A reasonably stereospecific multistep conversion of Boc-protected α-amino acids to Phth-protected β-amino acids

A method for the synthesis of β³-amino acids starting from α-amino acids is described. This conversion can be effected by an eight-step procedure which involves the transformation of the carboxylic group into an alkyne followed by a selenium-mediated conversion of the carbon-carbon triple bond to a Se-phenyl selenocarboxylate intermediate. The reactive Se-phenyl selenocarboxylate intermediates can be trapped with water, alcohols or the amine of an amino acid derivative to give β³-amino acids, β³-amino esters or mixed peptides, respectively. The whole transformations of the carboxylic group into an alkyne and of the alkyne group into β³-amino acids may not require purification of the intermediate products but a work-up and isolation procedure of crude materials.     

New water-soluble platinum(II) phenanthroline complexes tested as cisplatin analogues: First-time comparison of cytotoxic activity between analogous four- and five-coordinate species

Four- and five-coordinate platinum(II) complexes, cis-[PtCl2(A2)] (1) and [PtCl2(A2)(eta2-ethylene)] (2) {A2 = 4,7-diphenyl-1,10-phenanthroline disulfonic acid disodium salt, BPS (mixture of isomers) (a); 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonic acid disodium salt, BCS (mixture of isomers) (b)} have been synthesized and characterized by 1H, 13C, and 195Pt NMR spectroscopy. The stability and high water solubility of complexes 1a, 1b and 2b, due to the presence of the polar SO3- groups on the ligands skeleton, allowed to test their in vitro cytotoxicity on HeLa tumour cells in a wide range of drug concentration. At low and medium incubation doses (<200 microM) 1a, 1b and 2b all showed similar in vitro cytotoxicity, negligible or much lower with respect to cisplatin. At doses higher than 200 microM their activity increased and 1b, the most active among the new complexes, exhibited a cytotoxicity comparable, although still lower, with respect to cisplatin. GFAAS Platinum analytical data showed that the tested compounds 1a, 1b and 2b, although carrying sulfonate charged groups, may undergo cellular uptake, which, in the case of 1b and 2b, is even higher with respect to cisplatin. Furthermore, in the case of 1b and 2b it has been possible to compare, for the first time, the cytotoxic activity for square-planar four-coordinate and trigonal-bipyramidal five-coordinate platinum(II) complexes having the same carrier ligand. The tendency of the five-coordinate species 2b to give at longer incubation time similar cytotoxicity with respect to the square-planar compound 1b suggests a possible use of the trigonal-bipyramidal five-coordinate complexes as prodrugs.     

Final attack ratio in SIR epidemic models for multigroup populations

We analyse an SIR epidemic model in a closed population subdivided in n groups. Population mixing occurs at two levels: within each group, and uniformly in the population. We prove that, if within-group transmission rates are large enough and not all identical to each other, then the final attack ratio is lower than what would occur in a population mixing homogeneously with the average transmission rate. We also show that the opposite may hold for certain parameter values and explore numerically the parameter regions in which the final attack ratio is higher or lower than in the corresponding homogeneous model. Finally, we analyse simulations of the corresponding stochastic model with finite group size, studying how well final attack ratio is approximated by the deterministic outcome and its relations with exponential growth rate.     

Novel Chitosan-Based Schiff Base Compounds: Chemical Characterization and Antimicrobial Activity

Chitosan (CS) and its derivatives are receiving considerable attention for their great biocompatibility and broad-spectrum activities in many fields. In this work, we aimed to characterize the antimicrobial activity of novel chitosan Schiff bases (CSSB). CS was synthesized by double deacetylation of chitin (Cn) after its extraction from the armors of crustaceans Astacus leptodactylus, and CSSB-1 and CSSB-2 were synthesized by interaction of CS with 4-(2-chloroethyl) benzaldehyde (aldehyde-1) and 4-(bromoethyl) benzaldehyde (aldehyde-2), respectively, at room temperature. The synthesized compounds were characterized by elemental analysis, gel permeation chromatography (GPC), infrared spectroscopy (FTIR), thermogravimetry (TG), and differential scanning calorimetry (DSC). The antimicrobial activity against Gram-positive (Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa) bacteria and against yeasts (Candida albicans) was significantly increased due to their higher solubility as compared to unmodified CS opening perspectives for the use of these compounds for antimicrobial prevention in different fields as, for example, food industry, cosmetics, or restoration.     

Mononuclear rearrangement of heterocycles in zwitterionic micelles of amine oxide surfactants

The pH-induced swelling of poly(2-vinylpyridine) microgel particles was studied using dynamic light scattering. The increase in particle diameter with decreasing pH was modeled using a well-established thermodynamic model for microgel swelling. The Maxwell construction was applied to extend the model and yield a prediction for a pH-responsive microgel across the entire pH range. The model predicts a first order phase transition for polymer-solvent combinations with a Flory interaction parameter, χ, greater than a critical value χ(c). The modified theory compared favorably to the dynamic light scattering data for the hydrodynamic diameter of microgel particles based on 2-vinylpyridine at different pH values. In particular, the swelling transition is both predicted theoretically and observed experimentally to occur at a pH lower than the pK(a) of the polymer.     

