Voltammetric studies on the α-tocopherol anion and α-tocopheroxyl (Vitamin E) radical in acetonitrile

The α-tocopheroxyl radical was generated voltammetrically by one-electron oxidation of the α-tocopherol anion (E ^r_1/2=−0.73 V versus Ag|Ag⁺) that was prepared by reacting α-tocopherol with Et₄NOH in acetonitrile (with Bu₄NPF₆ as the supporting electrolyte). Cyclic voltammograms recorded at variable scan rates (0.05–10 V s⁻¹), temperatures (−20 to 20°C) and concentrations (0.5–10 mM) were modelled using digital simulation techniques to determine the rate of bimolecular self-reaction of α-tocopheroxyl radicals. The k values were calculated to be 3×10³ l mol⁻¹ s⁻¹ at 20°C, 2×10³ l mol⁻¹ s⁻¹ at 0°C and 1.2×10³ l mol⁻¹ s⁻¹ at −20°C. In situ electrochemical-EPR experiments performed at a channel electrode confirmed the existence of the α-tocopheroxyl radical.     

Magnetic and EPR Studies of α-, β-, and γ-Fe2WO6 Phases at Low Temperatures

The polymorphic modifications α-, β-, and γ-Fe₂WO₆ of the iron tungstate system were studied by means of magnetic susceptibility and EPR measurements at low temperatures. Both methods revealed a significant paramagnetic contribution, probably resulting from local distortions of the antiferromagnetic bulk structure induced by a disturbed cation ordering or the presence of Fe²⁺ ions. The magnetic susceptibility revealed a peak at 260 K for all samples which can be related with an AF phase transition. The EPR spectra comprised the contribution of various isolated paramagnetic iron centers, one arising from high-spin Fe³⁺ ions in rhombic crystal field symmetry with E/D ≈ 1/3 and D ≈ 0.22 cm^-1, an anisotropic EPR signal consistent with an S= 3/2 ground state with large zero-field splitting, and a dominant component in the g ≈ 2 region presumably arising from an S = 1/2; spin state. The latter spectra were tentatively attributed to the formation of multi-iron clusters, one of them invoking the presence of Fe²⁺ ions as well. For the βFe₂WO₆ phase an additional EPR spectrum was observed, which probably results from high-spin Fe³⁺ ions in a weak crystal field.     

Complexation and aromatization of α,β-unsaturated cyclic ketones by Ru(H2O)6 and (Bz)Ru(H2O)3: molecular structure of (η-Tosylate)(η-hydroxycyclopentadienyl)Ru and of (η-Tosylate)(η-1,4-dihydroxy-2,3,5,6-tetramethylbenzene)Ru

Ruaq²⁺(OTs)₂ complexes in aqueous solution to unsaturated cyclic ketones. These aromatized on heating to π-arene Ru complexes. Thus, with cyclohexonone the main product was Ru(η⁶-phenol)₂²⁺, 4, along with some Ru(η⁶-phenol)(η⁶-OTs)⁺, 6. Similarly gave cyclopentenone in the presence of various arenes Ru(η⁵-hydroxycyclopentadienyl)(η⁶-arene)⁺. Duruquinone complexed to Ruaq²⁺ as a monoprotanated hydroquinolate in Ru(η⁶-2,3,5,6-tetramethyl-1,4-hydroquinone)(η⁶-OTs), 14. Ru(η⁵-cyclopentadienyl)(η⁶-OTs), 8, and 14 were characterized by single crystal x-ray structure analyses, data see Table 1. Whereas both ligands in 8 are planar, the 1,4-hydroquinone ligand in 14 shows distinct bending of the COH groups.     

