A new technique for fluid velocimetry based on near field scattering

We show that the time evolution of near-field scattering speckles, originated by a fluid suspension of particles, provides information about the velocity field in the fluid. This information can be extracted from a statistical analysis of speckle fields taken at different times, either by measuring their cross-correlation function or by recovering the power spectrum corresponding to the difference between the two speckle fields. Experimental data are in accordance to the expected behaviors. The results are independent of the scatterer's size, allowing one to exploit the technique also with sub-wavelength tracking particles.     

Second-generation mimics of ganglioside GM1 oligosaccharide: a three-dimensional view of their interactions with bacterial enterotoxins by NMR and computational methods

As a step to delineate a strategy of ligand design for cholera toxin (CT), NMR studies were performed on several mimics of the GM1 ganglioside oligosaccharide. The conformation of these analogues was investigated first in solution and then upon binding to cholera toxin by transferred nuclear Overhauser effect (TR-NOE) measurements. It was demonstrated that CT selects a conformation similar to the global minima of the free saccharides from the ensemble of presented conformations. No evidence of major conformational distortions was obtained, but one or two of the available conformers of the hydroxyacid side chain appear to be selected in the bound state. The NMR data were interpreted with the aid of computer models, generated and analyzed by using a combination of different approaches (MacroModels' MC/EM and MC/SD, Autodock, and GRID). Analysis of the NMR data supported by computational studies allowed us to interpret the experimental observations and to derive workable models of the ligand:toxin complexes. These models suggest that the higher affinity of the (R)-lactic acid derivative 3 may stem from lipophilic interactions with a hydrophobic area in the toxin binding site located in the vicinity of the sialic acid side chain binding region of the CT:GM1 complex, and formed by the side chain of Ile-58 and Lys-34. Thus, the models obtained have allowed us to make useful design suggestions for the improvement of ligand affinity.     

A geometrically constraining bis(benzimidazole) ligand and its nearly tetrahedral complexes with Fe(II) and Mn(II)

2,2'-Bis[2-(1-propylbenzimidazol-2-yl)]biphenyl), 4, and its bis complexes with Fe(II) and Mn(II) have been prepared and characterized structurally and spectroscopically. Ligand 4 adopts an open, "trans" conformation in the solid state with the benzimidazole (BzIm) groups on opposite sides of the biphenyl unit. In its complexes with metal ions, a "cis" conformation is observed, and 4 behaves as a geometrically constraining bidentate ligand with four planar groups connected by three "hinges". Reaction of 4 with Fe(II) or Mn(II) yielded isomorphous crystals (space group Pnn2) of Fe(II)(4)2.(ClO4)2 and Mn(II)(4)2.(ClO4)2, in which the M(II)(4)2 cations exhibit distorted-tetrahedral coordination geometries (N-M-N angles, 109 +/- 11 degrees ) enforced by rigid, chiral nine-membered M(4) rings in the twist-boat-boat conformation. Individually, the cations show R,R or S,S stereochemistry, and the crystals are racemates. Mn(II)(4)2.(ClO4)2 exhibits a quasi-reversible Mn(II) --> Mn(III) oxidation at E(1/2) = 0.64 V; the corresponding Fe(II) --> Fe(III) oxidation occurs at E(1/2) = 1.76 V. The electrochemical stability of the Fe(III) oxidation state in this system suggests the possibility of isolating an unusual pseudotetrahedral Fe(III)N(BzIm)(4) species. Ultraviolet spectra of the iron and manganese complexes are dominated by absorptions of the ligand 4 blue-shifted by approximately 2000-3000 cm(-1). Ligand-field absorptions were observed for the Fe(II) complex; those for the Mn(II) complex were obscured by tailing ultraviolet absorptions. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-spin Mn(II) complex, while for the Fe(II) complex, the falloff of the magnetic moment with decreasing temperature is indicative of zero-field splitting with D approximately 4 cm(-1).     

