Biomimetic zinc funnel complexes based on calix[6]N3ArO ligands: an acid-base switch for guest binding

The coordination chemistry of Zn in an N(3)ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn(2+) coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endo-complexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N(3)ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N(3)ArOH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families.     

Fluorinated heterocyclic compounds. An effective strategy for the synthesis of fluorinated Z-oximes of 3-perfluoroalkyl-6-phenyl-2h-1,2,4-triazin-5-ones via a ring-enlargement reaction of 3-benzoyl-5-perfluoroalkyl-1,2,4-oxadiazoles and hydrazine

The reaction of 3-benzoyl-5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine has been investigated, evidencing the possibility of competitive reaction paths. Nucleophilic addition of the hydrazine to the electrophilic C(5) of the 1,2,4-oxadiazole ring, followed by ring opening and ring closure with enlargement, leads with high yield and in very mild experimental conditions to the formation of Z-oximes of 3-perfluoroalkyl-6-phenyl-2H-1,2,4-triazin-5-ones (11a-c) as major products of the reaction. In turn, the hydrazine can attack the electrophilic carbonyl carbon giving 4-perfluoroacylamino-5-phenyl-2H-1,2,3-triazoles (13a-c) through the well-known Boulton-Katritzky rearrangement of the intermediate hydrazones.     

Structural characterization of the regioisomers of di(hydroxybutyl) ether by GC‐EI MS and theoretical calculations

Di(hydroxybutyl) ether (DHBE), a liver protecting drug, is composed of a mixture of three regioisomers: 4‐(3‐hydroxybutoxy)‐2‐butanol (1), 3‐(4‐hydroxy‐2‐butoxy)‐1‐butanol (2), and 3‐(3‐hydroxybutoxy)‐1‐butanol (3). Unequivocal differentiation of each regioisomer of DHBE was rapidly obtained without isolation of the single components, using GC‐MS with electron ionization (EI). The mass spectrum of 1 showed a rearrangement ion at m/z 118, characteristic of the 3‐hydroxybutyl chain, deriving from loss of acetaldehyde from the molecular ion, whereas 2 and 3 were characterized by the ion at m/z 117, expected from α‐cleavage of the 4‐hydroxy‐2‐butyl chain. The species at m/z 118, in turn, loses a water molecule via a mechanism involving both alcohol hydrogens, as shown by deuterium exchange experiments. Both this finding and theoretical calculations support a mechanism in which the loss of acetaldehyde in 1 occurs via a cyclic intermediate, stabilized by a strong hydrogen bond between the alcohol oxygen bearing the charge and the other alcohol oxygen, and involves initial hydrogen transfer from the former to the latter. The EI spectrum of 2, having two 4‐hydroxy‐2‐butyl chains, showed the fragmentations expected from classical fragmentation rules of aliphatic ethers and alcohols, whereas the EI spectrum of 3, bearing one 4‐hydroxy‐2‐butyl and one 3‐hydroxybutyl chain, showed essentially the characteristic fragments of both chains. Copyright © 2009 John Wiley & Sons, Ltd.     

Continuum Thermodynamics and Phase-Field Models

Phase transitions between two phases are modelled as space regions where a phase-field changes smoothly. The two phases are separated by a thin transition layer, the so-called diffuse interface. All thermodynamic quantities are allowed to vary inside this layer, including the pressure and the mass density. A thermodynamic approach is developed by allowing for the nonlocal character of the continuum. It is based on an extra entropy flux which is proved to be non vanishing inside the transition layer, only. The phase-field is regarded as an internal variable and the kinetic or evolution equation is viewed as a constitutive equation of rate type. Necessary and sufficient restrictions placed by thermodynamics are derived for the constitutive equations and, furthermore, a general form of the evolution equation for the phase-field is obtained within the schemes of both a non-conserved and a conserved phase-field. Based on the thermodynamic restrictions, a phase-field model for the ice-water transition is established which allows for superheating and undercooling. A model ruling the liquid-vapor phase transition is also provided which accounts for both temperature and pressure variations during the evaporation process. The explicit expression of the Gibbs free enthalpy, the Clausius-Clapeyron formula and the customary form of the vapor pressure curve are recovered.     

