Measurement of 15N chemical shift anisotropy in a protein dissolved in a dilute liquid crystalline medium with the application of magic angle sample spinning

The chemical shifts of nuclei that have chemical shielding anisotropy, such as the 15N amide in a protein, show significant changes in their chemical shifts when the sample is altered from an isotropic state to an aligned state. Such orientation-dependent chemical shift changes provide information on the magnitudes and orientation of the chemical shielding tensors relative to the molecule's alignment frame. Because of the extremely high sensitivity of the chemical shifts to the sample conditions, the changes in chemical shifts induced by adding aligned bicelles do not arise only from the protein alignment but should also include the accumulated effects of environmental changes including protein-bicelle interactions. With the aim of determining accurate 15N chemical shielding tensor values for solution proteins, here we have used magic angle sample spinning (MAS) to observe discriminately the orientation-dependent changes in the 15N chemical shift. The application of MAS to an aligned bicelle solution removes the torque that aligns the bicelles against the magnetic field. Thus, the application of MAS to a protein in a bicelle solution eliminates only the molecular alignment effect, while keeping all other sample conditions the same. The observed chemical shift differences between experiments with and without MAS therefore provide accurate values of the orientation-dependent 15N chemical shifts. From the values for ubiquitin in a 7.5% (w/v) bicelle medium, we determined the 15N chemical shielding anisotropy (CSA) tensor. For this evaluation, we considered uncertainties in measuring the 1H-15N dipolar couplings and the 15N chemical shifts and also structural noise present in the reference X-ray structure, assuming a random distribution of each NH bond vector in a cone with 5 degrees deviation from the original orientation. Taking into account these types of noise, we determined the average 15N CSA tensor for the residues in ubiquitin as Delta sigma=-162.0+/-4.3 ppm, eta=0.18+/-0.02, and beta=18.6+/-0.5 degrees, assuming a 1H-15N bond length of 1.02 A. These tensor values are consistent with those obtained from solid-state NMR experiments.     

Highly sodium-selective fluoroionophore based on conformational restriction of oligoethyleneglycol-bridged biaryl boron-dipyrromethene

A non-PET and non-PCT fluoroionophore has been designed and synthesized based on the combination of a biaryl boron-dipyrromethene fluorophore with an oligoethyleneglycol bridge. A specific red-shift response of absorption for NaClO4 in acetonitrile was demonstrated based on conformational restriction triggered by cation recognition at the bridge. The concentration of Na+ can be determined accurately using fluorescence due to a high extinction coefficient (epsilon = 50 000), a high fluorescence quantum yield (Phif = 0.68), and the sharpness of absorption and emission peaks of the boron-dipyrromethene derivative.     

Blocks of central -group extensions

Let and be finite groups that have a common central -subgroup for a prime number , and let and respectively be -blocks of and induced by -blocks and respectively of and , both of which have the same defect group. We prove that if and are Morita equivalent via a certain special -bimodule, then such a Morita equivalence lifts to a Morita equivalence between and .

     

Mean wind in convective turbulence of mercury

The large-scale circulation, often called "wind," in the confined thermal turbulence of mercury is studied experimentally. The instantaneous velocity profile at 128 points is directly measured using ultrasonic velocimetry. The periodic velocity oscillation is observed in the case of the aspect-ratio Gamma = 1,2 but not in Gamma = 0.5. Its peak frequency is scaled by f(c) proportional Ra(gamma(c)), where Ra is the Rayleigh number and gamma(c) = 0.43,0.45 for Gamma = 1,2. f(c) is close to the wind circulation frequency f(p), and has the same order of transit time from the bottom to the top of the convection cell. A single roll circulation is expected in Gamma = 1; however, axisymmetric toroidal rings may exist near the upper and lower plate for Gamma = 0.5, which are stable up to Ra = 7 x 10 (10).     

