Rhodium-catalyzed 1,4-addition of alkenylzirconocene chlorides to electron deficient alkenes

The 1,4-conjugated addition of alkenylzirconocene chloride complexes to α,β-enones, α,β-enoic acid esters, and α,β-enoic acid amides can be efficiently achieved by the use of [RhCl(cod)]₂ catalyst. A high diastereoselectivity (95% yield, 90% de) was obtained through the reaction of α,β-enoic acid amide derived from Oppolzer's sultam and 2-butenoyl chloride, while the use of Evans' chiral oxazolidinone as a chiral auxiliary in place of Oppolzer's sultam gave a poor diastereoselectivity (98% yield, 26% de).     

Effect of the pore surface modification of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes

We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006     

Spectrophotometric determination of anthracycline anticancer agents with aluminum(III) and chromazurol S in a nonionic surfactant micellar medium.

A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations.     

Studies on the synthesis of condensed pyridazine derivatives. IV. Synthesis and anxiolytic activity of 2-aryl-5,6-dihydro-(1)benzothiepino[5,4- c]pyridazin-3(2H)-ones and related compound.

A series of 2-aryl-5,6-dihydro-(1)benzothiepino[5,4-c]pyridazin-3(2H)- ones and related compounds were synthesized and evaluated for their ability to displace 3H-diazepam from rat brain membranes in vitro, and to prevent bicuculline induced convulsions in mice in vivo. Compounds with a 4'-methoxyphenyl (36) or 4'-chlorophenyl group (37, 39--42) as 2-aryl substituents showed prominent activities in both the in vitro and in vivo tests. Among them, 2-(4'-chlorophenyl)-5,6-dihydro- (37) and 2-(4'-chlorophenyl)-5,6-dihydro-10-fluoro-(1)benzothiepino[5,4-c]+ ++pyridazin- 3(2H)-one 7-oxides (41) showed activity twice as potent as diazepam in an anticonflict test (Vogel type, rats) while exhibiting less muscle relaxation (rotarod test, mice) and augmentation of gamma-aminobutyric acid-induced chloride current (Icl) in isolated frog sensory neurones than diazepam. Compound 37 (Y-23684) was selected from this series as a candidate for further development. The structure-activity relationships are discussed.     

Time decay of solutions to the cauchy problem for time-dependent Schrödinger-Hartree equations

We consider the time-dependent Schrödinger-Hartree equation (1) $$iu_t + \Delta u = \left( {\frac{1}{r}*|u|^2 } \right)u + \lambda \frac{u}{r},(t, x) \in \mathbb{R} \times \mathbb{R}^3 ,$$ (2) $$u(0,x) = \phi (x) \in \Sigma ^{2,2} ,x \in \mathbb{R}^3 ,$$ where λ≧0 and \(\Sigma ^{2,2} = \{ g \in L^2 ;\parallel g\parallel _{\Sigma ^{2,2} }^2 = \sum\limits_{|a| \leqq 2} {\parallel D^a g\parallel _2^2 + \sum\limits_{|\beta | \leqq 2} {\parallel x^\beta g\parallel _2^2< \infty } } \} \) . We show that there exists a unique global solutionu of (1) and (2) such that $$u \in C(\mathbb{R};H^{1,2} ) \cap L^\infty (\mathbb{R};H^{2,2} ) \cap L_{loc}^\infty (\mathbb{R};\Sigma ^{2,2} )$$ with $$u \in L^\infty (\mathbb{R};L^2 ).$$ Furthermore, we show thatu has the following estimates: $$\parallel u(t)\parallel _{2,2} \leqq C,a.c. t \in \mathbb{R},$$ and $$\parallel u(t)\parallel _\infty \leqq C(1 + |t|)^{ - 1/2} ,a.e. t \in \mathbb{R}.$$      

Ruthenium(II)-catalyzed hydrogenation of carbon dioxide to formic acid. Theoretical study of real catalyst, ligand effects, and solvation effects

Ruthenium-catalyzed hydrogenation of carbon dioxide to formic acid was theoretically investigated with DFT and MP4(SDQ) methods, where a real catalyst, cis-Ru(H)2(PMe3)3, was employed in calculations and compared with a model catalyst, cis-Ru(H)2(PH3)3. Significant differences between the real and model systems are observed in CO2 insertion into the Ru(II)-H bond, isomerization of a ruthenium(II) eta1-formate intermediate, and metathesis of the eta1-formate intermediate with a dihydrogen molecule. All these reactions more easily occur in the real system than in the model system. The differences are interpreted in terms that PMe3 is more donating than PH3 and the trans-influence of PMe3 is stronger than that of PH3. The rate-determining step is the CO2 insertion into the Ru(II)-H bond. Its deltaG(o++) value is 16.8 (6.8) kcal/mol, where the value without parentheses is calculated with the MP4(SDQ) method and that in parentheses is calculated with the DFT method. Because this insertion is considerably endothermic, the coordination of the dihydrogen molecule with the ruthenium(II)-eta1-formate intermediate must necessarily occur to suppress the deinsertion. This means that the reaction rate increases with increase in the pressure of dihydrogen molecule, which is consistent with the experimental results. Solvent effects were investigated with the DPCM method. The activation barrier and reaction energy of the CO2 insertion reaction moderately decrease in the order gas phase > n-heptane > THF, while the activation barrier of the metathesis considerably increases in the order gas phase < n-heptane < THF. Thus, a polar solvent should be used because the insertion reaction is the rate-determining step.     

Pharmacokinetics of brain natriuretic peptide in rats.

The pharmacokinetics of rat brain natriuretic peptide (rBNP) was compared with that of alpha-rat atrial natriuretic peptide (alpha-rANP) in rats. After intravenous infusion in rats (600 pmol min-1kg-1 for 2 min), the disappearance of plasma rBNP was 4-fold slower than that of alpha-rANP. The estimated mean plasma clearance rates for rBNP and alpha-rANP were 45.9 ml min-1kg-1 and 74.4 ml min-1kg-1, respectively. The affinity of rBNP for the clearance receptor or degradation enzyme was considered to be lower than that of alpha-rANP.