Interaction of meso-tetrakis (4-sulfonatophenyl) porphyrin with cationic CTAC micelles investigated by small angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR)

Small angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been used to investigate the interaction of the water-soluble meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS(4)) with cationic cethyltrimethylammonium chloride (CTAC) micelles. To evaluate if the porphyrin protonation state affects its interaction with the micelle, both SAXS and EPR measurements were performed at pH 4.0 and 9.0. The best-fit SAXS curves were obtained assuming for CTAC micelle a prolate ellipsoidal shape in the absence and upon incorporation of 2-10 mM TPPS(4). SAXS results show that the presence of porphyrin impacts on micellar hydrophobic core, leading to a micellar reassembling into smaller micelles. Lineshapes of EPR spectra of 5- and 16-doxyl stearic acids (5- and 16-DSA, respectively) bound to 100 mM CTAC micelles exhibited slight changes as a function of porphyrin concentration. Spectral simulations revealed an increase of mobility restriction for both spin probes, especially at higher porphyrin concentration, where a small reduction of environment polarity was also observed for 16-DSA. The spin labels monitored only slight differences between pH 4.0 and 9.0, in agreement with the SAXS results.     

Crystallization and characterization of an inflammatory lectin purified from the seeds of Dioclea wilsonii

DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins.     

Determination of lead in seawater by inductively coupled plasma optical emission spectrometry after separation and pre-concentration with cocrystallized naphthalene alizarin

An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 8–9, and the metal was eluted using 5.0 ml of 2 mol l⁻¹ nitric acid. The effect of NaCl, KCl, BaCl₂, CaCl₂, Na₂SO₄, MgCl₂ and Na₃PO₄ on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% m/v) with Pb (50 μg) was prepared and the recommended procedure applied. The Na₃PO₄ was found to interfere; the other electrolytes did not interfere up to 5% m/v. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 μg l⁻¹, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.8–4.6%, and the recovery of lead added to seawater samples was 95–97%.     

Thermodynamic properties of quinoxaline-1,4-dioxide derivatives: a combined experimental and computational study

The mean (N-O) bond dissociation enthalpies were derived for three 2-methyl-3-(R)-quinoxaline 1,4-dioxide (1) derivatives, with R = methyl (1a), ethoxycarbonyl (1b), and benzyl (1c). The standard molar enthalpies of formation in the gaseous state at T = 298.15 K for the three 1 derivatives were determined from the enthalpies of combustion of the crystalline solids and their enthalpies of sublimation. In parallel, accurate density functional theory-based calculations were carried out in order to estimate the gas-phase enthalpies of formation for the corresponding quinoxaline derivatives. Also, theoretical calculations were used to obtain the first and second N-O dissociation enthalpies. These dissociation enthalpies are in excellent agreement with the experimental results herewith reported.     

Diastereoselective synthesis of cularine alkaloids via enium ions and an easy entry to isoquinolines by aza-Wittig electrocyclic ring closure

In preliminary communications, we reported the diastereoselective synthesis of cularine and sarcocapnine via the intramolecular ring closure of nitrenium and oxenium ions, a new highly diastereoselective reductive methylation with (+)-8-phenylmenthyl chloroacetate followed by reduction with sodium borohydride, and a facile entry to the isoquinoline precursors by aza-Wittig electrocyclic ring closure. We now report the full details of the syntheses of (+)-O-demethylcularine, (+)-cularine, (+)-sarcocapnidine, (+)-sarcocapnine, and (+)-crassifoline and describe different methods of synthesis of their precursors.     

Study of the Light‐Induced Spin Crossover Process of the [FeII(bpy)3]2+ Complex

Ab initio calculations have been performed on [Fe^II(bpy)₃]²⁺ (bpy=bipyridine) to establish the variation of the energy of the electronic states relevant to light‐induced excited‐state spin trapping as a function of the Fe? ligand distance. Light‐induced spin crossover takes place after excitation into the singlet metal‐to‐ligand charge‐transfer (MLCT) band. We found that the corresponding electronic states have their energy minimum in the same region as the low‐spin (LS) state and that the energy dependence of the triplet MLCT states are nearly identical to the ¹MLCT states. The high‐spin (HS) state is found to cross the MLCT band near the equilibrium geometry of the MLCT states. These findings give additional support to the hypothesis of a fast singlet–triplet interconversion in the MLCT manifold, followed by a ³MLCT–HS (⁵T₂) conversion accompanied by an elongation of the Fe? N distance.     

