Studies on internal structure of tablets. III. Manufacturing of tablets containing microcapsules

The aim of this study was to establish the best manufacturing conditions for preparation by the direct compression method of tablets which contain microcapsules having a minimal destruction rate of the coating wall, show the same dissolution pattern as microcapsules, and have enough mechanical strength for practical use, and to elucidate the internal structure of the tablets under the best manufacturing conditions. Degree of destruction of the microcapsule wall was evaluated by the dissolution rate of the medicine in the microcapsules. To learn the mechanical strength of tablets, the crushing strength and friability were measured; their internal structure was analyzed by the porosity and pore size distribution. The best manufacturing conditions for the tablets were thus determined, and it was clarified by analysis of the internal structure that these conditions are markedly affected by the flowability of prescribed powders and the packing state at compression.     

Synthesis and Physical Properties of Sterically Congested Cycloalkenes, 1,2-Di-tert-butyl-3,3,5,5-tetramethylcyclopentene and 1,2-Di-tert-butyl-3,3,6,6-tetramethylcyclohexene

Two sterically congested cycloalkenes (9 and 10), congeners of tetra-tert-butylethylene, were synthesized and characterized. Oxidation of the bicyclic 1,3-dithietane 8 with dimethyldioxirane (DMD) gave the endo,endo-disulfoxide 13, thermal isomerization of which to the endo,exo-disulfoxide 15 followed by oxidation with DMD gave the trioxide 18. Heating 18 in refluxing 1,3-dimethyl-2-imidazolidinone furnished 1,2-di-tert-butyl-3,3,5,5-tetramethylcyclopentene (9) in 69% yield by a 2-fold extrusion process. The reaction of the 1,6-diketone dihydrazone 23 with Se(2)Cl(2) gave the selenadiazoline 34 and the 1,3-diselenetane 35. Heating 34 at 115-130 degrees C gave 1,2-di-tert-butyl-3,3,6,6-tetramethylcyclohexene (10), a "didehydro" derivative of tetra-tert-butylethylene, in 43% yield. The C=C bond in 10 is strained in degree comparable to those of most strained alkenes reported so far.     

Electrochemical reduction of CO2 with high current density in a CO2 + methanol medium II. CO formation promoted by tetrabutylammonium cation

The cation of the supporting electrolyte was found to play an important role in the electrochemical reduction of highly concentrated CO₂ in a CO₂ + methanol medium. Electroreduction of CO₂ with tetrabutylammonium (TBA) salts yielded CO as the main product, while methyl formate was predominantly formed when lithium salts were used as supporting electrolytes. The latter supporting electrolytes showed a higher overvoltage than the former. When TBA salt was used, the reduction of CO₂ was catalysed by TBA ion to yield CO^−.₂. This intermediate may be stabilized by forming an ion pair, {TBA⁺---CO^−.₂}, or by being adsorbed on the electrode surface as CO^−._2ad. Then CO^−.₂ reacts with CO₂ to produce CO. The hydrophobic atmosphere at the electrode provided by TBA ion may be adequate for CO production. Lithium ion, on the other hand, suppressed the reduction of CO₂.     

Radical-copper wheels: structure and magnetism of hexanuclear hybrid arrays

Complexation of copper(II) bromide and chloride with 4-pyrimidinyl nitronyl nitroxide (4PMNN) as a bridging ligand gave discrete hexanuclear complexes carrying 12 spins, [CuX(2).(4PMNN)](6) [X = Br (1), Cl (2)], which crystallize in a trigonal space group. The crystallographic parameters are C(11)H(15)Br(2)CuN(4)O(2).0.3H(2)O, a = 28.172(2), c = 12.590(2) A, V = 8653(2) A(3), and Z = 18 for 1, and C(11)H(15)Cl(2)CuN(4)O(2).0.3H(2)O, a = 28.261(2), c = 12.378(1) A, and Z = 18 for 2. The hexanuclear arrays construct a perfect column perpendicular to the molecular plane. The diameter of the resultant honeycomblike channel is ca. 11.5 A defined by the interatomic distance of two opposing copper ions. Their magnetic behavior is interpreted as the simultaneous presence of ferro and antiferromagnetic couplings. The ferromagnetic couplings are attributed to the interactions between a copper spin and the axially coordinated nitronyl nitroxide spin and between nitronyl nitroxide groups through van der Waals contacts. The antiferromagnetic coupling is due to the interaction between copper ions across the pyrimidine bridges.     

