A special method of deformational correction in N.M.R. of molecules dissolved in liquid crystals

Abstract

A simple method of deformational correction for the N.M.R. spectral parameters of molecules dissolved in liquid crystals is described. The method is applicable to the different isotopically substituted derivatives of the molecules belonging to the cubic point groups. Its validity is verified for the dipolar and quadrupolar couplings observed in the molecules CH₄, CD₄ and CH₃D dissolved in the liquid crystals Merck Phase IV, Merck ZLI 1167 and their mixtures.     

Xenon porometry at room temperature

Xenon porometry is a method in which porous material is immersed in a medium and the properties of the material are studied by means of 129Xe nuclear magnetic resonance (NMR) of xenon gas dissolved in the medium. For instance, the chemical shift of a particular signal (referred to as signal D) arising from xenon inside small pockets formed in the pores during the freezing of the confined medium is highly sensitive to the pore size. In the present study, we show that when naphthalene is used as the medium the pore size distribution of the material can be determined by measuring a single one-dimensional spectrum near room temperature and converting the chemical shift scale of signal D to the pore radius scale by using an experimentally determined correlation. A model has been developed that explains the curious behavior of the chemical shift of signal D as a function of pore radius. The other signals of the spectra measured at different temperatures have also been identified, and the influence of xenon pressure on the spectra has been studied. For comparison, 129Xe NMR spectra of pure xenon gas adsorbed to porous materials have been measured and analyzed.     

Base-Modified Nucleosides Related to 2-Chloro-2′-deoxyadenosine

Derivatives of 2-chloro-2′-deoxyadenosine ( 1a ) containing secondary 6-NH₂ groups ( 5a-c ) or a 8-Br substituent ( 9 ) were synthesized. They were tested together with ring-modified congeners containing a pyrrolo[2,3-b]pyridine, pyrrolo[3,2-c]pyridine, or pyrazolo[3,4-d]pyrimidine ring system as inhibitors of various leukemic cell lines. Only the 8-Br derivatives 9 showed inhibitory activity, whereas the base-modified congeners were not active. Compound 1a was protonated at a pK_a = 1.4 (2′-deoxyadenosine at pK_a = 3.8). Protonation occurred at N(7) and not at N(1) as observed for dA.     

Comparative study for separation of aquatic humic substances by capillary zone electrophoresis using uncoated, polymer coated and gel-filled capillaries

Several comparative capillary zone electrophoresis (CZE) experiments were carried out by means of uncoated, polyvinyl alcohol (PVA) and polyacrylamide (PAA) coated silica open tubular capillaries and gel-filled capillaries (linear non-cross-linked polyacrylamide, PAGE, by a pre-coated PAA capillary) using different kinds of background electrolytes (BGEs) and organic modifiers for characterization of aquatic dissolved humic matter (DHM). Organic compounds, such as acetic acid, acetate buffer, methanol, ethylene glycol, acetonitrile, dimethylsulphoxide, 5 M urea and sodium dodecyl sulphate (SDS) were tested as sample modifiers to improve the separative power. The fractionation mode by a PVA coated open tubular capillary using 40 mM phosphate buffer at pH 6.8 and 5 M urea-water as the sample modifier turned out to be fairly practical as well as its PAA homologue. Linear non-cross-linked PAGE with 10% gel concentration and 5 M urea-water as the sample modifier using 40 mM phosphate buffer at pH 6.8 produced the most reliable results as to the adaptation of physical gels, especially if the interactions of humic solutes with the gel matrix are not critical. The addition of SDS in the linear PAGE gel increased the interaction of humic solutes with the gel matrix but also improved the separative power and strengthened the chaotropic effect of the urea modifier.     

A-weighted sound pressure level as a loudness/annoyance indicator for environmental sounds - Could it be improved?

A system is introduced with the purpose of showing how an auditory perception system may be built up to include the basic quantities on loudness domain. The quantities are the critical bands, the power law, and the weighting. The power law seems to be the most crucial basis for hypothesizing a loudness function. It has been shown that the power law could be applied as such by assuming the auditory perception system to have two essentially different stimuli: the intensity (sound pressure level) and pure pressure. These physically different quantities seem to be combined in the root of the power law, and in this study the roots are determined from equal-loudness contours. A loudness function is derived on the basis of this finding. By adding the weighting, a method has been constructed for assessing loudness. After defining the weighting, the equal-loudness contours are constructed and are seen to be virtually identical to the contours in ISO 226. It has also been found that the equations for deriving the contours in this standard and in the new ISO 226 may be incorrect, because there is no definition of a sensible loudness function. Finally, it is deduced that the derived weighting must be unequivocal for an auditory perception system (depending solely on the otologically representative group). Finally, the A-weighting (as part of an A-weighted sound pressure level) as such is reasonably similar to the weighting derived in this study. Therefore, this weighting is not the main problem when assessing sounds in respect to loudness. The A-weighting is thus chosen as the weighting for the indicator derived in the study for assessing environmental sounds.     

A 13C NMR study of pyridoxal-5′-phosphate oxime

Pyridoxal-5′-phosphate amino-oxy acetate oxime was titrated in water, over the pH range 4–12, and the changes followed using ¹³C NMR. The results were compared to those of analogous Schiff's bases presented in the literature. The chemical shifts and titration curves of the oxime were appreciably different from those of the Schiff's bases, and the differences are explained as being due to the absence of ketoenamine-enolimine tautomerism in the oxime. The low chemical shift value and the large changes of the oxime azomethine carbon during titration, as compared to the Schiff's bases, are discussed. The high stability of the oximes in water makes them suitable as model compounds for some tautomeric forms of the Iess stable Schiff's bases.     

Upper and lower error bounds for plate-bending finite elements

Summary. We compare the robustness of three different low-order mixed methods that have been proposed for plate-bending problems: the so-called MITC, Arnold-Falk and Arnold-Brezzi elements. We show that for free plates, the asymptotic rate of convergence in the presence of quasiuniform meshes approaches the optimal O(h) for MITC elements as the thickness approaches 0, but only approaches for the latter two. We accomplish this by establishing lower bounds for the error in the rotation. The deterioration occurs due to a consistency error associated with the boundary layer – we show how a modification of the elements at the boundary can fix the problem. Finally, we show that the Arnold-Brezzi element requires extra regularity for the convergence of the limiting (discrete Kirchhoff) case, and show that it fails to converge in the presence of point loads. Received June 9, 1998 / Published online December 6, 1999