A Convenient General Access to α-Sulfenylated Acetophenones and Alkanones

Friedel-Crafts acylation of arenes with methylthio- (1) or phenylthio-acetyl chloride (2) provides ready access to α-methylthio- or α-phenylthio-substituted acetophenones. The acyl chlorides 1 and 2 reacted also with organoaluminum reagents to give α-sulfenylated alkanones.     

Enzymatic syntheses of unnatural head-to-tail pentacyclic triterpenes by tetraprenyl-β-curcumene cyclase

Little is known of the biosynthesis of sesquarterpenes and the synthesis of unnatural terpenoids by sesquarterpene biosynthetic enzymes has not yet been reported. In this study, the enzymatic cyclization of head-to-tail acyclic triterpene β-hexaprene—a natural product isolated from Bacillus clausii—using tetraprenyl-β-curcumene cyclase (TC) from Bacillus subtilis resulted in the formation of two unnatural pentacyclic triterpenes. It was revealed that B. subtilis TC, which forms tetracyclic terpenoid scaffold from tetraprenyl-β-curcumene in vivo, could be used to construct the 6/6/6/6/6-fused pentacyclic scaffold in vitro, suggesting that the active site cavity of TC has sufficient space to accommodate this unnatural pentacyclic scaffold. This is the first report demonstrating the utility of a sesquarterpene cyclase toward the synthesis of unnatural terpenoids.     

Two‐dimensional replica‐exchange method for predicting protein–ligand binding structures

We have developed a two‐dimensional replica‐exchange method for the prediction of protein–ligand binding structures. The first dimension is the umbrella sampling along the reaction coordinate, which is the distance between a protein binding pocket and a ligand. The second dimension is the solute tempering, in which the interaction between a ligand and a protein and water is weakened. The second dimension is introduced to make a ligand follow the umbrella potential more easily and enhance the binding events, which should improve the sampling efficiency. As test cases, we applied our method to two protein‐ligand complex systems (MDM2 and HSP 90‐alpha). Starting from the configuration in which the protein and the ligand are far away from each other in each system, our method predicted the ligand binding structures in excellent agreement with the experimental data from Protein Data Bank much faster with the improved sampling efficiency than the replica‐exchange umbrella sampling method that we have previously developed. © 2013 Wiley Periodicals, Inc.     

Design and synthesis of 2-(1,3-dialkoxy-2-methylpropan-2-yl)-1,3-diarylpropanes as tethering units for folded H-stacking polymers

1,3-Diarylpropenes 9 having a 1,3-dialkoxy-2-methylpropan-2-yl group were designed as tethering monomers for folded H-stacking polymers, and were readily synthesized from 2-ethoxymethylidene malonate in four- or five-steps, including a facile sequential addition–elimination–addition reaction of benzyl zinc reagents. The preference for the closed (stacked) conformation in the resulting 2-substituted 1,3-diarylpropanes 9 was evaluated using MM2 calculations, ¹H NMR analyses, and fluorescence measurements. Copolymerization of the resulting monomers 9 with compounds containing π-units provided polymers with blue-shifted UV-absorptions both in solution and as films, compared with that of a model compound containing a single π-unit. This optical property is unique to H-aggregated π-units.     

Clinical Perspectives of Theranostics

Theranostics is a precision medicine which integrates diagnostic nuclear medicine and radionuclide therapy for various cancers throughout body using suitable tracers and treatment that target specific biological pathways or receptors. This review covers traditional theranostics for thyroid cancer and pheochromocytoma with radioiodine compounds. In addition, recent theranostics of radioimmunotherapy for non-Hodgkin lymphoma, and treatment of bone metastasis using bone seeking radiopharmaceuticals are described. Furthermore, new radiopharmaceuticals for prostatic cancer and pancreatic cancer have been added. Of particular, F-18 Fluoro-2-Deoxyglucose (FDG) Positron Emission Tomography (PET) is often used for treatment monitoring and estimating patient outcome. A recent clinical study highlighted the ability of alpha-radiotherapy with high linear energy transfer (LET) to overcome treatment resistance to beta--particle therapy. Theranostics will become an ever-increasing part of clinical nuclear medicine.     