Small-Angle X-Ray Scattering Studies on Nucleation Formation of Dextran Precipitation in the Presence of Boron

In the present study, the nucleation formation process of dextran precipitation in the presence of boron was investigated by small-angle X-ray scattering (SAXS) techniques. The formation mechanism of aggregates or nuclei is very important in the initial step of crystallization. SAXS measurement is an excellent technique for observing these processes. The results of SAXS measurement suggest that boron, as a trace impurity, induces the aggregating of dextran molecules intermolecularly as a process in the nucleation formation of dextran precipitate nuclei and causes precipitation of dextran through an elongation process. These reactions occur readily at low boron concentrations. In fact, boron, which was detected at low levels in dextran solutions, was concentrated in the precipitates. Therefore, an aqueous solution of boron-free dextran should be resistant to precipitation. Copyright 2000 Academic Press.     

Particle design of tolbutamide by the spherical crystallization technique. III. Micromeritic properties and dissolution rate of tolbutamide spherical agglomerates prepared by the quasi-emulsion solvent diffusion method and the solvent change method

With the objective of modifying the micromeritic properties of tolbutamide (i.e., to manufacture a highly functional powder form), particle design was attempted using a quasi-emulsion solvent diffusion (QESD) method, and the micromeritic properties and dissolution rate of the obtained spherical agglomerates were evaluated by comparison with agglomerates prepared by the solvent change (SC) method. For the production of tolbutamide agglomerates by the QESD method, a necessary condition was the addition of a sucrose fatty acid ester to the system as an emulsifying agent. The particle diameter of the agglomerates obtained by the QESD method depended on the size of the initially formed quasi-emulsion droplets, which in turn depended on the viscosity of the solution. In addition, the agglomerates were nearly perfectly spherical in shape. In the QESD method, the quasi-emulsion droplets crystallized instantaneously from the droplet surface inward. The resultant agglomerates were dense, had great mechanical strength and showed excellent flowability due to their perfect spherical shape. On the other hand, the agglomerates produced by the SC method were conglomerates of primary crystals, and fine, needle-like crystals formed on their surface. As a result, these agglomerates had a large specific surface area, and they therefore showed greater solubility than the agglomerates prepared by the QESD method.     

Semiclassical analysis of the spin polarization of 12B in the 100Mo(14N, 12B)102Ru reaction

Polarization of ¹²B in the ¹⁰⁰Mo(¹⁴N, ¹²B)¹⁰²Ru reaction at 90 MeV incident energy is studied on the basis of the semiclassical theory of transfer reactions proposed by Brink. Gross behaviors of both the polarization and the cross section as functions of product kinetic energy can be predicted successfully by the theory. But disagreement in the numerical values of the polarization is found for low-energy ¹²B.     

Preparation,characteristics, and application of an asparaginase tube

Conditions for the preparation of an asparaginase (L-asparagine amidohydrolase, EC 3.5.1.1) tube using polyacrylamide gel were investigated. The apparent yield of activity of the asparaginase tube was about 20%; the activity of the tube was dependent on inner surface area. The optimum pH of the asparaginase tube shifted by 1 pH unit to the acid side in comparison with that of native enzyme. The apparent Michaelis constant of the tube was about 200 times higher than that of the native enzyme. The half-life of the asparaginase tube in continuous operation was estimated to be 16 days at 37°C. The tube was found to be resistant to attack by proteolytic enzyme. The L-asparagine level in blood plasma of a dog was lowered to 1/4 by the performance of an extracorporeal shunt using the asparaginase tube.     

Phase transition in metal hexammine complexes—i the I.R. spectra of Ni(NO3)26NH31

Far i.r. spectra of Ni(NO₃)₂6NH₃ were recorded above and below the order-disorder phase transition at T_c = 243 K. The results are compared to the spectra of the isomorphous crystal NiCl₂6NH₃, which has no transition in the same temperature range. The antisymmetric stretching vibration of the ammonias shows a broken degeneracy below T_c for Ni(NO₃)₂6NH₃. No broken degeneracy was observed in the nickel-nitrogen vibration of the |Ni(NH₃)₆|²⁺ clusters. The discussion of our results lends support to the assumption that the phase transition is due to the collective freezing of the degrees of rotation of the ammonias.     

Two new dimeric acridone alkaloids from Glycosmis citrifolia

Two new acridone dimers, glycobismines-F (1) and -G (2), were isolated from the roots of Glycosmis citrifolia collected in Taiwan. The structures of the new compounds were determined based on spectral analysis.