Nonsymmetrical 3,4‐Dithienylmaleimides by Cross‐Coupling Reactions with Indium Organometallics: Synthesis and Photochemical Studies

The synthesis and photochemical study of novel nonsymmetrical 1,2‐dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium‐catalyzed cross‐coupling reactions of 5‐susbtituted‐2‐methyl‐3‐thiophenyl indium reagents with 3,4‐dichloromaleimides. The required organoindium reagents were prepared from 2‐methyl‐3,5‐dibromothiophene by a selective (C‐5) coupling reaction with triorganoindium compounds (R₃In) and subsequent metal–halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R₃In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON–OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process.     

Magnetic collapse of a neutron gas: Can magnetars indeed be formed?

A relativistic degenerate neutron gas in equilibrium with a background of electrons and protons in a magnetic field exerts its pressure anisotropically, having a smaller value perpendicular to than along the magnetic field. For critical fields the magnetic pressure may produce the vanishing of the equatorial pressure of the neutron gas. Taking this as a model for neutron stars, the outcome could be a transverse collapse of the star. This fixes a limit to the fields to be observable in stable neutron star pulsars as a function of their density. The final structure left over after the implosion might be a mixed phase of nucleons and a meson condensate, a strange star, or a highly distorted black hole or black ”cigar”, but not a magnetar, if viewed as a superstrongly magnetized neutron star. However, we do not exclude the possibility of superstrong magnetic fields arising in supernova explosions which lead directly to strange stars. In other words, if any magnetars exist, they cannot be neutron stars. Received: 25 November 2002 / Revised version: 25 February 2003 / Published online: 5 May 2003     

New nanomaterials for consolidating stone

A novel sol-gel synthesis, in which a surfactant acts to make the pore size of the gel network more coarse and uniform, is shown to provide an effective alternative for the consolidation of stone. The new mesoporous silica avoids the main inconvenience of current commercial consolidants, which is their tendency to crack inside the pores of the stone. Since the cracking of xerogels is a well-known drawback of the sol-gel process, the synthesis presented here can be extended to other applications. Finally, preliminary studies of the effectiveness of the novel surfactant-templated sol in consolidating a typical biocalcareous stone are also discussed.     

Energetics of binding and protein unfolding upon amphiphilic drug complexation with a globular protein in different aqueous media

The interactions and complexation process of the structurally related amphiphilic phenothiazines promazine and triflupromazine hydrochlorides with horse myoglobin in aqueous buffered solutions of pH 2.5, 5.5 and 9.0 have been examined by zeta-potential, isothermal titration calorimetry (ITC), UV-vis spectroscopy and dynamic light-scattering techniques with the aim of analyzing the effect of hydrophobic and electrostatic forces, the alteration of protein conformation and the effect of substituents in the drug molecular structure on the binding mechanism and structure of the resulting complexes. The energetics and stoichiometry of the binding process was derived from ITC. The enthalpies of binding obtained are small and exothermic, and the Gibbs energies of binding are dominated by large increases in entropy consistent with hydrophobic interactions. Binding isotherms were obtained from microcalorimetric data by using a theoretical model based on the Langmuir isotherm. zeta-Potential data showed a reversal in the sign of the protein charge at pH 9.0 as a consequence of drug binding. Gibbs energies of drug binding per mole of drug were also derived from zeta-potential data. On the other hand, binding of the phenothiazines causes a conformational transition on protein structure which was followed as a function of drug concentration by using UV-vis spectroscopy. These data were analyzed to obtain the Gibbs energy of the transition in water (DeltaG(w)(degrees)) and in a hydrophobic environment (DeltaG(hc)(degrees)). Finally, the population distribution of the different species in solution and their size was analyzed through dynamic light scattering. The existence of an aggregation process of drug/protein complexes, mainly at pH 2.5, was observed. We think this is a consequence of the already expanded structure of the protein at this pH and the subsequent binding of drug molecules to the protein.     

Interplay between hydrogen bond formation and multicenter pi-electron delocalization: intermolecular hydrogen bonds

The interplay between aromatic electron delocalization and intermolecular hydrogen bonding is thoroughly investigated using multicenter delocalization analysis. The effect on the hydrogen bond strength of aromatic electron delocalization within the acceptor and donor molecules is determined by means of the interaction energies between monomers, calculated at the B3LYP/6-311++G(d,p) level of theory. This magnitude is compared to variations of multicenter electron delocalization indices and covalent hydrogen bond indices, which are shown to correlate perfectly with the relative values of the interaction energies for the different complexes studied. The multicenter electron delocalization indices and covalent bond indices have been computed using the quantum theory of atoms in molecules approach. All the hydrogen bonds are formed with oxygen as the acceptor atom; however, the atom bonded to the donor hydrogen has been either oxygen or nitrogen. The water-water complex is taken as reference, where the donor and acceptor molecular environments are modified by substituting the hydrogens and the hydroxyl group by phenol, furan, and pyrrole aromatic rings. The results here shown match perfectly with the qualitative expectations derived from the resonance model.     

