Hidden Heptacyclic Chiral N-Acyl Iminium Ions: A New Entry to Enantioenriched Polycyclic Azepanes and Azocanes by Superacid-Promoted Intramolecular Pictet-Spengler Reaction

Enantioenriched complex fused-tricyclic azepanes or bridged-polycyclic azocanes were constructed via a two-step sequence involving an enantioselective organocascade followed by superacid activation of the domino adduct. The activated oxa-bridged azepane acts as a key hidden heptacyclic chiral N-acyl iminium ion triggering a chemo- and diastereoselective intramolecular mono- or di-arylation.     

Photocrosslinking in dichromated poly(acrylic acid) during hologram recording and comparison with dichromated poly(vinyl alcohol)

Phototransformations involved in dichromated poly(acrylic acid) (DCPAA) were analyzed under irradiation conditions representative of hologram formation. It was shown that, in parallel to the reduction of chromium(VI) into chromium(III), the crosslinking of the matrix occurred through formation of covalent bonds between macromolecular chains. A comparison with dichromated poly(vinyl alcohol) (DCPVA) irradiated under the same conditions was also reported giving evidence for the crucial role played by the chemical structure of the polymeric matrix in the hologram formation. The combined approach based on the fate of both the absorbing species, chromium(VI) and the polymer allowed to completely elucidate the reactions taking place upon irradiation. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 636–642, 2008     

Photodynamic therapy can improve warts' discomfort in renal transplant patients prospective multicenter study

Many studies have been conducted showing that aminolevulinic acid (ALA)-photodynamic therapy (PDT) can be an alternative treatment for recalcitrant warts. Recently, we performed a study evaluating methyl-aminolevulinic acid (MAL)-PDT for the treatment of hand warts in a population of renal transplant patients. Two symmetrical targets were selected on each hand and randomly assigned to chemical keratolytic treatment followed by three cycles of ALA-PDT (75 J cm(-2) red light). Patients were evaluated after 3 months and a second run of PDT was performed if the total area and number of warts decreased less than 50%, with evaluation every 3 months for 1 year. Twenty patients were included and 16 were evaluable (9 M, 7 F). After 6 months the reduction of warts' area was 48.4% on the treated side versus 18.4% in the control area (P = 0.021). The decrease in the total number of warts was 41%versus 19.4% (P = NS). The global tolerance of the treatment was good with acceptable pain during irradiation. These results suggest that ALA-PDT is a safe and efficient treatment for transplanted patient warts. The improvement between treated and control zone is 20% due to the decrease in untreated warts' area and number.     

Optimizing electrode-attached redox-peptide systems for kinetic characterization of protease action on immobilized substrates. Observation of dissimilar behavior of trypsin and thrombin enzymes

In this work, we experimentally address the issue of optimizing gold electrode attached ferrocene (Fc)-peptide systems for kinetic measurements of protease action. Considering human α-thrombin and bovine trypsin as proteases of interest, we show that the recurring problem of incomplete cleavage of the peptide layer by these enzymes can be solved by using ultraflat template-stripped gold, instead of polished polycrystalline gold, as the Fc-peptide bearing electrode material. We describe how these fragile surfaces can be mounted in a rotating disk configuration so that enzyme mass transfer no longer limits the overall measured cleavage kinetics. Finally, we demonstrate that, once the system has been optimized, in situ real-time cyclic voltammetry monitoring of the protease action can yield high-quality kinetic data, showing no sign of interfering effects. The cleavage progress curves then closely match the Langmuirian variation expected for a kinetically controlled surface process. Global fit of the progress curves yield accurate values of the peptide cleavage rate for both trypsin and thrombin. It is shown that, whereas trypsin action on the surface-attached peptide closely follows Michaelis-Menten kinetics, thrombin displays a specific and unexpected behavior characterized by a nearly enzyme-concentration-independent cleavage rate in the subnanomolar enzyme concentration range. The reason for this behavior has still to be clarified, but its occurrence may limit the sensitivity of thrombin sensors based on Fc-peptide layers.     

