Iterative deconvolution of quadrupole split NMR spectra

We propose a simple method to deconvolute NMR spectra of quadrupolar nuclei in order to separate the distribution of local magnetic hyperfine field from the quadrupole splitting. It is based on an iterative procedure which allows to express the intensity of a single NMR line directly as a linear combination of the intensities of the total experimental spectrum at a few related frequencies. This procedure is argued to be an interesting complement to Fourier transformation since it can lead to a significant noise reduction in some frequency ranges. This is demonstrated in the case of the ¹¹B-NMR spectrum in SrCu₂(BO₃)₂ at a field of 31.7 T, where a magnetization plateau at 1/6 of the saturation has been observed.     

NMR evidence for the persistence of a spin superlattice beyond the 1/8 magnetization plateau in SrCu2(BO3)_{2}

We present 11B NMR studies of the 2D frustrated dimer spin system SrCu2(BO3)_{2} in the field range 27-31 T covering the upper phase boundary of the 1/8 magnetization plateau, identified at 28.4 T. Our data provide a clear evidence that above 28.4 T the spin superlattice of the 1/8 plateau is modified but does not melt even though the magnetization increases. Although this is precisely what is expected for a supersolid phase, the microscopic nature of this new phase is much more complex. We discuss the field-temperature phase diagram on the basis of our NMR data.     

Entanglement properties of carboxymethyl cellulose and related polysaccharides

Entanglement network of carboxymethyl cellulose (CMC) was characterized based on the dynamic viscoelasticity of the concentrated solutions in an ionic liquid. According to the concentration dependence of the molecular weight between entanglements (M _e), M _e for the molten state (M _e,melt) for CMC was estimated to be 3.9 × 10³ as a chain variable reflecting the chemical structure of the polysaccharide. Furthermore, relations between M _e,melt and other chain variables were examined to elucidate the specificity in the entanglement properties of CMC and related polysaccharides. It was shown that the number of entanglement strands (P _e), the ratio of the cube of the tube diameter, and the volume occupied by the entanglement strand, for CMC was 72 being significantly larger than the universal value of ca. 20 recognized for flexible polymers. Anomalous values of P _e > 20 were also obtained for related polysaccharides such as cellulose and amylose.

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Molecular weight between entanglements for linear d-glucans

Dynamic viscoelasticity measurements were carried out for concentrated solutions of linear d-glucans in BmimCl to examine the effect of the linkage between repeating units of glucose on the rheological properties. The values of molecular weight between entanglements (M _e) were determined for four d-glucans: curdlan, pullulan, cellulose, and amylose. From the concentration dependence of M _e, the value of M _e in the molten state (M _e,melt) for each d-glucan was estimated as a material constant. The order of M _e,melt became cellulose?<?pullulan?<?curdlan?<?amylose, indicating that the linkage is actually influential in M _e,melt for the linear d-glucans. The relationship between M _e,melt and the molecular structure of the d-glucans were discussed assuming that the values of M _e,melt for the d-glucans primarily reflect the chain stiffness such as the characteristic ratio C _∞ on the analogy of synthetic polymers. Although the trend was not so clear, it was shown that N _unit is a decreasing function of C _∞ .     

Thermoynamic properties (Hm, CP,m, Vm, κT) of binary mixtures {x1,3-Dioxane + (1−x)Cyclohexane} at 298.15 K

Molar excess enthalpies H_m^E, isobaric heat capacities C_P,m^E, volumes V_m^E and isothermal compressibilities κT^E for the 1,3-dioxane(3DX) + cyclohexane mixture were measured at 298.15 K, in order to compare to those of the 1,4-dioxane(4DX) + cyclohexane mixture. H_m^E is endothermic and the maximum value about 1.5 kJ mol⁻¹ at x ≈ 0.45, and lower than that of the 4DX mixture by about 80 J mol⁻¹. V_m^E is positive over the whole concentration and the maximum value is about 0.85 cm³ mol⁻¹ at x ≈ 0.45, and lower than that of the 4DX mixture. The above results suggest the energetic unstabilization, resulting in the volume expansion in the mixture. C_P,m^E shows the characteristic W-shaped concentration dependence, which has maximum at x ≈ 0.45 and two minima at x ≈ 0.1 and 0.9. The maximum C_P,m^E value for 3DX mixture shifts toward the positive side, compared to that of 4DX mixture. κT^E were estimated from speeds of sound, densities, thermal expansion coefficients and isobaric heat capacities of the pure component liquids and the mixtures. The κT^E result shows the positive concentration dependence over the whole composition range. The 3DX mixture has the similar thermodynamic properties to the 4DX mixture, despite that 4DX is the nonpolar solvent and 3DX is the dipolar liquid. this means that there exists the local dipolar interaction between 4DX molecules, and the prevalence of “microheterogeneity” in the both mixtures.     

Stereoselective synthesis of β-fluoroallyl alcohols

β-Fluoroallyl alcohols ($\text{6}$) were obtained with high stereoselectivity by the LiA1H₄ reduction of 1-acetoxy-3-alkyl-2,2-difluorocyclopropanes ($\text{5}$).     

X-Ray Tube Voltage Dependence of Wiener Spectra of Screen Structure Mottle Recorded on Front and Back Emulsions

A low-speed screen/film system was used to investigate structure mottle, i.e., the density fluctuation of an x-ray film due to inhomogeneous screen structure. The tube voltage dependence of the Wiener spectra of the structure mottle was separately determined for front and back film emulsions. The Wiener spectral values of the structure mottle of the front emulsion were greater than those of the back emulsion at lower tube voltages. The spectral values of the structure mottle of the front emulsion decreased with tube voltage, while those of the back emulsion increased. We explain these phenomena by the behavior of the Wiener spectra of the relative spatial fluctuation of fluorescence intensity due to following reasons: (1) spatial thickness fluctuation of the screen produces a relative spatial fluctuation of x-ray energy absorbed in the screen, and (2) as the distance between the emulsion of the film and the average position of the x-ray absorption in the screen lengthens, the number of random scattering and absorption of light photons increase.Presented at the International Commission for Optics Topical Meeting, Kyoto, 1994.