A versatile route to 3-benzoheteroepines containing group 15 and 16 heavier elements involving several novel ring systems, and their thermal stabilities

The C-unsubstituted 3-benzoheteroepines (2a-g) containing group 15 (P, As, Sb, and Bi) and group 16 (S, Se, and Te) heavier elements were prepared by the reaction of the corresponding metal reagents with (Z,Z)-o-bis(beta-lithiovinyl)benzene (5) which was derived in two steps from a common o-phthalaldehyde (3). The heteroepines (2) thus obtained were thermally labile towards heteroatom extrusion, and their half-lives on heating estimated from (1)H-NMR spectral analysis showed that the 3-benzoheteroepines (2) were far less stable than the corresponding 1-benzoheteroepines (1). The 2,4-bis(trimethylsilyl)-3-benzoheteroepines (17) containing Sb, Bi, and Te were also prepared from o-diiodobenzene (9) in 6 steps and were found to be more stable than the corresponding C-unsubstituted heteroepines (2).     

Synthesis of polymer materials by low energy electron beam. VIII. Formation mechanism of microporous urethane-acrylamide film

The formation mechanism of microporous film which was obtained by casting a methyl ethyl ketone (MEK)/N,N-dimethlformamide (DMF) solution of an electron beam (EB)-reactive urethane-acrylamide prepolymer was discussed. The porosity and crystallinity increased with increasing DMF content in the solvent mixture. This correlation was explained by a progressive slight coagulation and nucleation of the prepolymer due to the difference in volatility between MEK and DMF. As the result, when the DMF content reached 25 vol%, micropores were formed throughout the film. Such a mechanism was supported by the localization of the acrylamide groups at the surface which was induced by the crystallization and by the interaction of amide groups with DMF. The polymerization of acrylamide groups by EB could fix the microporous morphology.     

Hydrogen-bonding effect on C NMR chemical shifts of amino acid residue carbonyl carbons of some peptides in the crystalline state

¹³C cross polarization-magic angle spinning NMR spectra were measured for a series of peptides containing -valine, -leucine and -aspartic acid residues, for which the crystal structures were already determined by X-ray diffraction, in order to investigate the relationship between hydrogen-bond lengths (R_N…O) and ¹³C chemical shifts of amide carbonyl carbons in the peptides. From these experimental results, it was found that the isotropic ¹³C chemical shifts (δ_iso) of the amino acid residues move linearly downfield with a decrease in R_N…O within the hydrogen-bonded length range considered here and also shown in our previous work on glycine and -alanine residues as expressed by δ_iso(ppm) = a − bR_N…O(Å) where a and b are 215.4 (ppm) and 14.2 (ppm Å⁻¹) for the -valine residue, 202.2 (ppm) and 10.0 (ppm Å⁻¹) for the -leucine residue, and 199.0 (ppm) and 9.6 (ppm Å⁻¹) for the -aspartic acid residue, respectively. Using these relations, the R_N…O values of some polypeptides in the crystalline state were determined through the observation of the amide carbonyl carbon chemical shifts. These values were compared with those determined by the X-ray diffraction method. Furthermore, quantum-chemical calculation of the ¹³C shielding constant for a model compound was carried out by the finite perturbation theory INDO method in order to ascertain the ¹³C shielding behavior in the formation of hydrogen bonds.     

Preparation of stimuli-responsive protein nanogel by quantum-ray irradiation

To prepare the functional nanoparticle with biological affinity, we tried to control the particle diameter and volume phase transition point of protein nanogel by quantum-ray irradiation. We succeeded in controlling the particle diameter of gelatin nanogel in the range of 20–70 nm by gamma-ray irradiation. It was also found that the prepared gelatin nanogel reversibly swelled and shrunk by pH and temperature change. Volume phase transition point and swelling ratio were found to change, depending on the absorbed dose and gelatin concentration.     

In vivo imaging of brain dopaminergic neurotransmission system in small animals with high-resolution single photon emission computed tomography.

High-resolution single photon emission computed tomography (SPECT) provides a unique capability to image the biodistribution of radiolabeled molecules in small laboratory animals. Thus, we applied the high-resolution SPECT to in vivo imaging of the brain dopaminergic neurotransmission system in common marmosets using two radiolabeled ligands, [123I]2beta-carbomethoxy-3beta-(4-iodophenyl)tropane (beta-CIT) as a dopamine transporter (DAT) ligand and [123I]iodobenzamide (IBZM) as a dopamine D2 receptor (D2R) ligand. Specific images of the striatum, a region with a high density of dopaminergic synapses, were obtained at 240 min and 60 min after injection of [123I]beta-CIT and [123I]IBZM, respectively. Furthermore, a significantly low accumulation of [123I]beta-CIT in the striatum was observed in MPTP-treated animals compared with results for a control group, and a similar accumulation in the control group was observed with the pretreatment of deprenyl in the MPTP-treated animals. However, the striatal accumulation of [123I]IBZM showed no changes among the control, MPTP-treated, and deprenyl-MPTP-treated groups. These SPECT imaging results agreed well with those of DA concentration and motor behavior. Since MPTP destroys nigrostriatal dopamine nerves and produces irreversible neurodegeneration associated with Parkinsonian syndrome, SPECT imaging data in this study demonstrated that deprenyl shows its neuroprotective effect on Parkinsonism by protecting against the destruction of presynaptic dopamine neurons.     