On the stability of a variety of organic photovoltaic devices by IPCE and in situ IPCE analyses - the ISOS-3 inter-laboratory collaboration

This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPV) devices prepared by leading research laboratories. All devices have been shipped to and degraded at RIS?-DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work, we apply the Incident Photon-to-Electron Conversion Efficiency (IPCE) and the in situ IPCE techniques to determine the relation between solar cell performance and solar cell stability. Different ageing conditions were considered: accelerated full sun simulation, low level indoor fluorescent lighting and dark storage. The devices were also monitored under conditions of ambient and inert (N(2)) atmospheres, which allows for the identification of the solar cell materials more susceptible to degradation by ambient air (oxygen and moisture). The different OPVs configurations permitted the study of the intrinsic stability of the devices depending on: two different ITO-replacement alternatives, two different hole extraction layers (PEDOT:PSS and MoO(3)), and two different P3HT-based polymers. The response of un-encapsulated devices to ambient atmosphere offered insight into the importance of moisture in solar cell performance. Our results demonstrate that the IPCE and the in situ IPCE techniques are valuable analytical methods to understand device degradation and solar cell lifetime.     

Stereoselective hydrofluorination of ynamides: a straightforward synthesis of novel α-fluoroenamides

α-Fluoroenamides, potent rigid fluorinated bioisosters of ureas, have been synthesized by a highly regio- and stereo-selective hydrofluorination of ynamides in anhydrous HF. This reaction provides the first general entry to α-fluoroenamides and can easily be applied to a wide range of substrates.     

Effects of spectral smearing on the identification of speech in noise filtered into low- and mid-frequency regions

Le?ger et al. [J. Acoust. Soc. Am. 131, 1502-1514 (2012)] reported deficits in the identification of consonants in noise by hearing-impaired listeners using stimuli filtered into low- or mid-frequency regions in which audiometric thresholds were normal or near-normal. The deficits could not be fully explained in terms of reduced audibility or temporal-envelope processing. However, previous studies indicate that the listeners may have had reduced frequency selectivity, with auditory filters broadened by a factor of about 1.3, despite having normal or near-normal audiometric thresholds in the tested regions. The present study aimed to determine whether the speech-perception deficits could be explained by such a small reduction of frequency selectivity. Consonant identification was measured for normal-hearing listeners in quiet and in unmodulated and modulated noises using the same method as Le?ger et al. The signal-to-noise ratio was set to -3 dB for the masked conditions. Various amounts of reduced frequency selectivity were simulated using a spectral-smearing algorithm. Performance was reduced only for spectral-smearing factors greater than 1.7. For all conditions, identification scores for hearing-impaired listeners could not be explained by a mild reduction of frequency selectivity.     

New improvements in methane detection using a Helmholtz resonant photoacoustic laser sensor: a comparison between near-IR diode lasers and mid-IR quantum cascade lasers

Atmospheric methane was detected by combining a photoacoustic (PA) sensor with several lasers emitting in both the near- and mid-infrared spectral ranges to check the achievable detection limits. The PA spectrometer is based on differential Helmholtz resonance. Near-infrared telecommunication-type laser diodes of increasing power, from Sensors Unlimited Inc. and Anritsu, were first used to scan the 2 nu(3) band of CH(4) near 1.65 microm. The best achieved detection limit is 0.15 ppm of methane at atmospheric pressure and with a 1s integration time. The PA sensor was then operated in conjunction with a quantum cascade laser from Alpes Lasers emitting near 7.9 microm on the nu(4) band of CH(4). The achieved detection limit is then of 3 ppb. The dramatic improvement in the detection limit obtained with the QC laser is due to the stronger optical power as well as to the capability of reaching the fundamental bands of methane lying in the mid-infrared spectral range.