Stannyl radical addition-cyclization of oxime ethers connected with olefins

Stannyl radical addition-cyclization of oxime ethers connected with olefin moieties was studied. The radical reactions proceeded effectively by the use of triethylborane as a radical initiator to provide the functionalized pyrrolidines via a carbon-carbon bond-forming process.     

Palladium-indium iodide-mediated allylation and propargylation of glyoxylic oxime ether and hydrazone: the role of water in directing the diastereoselective allylation

Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl.     

A one-pot procedure for trifluoroacetylation of arylamines using trifluoroacetic acid as a trifluoroacetylating reagent

A convenient procedure for the preparation of aryl trifluoroacetamides from aryl amines is described that employs 2-4 M equiv of trifluoroacetic acid in refluxing xylene as a trifluoroacetylating agent. Addition of an amount of pyridine that is equimolar to the amount of trifluoroacetic acid present in the reaction mixture facilitates the trifluoroacetylation of rather basic arylamines.     

Antibacterial metal implant with a TiO2‐conferred photocatalytic bactericidal effect against Staphylococcus aureus

Photocatalysis with anatase Titanium dioxide (TiO₂) under ultraviolet A (UVA) has a well recognized bactericidal effect. There have been a few reports, however, on the effects of photocatalysis on bio‐implant‐related infections. The purpose of present study was to evaluate the photocatalytic bactericidal effects of anatase TiO₂ on Staphylococcus aureus (S. aureus) associated with surgical site infections. TiO₂ films were synthesized on commercially pure titanium substrates and SUS316 stainless steel using a plasma source ion implantation method followed by annealing. The chemical composition of the surface layers was determined using GXRD and XPS. The disks were seeded with cultured S. aureus and exposed to UVA illumination from black light. The bactericidal effect of the TiO₂ films was evaluated by counting the survived colonies statistically. A structural gradient anatase type TiO₂ layer formed on all substrates. The viability of the bacteria on the photocatalytic TiO₂ film coated on titanium was suppressed to 7.0% at 30 minutes and 5.5% at 45 minutes, whereas that on a similarly coated stainless steel was suppressed to 45.8% at 30 minute and 28.6% at 45 minutes (ANOVA: p < 0.05). Complete bacterial inactivation was achieved after 90 minutes on titanium and after 60 minutes on stainless steel. The photocatalytic bactericidal effect of TiO₂ is useful for sterilizing the contaminated surfaces of bioimplants. Copyright © 2008 John Wiley & Sons, Ltd.     

Total Synthesis and Biological Evaluation of (+)‐Neopeltolide and Its Analogues

The stereocontrolled total synthesis of the originally proposed ( 1 ) and correct ( 2 ) structures of (+)‐neopeltolide, a novel marine macrolide natural product with highly potent antiproliferative activity against several cancer cell lines as well as potent antifungal activity, has been achieved by exploiting a newly developed Suzuki–Miyaura coupling/ring‐closing metathesis strategy. Alkylborate 44 , which was generated in situ from iodide 34 , was coupled with enol phosphate 8 by a Suzuki–Miyaura coupling. Ring‐closing metathesis of the derived diene 45 followed by stereoselective hydrogenation afforded tetrahydropyran 47 as a single stereoisomer in high overall yield from 34 . Our convergent strategy enabled us to construct the 14‐membered macrolactone core structure of 2 in a rapid and efficient manner. Total synthesis and biological evaluation of synthetic intermediates and designed synthetic analogues, performed to establish the structure–activity relationships of 2 , led to the discovery of a structurally simple yet potent cytotoxic analogue, 9‐demethylneopeltolide ( 54 ).     

Alternating-current electrolysis for the production of phenol from benzene

Works both ways: phenol was produced by both anodic and cathodic benzene oxidations over the V(x)O(y)-Sn(0.9)In(0.1)P(2)O(7) electrode in an electrochemical cell, thus allowing the use of AC electrolysis for phenol production. AC electrolysis was found to be more efficient and selective toward phenol production than DC electrolysis.     

New Chiral Kemp's Acid Diamides for Chiral Amine Recognition by 1 H NMR

Two Kemp's acid diamides were synthesized and applied to chiral amine recognition using ¹H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and –– interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on ¹H NMR data and computer simulation.     

Characteristics of hyaluronate-hydroxyethyl acrylate blend gel and release of cationic amphiphilic solutes

Hyaluronate-hydroxyethyl acrylate blend gel (HA-PHEA) were prepared to modify the brittleness of hyaluronate gel (HA) and the characteristics of HA-PHEA gel were compared with those of HA and polyhydroxyethyl acrylate (PHEA) gels. These gels were high in water content and transparent. HA-PHEA gel was improved in viscoelastic properties due to the elasticity and the high affinity with water of PHEA, and the drying-swelling cycles became reversible. The effective charge densities theta of the gels estimated from membrane potentials were -0.002, -0.008 and 0 mol dm(-3) for HA-PHEA, HA and PHEA gels. Effects of electro- static and nonelectrostatic interactions on absorptions and releases were studied using sodium benzoate (NaBA) as an anionic solute, and methylene blue (MB), chlorpromazine (CPHCl) and benzethonium chloride (BZTCl) as cationic solutes, in which CPHCl and BZTCl are cationic amphiphilic solutes. The releases of MB, CPHCl and BZTCl from HA-PHEA and HA gels were suppressed comparing with those of NaBA. By adding salts, the releases of MB and CPHCl were enhanced but those of BZTCl were suppressed due to enhancement of the intra- and intermicelle formation. In the releases of the cationic solutes from HA-PHEA gel, electrostatic and nonelectrostatic interactions with HA were found to play important roles. Behaviors of the releases from HA-PHEA gel were found to possess the features of HA gel.     

Fragmentation study of peptides using Fourier transform ion cyclotron resonance with infrared multiphoton dissociation: experiment and simulation

In this study, the fragmentation of gas-phase protonated Angiotensin II is investigated using electrospray ionization (ESI), Fourier-transform ion cyclotron resonance (FT-ICR), and mass spectrometry (MS) with a laser cleavage infrared multiphoton dissociation (IRMPD) technique. The experimental results show that the spectra peaks for the photoproducts are y2/b6- and y7-type ions, corresponding to the cleavage of His-Pro and Asp-Arg in the parent amino acid sequence. The fragmentation of the peptide under collision-free vacuum conditions is modeled using molecular dynamics simulations (MD). The binding energy for the peptide bonds (C'-N bond) of Angiotensin II is estimated from ab initio calculations. The calculations are directed at predicting experimental measurements of the product ions from the photodissociation of the peptide. The product distributions simulated by the MD dissociation trajectories include predominantly y7/b1 and y2/b6 pair ions.