Long-lasting dashed waves in a reactive microemulsion

In the Belousov-Zhabotinsky (BZ) reaction carried out in a reverse microemulsion with Aerosol OT as surfactant, the existence of two different sizes of droplets containing the BZ reactants leads to the emergence of segmented (dashed) waves. This bimodal distribution of sizes is stabilized by adding small amounts of the homopolymer poly(ethylene oxide) (PEO). Addition of PEO lengthens the period during which these patterns are observed, so that dashed waves can persist for 12-14 h, in contrast to the 2-3 h found in earlier studies without added polymer.     

D(+)-pi-A(-) charge-transfer molecules based on tricyanoquinodimethane and diphosphine metal complexes

A new family of D (+)-pi-A (-) chromophores in which the donor group is an organometallic complex and the acceptor group a tricyanoquinodimethane moiety has been synthesized by the reaction of diphosphinomethanide transition-metal complexes and 7,7',8,8'-tetracyanoquinodimethane.     

QTAIM N-center delocalization indices as descriptors of aromaticity in mono and poly heterocycles

The implementation of the n-center electron delocalization indices, n-DIs, and n-order electron localization indices, n-LIs, within the framework of the quantum theory of atoms in molecules, QTAIM, is performed. n-DIs are shown to be very useful to study the local aromaticity in monocyclic and polycyclic compounds. Total and pi n-DIs from n=4 to 7 were computed for a series of typical 4, 5, 6, and 7-center aromatic and antiaromatic rings. For n>or=5 the pi n-DI accounts for the 95% of the total n-DI and can be employed alone to measure the aromaticity. A scaling factor on the n-DIs is required in order to compare the aromaticity of [5c-6e] and [6c-6e] rings, the same correction allows to estimate the relative aromatic stabilization of polycyclic compounds using the sum of its values for individual rings. This is called Effective Scaled Electron Delocalization, ESED. The comparison with other aromaticity indices reflects a good correlation between ESED and both resonance energies, and HOMA indices. The most important differences between scaled pi n-DIs and NICS(0) indices are found for compounds that contain rings with different number of centers or pi electrons.     

Reactions of Sn(NMe2)2 with MPHCy: the effects of alkali metal phosphide coupling (Cy=cyclohexyl; M=Li, Na, K, Rb)

The reactions of the SnII base Sn(NMe2)2 with CyPHM (Cy=cyclohexyl) produce a range of products, depending primarily on the alkali metal (M) involved. The 1:3 stoichiometric reaction of Sn(NMe2)2 with CyPHNa in the presence of the Lewis base donor PMDETA (PMDETA=(Me2NCH2CH2)2NMe) gives [(NaPMDETA)2{Sn(mu-PCy)}3] (3), containing the electron-deficient [{Sn(mu-PCy)}3]2- dianion. Natural bond order (NBO) and electron localisation function (ELF) calculations show that this species is described most appropriately by a two-electron, three-centre Sn3 bonding model. Evidence that 3 results from phosphide coupling is provided by the 1:1 reaction of Sn(NMe2)2 with CyPHNa in the presence of PMDETA, which gives 3 and trace amounts of (NaPMDETA)2[{Sn(mu-PCy)}2(mu-PCyPCy)] (4) (containing one PCyPCy2- dianion). Greater extents of phosphide coupling are observed as the size of the Group 1 metal is increased. Thus, the 1:3 reaction of Sn(NMe2)2 with CyPHK in THF gives the co-crystalline product {(K2 THF)2[{Sn(mu-PCyPCy)}2(mu-PCy)]}0.9{(K2 THF)2[{Sn(mu-PCy)}2(mu-PCyPCy)]}0.1 (5) (containing [{Sn(mu-PCyPCy)}2(mu-PCy)]2- and [{Sn(mu-PCy)}2(mu-PCyPCy)]2- dianions), whereas the analogous reaction of Sn(NMe2)2 with RbPHCy gives [RbPMDETA{(CyP)3SnP(H)Cy}] (6) (containing a cyclic {(CyP)3Sn} unit).