Microwave-assisted Paal-Knorr reaction. A rapid approach to substituted pyrroles and furans

[reaction: see text] An array of tetrasubstituted pyrroles (and trisubstituted furans) was obtained using a simple three-step procedure. Functional homologation of a beta-ketoester with an aldehyde followed by oxidation gave a series of differently substituted 1,4-dicarbonyl compounds that can be rapidly cyclized with the Paal-Knorr procedure carried out under microwave irradiation.     

Laser induced breakdown spectroscopy on meteorites

The classification of meteorites when geological analysis is unfeasible is generally made by the spectral line emission ratio of some characteristic elements. Indeed when a meteorite impacts Earth's atmosphere, hot plasma is generated, as a consequence of the braking effect of air, with the consequent ablation of the falling body. Usually, by the plasma emission spectrum, the meteorite composition is determined, assuming the Boltzmann equilibrium. The plasma generated during Laser Induced Breakdown Spectroscopy (LIBS) experiment shows similar characteristics and allows one to verify the mentioned method with higher accuracy. On the other hand the study of Laser Induced Breakdown Spectroscopy on meteorite can be useful for both improving meteorite classification methods and developing on-flight techniques for asteroid investigation.

In this paper certified meteorites belonging to different typologies have been investigated by LIBS: Dofhar 461 (lunar meteorite), Chondrite L6 (stony meteorite), Dofhar 019 (Mars meteorite) and Sikhote Alin (irony meteorite).     

The Michelson interferometer

The apparatus that Michelson brought to the BIPM in 1892 to determine the value of the metre in luminous wavelengths has generated a vast family of instruments typically used for length measurement. Looking at them from this point of view teaches us a lot about the characteristics of the Michelson interferometer that make it specially convenient for Fourier transform spectroscopy (FTS). Michelson himself used the principle of the FTS to check the monochromaticity of various spectral lines. He was looking for a good standard of length, hence he did not care so much about the general problem of spectroscopy. Furthermore, he was limited to the parameter that he called the visibility of the fringes, i.e. the modulus of the Fourier transform of the spectral distribution, in fact the only parameter that the naked eye can roughly estimate, besides the fringe spacing. As he counted only up to 1212 fringes, and thereafter used a stepping process by optical addition, he did not worry about the optical defects that impair direct interferometric measurement of long distances. A few technological improvements have made the fringe-counting technique the current way of measuring length. It is shown that the analysis required for accurate length measurements with a Michelson interferometer is similar to the one required to make accurate FTS.     

Separation of proteins in a multicompartment electrolyzer with chambers defined by a bed of gel beads

Multicompartment electrolyzers (MEs) with isoelectric membranes were introduced in 1989 for purifying proteins in an electric field. At the basis of ME technology there are membranes consisting of cross-linked copolymers of acrylamide and acrylamido monomers bearing protolytic groups. The technology employed for casting the membranes is an extension of the isoelectric focusing in immobilized pH gradient technique for which specific acrylamido monomers, known with the trade name of Immobiline, have been developed. However, the use of continuous membranes presents several disadvantages. Due to the mechanical characteristics of polyacrylamide, the gel must physically adhere onto a rigid support, which prevents it from collapsing. The support must have a highly porous structure in order to be permeable to proteins. The mechanical fragility of the membranes is one of the main problems that hinders the industrial scale application of ME separators. In order to overcome this problem, we propose to substitute the continuous membranes with a bed of gel beads of identical comonomer composition, obtained by an inverse emulsion polymerization process.     

Homogeneous immunoassay of atrazine in water by terbium-entrapping liposomes as fluorescent markers

Atrazine (Atr) was conjugated to mastoparan (Mast) cytolytic peptide; Mast-Atr derivative was used as cytolytic agent on liposomes trapping Tb/citrate complex. This was applied in a time-resolved fluoroimmunoassay for detection of Atr in water. The cytolytic activity was read by means of time-resolved fluorescence after adding an excess of dipicolinic acid (DPA). Tb/citrate-entrapping liposomes are easy to prepare, and the assay is carried out in a short incubation time and in a range between 10 pg and 100 ng. The procedure was applied to analyse samples taken from Adda River and from irrigation ditches in an agricultural area around the town of Lodi. Recovery in samples spiked with two different Atr concentrations was between 95 and 105%.     

