Perturbation analysis for the rotational spectrum of the NiBr radical in the X2Pi3/2 and A2Delta5/2 states

The millimeter- and submillimeter-wave spectra of the NiBr radical in the X (2)Pi(3/2) and A (2)Delta(5/2) states were observed by a source-modulated microwave spectrometer. The NiBr radical was generated in a dc glow discharge through the mixture of Br(2) vapor and Ar gas by the sputtering reaction with a Ni cathode. Observed transition frequencies were independently analyzed for both electronic states using a standard polynomial expression of a Hund's case (c) approximation. Anomalous behavior of the effective molecular constants in the X (2)Pi(3/2) state was interpreted as the result of the perturbation between the X (2)Pi(3/2) and A (2)Delta(5/2) states. The deperturbed molecular constants were derived using a simplified supermultiplet Hamiltonian including the interaction terms between the two electronic states.     

New method for the determination of pentachlorophenol by atomic absorption spectrophotometry

A new application of atomic absorption is reported for the determination of pentachlorophenol. The method is based on solvent extraction into nitrobenzene of the ion-pair formed between tris(1,10-phenanthroline) iron(II) and the anion of pentachlorophenol, and the subsequent determination of the iron concentration m the extract by atomic absorption at the 2483 A iron line.     

Chiral self-dimerization of vanadium complexes on a SiO2 surface: the first heterogeneous catalyst for asymmetric 2-naphthol coupling

The self-dimerized chiral assembly of vanadium-Schiff-base complexes was found to occur on a SiO2 surface and to be the first heterogeneous catalyst for the asymmetric oxidative coupling of 2-naphthol with 100% selectivity and 90% enantioselectivity.     

Different reaction modes for the oxidative dimerization of epoxyquinols and epoxyquinones. Importance of intermolecular hydrogen-bonding

An oxidative dimerization reaction, involving the three successive steps of oxidation, 6 pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6 pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6 pi-electrocyclization.     

An approach to analysis of pigment release from microcapsules with size distribution

We have studied the release curve for microcapsules with size distribution. On the basis of an analogy to the relaxation phenomena with multiple characteristic times, we propose a stretched exponential release curve for the system with size distribution and relate the release curve to the size distribution function of the microcapsule. This method was successfully applied to the transfer of azo-pigments from inner medium of dioctyl phthalate to dispersing medium of methanol through poly(ureaurethane) microcapsule membrane.     

TUMOR IMAGING WITH [111niIn]MONO-DTPA-ETHYLENEGLYCOL-Ga-DEUTEROPORPHYRIN

Abstract Mono-DPTA-ethyleneglycol-Ga-deuteroporphyrin (MDEGD) was synthesized, by coordinating non-radioactive Ga in the porphyrin ring and connecting DTPA (diethylene-triamine-N,N,N,N,N,-pentaacetic acid) to its side chain. By labeling with 111_In, chemicals for scintigraphy were developed. They were applied to Syrian golden hamsters with implanted pancreatic gland cancers and C57-black mice with Lewis lung cancer to enable tumor imaging and biodistribution examination. A comparative study was also conducted with [⁶⁷Ga]citrate. In the resultant data, [¹¹¹In]MDEGD showed larger tumor/lung, tumor/kidney and tumor/blood ratio with [⁶⁷Ga]citrate. The affinity of [ⁿIn]MDEGD in inflammatory tissue was much lower than that of ⁶⁷Ga citrate. [¹¹¹In]MDEGD lost its photosensitivity.     

Synthesis of thromboxane A2 analog DL-(9,11), (11,12)-dideoxa-(9,11)-epithio-(11,12)-methylene-thromboxane A2

A synthesis of the thromboxane A₂ analog, $\text{dl}$-(9,11), (11,12)-dideoxa-(9,11)-epithio-(11,12)-methylene-thromboxane A₂ is described.     

Automated direct high-performance liquid chromatographic assay for estetrol, estriol, cortisone and cortisol in serum and amniotic fluid.

An automated direct assay for the simultaneous determination of unconjugated estetrol, estriol, cortisone and cortisol in serum and amniotic fluid, using high-performance liquid chromatography with electrochemical detection and ultraviolet detection, has been developed. The analysis time is ca. 1 h. This system offers good reproducibility with low coefficients of variation (estetrol, 2.3%; estriol, 2.3%; cortisone, 2.6%; cortisol, 1.9%). Detection limits are low enough for routine determinations (estetrol and estriol, 150 pg; cortisone and cortisol, 5 ng). Comparison of the values measured by the present method and by radioimmunoassay revealed significant correlations for estetrol (r = 0.787, p less than 0.01), estriol (r = 0.957, p less than 0.01), cortisone (r = 0.956, p less than 0.01) and cortisol (r = 0.865, p less than 0.01). This system proved to be valuable in monitoring feto-placental function.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.