Mesonic and non-mesonic decay widths of ΛC

Results are reported on the precise measurement of the lifetime and the weak-decay branching ratios with charged particle(π⁻ and proton) emission from _Λ¹²C formed via ¹²C(π⁺,K⁺) reaction. The π⁻ mesonic decay width is consistent with the calculations including the pion wave function distortion effect. We observed large contribution of the neutron-stimulated decay widths, Γ(Λ + n → n + n), in the non-mesonic weak decay, which cannot be explained by the current theoretical calculations.     

On the regioselectivity for the Michael addition of thiols to unsymmetrical fumaric derivatives

The regiochemistry of the Michael addition of thiols to unsymmetrical fumaric derivatives was investigated. Conjugate addition of thiols to unsymmetrical fumaric diester was well controlled by the presence of lithium cation and one of the two possible regioisomers was prepared in a highly selective manner. Fumaric ester amides underwent the regioselective Michael addition that was controlled by the presence or absence of the base; either of the regioisomers was prepared as an almost diastereomerically pure form. The present control of the regiochemistry can be explained by the factors of change of active site for the addition by the coordination or non-coordination of proton or lithium cation to the carbonyls. To clarify the origin of the regioselectivity, the relative rates of the conjugate addition of thiol to acrylate derivatives were measured under competitive conditions. Ethyl acrylate reacted with thiol faster than tert-butyl acrylate and the rate difference was enhanced by the presence of lithium cation. In the presence of base, ethyl acrylate gave the adducts much faster than acrylamide, while under non-basic conditions acrylamide showed higher reactivity than the ester. This regioselectivity was also observed in the Michael/aldol reaction and multi-substituted γ-butyrolactones were prepared in a stereoselective manner. The thio groups introduced here served as a leaving group and a convenient stereoselective synthesis of β-, γ- and δ-lactams was developed.     

Direct observation of slow molecular relaxation by high-resolution light scattering spectroscopy

We developed a novel dynamic light scattering system to observe elastic relaxation phenomena with hyper frequency resolution. The principle of the measurement is based on the theory, which describes the dynamic structure factor of fluid under the condition of the frequency dependent compressibility. The dynamic structure factor, which is usually composed of the Brillouin and Rayleigh triplet, is modulated and shows an additional central component that directly reflects the whole aspect of the relaxation. In the experiment, the output from a frequency-doubled cw-YAG laser was incident into the liquid sample and the power spectrum of the light scattered into the backward direction was analyzed by the optical beating spectroscopy technique. The sample is liquid acetic acid that is known to show a strong ultrasonic relaxation around 1 MHz due to the molecular association process. We could find in the observed spectrum, the central component introduced by the phenomenon, whose relaxation frequency and the strength can be obtained from the width and the intensity of the observed central peak, respectively. The results show very good agreement with those previously obtained by the conventional ultrasonic spectroscopy technique.     

Beta-NMR detection of beta-emitting fragment43Ti

NMR on the beta emitter⁴³Ti has been observed by use of the -NMR technique. From the observed NMR spectrum, the magnetic moment of⁴³Ti was determined to be || =0.85±0.02 µ_N. The value is significantly quenched from the single particle value –1.91 µ_N, which shows a strong effect resulting from meson-exchange currents andconfiguration mixing.     

Photoluminescence excitation spectroscopy of GaP1−xNx alloys: conduction-band-edge formation by nitrogen incorporation

We have investigated the conduction-band-edge formation in GaP_1−xN_x alloys by nitrogen incorporation into GaP using photoluminescence excitation (PLE) spectroscopy. The PLE spectra of GaP_1−xN_x alloys with various nitrogen concentrations show that the absorption edge shifts to lower energies with increasing nitrogen concentration. From the nitrogen concentration dependence of the absorption edge energy we found that the conduction-band-edge formation in GaP_1−xN_x alloys originates from the formation of the A line.