Highly efficient racemisation of a key intermediate of the antibiotic moxifloxacin

N-Chlorination by sodium dichloroisocyanurate and dehydrochlorination by TEA, followed by hydrogenation, allowed (1R,6S)-8-benzyl-7,9-dioxo-2,8-diazabicyclo[4.3.0]nonane to be quantitatively racemised and the resulting trans-free cis racemate to be recycled into the resolution process to yield (1S,6R)-8-benzyl-7,9-dioxo-2,8-diazabicyclo[4.3.0]nonane, a key intermediate of moxifloxacin.     

Relativistic Spontaneous Localization: A Proposal

A new proposal for a Lorentz-invariant spontaneous localization process in the framework of relativistic quantum field theory is presented. As in all dynamical reduction models, a stochastic process is introduced, which drives the state vector towards the eigenspaces of a set of operators representing suitably chosen physical quantities. Such operators constitute a Lorentz scalar field and are built as time averages and space integrals of a local field-theoretic operator in such a way that the quantities they represent acquire a macroscopic character. As always in dynamical reduction theories, the action of the process on microscopic systems takes place via the micro-macro correlations which arise, e.g., as a consequence of measurements.     

Dissipation and reduction effects of spontaneous localization on superconducting states

The problem of quantum measurement is briefly recalled with particular reference to theories of reduction as a real physical process. The spontaneous localization models for systems containing identical particles are described and the choice of the model when several kinds of particles are present is discussed. Dissipation and reduction effects induced by spontaneous localization in superconducting systems are analyzed. It is found that dissipation effects are negligibly small; on the other hand, reduction effects are present, but their characteristic time is long, say of the order of one hour. It follows that testing reduction experimentally is far beyond present day technology.Supported in part by the Ministero dell'Università e della Ricerca Scientifica e Tecnologica and by the Istituto Nazionale di Fisica Nucleare, Italy.On leave from INFN, Sezione di Pavia, Pavia, Italy.     

Ester,amide and ether derivatives of 1-(p-phenyl-substituted)-1,2,3-triazoles

This paper describes the preparation of three series of 1-phenyl-1,2,3-triazol derivatives with an ester, amide or ether group on the phenyl ring. These derivatives were obtained from 4-hydroxyphenyl- and 4-aminophenyltriazoles, previously synthesized by us, by means of a nucleophilic substitution reaction with acetic anhydride, acyl and alkyl halides. The largest part of compounds were tested in an agricultural chemicals, nutrition and animal health screening programme.     

2,5-Dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene: first member of the hetero-DuPHOS family

[reaction: see text] The 2,5-dimethyl-3,4-bis[(2R,5R)-2,5-dimethylphospholano]thiophene (UlluPHOS), a new thiophene-based analogue of (R,R)-1,2-bis(phospholano)benzene (Me-DuPHOS), was synthesized, geometrically and electronically characterized, and employed as ligand of Rh and Ru in some standard hydrogenation reactions of prostereogenic functionalized carbon-carbon and carbon-oxygen double bonds. The synthesis of UlluPHOS is much easier than that provided for Me-DuPHOS. UlluPHOS and Me-DuPHOS display very similar geometries, while the electronic availability of the former is higher than that exhibited by the latter. The Rh and Ru complexes of UlluPHOS produced excellent enantiomeric excesses (98.9-99.5%) in the hydrogenation of N-acetyl-alpha-enamino acids and reaction rates higher than those found when employing the analogous complexes of Me-DuPHOS.     

Synthesis of new 1,2,3-triazolo[1,2-a]benzotriazoles or 2,3-benzo-1,3a,6,6a-tetraazapentalenes

Some new v-triazolo[1,2-a]benzotriazoles or 2,3-benzo-1,3a,6,6a-tetraazapentalenes were prepared according to previously employed synthetic routes concerning deoxycyclization reactions of appropriate nitrophenyl-1,2,3-triazole derivatives and/or thermal decompositions of appropriate azidophenyl-1,2,3-triazoles. The nitration of 9-phenyl-1,2,3-triazolo[1,2-a]benzotriazoles allowed the isolation of some mononitro- and trinitro-derivatives, whose structures were assigned by chemical and spectroscopic methods.     

Pharmacological Extracts and Molecules from Virola Species: Traditional Uses,Phytochemistry, and Biological Activity

Virola is the largest genus of Myristicaceae in America, comprising about 60 species of medium-sized trees geographically spread from Mexico to southern Brazil. The plant species of this genus have been widely used in folk medicine for the treatment of several ailments, such as rheumatic pain, bronchial asthma, tumors in the joints, intestinal worms, halitosis, ulcers, and multiple infections, due to their pharmacological activity. This review presents an updated and comprehensive summary of Virola species, particularly their ethnomedicinal uses, phytochemistry, and biological activity, to support the safe medicinal use of plant extracts and provide guidance for future research. The Virola spp.’s ethnopharmacology, including in the treatment of stomach pain and gastric ulcers, as well as antimicrobial and tryponosomicidal activities, is attributable to the presence of a myriad of phytoconstituents, such as flavonoids, tannins, phenolic acids, lignans, arylalkanones, and sitosterol. Hence, such species yield potential leads or molecular scaffolds for the development of new pharmaceutical formulations, encouraging the elucidation of not-yet-understood action mechanisms and ascertaining their safety for humans.     

