Influence of interchain interactions on the electronic properties of neutral and charged oligodiacetylenes carrying bulk substituents

We discuss the effect of the interchain interactions on the electronic properties of a "dimer", named (CHD(4))(2), built from two molecules of a fully carbazolyl-substituted oligodiacetylene containing four repeating units. Each carbazolyl moiety is connected to its respective backbone through a methylene spacer, and the excitations of the neutral and doubly positively charged dimer are obtained using the CIS (configuration interaction including singles) and CEO (collective electronic oscillator) models. The separation distance between the backbones is fixed to a value that could possibly imply a very weak, if any, interchain interaction between the oligomers. In the charged dimer, where we have not been able to perform CEO calculations, it can be expected from previous results that the CIS method will behave satisfactorily. Contrary to the neutral case and surprisingly enough, the simulated photoinduced absorption (PA) spectra indicate a substituent-induced strong interaction between the oligomers, due to the very large amount of excess charge on the distorted oligomer which is spread over its carbazolyl moieties. Broadening of the lowest energy band due to the latter interaction improves the agreement between the theoretical and the experimental PA spectrum for the corresponding polymer. The through-space charge transfer directly connecting the charged with the neutral molecule could supply an efficient channel for charge transport in substituted polydiacetylenes.     

Electron impact mass spectrometry of new tris(polyoxalkyl)amines (tridents)

The mass spectrometric behavior of new tris(polyoxalkyl)amines (tridents) 1–5 have been studied and compared with N-(3,6,9,12-tetraoxatridecyl)-16-aza-18-crown-6 ( 6 ) and 1-morpholino-3,6,9-trioxadecane ( 7 ). The peculiar fragmentation patterns are emphasized.     

Functional and structural characterization of ovine ornithine transcarbamoylase

Ornithine transcarbamoylase from ovine liver has been purified to homogeneity. Like all anabolic OTCs, the ovine enzyme is a trimer, constituted by identical subunits of 34 kDa. Sequence analysis of the 54 N-terminal residues of ovine OTC shows a high degree of homology with the human enzyme. The optimum pH and the Michaelis constants for the catalytic reaction were determined. The ovine enzyme is the most thermostable one among mammals OTCs, its critical temperature being 6 degrees C higher than those measured for the other enzymes. The enzyme has been crystallised and the structure determined at 3.5 A resolution. Crystals belong to the cubic P4(3)32 space group, with a = b = c = 184.7 A and a solvent content of about 80%. There is no evidence of any ligand in the active site cavity, indicating that the crystals contain an unliganded or T state of the enzyme. The unliganded OTCase enzyme adopts a trimeric structure which, in the crystal, presents a three-fold axis coincident with the crystallographic one. The conformation of each monomer in the trimer is quite similar to that of the liganded human protein, with the exception of a few loops, directly interacting with the substrate(s), which are able to induce a rearrangement of the quaternary organisation of the trimer, that accounts for the cooperative behaviour of the enzyme following the binding of the substrates.     

Distorted hexagonal phase studied by neutron diffraction: lipid components demixed in a bent monolayer

The recent discovery of a distorted hexagonal phase in 1,2-dioleoyl-sn-glycero-3-phosphatidylethanolamine/1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPE/DOPC) mixtures raised the intriguing question as to whether lipid mixtures demix in a bent monolayer. We performed neutron diffraction on a mixture of headgroup deuterated DOPC-d(13) and nondeuterated DOPE to study the lipid distribution in the distorted hexagonal phase. The 1:1 lipid mixture in full hydration and 25 degrees C was in a homogeneous lamellar phase. Upon dehydration the mixture transformed to a rhombohedral phase, then to a distorted inverted hexagonal phase, and finally to a regular inverted hexagonal phase. In the distorted hexagonal phase, the diffraction pattern showed a two-dimensional monoclinic lattice with two reciprocal vectors of equal length (1.5 nm(-)(1)) forming an angle 53 degrees between them. Diffraction intensities measured while varying the D(2)O/H(2)O ratio in the humidity was used to solve the phase problem. The neutron scattering length density distribution of the distorted hexagonal phase was constructed. The constant density contours are approximately elliptical. The difference in the eccentricities of the contours between the water and lipid distributions indicates that the DOPE/DOPC ratio is not uniform around the elliptical lipid tube in the unit cell. DOPE is preferentially distributed at the vertex regions where the curvature is the highest. Thus for the first time it is shown that when a monolayer of a homogeneous lipid mixture is bent, the lipid components are partially demixed in reaching the free energy minimum.     

Effect of organotin compounds on membrane lipids: Fluorescence spectroscopy studies

The temperature dependence of 1,6-diphenyl-1,3,5-hexatriene (DPH) and 1-(4-trimethylaminophenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH) fluorescence anisotropy has been studied to investigate the influence of mono-n-butyltin chloride (MBTC), di-n-butyltin chloride (DBTC) and tri-n-phenyl chloride (TPTC) on the physicochemical state of dipalmitoyl phosphatidylcholine. Below the lipid chain melting transition (T_m), fluorescence anisotropy values of DPH and TMA-DPH are increased by the presence of the organotins, without important modifications of the phase transition temperature. A possible difference in localization of the organotin compounds is suggested by the differential effect of the probes. It is suggested that there is localization in the hydrophobic core of the bilayer for TPTC, and at the head-group level for DBTC, and a homogeneous distribution in the bilayer for MBTC. Similar studies have been performed in liposomal suspensions of cardiolipin, phosphatidylserine and egg phosphatidylcholine.     

