The structure of new cis and trans 3′-phenyl-3′,3a′,4′,5′,6′,7a′-hexahydro-2,1-benzisoxazole-7a′-spiro-2-(3-phenylaziridine)

The reaction of dibenzalcyclohexanone with hydroxylamine hydrochloride afforded three compounds 1–3 including the aziridine 3 showing a 3′,3a′-trans configuration. Now we report on the isolation of a new aziridine 4 , possessing a 3′,3a′-cis configuration. Its structure was deduced by 2D nmr and single crystal X-ray diffraction studies.     

The structures of 2-(4,5-dihydro-5-aryl-3-isoxazolyl)-1-arylethanone oximes. An unusual behaviour in its 1H-NMR and mass spectra

The reaction of dibenzalacetones substituted on the aromatic ring with hydroxylamine hydrochloride and potassium hydroxide in refluxing ethanol affords several compounds. Herein, we report the structures and spectral properties of several oximes of 2-(4,5-dihydro-5-aryl-3-isoxazolyl)-1-arylethanones 6 . Unusual behaviour on its ¹H-nmr and mass spectra was observed. Single crystal X-ray diffraction was performed on compound 6d to support our structural considerations abouth the title compounds.     

Geranyl Functionalized Materials for Site-Specific Co-Immobilization of Proteins

Different materials containing carboxylic groups have been functionalized with geranyl-amine molecules by using an EDC/NHS strategy. Chemical modification of the support was confirmed by XRD, UV-spectrophotometer, and FT-IR. This geranyl-functionalized material was successfully applied for four different strategies of site-selective immobilization of proteins at room temperature and aqueous media. A reversible hydrophobic immobilization of proteins (lipases, phosphoglucosidases, or tyrosinase) was performed in neutral pH in yields from 40 to >99%. An increase of the activity in the case of lipases was observed from a range of 2 to 4 times with respect to the initial activity in solution. When chemically or genetically functionalized cysteine enzymes were used, the covalent immobilization, via a selective thiol-alkene reaction, was observed in the presence of geranyl support at pH 8 in lipases in the presence of detergent (to avoid the previous hydrophobic interactions). Covalent attachment was confirmed with no release of protein after immobilization by incubation with hydrophobic molecules. In the case of a selenium-containing enzyme produced by the selenomethionine pathway, the selective immobilization was successfully yielded at acidic pH (pH 5) (89%) much better than at pH 8. In addition, when an azido-enzyme was produced by the azide–homoalanine pathway, the selective immobilization was successful at pH 6 and in the presence of CuI for the click chemistry reaction.     

Effect of Nail Thickness on Visible Radiation Transmittance: Implications for New Photodynamic Therapy Technologies in Onychomycosis

Photodynamic therapy is taking importance as a nonintrusive treatment for nail onychomycosis. Knowledge of true transmittance values across nails could lead to qualitative and quantitative improvements in light-based treatments. We have characterized the spectral transmittance of healthy and fungally infected human fingernails and toenails according to nail thickness, and we propose a surface transmittance model for the small-scale optimization of light-based treatments. Transmittance of fingernails and toenails was analyzed by means of spectroradiometric measurements under solar-simulated visible light radiation (400 nm to 750 nm). The nail thickness was measured by means of microscope measurement. Transmittance was highest at longer wavelengths and decreased gradually as the wavelengths became shorter but with a significant nail transmittance of around 20% in the blue region of the spectrum. In the case of nails affected by onychomycosis, transmittance fell to under 10% because of the thickness of the nails, with no changes in spectral characteristics of transmitted light. Nail thickness is the main variable controlling exponentially light transmission in the visible spectrum and not only red radiation is effective for nail onychomycosis PDT. Blue light, the spectral band more effective for PPIX absorption is also effectively transmitted.     

Synthesis and Thermotropic Properties of Twin Mesogens Containing a Polymethylene Spacer

DSC and microscopic data are presented for a thermotropic twin mesogen series. Deviations from normal trends were observed.     