Thermal and photochemical transformations of 2-methylthiothiophene in triosmium clusters: photoinduced migrations of MeS from carbon to metal and back again

2-Methylthiothiophene (2-MeSC₄H₃S) oxidatively adds to [Os₃(CO)₁₀(MeCN)₂] with cleavage of the C–H bond at the 3-position to give [Os₃(μ-H)(μ-MeSC₄H₂S)(CO)₁₀] 1, the X-ray structure of which shows that the MeS group is coordinated to osmium through the S atom while the thiophene ring is coordinated to osmium through the 3-carbon atom. Only one invertomer at sulfur is observed in solution and in the crystal the Me group is exo. Thermal treatment of 1 in the dark gives only one product, [Os₃(μ-H)(μ₃-MeSC₄H₂S)(CO)₉] 2 (X-ray structure), derived by loss of a CO from the Os(CO)₄ unit of 1 with concomitant η²-coordination of the thiophene ring of bridging MeSC₄H₂S at the third metal atom. Whereas thermal reaction in the dark leads only to C–H cleavage products, visible irradiation at room temperature leads to various products derived by migration of the MeS group. Thus thermal treatment of 1 in daylight for 2 h gave 2, together with an isomer 3. Cluster 2 converts at room temperature to 3 in daylight while thermal treatment of 2 in the dark (125°C) gave no reaction. Isomer 3 of [Os₃(μ-H)(μ₃-MeSC₄H₂S)(CO)₉] (X-ray structure) is closely related to 2 except that the MeS group and the Os–C σ-bond have interchanged sites at the thiophene ring between the 2- and the 3-positions. Visible irradiation of 1 at room temperature for 3 days in daylight gave further chemical change leading to two bridging thienyl clusters, [Os₃(μ-MeS)(μ-2-C₄H₂S)(CO)₁₀] 4 and [Os₃(μ-MeS)(μ₃-2-C₄H₂S)(CO)₉] 5. Cluster 5 is the ultimate product of daylight irradiation of any of the clusters 1 to 4.     

ARDESIA: A fast silicon drift detector X-ray spectrometer for synchrotron applications

ARDESIA, a four-channel X-ray spectrometer based on silicon drift detectors (SDDs), is presented. It has been developed for synchrotron applications targeting especially X-ray fluorescence (XRF) and X-ray absorption spectroscopy (XAS) with good energy resolution at high count rates (a few Mcps per second). The main target applications are XRF and XAFS techniques. The system features a 2 × 2 monolithic array of 5-mm-pitch SDDs cooled with a double Peltier scheme and coupled to a four-channel CUBE charge preamplifier. Different digital pulse processors allowing operation in Mcps per second count rates are employed. The results of preliminary characterization measurements performed at both the LNF DAΦNE-Light DXR1 beamline and the ESRF LISA BM-08 are reported, in particular, XRF measurements on low atomic number elements (down to the Carbon K-line, 270 eV) and extended X-ray absorption fine structure of trace materials in pyrite.     

Torque detection using Brownian fluctuations

We report the statistical analysis of the movement of a submicron particle confined in a harmonic potential in the presence of a torque. The absolute value of the torque can be found from the auto- and cross-correlation functions of the particle's coordinates. We experimentally prove this analysis by detecting the torque produced onto an optically trapped particle by an optical beam with orbital angular momentum.     

Waiting time distributions of the volatility in the Italian MIB30 index: Clustering or Poisson functions?

We investigate the time behaviour of the Italian MIB30 stock index collected every minute during two months in the period from May 17, 2006, up to July 24, 2006. We find short-range correlations in the price returns and, on the contrary, a long persistent time lag and slow decay in the autocorrelation functions of volatility. Besides, we find that the probability density functions (PDFs) of returns show fat tails, which are well fit by the log-normal model of Castaing [B. Castaing, Y. Gagne, E.J. Hopfinger, Physica D 46 (1990) 177], and a convergence toward a normal distribution for large time scales; we also find that the PDFs of volatility, for short time horizons, fit better with a log-normal distribution than with a Gaussian. Most of these features characterize the indexes and stocks of the largest American, European and Asian markets.We also investigate the distribution of stochastic separation between isolated strong events in the volatility signal. This is interesting because this gives us a deeper understanding about the price formation process. By using a test for the occurrence of local Poisson hypothesis, we show that the process we examined strongly departs from a Poisson statistics, the origin of this failure stemming from the presence of temporal clustering and of a certain amount of memory.     

Isolation and epimerization kinetics of the first diastereoisomer of an inherently chiral uranyl-salophen complex

The first diastereoisomeric mixture of an inherently chiral uranyl-salophen complex was prepared using (S)-naproxen as a chiral derivatizing agent. Slow crystallization from diisopropyl ether-chloroform afforded one pure diastereoisomer in 45% yield. Kinetic studies allowed the determination of the epimerization rate. [reaction--see text]