Reductive metalation of 1,2-diaryl-substituted ethenes: synthetic applications

Reduction of 1,2-diaryl-substituted ethenes with Na metal in dry THF allowed easy access to a variety of 1,2-diaryl-1,2-disodiumethanes. These diorganometallic intermediates were elaborated into the corresponding 1,2-diarylethanes (aqueous work up), or cycloalkylated with 1,3-dichloropropanes. The last reaction led to a highly diastereoselective synthesis of trans-1,2-diaryl-substituted cyclopentanes.     

Antimicrobial activities,toxicity and phenolic composition of Asphodeline anatolica E. Tuzlaci leaf extracts from Turkey

The antimicrobial activity of acetone, methanol and aqueous extracts of Asphodeline anatolica E. Tuzlaci leaves was evaluated against American type culture collection, food and clinical isolates (Listeria monocytogenes and Staphylococcus aureus including methicillin-resistant strains-MRSA). Biofilm formation, toxicity and characterisation of the polyphenolic content were analysed. The acetone extract demonstrated a higher antibacterial activity against S. aureus including MRSA strains, L. monocytogenes and Pseudomonas aeruginosa than against other extracts. No effect was observed in biofilm formation. The extracts resulted non-toxic against Artemia salina Leach. The phytochemical screening of extracts indicated that they mainly contained six polyphenols identified as catechin 3-O-gallate, protocatechuic acid, diosmin, rutin, cirsimaritin and kaempferol glucoside. This study is the first report on antimicrobial activity and phenolic content of A. anatolica and contributes to enrich the literature data on the biological properties of this plant. A. anatolica leaves have a potential as source of natural antimicrobial compounds.     

Interactions of a water-soluble calix[4]arene with spermine: solution and solid-state characterisation

Abstract

The octaanionic 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis(hydroxycarbonylmethoxy)-calix[4]arene (cone conformation) (C₄TsTc) was investigated as a sensor for the biogenic tetracationic polyamine, spermine _.(H₄Spe⁴⁺). Fluorescence titration experiments of the water-soluble calixarene with spermine showed the formation of the 2:1 and 1:1 calixarene:spermine complexes in solution. The single crystal X-ray diffraction analysis of [(NaC₄TsTc)₄·(H₄Spe)₇] confirmed the formation of 2:1 and 1:1 calixarene:spermine species and showed that the water-soluble calixarene binds the spermine either by partially hosting it in the inner cavity or through the carboxylate groups on the lower rim. In order to investigate the effect of multivalent systems, supramolecular assemblies of octaanionic calixarene molecules templated by meso-tetrakis(4-N-methylpyridyl)porphyrin (H₂T₄) in different stoichiometric porphyrin:calixarene ratios (1:4 and 3:4) were also tested for spermine binding in solution. Fluorescence titration experiments with the 1:4 and 3:4 H₂T₄:C₄TsTc supramolecular complexes showed that the multivalent assemblies are more sensitive to the presence of spermine than the calixarene alone.     

Febantel: looking for new polymorphs

The aim of this work was to search for new polymorphic forms of febantel, an anthelminthic drug of great present interest for the veterinary industry. Solvent-based recrystallization, thermal and mechanical treatments and spray drying were chosen to discover new solid forms. The solids obtained were physicochemically characterized by thermal techniques (DSC and TG), FTIR spectroscopy, laboratory and synchrotron X-ray powder diffraction and scanning electron microscopy. Our work leads to obtain a new solid form never described in the literature. In particular, the new polymorph was obtained by the anti-solvent method and the crystallization from isopropanol. The experimental conditions of crystallization favorable to the formation of the highest amount of the new solid phase were selected. The new phase shows a thermal, spectroscopic and diffractometric behavior unique. Furthermore, the preliminary structure investigation suggests two possible crystal systems: an orthorhombic or a monoclinic one, with really comparable lattice parameters and cell volume. Measurements put into evidence that the new phase is a metastable polymorph that is in monotropic relationship with the stable and known form.

     

Quantification of drug amorphous fraction by DSC

The processes of production of drugs and dosage forms in the solid state often cause unwanted transformation of portions of the substances into amorphous state, with significant changes of properties such as stability and bio-availability. When this amorphous fraction is of the order of a few percent, it usually goes unnoticed, but it should be accurately determined within a quality control system. In this work, we consider a model drug, perphenazine, where partial amorphisation may be induced by standard mechanical treatments. We show that Differential Scanning Calorimetry (DSC) leads to consistent estimations of the amorphous fractions induced by the treatment. Furthermore, DSC also yields the expected amounts of amorphous perphenazine when analysing known mixtures of perfectly crystalline samples (untreated) and partially amorphous samples (treated). We show that even amorphous fractions of the order of 1% are accurately estimated by our method.