Contributions to the synthesis of some ferrocene-containing antibiotics

This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and ¹H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria.     

Metallocene monomers and polymers. Ferrocenyl and ferrocenylene derivatives

The synthesis and study of some polyenes, polýiminoimides and Schiff polybases with ferrocene obtained by either polymerization or polycondensation are reported.The following monomers were used: ethynylferrocene, 1-chloro-1′-ethynyl-ferrocene, α-chloro-β-formyl-p-ferrocenylstyrene, p-ferrocenylphenylacetylene, p-ferrocenylacetophenone, 1,1′-diacetylferrocene and 1,1′-bis[β-(2-furyl)acryloyl]ferrocene which were characterized by spectral and thermodifferential analyses and Hückel MO calculations. The polymerization was performed in the presence of benzoyl and lauroyl peroxides, triisopropylboron and complex catalysts of [P(C₆H₅)₃]₂ NiX₂ type. The ferrocene derivatives were polycondensed with biuret, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, 4,4′-diamino-2,2′-dinitrodiphenyl disulphide in the presence of metallic salts and p-toluene sulphonic acid as catalysts.Polymers with either linear or tridimensional structure showing good thermal stability and semiconducting properties have been obtained. Some polymers show catalytical activity in the polymerization of chloroformylated vinylic derivatives.     

TM-polarized nonlinear waves guided by asymmetric dielectric layered structures

We found the field structure, exact dispersion relations and power flow ofp-polarized nonlinear guided and surface waves travelling along a three-component layered structure consisting of a film of thicknessd with dielectric constant _b bounded at the negativez-side by a linear medium with dielectric constant _a and at the positivez-side by a nonlinear uniaxial substrate characterized by the diagonal dielectric tensor ₁₁ = ₂₂ = + (|E ₁|² + |E ₂|²), ₃₃ = , <0 (self-defocusing medium),E ₁ andE ₂ being the components of the electric field in thex andy-direction, respectively. It is shown that for sufficiently smalld/ (: wavelength) the nonlinear wave may exist only at power flows exceeding some certain minimum values. For sufficiently larged/ to some values of the power flow there correspond two distinct values of the propagation constant. In this case with increasing of the power flow the number of waveguide modes is decreasing and for higher-order modes the film-waveguide exhibits an optical-power limiter from the above behaviour.     

Oil-in-water emulsions stabilized by highly charged polyelectrolyte-grafted silica nanoparticles

Fully sulfonated poly(styrenesulfonate) brushes were grown from the surface of colloidal silica particles and used to prepare stable trichloroethylene-in-water and heptane-in-water Pickering emulsions. These particles were highly charged and colloidally stable in water but could not be dispersed in trichloroethylene or heptane. Both two-phase (emulsion plus neat water) and three-phase (emulsion separating neat oil and water phases) systems were observed, with water-continuous emulsion phases in all cases. Emulsion phases containing as much as 83% (v/v) oil were stable for over six months. Poly(styrenesulfonate)-grafted particles were very efficient emulsifiers; stable emulsion phases were prepared when using as little as 0.04 wt% particles. The emulsifying effectiveness of the poly(styrenesulfonate)-grafted silica particles can be attributed to the hydrophobicity of the vinylic polymer backbone that makes this highly charged polyelectrolyte unusually surface active at the oil/water interface.     

Capillary zone electrophoresis of alpha-helical diastereomeric peptide pairs with anionic ion-pairing reagents

The present study uses an unique capillary electrophoresis (CE) approach, that we have termed ion-interaction capillary zone electrophoresis (II-CZE), for the separation of diastereomeric peptide pairs where a single site in the centre of the non-polar face of an 18-residue amphipathic alpha-helical peptide is substituted by the 19 L- or D-amino acids. Through the addition of perfluorinated acids at very high concentrations (up to 400 mM), such concentration levels not having been used previously in chromatography or CE, to the background electrolyte (pH 2.0), we have been able to achieve baseline resolution of all 19 diastereomeric peptide pairs with an uncoated capillary. Since each diastereomeric peptide pair has the same sequence, identical mass-to-charge ratio and identical intrinsic hydrophobicity, such a separation by CZE has previously been considered theoretically impossible. Excellent resolution was achieved due to maximum advantage being taken of even subtle disruption of peptide structure/conformation (due to the presence of D-amino acids) of the non-polar face of the amphipathic alpha-helix and its interaction with the hydrophobic anionic ion-pairing reagents. In addition, due to the excellent resolution of diastereomeric peptide pairs by this novel CZE approach, we have also been able to separate a mixture of these closely-related alpha-helical peptides.     

Capillary electrophoresis of cationic random coil peptide standards: effect of anionic ion-pairing reagents and comparison with reversed-phase chromatography

The present study compares a charge/hydrophobicity capillary electrophoresis (CE) approach to reversed-phase high-performance liquid chromatography (RP-HPLC) for the separation of three series of four synthetic, random coil peptide standards. Each series has peptides of the same positive charge (+1, +2 and +3 series) and length but differing in hydrophobicity. Complete resolution of the 12 peptides was achieved via a novel CE approach: a capillary zone electrophoresis (CZE) mode effected a separation of identically charged peptides; within each charged group of peptides, the addition of perfluorinated acid anionic ion-pairing reagents allowed resolution of the peptides through a mechanism based on peptide hydrophobicity which we have termed ioninteraction (II)-CZE. The peak capacity and peptide resolution of this CE approach was superior to that of RP-HPLC and stresses an important role for CE for peptide/proteomic applications.     

The eigenpairs of a Sylvester–Kac type matrix associated with a simple model for one-dimensional deposition and evaporation

A straightforward model for deposition and evaporation on discrete cells of a finite array of any dimension leads to a matrix equation involving a Sylvester–Kac type matrix. The eigenvalues and eigenvectors of the general matrix are determined for an arbitrary number of cells. A variety of models to which this solution may be applied are discussed.     

金纳米粒子在TiO2气凝胶基质上的行为: 光催化活性评价和结构研究

TiO2 -Au aerogels containing different amounts of gold nanoparticles of different sizes (5 and 16 nm) were successfully synthesized using a sol-gel procedure, and were tested for salicylic acid photodegradation under UV irradiation. The structure and morphology of the obtained materials were investigated using X-ray diffraction, transmission electron microscopy, and N2 adsorption-desorption measurements. UV-Vis spectroscopy was used to study the optical properties. The effects of the gold nanoparticles on the TiO2 crystallization process were twofold, as follows: (i) the number of crystallized zones was strongly related to the concentration of the gold nanoparticles, and (ii) the smaller gold particles increased the time taken for the crystallization of the samples. It was found that the noble metal-doped samples exhibited higher degradation rates compared with bare titania. It was found that the most active photocatalyst in each studied system was the sample with the highest concentration of gold nanoparticles. Additionally, the highest degradation rate value was obtained with the smallest Au nanoparticles (46.4 10-3 μmol/(L·s).     

A stochastic model for microtubule length dynamics

In this paper, we use random walk theory to describe the length dynamics of microtubules, one of the principal components of the cytoskeleton. We present a simple two-state model (growing and shrinking) of microtubule length evolution that incorporates a variable rate of switching between the states. Using the generating function technique, we calculate the mean length of microtubule, its variance and diffusion coefficient. We also report analytical and computer simulation results for the mean number of positive monomers in microtubule, and find good qualitative agreement with experimental data.