Isotopic dependence of the giant monopole resonance in the even-A 112-124Sn isotopes and the asymmetry term in nuclear incompressibility

The strength distributions of the giant monopole resonance (GMR) have been measured in the even-A Sn isotopes (A=112-124) with inelastic scattering of 400-MeV alpha particles in the angular range 0 degrees -8.5 degrees . We find that the experimentally observed GMR energies of the Sn isotopes are lower than the values predicted by theoretical calculations that reproduce the GMR energies in 208Pb and 90Zr very well. From the GMR data, a value of Ktau = -550 +/- 100 MeV is obtained for the asymmetry term in the nuclear incompressibility.     

Involvement of Proton Transfer for Carbon Dioxide Reduction Coupled with Extracellular Electron Uptake in Shewanella oneidensis MR‐1

Microbial biosynthesis of hydrocarbon from CO₂ reduction driven by electron uptake process from the cathodic electrode has gained intensive attention in terms of potential industrial application. However, a lack of a model system for detailed studies on the mechanism of the CO₂ reduction hinders the improvement in efficiency for microbial electrosynthesis. Here, we examined the mechanism of microbial CO₂ reduction at the cathode by a well‐described microbe for extracellular electron uptake, Shewanella oneidensis MR‐1, capable of reducing gaseous CO₂ to produce formic acid. Using whole‐cell electrochemical assay, we observed stable cathodic current production at ?0.65 V vs Ag/AgCl KCl sat. associated with the introduction of CO₂. The observed cathodic current was enhanced by the addition of 4 μM riboflavin, which specifically accelerates the electron uptake process of MR‐1 by the interaction to its outer‐membrane c‐type cytochromes. The significant impact of an uncoupler agent and a mutant strain of MR‐1 lacking sole F‐type ATPase suggested the importance of proton import to the cytoplasm for the cathodic CO₂ reduction. The present data suggest that MR‐1 potentially serves as a model system for microbial electrosynthesis from CO₂.     

Discotic Liquid Crystals of Transition Metal Complexes, 19: Discotic Mesomorphism and Double Clearing Behavior of Octakis(dialkoxyphenyl)phthalocyanine Derivatives

Eight novel octakis(3,4-dialkoxyphenyl)- phthalocyanine derivatives, Cn-M (2, M=2H; 3, M=Ni; 4, M=Cu; a, decyloxy; b, undecyloxy; c, dodecyloxy), have been synthesized and characterized. It was found that each of the derivatives exhibits discotic liquid crystalline properties, and that each of the Cn–Cu (4) derivatives has two kinds of D_rd2( P 2₁/ a ) mesophases. These Cn–Cu (4a,b,c) and C₁₂–2H (2c) derivatives exhibit a unique double clearing behavior.     

Electrochemical formation of cation-exchanging polypyrrole films within various hydrophilic–hydrophobic domains

The electrochemical polymerization technique has been successfully applied to produce conducting polymer film of controlled ion exchange properties. Polypyrrole films were prepared by electro-oxidative polymerization with doping some alkylsulfonates or Nafion. The ion exchange characteristics across polypyrrole films were examined by means of a novel electrochemical technique, namely, the in situ electrochemical quartz crystal microbalance (EQCM) method. According to EQCM measurements, exchanging ion species was found to be successfully controlled by changing the hydrophilic–hydrophobic balance of the incorporated sulfonated-based dopants. The film's characteristics became anion- to cation-exchanging as the dopants became more hydrophobic in nature. The polypyrrole–Nafion(poly(perfluoroethylene sulfonate)) composite film became to be a complete cation exchanger.