Mixed Monolayers of Amphiphilic Cyclodextrins and Phospholipids: II. Surface Potential–Area Behavior of Per-(6-amino-2,3-di-O-hexyl) β-CD Hydrochloride Salt and 1,2 Dipalmitoyl, 3-sn-Phosphatidic Acid Mixed Monolayers

The dielectric properties of mixed monolayers of per-(6-amino-2,3-di-O-hexyl) β-CD hydrochloride (NH₃-β-CD-OC6) and 1,2 dipalmitoyl, 3-sn-phosphatidic acid (DPPA) have been assessed using surface potential measurements at constant area. From the comparison of these surface potential (ΔV) versus surface density (δ) relationships with those of surface pressure (π) against surface density (δ) it was apparent that the increase in the NH₃-β-CD-OC6 content in mixed films gave rise to a gradual increase in the saturation value of the surface potential (ΔV_max). This potential for pure DPPA was found to be equal to 396 mV and for pure CD 554 mV. The ΔV_maxvalues reflect the onset of reorientation effects that arrive at molar areas before the collapse of these films. Independently of reorientation effects, the obtained results strongly indicate that the dipolar term contributing to the overall ΔVvalue was for NH₃-β-CD-OC6 due to the hydration of its NH⁺₃group. For both DPPA and NH₃-β-CD-OC6 molecules the contribution of the electric double layer (Ψ) was calculated and was found for DPPA and NH₃-β-CD-OC6 to be equal to −249 and +252 mV, respectively. These calculated Ψ values made possible the evaluation of dipole moments for NH₃-β-CD-OC6 and DPPA monolayers which revealed a marked difference in dipolar properties between these two film forming components. In contrast to DPPA which exhibited a decrease in the surface dipole moment (μ) with the decrease inA, NH₃-β-CD-OC6 displayed an increase in μwith the decrease inAforAvalues above 580 Ų. Below this value μdecreases with decreasing molecular area and this variation arises from a change in the polarity of the electric double layer arising from interactions with the complementary anion. The differences in dielectric properties between the two film forming molecules have been attributed to modification, during compression, in the structure of the interfacial water bound to the cyclodextrin.     

Powder neutron diffraction of α-UB2C (α-UB2C-type)

The crystal structure of α-UB₂C (low temperature modification below T = 1675(25)°C) was determined from powder X-ray data (RT) and powder neutron diffraction data (at 29 K) employing the Rietveld-Young-Wiles profile analysis method. α-UB₂C crystallizes in the orthorhombic space group Pmma with a = 0.60338(3), B = 0.35177(2), C = 0.41067(2) nm, V = 0.0872 nm³, Z = 2. The residuals of the neutron refinement were R₁ = 0.032 and R_F = 0.043. The crystal structure of α-UB₂C is a new structure type where planar nonregular 6³-U-metal layers alternate with planar nonmetal layers of the type (B₆C₂)³. Boron atoms are in a typical triangular prismatic metal surrounding with a tetrakaidekahedral coordination B[U₆B₂C₁], whereas carbon atoms occupy the center points of rectangular bipyramids C[U₄B₂]. The crystal structure of α-UB₂C derives from the high temperature modification β-UB₂C (ThB₂C-type, ), which reveals a similar stacking of slightly puckered metal layers 6³, alternating with planar layers B₆ · (B₆C₃)². The phase transition from β-UB₂C to α-UB₂C is thus essentially generated by carbon diffusion within the B₆ · (B₆C₃)² layers to form (B₆C₂)³ layers.     

Adsorption mechanism of Cu from aqueous solution by chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid

In order to better understand the adsorption mechanism of chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid (α-KA-CCMNPs), the removal of Cu²⁺ by α-KA-CCMNPs from aqueous solution was investigated in a batch system at 18, 35 and 50 °C. Different experimental approaches were applied to show mechanistic aspects, such as adsorption isotherms, kinetics and thermodynamics studies. Adsorption equilibrium studies showed that Cu²⁺ adsorption followed Langmuir model. The kinetics of the interactions was best described by pseudo-second-order mechanism. The thermodynamic parameters (ΔG°, ΔH° and ΔS°) analysis predicted that the adsorption process was strongly dependent on temperature of medium, and spontaneous and endothermic process. The XPS combined with FT-IR spectra revealed that N atom of –NH– group and O atom of carboxyl group in α-KA-CCMNPs coordinated with Cu²⁺. Experimental results from this study provide data that would be required if this heavy metal adsorption system was to be “scaled up” for industrial application.     

