Electroactive ligands: the first metal complexes of tetrathiafulvenyl-acetylacetonate

The reaction of tris(alkylthio)tetrathiafulvalene thiolates with 3-chloro-2,4-pentanedione affords tetrathiafulvalene (TTF) moieties substituted by the acetylacetone function (TTFSacacH), precursors of novel redox-active ligands: the acetylacetonate ions (TTFSacac). These TTFSacacHs have been characterized by X-ray diffraction analyses, and similar trends have been observed, such as a TTF core almost planar and the acetylacetone substituent located in a plane almost perpendicular to the plane formed by the TTF core. Their chelating ability has been demonstrated by the formation of the corresponding M(TTFSacac)2(pyridine)2 complexes in the presence of M(II)(OAc)2.H2O (M = Ni2+, Zn2+). These complexes with TTFSacac moieties, Ni(TTFSacac)2(pyridine)2, 6b, and Zn(TTFSacac)2(pyridine)2, 7b, have been characterized by X-ray diffraction analyses, showing in all structures the metal(II) center chelated by two TTFacac units in the equatorial plane and the octahedral coordination geometry around the metal completed by two axial pyridine ligands. Cyclic voltammetry and UV-visible-near infrared spectroscopic measurements have evidenced a sizable interaction between the two electroactive ligands and the stabilization of a mixed-valence state in the one-electron oxidized complexes.     

A Chemical Study of Burley Tobacco Flavour (Nicotiana tabacum L.). I. Volatile to medium-volatile constituents (b.p. ≦ 84°/0.001 Torr

The fraction b.p. ≦ 84° (0.001 Torr) from Burley tobacco condensate was carefully investigated using fractional distillation and preparative column and gas liquid chromatography aided by GLC/MS coupling. Among the 193 compounds thus separated and characterized by their spectral data, 81 were newly identified tobacco constituents. Most of the compounds isolated in the course of this work display flavouring properties which make them highly suitable for improving the flavour and aroma of tobacco and tobacco smoke.     

Ultraviolet emission spectra of sunbeds

It is well known that UV radiation contributes to the development of skin cancer. Exposure to solar radiation is predominantly responsible for the high incidence rate of skin cancer, but there are also indications that sunbeds are involved. The aim of the present investigation was to determine the UV emission spectra of sunbeds. It included the most common sunbed models, which cover more than 50% of the Swiss market. The UV emission spectra of sunbeds have special characteristics and are different from the sun spectrum, which can be seen in high-resolution spectral measurements. Sunbed emission spectra are similar to the sun spectrum in the UVB (280-320 nm) range but reach values 10 to 15 times higher in the UVA (320-400 nm) range. An average erythema-effective irradiance of 0.33 W/m2 was determined for sunbeds. This corresponds to a UV index of 13, which is significantly higher than the UV index of 8.5 of the high summer sun at noon at intermediate latitudes. The measurements were spread over the whole effective area of the sunbeds, and an inhomogeneous distribution of the irradiances with variations of up to 30% from the average value was found.     

Volumetric properties of the boldine + alcohol mixtures at atmospheric pressure from 283.15 to 333.15 K: A new method for the determination of the density of pure boldine

Densities of boldine + alcohol binary mixtures were measured over the whole accessible range of boldine compositions at temperatures from 283.15 to 333.15 K using an Anton-Paar digital vibrating glass tube densimeter. The binary systems studied include, as a solvent, seven normal alcohols from n-C₁ to n-C₆, n-C₈, and isopropanol. The density of these systems has been found an increasing function of the boldine composition. A new methodology based on density data of solutions of solid solutes with normal alcohols is described in order to determine solid molar volume of pure solutes. This methodology was validated with pure solid naphthalene molar volumes data at 298.15 K, with an average uncertainty of 6%.     