Influence of mesoporous structure type on the controlled delivery of drugs: release of ibuprofen from MCM-48, SBA-15 and functionalized SBA-15

Ordered mesoporous materials exhibit potential features to be used as controlled drug delivery systems, including their wide range of chemical compositions and their outstanding textural and structural properties. Therefore, it is possible to control the drug release kinetics by tailoring such parameters. In this paper, mesoporous materials such as MCM-48 and SBA-15, which present different pore sizes (3.7 and 8.8 nm) and structural characteristics (3D-bicontinuous cubic and 2D-hexagonal, respectively) have been synthesized to evaluate their application as drug delivery system and to determine their influence on release kinetic of ibuprofen. Moreover, a chemical modification of the SBA-15 mesoporous material with octadecyltrimethoxysilane has also been performed to study its influence on the release rate of ibuprofen. The structural characteristics (3D cubic and 2D hexagonal pore system) do not affect the release kinetic profiles of ibuprofen. On the contrary, the pore size affects highly to the release kinetic profiles from first-order kinetic to zero-order kinetic for MCM-48 and SBA-15, respectively. Moreover, the importance of surface functionalization was demonstrate through the very fast delivery of ibuprofen from SBA-15 mesoporous materials functionalized with octadecyl chains.     

Thermochemical study of some methoxytetralones

The standard (p^° = 0.1 MPa) molar energies of combustion in oxygen, at T = 298.15 K, of 5-, 6- and 7-methoxy-α-tetralone were measured by static bomb calorimetry. The values of the standard molar enthalpies of sublimation were obtained by Calvet microcalorimetry and corrected to T = 298.15 K. Combining these results, the standard molar enthalpies of formation of the compounds, in the gas phase, at T = 298.15 K, have been calculated, 5-methoxy-α-tetralone -(244.8 ± 1.9) kJ · mol^?1, 6-methoxy-α-tetralone ?(243.0 ± 2.8) kJ · mol^?1 and 7-methoxy-α-tetralone ?(242.3 ± 2.6) kJ · mol^?1.Additionally, high-level density functional theory calculations using the B3LYP hybrid exchange–correlation energy functional with extended basis sets and more accurate correlated computational techniques of the MCCM/3 suite have been performed for the compounds. The agreement between experiment and theory gives confidence to estimate the enthalpy of formation of 8-methoxy-α-tetralone. Similar calculations were done for the 5-, 6-, 7- and 8-methoxy-β-tetralone, for which experimental work was not done.     

Ethylbenzene to chemicals: Catalytic conversion of ethylbenzene into styrene over metal-containing MCM-41

Isomorphously substituted (MeDM) and impregnated metal-containing MCM-41 (MeO_x/IM) catalysts, in which Me = Co, Cu, Cr, Fe or Ni, have been prepared. Structural and textural characterizations of the catalysts were performed by means of X-ray diffraction (XRD), chemical analysis, Raman spectroscopy, electron paramagnetic resonance (EPR), N₂ adsorption isotherms and temperature programmed reduction (TPR). Cu²⁺, Co²⁺, and Cr⁴⁺/Cr³⁺ species were found over the catalysts as cations incorporated in the MCM-41 structure (MeDM) or highly dispersed oxides on the surface (MeO_x/IM). The MeDM catalysts exhibited a good performance in the dehydrogenation of ethylbenzene with CO₂. However, MeO_x/IM catalysts had a low performance in styrene production (activity less than 15 × 10^?3 mmol h^?1 and selectivity for styrene less than 80%) due to the high reducibility of the metals species. However, Ni²⁺ or Fe³⁺ coordinated with the MCM-41 framework, as well as NiO_x and Fe₂O₃ extra-framework species, is continuously oxidized by the CO₂ to maintain the active sites for dehydrogenating ethylbenzene. Deactivation studies on the FeDM sample showed that Fe³⁺ species produced active sp² carbon compounds, which are removed by CO₂; the referred sample is catalytically selective for styrene and stable over 24 h of reaction. In contrast, highly active Ni²⁺ and Ni⁰ species produced a large amount of polyaromatic carbonaceous deposits from styrene, as identified by TPO, TG and Raman spectroscopy. An acid–base mechanism is proposed to operate to adsorb ethylbenzene and abstract the β-hydrogen. CO₂ plays a role in furnishing the lattice oxygen to maintain the Fe³⁺ active sites in the dehydrogenation of ethylbenzene to form styrene.     

An inorganic iron complex that inhibits wild-type and an isoniazid-resistant mutant 2-trans-enoyl-ACP (CoA) reductase from Mycobacterium tuberculosis

The in vitro kinetics of inactivation of both wild-type and I21V InhA enzymes by [FeII(CN)5(INH)]3- indicate that this process requires no activation by KatG, and no need for the presence of NADH. This inorganic complex may represent a new class of lead compounds to the development of anti-tubercular agents aiming at inhibition of a validated target.