underlying reasons. 

Picosecond time-resolved total internal reflection fluorescence spectroscopy was applied to analyze the proton-transfer reaction of INpOH in water-sapphire interface layers [206], The rate constant of the proton-transfer reaction from excited neutral species became slow in the interface layer as compared with that in the bulk aqueous solution and decreased smoothly with increasing penetration depth in the interfacial layer up to 100 nm. The anomaly was interpreted in terms of rotational fluctuations of water aggregates in the interface layer. 

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