A beta-glucosidase from Sclerotinia sclerotiorum: biochemical characterization and use in oligosaccharide synthesis

The filamentous fungus Sclerotinia sclerotiorum, grown on a xylose medium, was found to excrete one beta-glucosidase (beta-glu x). The enzyme was purified to apparent homogeneity by ammonium sulfate precipitation, gel filtration, anion-exchange chromatography, and high-performance liquid chromatography (HPLC) gel filtration chromatography. Its molecular mass was estimated to be 130 kDa by HPLC gel filtration and 60 kDa by sodium dodecyl sulfate polyacrylamide gel electrophoresis, suggesting that beta-glu x may be a homodimer. For p-nitrophenyl beta-d-glucopyranoside hydrolysis, apparent Km and Vmax values were found to be 0.09 mM and 193 U/mg, respectively, while optimum temperature and pH were 55-60 degrees C and pH 5.0, respectively. beta-Glu x was strongly inhibited by Fe2+ and activated about 35% by Ca2+. beta-Glu x possesses strong transglucosylation activity in comparison with commercially available beta-glucosidases. The production rate of total glucooligosaccharides (GOSs) from 30% cellobiose at 50 degrees C and pH 5.0 for 6 h with 0.6 U/mL of enzyme preparation was 80 g/L. It reached 105 g/L under the same conditions when using cellobiose at 350 g/L (1.023 M). Finally, GOS structure was determined by mass spectrometry and 3C nuclear magnetic resonance spectroscopy.     

IR and theoretical studies of monocarbonyl Ni complexes formed by adsorption of CO at low pressure on silica-supported Ni(II) ions

This work reports on the reactivity of coordination vacancies of Ni(II) ions grafted onto the tridentate silica support (Ni(II)(3c) ions) with respect to CO used as a probe molecule. The adsorption of CO at 77 K in the 0.3 to 3.5 Pa CO pressure range is studied by FTIR on two samples differing in the dispersion of nickel. Quantum chemical calculations by the DFT method are performed to investigate, using a cluster approach, the binding of Ni to silica and, after CO adsorption, the geometry of the resulting carbonyl Ni complexes. Silica is modeled by using clusters composed of three types of monodentate ligands, SiO(-), SiOSi and/or SiOH, found on the surface of silica. This work is devoted to the monocarbonyl complexes. Whatever the sample, only one type of monocarbonyl is formed from Ni(II)(3c) ions. It is shown that the charge of the silica cluster is the major parameter influencing the CO IR frequency whereas the nature and the size of the silica cluster do not affect the CO bond length, confirming that local electrostatic interactions predominate. Only the 1- charged silica cluster Si(5)O(3)(-), composed of SiO(-), 2SiOSi fragments, respectively, reproduces the Ni[bond]O distances derived from EXAFS for the Ni(II)(3c) grafted site and gives CO frequencies in good agreement with the experimental values. It is shown that CO is stabilized by a magnetic transition from the (3)Ni(2+) triplet to the (1)Ni(2+) singlet state occurring upon adsorption.     

Characterization of Two Light-Harvesting Subunits Isolated from the Brown Alga Pelvetia canaliculata: Heterogeneity of Xanthophyll Distribution

The main light-harvesting fraction from Pelvetia canaliculata was isolated on a sucrose density gradient from digitonin-solubilized chloroplasts. After further solubilization by dodecyl maltoside, the bulk fraction was separated into two subunits by preparative isoelectric focusing. The more acidic brown fraction was mainly composed of 22 kDa polypeptides having an apparent pI of 4.55. Its pigment composition was very simple, containing chlorophyll (Chi) a, Chi c and fucoxanthin. The in vivo spectral properties of fucoxanthin, namely a shift in light absorption to the green and efficient energy transmission to Chi a, were conserved in this subunit. No xanthophyll associated with photoprotection was found in this band, even when obtained from photoinhibited thalli. The less acidic green band contained predominantly 22 kDa polypeptides that were resolved into numerous components by denaturing isoelectric focusing. Its pigment composition was more complex, containing, in addition, pigments of the so-called xanthophyll cycle. In photoinhibited thalli, about half of the violaxanthin was converted into antheraxanthin and zeaxanthin. All the pigments of the xanthophyll cycle were specifically associated with this subunit, and it may thus have a central role in the thermal dissipation of the absorbed light energy as postulated for light-harvesting complex II isolated from green plants.     

