The photochemical [4+4] cyclodimerization of 2-pyrazinone in the solid state

Irradiation of 1-methyl-5,6-diphenyl-2-pyrazinone (Ia) in the solid state gave the [4+4] anti dimer (II) in 100% yield, while (Ia) in a solution phase was inert upon irradiation.     

Common bile duct anteroposterior movement synchronized with inferior vena cava pulsation observed by cine magnetic resonance imaging

Purpose

To reveal the phenomenon of common bile duct (CBD) anteroposterior movement caused by inferior vena cava (IVC) pulsation depending on the cardiac cycle using cine magnetic resonance imaging.

Materials and Methods

A breath-hold trans-axial cine segmented true fast imaging with steady-state precession (trueFISP) sequence was prospectively performed on 11 healthy volunteers to observe CBD anteroposterior movement and IVC pulsation during the cardiac cycle. Changes in IVC anterior–posterior diameter and CBD location were compared using Pearson rank correlation analysis.

Results

Nine (81.8%) of 11 CBDs moved back and forth in synchronicity with IVC anterior wall motion depending on the cardiac cycle; the mean maximum and minimum IVC diameters were 16.2±2.7 and 12.9±3.1 mm, respectively. Two (18.2%) of 11 CBDs and IVC walls did not move; the mean unchanged IVC diameter was 5.3±2.1 mm. There were significant correlations between the mean change in IVC diameter and distance of CBD anteroposterior movement (2.7±2.1 and 1.8±1.4 mm, respectively, r=0.911, P<.05).

Conclusion

Many CBDs move back and forth in synchronicity with IVC pulsation depending on the cardiac cycle.     

Enantioselective adsorption of phenylalanine onto self-assembled monolayers of 1,1'binaphthalene-2,2'-dithiol on gold

Self-assembled monolayer of atropisomeric compound, 1,1'-binaphthalene-2,2'-dithiol (BNSH), provides a field for chiral discrimination. The two-dimensional chiral arrangement with screw-like units, each of which is composed of three BNSH molecules, plays an important role in the enantioselectivity of adsorption of phenylalanine, as revealed by a quartz crystal microbalance technique.     

New protocol for oxidation in water: micellar oxidation systems composed of novel amphiphilic hydroperoxides

A series of novel amphiphilic hydroperoxides, alpha-alkoxyalkyl hydroperoxides (alpha-AHPs) and their related hydroperoxides, were designed and prepared with the intention of developing new oxidizing agents bearing a micelle-forming character in water. After their fundamental physical and interfacial properties were elucidated, both oxidation of benzyl sulfide and epoxidation of geraniol promoted by these hydroperoxides were investigated in detail under various conditions. Effective oxidation ofbenzyl sulfide to the corresponding sulfoxide was achieved in aqueous micellar systems composed of alpha-AHPs la-d and a catalytic amount of MoO2(acac)2 at 30 degrees C. Up to 100% conversion was observed under the optimum conditions. In the case of epoxidation of geraniol in water, the corresponding 2,3-epoxide was selectively formed in good yields. Because the conversion of each substrate in the micellar systems was higher than that in nonmicellar media, the solubilization of substrates into micelles was certainly effective in promoting oxidations of insoluble substrates in aqueous media. Micellar oxidation systems composed of novel amphiphilic hydroperoxides afford a new protocol in order to derive safer conditions under which these reactions may be carried out.     

Oxidation of nitrotoluenes with air using N-hydroxyphthalimide analogues as key catalysts

Nitrotoluenes are efficiently oxidized with air to the corresponding nitrobenzoic acids by the use of N-acetoxyphthalimide (NAPI) as a key catalyst. Thus, p- and m-nitrotoluenes under 10 atm of air in the presence of NAPI combined with Co(OAc)₂ (0.5 mol%) and Mn(OAc)₂ (0.05 mol%) at 130°C afforded p- and m-nitrobenzoic acids in 81 and 92% yields, respectively. o-Nitrotoluene was oxidized to o-nitrobenzoic acid in 51% yield by the aid of NO₂.     

Ion-specific swelling behaviors of partially quaternized poly(4-vinyl pyridine) gel

Swelling degrees of partially quaternized poly(4-vinyl pyridine) (p.q.P4VP) were measured as functions of the degree of quaternization (D.Q.: 5, 10, 15, 30, and 50 mol%), salt concentration (0–4 M), and salt species (KF, LiCl, NaCl, KCl, CsCl, MgCl₂, KBr, LiSCN, KSCN, Na₂SO₄, and MgSO₄) to study ion effects on the three kinds of interactions involved with p.q.P4VP in aqueous systems, i.e., electrostatic interaction, hydrogen bonding to the nitrogen of the pyridine ring, and hydrophobic interaction, as well as to estimate the relative contributions of the respective ion effects to gel swelling. Upon addition of salts at the lowest salt concentration studied (0.01 M), p.q.P4VP gels, except for one with D.Q.=10%, significantly deswelled depending on the counterion species; the lowest swelling degree was observed for the thiocyanates and the highest one for KF. In the higher salt concentration region (≧1 M) where electrostatic interactions might well be screened, however, some salt systems (e.g., LiCl, KSCN) showed swelling with increased salt concentration, contrary to the common behavior of usual ionic gels. These ion-specific swelling behaviors were interpreted as being caused by additive ionic effects on the three kinds of interactions.     

Dispersion stability of TiO2 nanoparticles covered with SiOx monolayers in water

The repetition of a two-step route consisting of chemisorption of 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS) and its subsequent photooxidation has formed SiOx monolayers on the surfaces of TiO2 particles layer by layer (SiOx(n < or = 4)/TiO2, n = repeated number). The trace of these processes using diffuse reflectance FT-IR and solid-state 29Si NMR spectroscopy reveals that TMCTS is chemisorbed on TiO2 through Ti-O-Si bonds followed by growth of Si-O-Si networks via dehydration-condensation of the Si-OH groups generated by TiO2 photocatalytic oxidation of the Si-H and Si-CH3 groups. The point of zero charge of the TiO2 particles decreases from 6.5 to 5.4 at n = 1, reaching 4.9 at n2. As a result of coverage with the SiOx monolayers, the dispersion stability of TiO2 particles in neutral water is significantly improved without changing their optical properties. The dispersion stability further increases with accumulation of SiOx monolayers.     

New iridoids from Gelsemium species

Four new iridoids structurally related to gelsemide (5) were isolated from two Loganiaceous plants, Gelsemium elegans and G. rankinii. Among them, GEIR-1 (1) has a novel tetracyclic caged structure.