Effect of omega-hydrogenation on the adsorption of fluorononanols at the hexane/water interface: pressure effect on the adsorption of fluorononanols

The interfacial tension gamma of the hexane solution of 1H,1H-perfluorononanol (FDFC(9)OH) and its omega-hydrogenated analogue, 1H,1H,9H-perfluorononanol (HDFC(9)OH), against water was measured as a function of pressure and concentration at 298.15 K in order to clarify the effect of omega-dipole on the orientation of fluorononanol molecules from the viewpoint of volume. The adsorbed films of both alcohols exhibit two kinds of phase transitions among three different states: the gaseous, expanded, and condensed states. The partial molar volume changes of adsorption - in the expanded and condensed states were evaluated and compared between the two systems. The - values of both alcohols are negative, and thus the alcohol molecules have smaller volume in the adsorbed film than in the bulk solution. Furthermore, the value was obtained through the evaluation of by the density measurement of the bulk hexane solution. It was found that the value of HDFC(9)OH is smaller than that of FDFC(9)OH in the condensed state. On the basis of three matters concerning the molecular structure of alcohols, the occupied area at the interface, and the orientation of FDFC(9)OH in the adsorbed film deduced from the earlier results of X-ray reflectivity measurement, the mean tilt angle of HDFC(9)OH from the interface normal in the condensed film was estimated to be 15 degrees . The thermodynamic estimation demonstrated here is highly valuable one to provide structure information on an adsorbed film.     

Unprecedented double nucleophilic addition of a hydride at a central carbon of an eta3-allyl ligand

Treatment of eta(3)-allyl compound [Cp(2)Mo(eta(3)-C(3)H(5))](+)(1; Cp =eta(5)-C(5)H(5)) with MH (M = Li, Na) resulted in reduction of the allyl ligand to give propane. Deuterium-labeling studies were used to trace the origins and fates of the hydrogen atoms. The mechanism is discussed in light of the HSAB principle. The studies showed that the formation of propane can be explained by 1,2-hydrogen migration from the central to the terminal carbon of the allyl ligand, and the subsequent double nucleophilic addition of the hydride at the central carbon.     

Attenuation correction of SPECT imaging by dual energy method--quantification of 111In-labeled monoclonal anti-tumor antibody localization

Application of radiolabeled monoclonal anti-tumor antibodies for diagnosis and therapy has made remarkable progress in the past few years. Quantification of radiopharmaceutical localization is required adequate attenuation correction in SPECT imaging. Attenuation correction by transmission CT (TCT) data is one of the best method at present time. However, if a patient is moved between TCT and SPECT, this method is no more applicable. We developed a new attenuation correction algorithm by dual energy method, using 99mTc and 111In because of similarity of these linear attenuation coefficients. The new algorithm uses data of TCT with an external source of 99mTc, and requires another data from SPECT of 111In labeled monoclonal anti-tumor antibody, which are simultaneously obtained. TCT results in an attenuation map, which then serves as input into the final intrinsic correction algorithm to uncorrected SPECT data. In chest phantom experiment, the attenuation corrected SPECT images revealed nearly same distribution of actual radioactivity of 111In as compared to that of uncorrected one.     

Synthesis and alpha-glucosidase-inhibiting activity of a new alpha-glucosidase inhibitor, 4-O-alpha-D-glucopyranosylmoranoline and its N-substituted derivatives

Various N-substituted derivatives of 4-O-alpha-D-glucopyranosylmoranoline have been synthesized, and their inhibitory activities against rabbit sucrase and maltase have been measured, as well as their effects on postprandial hyperglycemia in the sucrose-loaded rat, 4-O-alpha-D-Glucopyranosylmoranoline was also shown to have potent hypoglycemic activity in starch-loaded dogs.     

Novel synthesis and properties of 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate: autorecycling oxidation of some alcohols under photo-irradiation

Three-step reactions starting from 2-chlorotropone with barbituric acid afforded novel 7,9-dimethylcyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate (9·BF₄⁻), which is the isoelectronic compound of the 5-ethyl-3-methyllumiflavinium ion. The stability of cation 9 is expressed by the pK_R+ value, which was determined spectrophotometrically, as ca. 6.0. The electrochemical reduction of 9 exhibited low reduction potential at −0.58 (V vs Ag/AgNO₃), upon cyclic voltammetry (CV). In a search for the reactivity, reactions of 9·BF₄⁻ with some nucleophiles, hydroxide, hydride, amines, thiols, and methanol, were carried out to exhibit that the introduction of nucleophiles is dependent on the nucleophile itself. The photo-induced oxidation reactions of some alcohols catalyzed by 9·BF₄⁻ under aerobic conditions were carried out to give the corresponding carbonyl compounds in more than 100% yield [based on compound 9·BF₄⁻], suggesting the oxidizing function of 9·BF₄⁻ toward alcohols in the autorecycling process. The UV-vis and fluorescence spectra of 9 were studied to suggest the electron transfer from alcohols to the excited 9.     

A mixed version of Menger's theorem

An(a, b)-n-fan means a union ofn internally disjoint paths. Menger's theorem states that a graphG has an(a, b)-n-fan if and only ifG isn-connected betweena andb. We show thatG contains edge-disjoint(a, b)-n-fans if and only if for anyk withk0min{n–1, |V(G)|–2} and for any subsetX ofV(G)-{a, b} with cardinalityk, G-X is (n-k)-edge-connected betweena andb.     

Light polarization in iodine-doped polyvinyl alcohol films

¹²⁹I Mössbauer measurements have been performed on unidirectionally stretched iodinedoped polyvinyl alcohol(PVA) films which are widely used as optical polarizers. In the films iodine is observed to be in the form of I^?, I ₃ ^? , and I ₅ ^? and the stretch of the films increases the abundance of the polyiodides, I ₃ ^? and I ₅ ^? . In the stretched PVA films, it has become clear that the linear polyiodides lie parallel to the stretching direction.     

Chemical structure of iodine-doped polyisoprene

A nonconjugated conducting polymer (1,4-rans-polyisoprene) at different iodine doping levels has been studied with the 27.7-keV Mössbauer resonance of¹²⁹I. At the light doping level, almost all iodines are covalently bonding to the carbon atoms, breaking the double bonds of the main chain. At the medium doping level, other iodine species are found, which are idendified as anion species, l^?, l ₃ ^? and l ₃ ^? .At the heavy doping level, polyiodide anions, l ₃ ^? and l ₅ ^? , increase as compared to the covalently bonding iodine atoms and addtionally molecular iodine l₂ exists.     

Limit theorems for trimmed sums

This paper studies the heavily trimmed sums (*) _{[ns] + 1} ^[nt] X _j ⁽ⁿ⁾ , where {X _j ⁽ⁿ⁾ } _{j = 1} ⁿ are the order statistics from independent random variables {X ₁,...,X _n } having a common distributionF. The main theorem gives the limiting process of (*) as a process oft. More smoothly trimmed sums like _{j = 1} ^[nt] J(j/n)X _j ⁽ⁿ⁾ are also discussed.