Luminescence de l'europium divalent dans les composés α- et β-RbLu3F10

The effect of the crystal structure upon the luminescence of the divalent europium within the RbLu₃F₁₀ dimorphous matrix has been investigated. The obtained results essentially show that the difference between the rubidium coordination numbers in both α- and β-RbLu₃F₁₀ phases (15 or 16 and 8 or 10 respectively) is responsible for the change over from a 4f⁷ → 4f⁷ emission to a 4f⁶5d¹ → 4f⁷ emission.     

Trityl Cation-Catalyzed Hosomi-Sakurai Reaction of Allylsilane with β,γ-Unsaturated α-Ketoester to Form γ,γ-Disubstituted α-Ketoesters

(Ph₃C)[BPh(^F)₄]-catalyzed Hosomi-Sakurai allylation of allylsilanes with β,γ-unsaturated α-ketoesters has been developed to give γ,γ-disubstituted α-ketoesters in high yields with excellent chemoselectivity. Preliminary mechanistic studies suggest that trityl cation dominates the catalysis, while the silyl cation plays a minor role.     

Cyclopentadienyl-ruthenium and -osmium chemistry : XXXIX. Syntheses of novel alkynyl-ruthenium complexes. X-Ray structures of two forms of {Ru(PPh3)2(η-C5H5)}2(μ-C4) and of Ru{CCC(O)Me}(PPh3)2(η-C5H5)

Reactions between [Ru(thf)(PPh₃)₂(η-C₅H₅)]⁺ and lithium acetylides have given further examples of substituted ethynylruthenium complexes that are useful precursors of allenylidene and cumulenylidene derivatives. From Li₂C₄, mono- and bi-nuclear ruthenium complexes were obtained: single-crystal X-ray studies have characterised two rotamers of {Ru(PPh₃)₂(η-C₅H₅)}₂(μ-C₄), which differ in the relative cis and trans orientations of the RuL_n groups. Protonation of Ru(CCCCH)(PPh₃)₂(η-C₅H₅) afforded the butatrienylidene cation [Ru(C=C=C=CH₂)(PPh₃)₂(η-C₅H₅)]⁺, which reacted readily with atmospheric moisture to give the acetylethynyl complex Ru{CCC(O)Me}(PPh₃)₂(η-C₅H₅), also fully characterised by an X-ray structural study.     

The Amyloid Fibril-Forming β-Sheet Regions of Amyloid β and α-Synuclein Preferentially Interact with the Molecular Chaperone 14-3-3ζ

14-3-3 proteins are abundant, intramolecular proteins that play a pivotal role in cellular signal transduction by interacting with phosphorylated ligands. In addition, they are molecular chaperones that prevent protein unfolding and aggregation under cellular stress conditions in a similar manner to the unrelated small heat-shock proteins. In vivo, amyloid β (Aβ) and α-synuclein (α-syn) form amyloid fibrils in Alzheimer’s and Parkinson’s diseases, respectively, a process that is intimately linked to the diseases’ progression. The 14-3-3ζ isoform potently inhibited in vitro fibril formation of the 40-amino acid form of Aβ (Aβ₄₀) but had little effect on α-syn aggregation. Solution-phase NMR spectroscopy of ¹⁵N-labeled Aβ₄₀ and A53T α-syn determined that unlabeled 14-3-3ζ interacted preferentially with hydrophobic regions of Aβ₄₀ (L11-H21 and G29-V40) and α-syn (V3-K10 and V40-K60). In both proteins, these regions adopt β-strands within the core of the amyloid fibrils prepared in vitro as well as those isolated from the inclusions of diseased individuals. The interaction with 14-3-3ζ is transient and occurs at the early stages of the fibrillar aggregation pathway to maintain the native, monomeric, and unfolded structure of Aβ₄₀ and α-syn. The N-terminal regions of α-syn interacting with 14-3-3ζ correspond with those that interact with other molecular chaperones as monitored by in-cell NMR spectroscopy.     

