Analysis of the phase solubility diagram of a phenacetin/competitor/beta-cyclodextrin ternary system, involving competitive inclusion complexation

The competitive inclusion complexations in the ternary phenacetin/competitors/beta-cyclodextrin (beta-CyD) systems were investigated by the solubility method, where m-bromobenzoic acid (m-BBA) and o-toluic acid (o-TA) were used as competitors. The solubility changes of the drug and competitors as a function of beta-CyD concentration in the ternary systems were formulated using their stability constants and intrinsic solubilities. The decrease in solubility of phenacetin by the addition of competitors could be quantitatively simulated by the formulation, when both drug and competitor give A(L) type solubility diagrams. On the other hand, when one of the guests gives a B(S) type solubility diagram, its solubility change was clearly reflected in that of the another guest, i.e., phenacetin gave an A(L) type solubility diagram in the binary phenacetin/beta-CyD system and o-TA gave a B(S) type diagram in the binary o-TA/beta-CyD system, but in the ternary phenacetin/o-TA/beta-CyD system, a new plateau region appeared in the original A(L) type diagram of phenacetin. This was explained by the solubilization theory of Higuchi and Connors. The solubility analysis of the ternary drug/competitor/CyD systems may be particularly useful for determination of the stability constant of a drug whose physicochemical and spectroscopic analyses are difficult, because they can be calculated by monitoring the solubility change of a competitor, without monitoring that of a drug. Furthermore, the present results suggest that attention should be paid to the type of the phase solubility diagram, as well as the magnitude of the stability constant and the solubility of the complex, for a rational formulation design of CyD complexes.     

10B quantitative determination in ppb range by particle tracks reading for boron neutron capture therapy

Quantitative determination of ppb-order ¹⁰B was carried out in a small number of cultured tumor cells by particle tracks by the ₁₀B(n,)⁷Li reactions using solid state nuclear track detector (SSNTD) for boron neutron capture therapy research. The detection limit of ¹⁰B concentration in tumor cells is less than 1·10^-3 ppm under our experimental conditions which permits the quantitative determination of ¹⁰B in a small number of boronated tumor cells (10⁵/ml = ca. 0.1 mg). Boron quantities in tumor cells determined were well compatible with the tumor cell killing effects of boron neutron capture therapy.     

Siladenoserinols M–P,sulfonated serinol derivatives from a tunicate

Four new sulfonated serinol derivatives, siladenoserinols M–P (1–4), were isolated from a tunicate of the family Didemnidae collected in Indonesia. Their chemical structures were elucidated by the interpretation of NMR and mass spectroscopic data. Two of them (2 and 4) were revealed to be disulfonate serinol derivatives, and the others were monosulfonates. Siladenoserinols A (5) and B (6), which we previously isolated from the same tunicate, inhibited the p53–Hdm2 interaction with an IC₅₀ value of 2.0?μM. However, 1–4 did not inhibit the activity. The result suggested that the acetyl group in the bicyclic ketal unit and/or the glycerophospholipid moiety in 5 and 6 were responsible for the inhibition of the p53–Hdm2 interaction.     

Application of negative chemical ionization mass spectrometry to the structure elucidation of perfluorochemicals and related compounds

The negative chemical ionization mass spectra of representative perfluorinated alkanes, cycloalkanes, ethers and tertiary amines have been examined, using Ar at about 0.5 torr as the reagent gas. The compounds chosen are typical of those under study as components of fluorochemical emulsion blood substitutes. Many such PFC's, particularly those with cyclic or branched structures, give intense molecular ions; most give simple spectra with a few major fragment ions at high mass, in marked contrast to the EI spectra which are dominated by m/e 69 (CF₃+) and 131 (C₃F₅+) of no value for structure elucidation. NCI-GC/MS is more sensitive than conventional EI-GC/MS and promises to be more generally useful for structure determination. Specific examples from the various classes will be presented, and their NCI and EI mass spectra compared.     

Interaction between dyes and polyelectrolytes. XIII. Effect of dye aggregation on the excitation energy transfer between bound dyes

Effect of polyanions on the aggregation of methylene blue (MB) was investigated spectrophotometrically. The following polyanions were used: potassium poly(vinyl sulfate), potassium poly(styrenesulfonate), sodium poly(methacrylate), and sodium poly(acrylate). The state of aggregation was largely dependent on the kind of polyanion and polyanion-MB ratio. MB-photo-sensitized isomerization of cis-p-(phenylazo)phenyltrimethylammonium iodide(cis-PTA) to the transisomer was used advantageously to investigate the effect of dye aggregation on the triplet excitation energy transfer between cationic dyes bound to polyanions. Although the efficiency of the excitation energy transfer between MB and cis-PTA was enhanced by the addition of polyanions, the formation of highly aggregated MB reduced the efficiency of the excitation energy transfer. Correlation with the dye aggregation induced by polyanions and the efficiency of excitation energy transfer between dyes was discussed.     

Glivenko theorems and negative translations in substructural predicate logics

Along the same line as that in Ono (Ann Pure Appl Logic 161:246–250, 2009), a proof-theoretic approach to Glivenko theorems is developed here for substructural predicate logics relative not only to classical predicate logic but also to arbitrary involutive substructural predicate logics over intuitionistic linear predicate logic without exponentials QFL _e . It is shown that there exists the weakest logic over QFL _e among substructural predicate logics for which the Glivenko theorem holds. Negative translations of substructural predicate logics are studied by using the same approach. First, a negative translation, called extended Kuroda translation is introduced. Then a translation result of an arbitrary involutive substructural predicate logics over QFL _e is shown, and the existence of the weakest logic is proved among such logics for which the extended Kuroda translation works. They are obtained by a slight modification of the proof of the Glivenko theorem. Relations of our extended Kuroda translation with other standard negative translations will be discussed. Lastly, algebraic aspects of these results will be mentioned briefly. In this way, a clear and comprehensive understanding of Glivenko theorems and negative translations will be obtained from a substructural viewpoint.     

Floer–Novikov cohomology and the flux conjecture

We study Floer–Novikov cohomology with local coefficients and prove the flux conjecture for general closed symplectic manifolds. Received: February 2005, Revised: May 2006, Accepted: May 2006 Partially supported by the Grant-in-Aid for Scientific Research No. 14003419, Japan Society for the Promotion of Sciences.     

Deformations of locally abelian Galois representations and unramified extensions

We study the deformation theory of Galois representations whose restriction to every decomposition subgroup is abelian. As an application, we construct unramified non-solvable extensions over the field obtained by adjoining all p-power roots of unity to the field of rational numbers.