Synthesis and two-electron redox behavior of diazuleno[2,1-a:1,2-c]naphthalenes

The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement.     

Second-derivative spectrophotometric study on the interactions of chlorpromazine and triflupromazine with bovine serum albumin

The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures.     

Subincanadines A-C,novel quaternary indole alkaloids from Aspidosperma subincanum

Three novel quaternary indole alkaloids with an unprecedented 1-azoniatricyclo[4.3.3.0(1,5)]undecane moiety, subincanadines A-C (1-3), as well as two new indole alkaloids with a 1-azabicyclo[5.2.2]undecane moiety, subincanadines D (4) and E (5), and a new indole alkaloid with a 1-azabicyclo[4.3.1]decane moiety, subincanadine F (6), have been isolated from the barks of Aspidosperma subincanum Mart, and the structures of 1-6 and the stereochemistry of 1-3 were elucidated by spectroscopic data and chemical means.     

Control of charge-transfer-induced spin transition temperature on cobalt-iron Prussian blue analogues

The electronic and spin states of a series of Co-Fe Prussian blue analogues containing Na(+) ion in the lattice, Na(x)()Co(y)()Fe(CN)(6) x zH(2)O, strongly depended on the atomic composition ratio of Co to Fe (Co/Fe) and temperature. Compounds of Co/Fe = 1.5 and 1.15 consisted mostly of the Fe(III)(t(2g)(5)e(g)(0), LS, S = 1/2)-CN-Co(II)(t(2g)(5)e(g)(2), HS, S = 3/2) site and the Fe(II)(t(2g)(6)e(g)(0), LS, S = 0)-CN-Co(III)(t(2g)(6)e(g)(0), LS, S = 0) site, respectively, over the entire temperature region from 5 to 350 K. Conversely, compounds of Co/Fe = 1.37, 1.32, and 1.26 showed a change in their electronic and spin states depending on the temperature. These compounds consisted mainly of the Fe(III)-CN-Co(II) site (HT phase) around room temperature but turned to the state consisting mainly of the Fe(II)-CN-Co(III) site (LT phase) at low temperatures. This charge-transfer-induced spin transition (CTIST) phenomenon occurred reversibly with a large thermal hysteresis of about 40 K. The CTIST temperature (T(1/2) = (T(1/2) descending + T(1/2) ascending)/2) increased from 200 to 280 K with decreasing Co/Fe from 1.37 to 1.26. Furthermore, by light illumination at 5 K, the LT phase of compounds of Co/Fe = 1.37, 1.32, and 1.26 was converted to the HT phase, and the relaxation temperature from this photoproduced HT phase also strongly depended on the Co/Fe ratio; 145 K for Co/Fe = 1.37, 125 K for Co/Fe = 1.32, and 110 K for Co/Fe = 1.26. All these phenomena are explained by a simple model using potential energy curves of the LT and HT phases. The energy difference of two phases is determined by the ligand field strength around Co(II) ions, which can be controlled by Co/Fe.     

Synthesis of 5H-pyrido[2,3-a]phenoxazin-5-one and 5H-pyrido[3,2-a]phenoxazin-5-one derivatives

The 5H-pyrido[2,3-a]phenoxazin-5-one derivatives and 5H-pyrido[3,2-a]phenoxazin-5-one derivatives were prepared by the condensation of substituted 2-aminophenols with 6,7-dibromo-5,8-quinolinequinone followed by dehalogenation in the presence of sodium hydrosulfite dissolved in aqueous pyridine under a nitrogen atmosphere.     

Effects of physiological factors on the bioavailability of ethyl 2-chloro-3-[4-(2-methyl-2-phenylpropyloxy)phenyl]propionate in an emulsion in rats

The main absorption site of ethyl 2-chloro-3-[4-(2-methyl-2-phenylpropyloxy)phenyl]propionate (AL-294) in rats was the upper portion of the small intestine. Both AL-294 and AL-294 acid (2-chloro-3-[4-(2-methyl-2-phenylpropyloxy)phenyl]propionic acid), a hydrolyzed form of AL-294, were absorbed in a smaller quantity under the bile fistula condition (pancreatic juice and bile were excluded). Compared with the absorption of AL-294 as an emulsion under the sham operation condition, the absorption of AL-294 as the emulsion decreased under the condition where only pancreatic juice was excluded. The bioavailability under this condition was very similar to that under the bile fistula condition, whereas the absorption of AL-294 acid did not decrease when the pancreatic juice was excluded. From these results, the absorption mechanism of AL-294 is considered as follows: AL-294 was hydrolyzed to AL-294 acid by lipase in pancreatic juice, then AL-294 acid was solubilized with bile salts to form mixed micelles in the intestinal lumen. AL-294 acid from this form was easily absorbed into the systemic circulation. Absorption of AL-294 increased when the particle size of the emulsion was smaller. The reason was assumed to be that the smaller particle size offered the greater oil-water interface for lipase activity against AL-294.     

Degradation of hydroxymaleimide in 2-propanol by irradiation of energetic heavy ions (II)—N2-saturated system

Hydroxymaleimide was irradiated in N₂-saturated 2-propanol solutions by high-energy heavy ions over a wide range of LET values. The differential G-values of the degradation of hydroxymaleimide by irradiation with the heavier ions were lower than those of the lighter ions for the same LET value. An opposite result obtained in the air-saturated system. The degradation efficiency was 1.5 times higher, when the dose rate was 1/10 times lower. When irradiated at an LET value lower than 8 eV/nm, the G-values converged to a value less than that obtained by γ-irradiation.