Photocatalytic formation of dimethyllepidopterene from 9,10-dimethylanthracene via electron-transfer oxidation

[Structure: see text] Photocatalytic carbon-carbon bond formation of 9,10-dimethylanthracene (DMA) in chloroform occurs efficiently via the electron-transfer oxidation of DMA with the photoinduced electron-transfer state of 9-mesityl-10-methylacridinium ion (Acr+-Mes), followed by deprotonation from the methyl group of DMA radical cation and the radical coupling reaction between anthracenylmethyl radicals to produce dimethyllepidopterene.     

Adsorption of biopolyester depolymerase on silicon wafer and poly[(R)-3-hydroxybutyric acid] single crystal revealed by real-time AFM

The adsorption behavior of PHB depolymerase from R. pickettii T1 on a silicon wafer and on P(3HB) single crystals has been studied by real-time and AFM in air and a buffer solution. First, the morphology of PHB depolymerase adsorbed on a silicon wafer was characterized to show that one molecule of PHB depolymerase has dimensions of 2.2 +/- 0.7 nm height and 16 +/- 5 nm width. The observation of PHB depolymerase adsorbed on a P(3HB) single crystal indicated that the dimensions of enzyme on the crystalline surface in air were 1.2 +/- 0.5 nm high and 28 +/- 7 nm wide, while enzyme molecules with dimensions of 2.1 +/- 0.6 nm height and 16 +/- 7 nm width were detected in a buffer solution. Comparison of the dimensions of PHB depolymerase in air with those in a buffer solution showed that the enzyme was squashed in air, but not in a buffer solution. In addition, the influence of enzymatic adsorption on the molecular state of the P(3HB) crystalline surface was investigated. The AFM images of P(3HB) single crystals after enzymatic adsorption and washing with ethanol indicated that the adhesion of PHB depolymerase changed the molecular state and generated holes on the crystalline surface.     

Enhanced theophylline metabolism in patients with bronchial asthma at age 4 and under.

The plasma levels of theophylline (TP) and its metabolites were measured in patients with bronchial asthma who were treated with a slow-release preparation of TP. The ratios of the plasma levels of these metabolites to TP levels in the group aged 1-4 years were larger than those in the group aged 5 years and older, suggesting enhanced activity of drug-metabolizing enzymes during infancy.     

Fast Cycle Canceling Algorithms for Minimum Cost Submodular Flow*

This paper presents two fast cycle canceling algorithms for the submodular ow problem. The rst uses an assignment problem whose optimal solution identies most negative node-disjoint cycles in an auxiliary network. Canceling these cycles lexicographically makes it possible to obtain an optimal submodular ow in O(n ⁴ h log(nC)) time, which almost matches the current fastest weakly polynomial time for submodular flow (where n is the number of nodes, h is the time for computing an exchange capacity, and C is the maximum absolute value of arc costs). The second algorithm generalizes Goldbergs cycle canceling algorithm for min cost flow to submodular flow to also get a running time of O(n ⁴ h log(nC)).. We show how to modify these algorithms to make them strongly polynomial, with running times of O(n ⁶ h log n), which matches the fastest strongly polynomial time bound for submodular flow. We also show how to extend both algorithms to solve submodular flow with separable convex objectives. * An extended abstract of a preliminary version of part of this paper appeared in [22]. Research supported in part by a Grant-in-Aid of the Ministry of Education, Science, Sports and Culture of Japan. Research supported by an NSERC Operating Grant. Part of this research was done during a sabbatical leave at Cornell SORIE.§ Research supported in part by a Grant-in-Aid of the Ministry of Education, Science, Sports and Culture of Japan.     

The influence of chloro-substituent sites of hexachlorobiphenyl on the respiration of rat liver mitochondria.

The actions of three hexachlorobiphenyls (HCBs) 2,3,4,2',3',4'-, 2,3,4,3',4',5'- and 3,4,5,3',4',5'-HCBs, on the respiration of rat liver mitochondria with succinate as the substrate were compared, and the effect of chloro-substitution sites in HCB on the respiration was examined. 2,3,4,2',3',4'-HCB strongly inhibited both state 3 and 2,4-dinitrophenol (DNP)-stimulated respiration with 50% inhibition dose of 52 and 54 microM for state 3 and DNP-stimulated respiration, respectively. The inhibitory action of 2,3,4,3',4',5'-HCB on both respiration was approximately half as potent as that of 2,3,4,2',3',4'-HCB. On the other hand, 3,4,5,3',4',5'-HCB did not inhibit any respiration at all. These results indicate that both inside (ortho) and outside (meta or para) positions in each phenyl ring of the biphenyl molecule should be replaced with chlorines for HCB to be an effective inhibitor. Either the actual position of chloro-substituent or steric conformation caused by its substitution or both can be considered as factors affecting the inhibition. On the basis of the conformational energy, calculated by AM1 (Austin model 1) method, with increases in chlorine number in ortho position, HCB molecule became angulated. Furthermore, calculated probability of the conformation distribution for HCB indicated that the probability of nonplanarity was higher for effective HCB than for less effective HCB. These structural features suggest the significance of steric conformation as well as chloro-substituent sites in determining the inhibitory ability of HCB.(ABSTRACT TRUNCATED AT 250 WORDS)     

Efficient one-step conversion of primary aliphatic amines into primary alcohols: application to a model study for the total synthesis of (+/-)-scopadulin

[reaction: see text] Treatment of primary aliphatic amines with KOH in diethylene glycol at 210 degrees C gives primary alcohols directly in good yields. A synthetic application to a model study of (+/-)-scopadulin is also described.     

Molecular orbital studies of hydrogen bonds. IV. Hydrogen bonds in excited states of H2CO with H2O

Ab initio calculations for the interacting system of lower excited states of planar and bent H₂CO with H₂O have been carried out with a minimum basis set, using the recently proposed electron-hole potential method. The blue shifts of the η-π* transition are evaluated as 1100 and 1420 cm^?1 for the singlet and triplet transitions, respectively. In the η-π* states of bent H₂CO, the most stable geometry is one in which an H₂O hydrogen atom is coordinated to the carbon atom.     

Novel bifunctional probe for radioisotope-free photoaffinity labeling: compact structure comprised of photospecific ligand ligation and detectable tag anchoring units

A novel method for radioisotope-free photoaffinity labeling was developed, in which a bifunctional ligand is connected to a target protein by activation of a photoreactive group, such as an aromatic azido or 3-trifluoromethyl-3H-diazirin-3-yl group, and identification of the ligated product is achieved by anchoring of a detectable tag through the Staudinger-Bertozzi reaction with an alkyl azido moiety that survives photolysis. The chemical ground of this method was confirmed using model compounds with the bifunctional group under photoirradiation in the presence of trapping agents for reactive intermediates. The utility of the method has been demonstrated by specific labeling of the catalytic portion of human HMG-CoA reductase.