Pressure-induced buckling of spin ladder in SrCu2O3

Pressure-induced structural phase transition of spin ladder compound SrCu2O3 was investigated by synchrotron X-ray powder diffraction with a diamond anvil cell (DAC). The change was characterized by a buckling of the Cu2O3 plane in the rung direction of the ladder. The structure of the high-pressure phase was found to be essentially the same as that of CaCu2O3. Application of an external pressure of 3.4 GPa therefore affected the structure in the same manner that the chemical (internal) pressure does.     

Blue photoluminescence in Ti-doped alkaline-earth stannates

Blue photoluminescence properties of Ti-doped alkaline-earth stannates, A₂(Sn_1−xTi_x)O₄ (A=Ca, Sr, Ba) (x=0.005-0.15), were examined at room temperature. These stannates showed intense broad emission bands peaking at 445 nm for Ca₂SnO₄, at 410 nm for Sr₂SnO₄, and at 425 nm for Ba₂SnO₄ under UV excitation. Emission intensities were relatively insensitive to Ti concentration and no sharp concentration quenching was observed. Mixing alkaline-earth ions in the crystal structures did not increase the emission intensities in the A₂(Sn_1−xTi_x)O₄ system. The excitation spectra of these stannates exhibited broad bands just below the fundamental absorption edges, implying that luminescence centers do not consist of the component elements in the host materials. It was suggested that the isolated TiO₆ complexes are possible luminescence centers in these materials, as previously proposed in other Ti-doped stannates such as Mg₂SnO₄ and Y₂Sn₂O₇.     

Global convergence of the affine scaling methods for degenerate linear programming problems

In this paper we show the global convergence of the affine scaling methods without assuming any condition on degeneracy. The behavior of the method near degenerate faces is analyzed in detail on the basis of the equivalence between the affine scaling methods for homogeneous LP problems and Karmarkar's method. It is shown that the step-size 1/8, where the displacement vector is normalized with respect to the distance in the scaled space, is sufficient to guarantee the global convergence of the affine scaling methods.This paper was presented at the International Symposium Interior Point Methods for Linear Programming: Theory and Practice, held on January 18–19, 1990, at the Europa Hotel, Scheveningen, the Netherlands.     

The solubilization of Orange OT in aqueous solutions of alkyl-substituted ammonium salts of polystyrenesulfonic acid

Summary The solubilization of Orange OT in aqueous solutions of alkyl-substituted ammonium salts of polystyrenesulfonic acid has been studied. It has been found that the solubilizing power of polyelectrolytes increases with the increase of the carbon atom number of alkyl groups of counter-ions. It is suggested that the phenomenon originates from the increased hydrophobic nature of polyelectrolytes due to counter-ion binding.

---

Zusammenfassung Es wurde die Solubilisation von Orange OT in wässerigen Lösungen alkylsubstituierter Ammoniumsalze von Polystyrolsulfonsäure untersucht. Es wurde gefunden, daß die Wirksamkeit zur Solubilisation von Polyelektrolyten mit der Zunahme der Kohlenstoffatomzahl der Alkylketten der Gegenionen steigt. Die experimentellen Ergebnisse deuten darauf hin, daß die Erscheinung durch die zunehmende hydrophobe Eigenschaft von Polyelektrolyten infolge der Gegenionenbindung verständlich ist.

     

Determination of malotilate and its metabolites in plasma and urine

A method for the determination of malotilate (I), the corresponding monocarboxylic acid (II) and its decarboxylated product (III) in plasma is described. Plasma was extracted with chloroform spiked with internal standard. The residue, dissolved in methanol, was chromatographed on a reversed-phase column with a mobile phase of 60% acetonitrile and 1% acetic acid in water. The sensitivity limit for I, II and III was 50, 25 and 100 ng/ml of plasma, respectively. Compound I in the same plasma extract was also analysed by gas chromatography--electron-impact mass spectrometry. The base peaks m/z 160 for I and m/z 162 for internal standard (IV) were monitored; the sensitivity limit for I was 2.5 ng/ml of plasma. The determination of the metabolites of I, II and its conjugate (V), and isopropyl-hydrogen malonate (VI) in urine by high-performance liquid chromatography is also described. The limit of quantification for VI was 2.0 micrograms/ml, and the overall coefficient of variation of VI was 4.7%. The limit of quantification for II in urine was 0.5 micrograms/ml and that for V was 1.0 micrograms/ml as total II (II + V). The overall precision of the method was satisfactory. The method was used to determine plasma and urine concentrations in four dogs orally dosed with 100, 200 or 400 mg of malotilate.