Analysis of egg-based model wall paintings by use of an innovative combined dot-ELISA and UPLC-based approach

The chemical analysis of egg-based wall paintings—the mezzo fresco technique—is an interesting topic in the characterisation of organic binders. A revised procedure for a dot-enzyme-linked immunosorbent assay (dot-ELISA) able to detect protein components of egg-based wall paintings is reported. In the new dot-ELISA procedure we succeeded in maximizing the staining colour by adjusting the temperature during the staining reaction. Quantification of the colour intensity by visible reflectance spectroscopy resulted in a straight line plot of protein concentration against reflectance in the wavelength range 380–780 nm. The modified dot-ELISA procedure is proposed as a semi-quantitative analytical method for characterisation of protein binders in egg-based paintings. To evaluate its performance, the method was first applied to standard samples (ovalbumin, whole egg, egg white), then to model specimens, and finally to real samples (Giotto’s wall paintings). Moreover, amino acid analysis performed by innovative ultra-performance liquid chromatography was applied both to standards and to model samples and the results were compared with those from the dot-ELISA tests. In particular, after protein hydrolysis (24 h, 114 °C, 6 mol L^?1 HCl) of the samples, amino acid derivatization by use of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate enabled reproducible analysis of amino acids. This UPLC amino acid analysis was rapid and reproducible and was applied for the first time to egg-based paintings. Because the painting technique involved the use of egg-based tempera on fresh lime-based mortar, the study enabled investigation of the effect of the alkaline environment on egg-protein detection by both methods.

Competing symmetries and broken bonds in superconducting vortex-antivortex molecular crystals

Hall probe microscopy has been used to image vortex-antivortex molecules induced in superconducting Pb films by the stray fields from square arrays of magnetic dots. We have directly observed spontaneous vortex-antivortex pairs and studied how they interact with added free (anti)fluxons in an applied magnetic field. We observe a variety of phenomena arising from competing symmetries which either drive added antivortices to join antivortex shells around dots or stabilize the translationally symmetric antivortex lattice between the dots. Added vortices annihilate antivortex shells, leading first to a stable "nulling state" with no free fluxons and then, at high densities, to vortex shells around the dots stabilized by the asymmetric antipinning potential. Our experimental findings are in good agreement with Ginzburg-Landau calculations.     

Molecular structure and mass spectrum of dicarbonylbis(tetraphenylcyclobutadiene)molybdenum

The crystal structure on dicarbonylbis(tetraphenylcyclobutadiene)molybdenum has been determined from three-dimensional X-ray data collected by counter methods. The structure consists of monomeric units with each Mo atom bonded to two carbonyl and two Ph₄C₄ groups. Excluding phenyl substituents, the local symmetry about Mo is very nearly C_2υ. Both cyclobutadiene (CBD) groups are asymmetrically bonded to Mo, and the spread in Mo—C(CBD) distances (2.26 to 2.38 Å;) is significantly larger than that found with other structures containing substituted cyclobutadiene groups. The carbonyl groups show several short intramolecular C?C contacts with the cyclobutadiene C atoms (2.68 to 3.03 Å;) and with each other (2.63 Å;). They appear to be wedged between the Ph₄C₄ groups and to be responsible for the asymmetric bonding of the cyclobutadiene groups. The mass spectrum, which shows the characteristic fragmentation pattern of cyclobutadienemetal complexes, suggests a relatively high thermal stability for the title compound. Crystallographic data are as follows: space group P2₁/n; unit cell a 20.15(2), b 18.82(3), c 11.03(1) Å;, β 91.59(6)°; V 4181 Å;³; d_calc for Z = 4 is 1.380 and d_obs is 1.365(7) g/cm³. A total of 1659 reflections with F² ≥ 2σ were used to refine the structure to final values of R_F = 0.063 and R_wF = 0.041.     

Combinational tasks performed by second-harmonic-generated holograms

Second-harmonic-generated holograms directly provide the outputs of logical gates AND and NAND operating on optical bits encoded as amplitude modulations in the object and reference wave fronts. By use of a Nd:YAG laser and a beta-barium borate crystal, we realized a real-time half-adder of two one-digit binary numbers. The feasibility of highly parallel operation is also discussed.     

Theory of scattering in multimode optical fibres

The problem of scattering in multimode optical fibres is treated in a rigorous way by means of both a ray and a statistical approach. These two methods are interlaced and harmonized. Applications to microbending, ellipticity, core radius and maximum numerical aperture variations, and fluctuations of index profile shape are performed. Useful results about power distribution and fibre attenuation are derived in each case.