Intramolecular Dynamics of Tetranuclear Iridium Carbonyl Cluster Compounds. Part V. Polysubstituted derivatives of [Ir4(CO)12]

The dynamic behaviour of twelve polysubstituted derivatives of [Ir₄(CO)₁₂] has been investigated in solution, using 2D-EXSY, and VT-³¹P- and ¹³C-NMR. [Ir₄(CO)₆(μ₂-CO)₃(η⁴-diarsine) PPh₃] and [Ir₄(CO)₆(μ₂-CO)₃(η⁴-nor-bornadiene)(PMePh₂)] exhibit two isomeric forms in solution, which interconvert through an intramolecular change of basal face. The related cluster [Ir₄(CO)₆(μ₂-CO)₃(η⁴-norbornadiene)PPh₃] exists as a single isomer in solution. It displays rotation of CO ligands about the apical Ir-atom, followed by two consecutive changes of basal face. The tetrasubstituted clusters with two chelating ligands [Ir₄(CO)₅(μ₂-CO)₃(η⁴-diolefin)₂] also exhibit rotation of apical CO's, the activation energy increases with greater steric hindrance of the radical ligands. A quantitative analysis of the ³¹P- and ¹³C-2D-EXSY spectra followed by simulation of the corresponding VT-NMR spectra of [IR₄(CO)₅(μ₂-CO)₃(μ₂-L)₂] (L = bis(diphenylphosphino)methane and 1,3-bis(diphenylphosphino)propane) revealed a pairwise averaging of the P-atoms, caused by two parallel changes of basal face averaging all CO ligands. In addition, the restricted rotation of ligands about the apical Ir-atom was identified at higher temperatures. The remaining clusters are either rigid on the NMR time scale, or display CO-scrambling about a single Ir-atom.     

Cp*Rh(bpy)(H2O)]2+ as a coenzyme substitute in enzymatic oxidations catalyzed by Baeyer-Villiger monooxygenases

[Cp*Rh(bpy)(H2O)]2+ was applied as a flavin regenerating reagent in BVMO catalyzed oxidations of organic sulfides to chiral sulfoxides.     

First general approach to cyclohex-3-ene-1,1-bis(phosphonates) by Diels-Alder cycloaddition of tetraethyl vinylidenebis(phosphonate) to 1,3-dienes

Tetraethyl vinylidenebis(phosphonate) (VBP) reacts smoothly with substituted 1,3-dienes at 90-110 degrees C without solvent to give the corresponding cyclohex-3-ene-1,1-bis(phosphonates) in good yields (60-85%). With nonsymmetrically substituted dienes, mixtures of regioisomers are obtained, the regioisomeric ratio being exclusively controlled by electronic effects. Danishefsky's diene allows tetraethyl 4-oxocyclohex-2-ene-1,1-bis(phosphonate) to be obtained in an 81% overall yield after the acid-catalyzed hydrolysis of the Diels-Alder cycloadduct. With 2,3-dimethoxy-1,3-butadiene, a mixture of regioisomeric dimethoxycyclohexene-1,1-bis(phosphonates) is formed by the VBP-catalyzed isomerization of the normal Diels-Alder cycloadduct. The mixture converges into tetraethyl 3,4-dimethoxycyclohex-2-ene-1,1-bis(phosphonate) at prolonged reaction times.     

Preparation and structure of polymers from methoxy and hydroxy alkyl phenyl vinyl ketones

The preparation of 2-methoxy-5-t-butylphenyl vinyl ketone (MeOBVK), 2-hydroxy-5-t-butylphenyl vinyl ketone (HOBVK), and 2-methoxy-5-isooctylphenyl vinyl ketone (MeOOVK) is reported. These compounds can be considered as precursors of polymerizable derivatives of polyoxyethylated alkylphenols—a very important class of nonionic surface active compounds. The homopolymerization and copolymerization of MeOBVK, HOBVK, and MeOOVK with butylacrylate (BA), (–) menthylacrylate [(–)MtA], styrene (STY), and vinylacetate (VA) by free radical initiators, both in solution and emulsion, have been investigated. Copolymer formation has been demonstrated by fractionation and by the presence of induced optical activity in the electronic transitions of the achiral MeOBVK and HOBVK units in copolymers with the optically active comonomer (—)MtA. MeOBVK, HOBVK and MeOOVK give substantially random copolymers with STY, BA, or VA under all conditions investigated, and always show larger reactivity; thus, depending on feed composition, sequences of the vinyl ketone units can be expected in the macromolecules.     

Designing systems for a multiple use of light signals.

The photochemical and photophysical behavior of two dendrimers consisting of a benzophenone core and branches that contain dimethoxybenzene units has been investigated. Such dendrimers can undergo a variety of photochemical and photophysical processes, namely: 1) quenching of the fluorescence and phosphorescence of the dimethoxybenzene units by energy transfer to the benzophenone core (antenna effect), 2) direct and sensitized phosphorescence (and delayed fluorescence) of the benzophenone core, 3) hydrogen abstraction by the triplet excited state of the benzophenone core from solvent molecules, 4) intramolecular hydrogen abstraction by the triplet excited state of the benzophenone core from the dendrimer branches, 5) quenching of the phosphorescence and hydrogen abstraction reaction of the benzophenone core by energy transfer to terbium ions and dioxygen; 6) conversion of the UV light absorbed by the dendrimer branches into visible (Tb3+) or near infrared (O2) emission via the sequence of processes 1) and 5). The results obtained emphasize the great potential of suitably designed dendrimers for a multiple use of light signals.