New class of N-dimensional braneworlds

The new class of the non-stationary solutions to the system of N-dimensional equations for coupled gravitational and massless scalar field is found. The model represents a single (N-1)-brane in a space-time with one large (infinite) and (N-5) small (compact) space-like extra dimensions. In some particular cases the model corresponds to the gravitational and scalar field standing waves bounded by the brane. These braneworlds can be relevant in string and other higher dimensional models.     

New Strong MM FIR Emissions in CH2=CF2 Pumped by a Pulsed CO2 Laser

By pumping with a suitable pulsed CO₂ laser we have produced several strong MM laser lines in 1,1 difluoroethene. All the emissions are easily identified because the emission spectroscopy is simplified in pulsed optical pumping.     

High-Q factor single mode circular photonic crystal nano-resonator

In this work, the analysis, fabrication and optical characterization of a two-dimensional circular photonic crystal (2D-CPC) nano-resonator based on an air/GaAs/air slab waveguide are presented. Four InAs/InGaAs quantum dots (QDs) stacked layers emitting around 1300 nm at room temperature were embedded in a GaAs waveguide layer grown on an Al_0.7Ga_0.3As layer and GaAs substrate. The patterning of the structure and the membrane release were achieved by using electron beam lithography, ICP plasma etching and selective wet etching of the AlGaAs sacrificial layer. The micro-luminescence spectrum recorded from the fabricated nano-cavity shows a narrow optical transition at the resonance wavelength of about 1282 nm with a FWHM and Q-factor of 6.2 Å and more than 2000, respectively.     

Optical characterization of pigments by reflectance spectroscopy in support of UV laser cleaning treatments

The study of optical properties of artwork materials is of fundamental importance for laser-based restoration techniques. In this work, reflectance spectroscopic measurements and colorimetric analyses of painted wooden models were performed to discriminate between pigments on the basis of their spectral features. In particular, the spectral reflection factors of different white pigments were recorded with a fibre optics reflectance spectroscopy module, both before and after excimer laser (248 nm) irradiation. Colour data were obtained and monitored with an integrating sphere spectrophotometer and expressed with the CIE L^*a^*b^* colour coordinates. Moreover, the laser-induced morphological changes of the samples were investigated by scanning electron microscopy. PACS  42.62-b; 61.80.Ba; 07.60.Dq     

Multidimensional custom-made non-linear microscope: from ex-vivo to in-vivo imaging

We have built a custom-made multidimensional non-linear microscope equipped with a combination of several non-linear laser imaging techniques involving fluorescence lifetime, multispectral two-photon and second-harmonic generation imaging. The optical system was mounted on a vertical honeycomb breadboard in an upright configuration, using two galvo-mirrors relayed by two spherical mirrors as scanners. A double detection system working in non-descanning mode has allowed both photon counting and a proportional regime. This experimental setup offering high spatial (micrometric) and temporal (sub-nanosecond) resolution has been used to image both ex-vivo and in-vivo biological samples, including cells, tissues, and living animals. Multidimensional imaging was used to spectroscopically characterize human skin lesions, as malignant melanoma and naevi. Moreover, two-color detection of two photon excited fluorescence was applied to in-vivo imaging of living mice intact neocortex, as well as to induce neuronal microlesions by femtosecond laser burning. The presented applications demonstrate the capability of the instrument to be used in a wide range of biological and biomedical studies. PACS  87.64.mn; 78.47.Cd; 87.19.lw     

Specific heat of A-15 Nb3Al0.83Ge0.21

The specific heat of A-15 Nb₃Al_.83Ge_.21 with a transition temperature, T_c, of 20.0 K has been measured from 6 to 25 K. Values of the parameters derived from the data are γ=35.0±2 mJ/mole-K²; the Debye temperature, θ_D=278±5 K; the energy gap, △, normalized as 2△/kT_c, is 4.9±.3, and the thermodynamic critical field, H_c(0), is 4700±300 Gauss.