Planning and certification of new multielemental reference materials for research in antarctica

The adoption of the principles of Good Laboratory Practice (GLP) and the implementation of the ensuing procedures for quality assurance (QA) and quality control (QC) of analytical determinations are nowadays deemed essential to the achievement of sound, credible and comparable experimental information. This is certainly also applicable to research projects currently being carried out in the antarctic continent, in particular as regards investigations on global change phenomena. Worldwide investments made so far in this field do require in fact that reliability of data be optimized so as to allow for a harmonized assessment of ongoing trends. In this context the Italian National Programme for Research in Antarctica has recently launched a project for the preparation of new multielemental certified reference materials (CRMs) to be used for QC of analyses performed on environmentally significant materials. The suitability of CRMs to verify the accuracy of experimental measurements acknowledgedly depends, among others, on the degree of similarity of their matrix composition and analyte levels to those expected for real samples. From this standpoint three CRMs are planned, namely: i) marine sediment certified for Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn and Zn; ii) ocean water certified for Cd, Cr, Cu, Fe, Hg, Mn, Ni and Pb; iii) krill certified for As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn and Zn. Regarding the first two matrices, amounts of ca. 100 kg and ca. 1001, respectively, have been collected during the IX (1993–1994) antarctic expedition, while krill was taken in the course of the X (1994–1995) campaign. The pretreatment of sediment has been accomplished in terms of homogenization, stabilization and characterization of the preliminary ground mass. Approximately 500 bottles, each containing 75 g of material are now ready for distribution to interested laboratories involved in chemical measurements of antarctic matrices, whereas ocean water and krill will follow at a later stage. Finally, depending on circumstances, also the certification of organochlorine compounds in the same materials will be attempted.     

Kinetic ion-acoustic solitary waves in collisional plasmas

In this study, a bipolar high-voltage pulse with 20 ns rising time is employed to generate diffuse dielectric barrier discharge plasma using wire-plate electrode configuration in nitrogen at atmospheric pressure. The gas temperature of the plasma is determined by comparing the experimental and the best fitted optical emission spectra of the second positive bands of N₂(C³Π_u → B³ Π_g, 0-2) and the first negative bands of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0). The effects of the concentration of argon and oxygen on the emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH?(A ²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) are investigated. It is shown that the plasma gas temperature keeps almost constant with the pulse repetition rate and pulse peak voltage increasing. The emission intensities of N₂ (C³Π_u → B³Π_g, 0-0, 337.1 nm), OH(A²Σ → X²Π, 0-0) and N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm) rise with increasing the concentration of argon, but decrease with increasing the concentration of oxygen, and the influences of oxygen concentration on the emission intensities of N₂(C³Π_u → B³Π_g, 0-0, 337.1 nm) and OH (A²Σ → X²Π, 0-0) are more greater than that on the emission intensity of N₂ ⁺ (B² Σ_u ⁺ → X² Σ_g ⁺, 0-0, 391.4 nm).     

XAS analysis of iron and palladium bonded to a polysaccharide produced anaerobically by a strain of Klebsiella oxytoca

Klebsiella oxytoca BAS‐10 ferments citrate to acetic acid and CO₂, and secretes a specific exopolysaccharide (EPS), which is able to bind different metallic species. These biomaterials may be used for different biotechnological purposes, including applications as innovative green biogenerated catalysts. In production of biogenerated Pd species, the Fe(III) as ferric citrate is added to anaerobic culture of K. oxytoca BAS‐10, in the presence of palladium species, to increase the EPS secretion and improve Pd‐EPS yield. In this process, bi‐metallic (FePd‐EPS) biomaterials were produced for the first time. The morphology of bi‐metallic EPS, and the chemical state of the two metals in the FePd‐EPS, are investigated by transmission electron microscopy, Fourier transform infra‐red spectroscopy, micro‐X‐ray fluorescence, and X‐ray absorption spectroscopy methods (XANES and EXAFS), and compared with mono‐metallic Pd‐EPS and Fe‐EPS complexes. Iron in FePd‐EPS is in the mineralized form of iron oxides/hydroxides, predominantly in the form of Fe³⁺, with a small amount of Fe²⁺ in the structure, most probably a mixture of different nano‐crystalline iron oxides and hydroxides, as in mono‐metallic Fe‐EPS. Palladium is found as Pd(0) in the form of metallic nanoparticles with face‐centred cubic structure in both bi‐metallic (FePd‐EPS) and mono‐metallic (Pd‐EPS) species. In bi‐metallic species, Pd and Fe nanoparticles agglomerate in larger clusters, but they remain spatially separated. The catalytic ability of bi‐metallic species (FePd‐EPS) in a hydrodechlorination reaction is improved in comparison with mono‐metallic Pd‐EPS.