Tetranuclear manganese(II) complexes of thiacalixarene macrocycles with trigonal prismatic six-coordinate geometries: synthesis, structure, and magnetic properties

Two tetranuclear manganese(II) complexes [Mn(II)4(thiaS)2] (1) and [Mn(II)4(thiaSO)2] (2) have been synthesized under solvothermal conditions in methanol with p-tert-butylthiacalix[4]arene (thiaS) and p-tert-butylsulfinylthiacalix[4]arene (thiaSO). For both complexes, the structure has been established from single-crystal X-ray diffraction. [Mn4(thiaS)2].H2O (1) crystallizes in the orthorhombic Immm (No. 71) space group with the following parameters: a = 18.213 (5) angstroms, b = 19.037 (5) angstroms, c = 29.159 (5) angstroms, V = 10110 (4) angstroms3, and Z = 4. [Mn4(thiaSO)2].H2O (2) crystallizes in the monoclinic C2/m (No. 12) space group with the following parameters: a = 33.046(1) angstroms, b = 19.5363 (8) angstroms, c = 15.7773 (9) angstroms, beta = 115.176 (2) degrees, V = 9218.3 (8) angstroms3, and Z = 4. The two complexes are neutral and are best described as manganese squares sandwiched between two thiacalixarene macrocycles. In both complexes, each manganese center is six-coordinated in a trigonal prismatic geometry with four phenoxo oxygen atoms plus two sulfur atoms for 1 or two oxygen atoms from SO groups for 2. The two tetranuclear complexes exhibit identical magnetic behaviors resulting from antiferromagnetic interactions between the four manganese centers. The simulation of the magnetic susceptibility was done considering a single exchange-coupling constant between the manganese(II) ions, J (H = -J(S1S2 + S2S3 + S3S4 + S1S4)). The best fits give the same result for the two complexes: g = 1.94 and J = -5.57 cm(-1).     

Effects of substituted ligands on the mobility of complexed anions

From conductance and viscosities measurements on Pr₄NCl, Et₄NBr, and AgNO₃ in acetonitrile and Et₃NBr in nitrobenzene, the Walden products of the anion at infinite dilution were determined in presence of various concentrations of substituted benzoic acids. From these data it was possible to compute the values of the Walden products of the once complexed anions and to estimate the order of magnitude of the Walden products of twice complexed anions. Stokes' law is not obeyed, and the Walden products are not proportional to the third root of the molar volume of the complexed ions, as a consequence of their lack of sphericity. The assumption that the drag force which acts on the ions is proportional to the volume of the substituents results in a linear expression between the reciprocals of the Walden products and the molar volume of the ligands. The experimental results fit this expression within the limits of the experimental errors, and the slopes of the lines are nearly the same for all the anions and for the two solvents studied here, namely, 2.5×10^–4 ohm-cm^–5 mole-cP^–1.     

Matrix-isolation FT-IR and DFT theoretical studies of the intramolecular hydrogen bonding in Mannich bases

FT-IR Ar-matrix isolated spectra were studied for dichloro- (Cl₂-MB) and tetrachloroderivatives (Cl₄-MB) of the ortho Mannich base. The spectra were analyzed based on the DFT calculated frequencies and intensities and compared with those recorded in CCl₄ solution in the region of the ν(OH) and ν(OD) vibrations. The matrix-isolated spectra are characterized by narrower ν(OH) and ν(OD) bands with much better resolved fine structure than in solution. The fine structure originates from the anharmonic coupling with the low frequency modes as well as from Fermi resonance. The ν(OD) band shapes can be reproduced exclusively by assuming the Fermi resonance with overtones and summation of the frequencies of modes into which the bridge atoms are involved. The frequency isotopic ratio (ISR) is for both compounds 1.33 while the half-width ratios are equal to 1.82 and 1.94, for Cl₂-MB and Cl₄-MB, respectively.