Characterization of a laser-induced plasma by spatially resolved spectroscopy of neutral atom and ion emissions.: Comparison of local and spatially integrated measurements

The local values of the parameters that characterize a laser-induced plasma (temperature, electron density, relative number densities of neutral atoms and ions) have been obtained by spatially resolved emission spectroscopy, including the deconvolution of the measured intensity spectra. The plasma has been generated using a Nd:YAG laser with a Fe–Ni alloy in air at atmospheric pressure, and the emission in the time window 3.0–3.5 μs has been detected. The temperature values obtained from neutral atom and ion emissions have been compared in the cases of local and spatially-integrated measurements. Local Boltzmann and Saha–Boltzmann plots with high correlation to linear fittings have been obtained using two broad sets of optically thin neutral atom and ion lines (21 Fe I lines and 15 Fe II lines), resulting in local values of the electronic temperature that coincide within the error. These results of local measurements contrast with those of spatially integrated measurements, for which two different temperatures are obtained from the Boltzmann plots of neutral atoms (9100±150 K) and ions (13 700±300 K). This difference is explained according to the measured distributions of the electronic temperature and the neutral atom and ion number densities, that result in separated emissivity (or population) distributions of neutral atom and ion lines, leading to different neutral atom and ion apparent temperatures (population-averages of the local electronic temperature). Local values of the plasma parameters have been obtained at all the positions with significant emission, including the determination of the electronic temperature from Saha–Boltzmann or Boltzmann plots. The ionization degree is high- and low-varying at the inner part of the plasma, decaying only near the plasma front. The maximum of the ion density does not coincide with the temperature maximum; on the contrary, the axial variation of both the neutral atom and ion densities (that decrease towards the sample surface) is opposite to that of the temperature, a behaviour that is interpreted to result from the plasma expansion process.     

Synthesis and photoinitiated polymerization of diacrylate derivates of halobenzoates

The synthesis, characterization, mesomorphism and photoinitiated polymerization of new thermotropic derivatives of bis{4-[6-(acryloyloxy)hexyloxy]halobenzoate}-1,4-phenylene were studied. Halogen incorporation in the mesogenic unit decreases the stability of the mesophases of monomers containing three aromatic rings. The monomer MIII exhibits a nematic phase which has been macroscopically oriented by surface pre-treatment and fixed by photopolymerization in situ, yielding a uniaxially crosslinked network. The molecular ordering of liquid crystalline diacrylate films was visualized by examining the fracture surface by scanning electron microscopy. These films exhibit a fine texture, illustrating the presence of an oriented layered structure.     

Weak solutions for time‐dependent boundary integral equations associated with the bending of elastic plates under combined boundary data

The existence, uniqueness, stability, and integral representation of distributional solutions are investigated for the equations of motion of a thin elastic plate with a combination of displacement and moment‐stress components prescribed on the boundary. Copyright © 2004 John Wiley & Sons, Ltd.     

What are we determining using gas chromatographic multiresidue methods: tralomethrin or deltamethrin?

The analytical behaviour of the relatively new pyrethroid insecticide tralomethrin has been evaluated by using gas chromatography (GC) with electron-capture and mass spectrometry (MS) detectors, and liquid chromatography (LC)-atmospheric pressure ionization mass spectrometry with electrospray interfacing. Under the GC conditions commonly used in pesticide residue analysis, it was found that tralomethrin is transformed into deltamethrin (in a reproducible way) in the injector port of the GC system. Results obtained in this work indicate that the GC multiresidue methodologies routinely applied in the analysis of pyrethroid pesticides in foods cannot distinguish between these two pesticides, and the chromatographic signal obtained at the retention time of deltamethrin/tralomethrin can be really quantified as either deltamethrin or tralomethrin, including when it is confirmed as deltamethrin by MS. Under the LC-MS conditions assessed in this work, deltamethrin and the two diasteroisomers of tralomethrin were well separated and identified.