Thermochemistry of the solid complex Gd(Et<Subscript>2</Subscript>dtc)<Subscript>3</Subscript>(phen)

Summary A ternary solid complex Gd(Et₂dtc)₃(phen) has been obtained from reactions of sodium diethyldithiocarbamate (NaEt₂dtc), 1,10-phenanthroline (phen) and hydrated gadolinium chloride in absolute ethanol. The title complex was described by chemical and elemental analyses, TG-DTG and IR spectrum. The enthalpy change of liquid-phase reaction of formation of the complex, Δ_rH^Θ_m(l), was determined as (-11.628±0.0204) kJ mol^-1 at 298.15 K by a RD-496 III heat conduction microcalorimeter. The enthalpy change of the solid-phase reaction of formation of the complex, Δ_rH^Θ_m(s), was calculated as (145.306±0.519) kJ mol^-1 on the basis of a designed thermochemical cycle. The thermodynamics of reaction of formation of the complex was investigated by changing the temperature of liquid-phase reaction. Fundamental parameters, the apparent reaction rate constant (k), the apparent activation energy (E), the pre-exponential constant (A), the reaction order (n), the activation enthalpy (Δ_rH^Θ_≠), the activation entropy (Δ_rS^Θ_≠), the activation free energy (Δ_rG^Θ_≠) and the enthalpy (Δ_rH^Θ_≠), were obtained by combination of the thermodynamic and kinetic equations for the reaction with the data of thermokinetic experiments. The constant-volume combustion energy of the complex, Δ_cU, was determined as (-18673.71±8.15) kJ mol^-1 by a RBC-II rotating-bomb calorimeter at 298.15 K. Its standard enthalpy of combustion, Δ_cH^Θ_m, and standard enthalpy of formation, Δ_fH^Θ_m, were calculated to be (-18692.92±8.15) kJ mol^-1 and (-51.28±9.17) kJ mol^-1, respectively.     

Molecular Structure and Conformational Preferences of Trimethyl Phosphorotrithioite,P(SMe)<Subscript>3</Subscript>, Evaluated by Gas-Phase Electron Diffraction and Quantum Chemical Calculations

Free P(SMe)₃ molecule was studied by gas electron diffraction (GED) and by B3PW91/6-311+G* (DFT) and MP2/6-31+G* calculations. Each conformer is characterized by three dihedral angles τ(CSPlp), where lp denotes the direction of the lone electron lone pair on the P atom. DFT calculations indicate that the most stable conformer is an anti,gauche+,gauche- (ag+g-) conformer of C _s symmetry; the next are the ag+g+ (ΔE = 2.5 kJ mol⁻¹), g+g+g+ (ΔE = 5.2 kJ mol⁻¹), and aa+g+ (Δ E = 12.5 kJ mol⁻¹) conformers. The MP2 calculations give the similar order, with the relative energies of 0.3, 4.3, and 10.6 kJ mol⁻¹, respectively. The experimental GED data agree well with the presence of only two conformers: χ(ag+g+) = 80(20)% and χ(ag+g-) = 20(10)%.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 742–750.Original Russian Text Copyright © 2005 by Belyakov, Khramov, Baskakova, Naumov.     

The structure and dynamic properties of mixed adsorption and penetration layers of α-dipalmitoylphosphatidylcholine/β-lactoglobulin at water/fluid interfaces

The interfacial tensions of mixed α-dipalmitoylphosphatidylcholine (DPPC)/β-lactoglobulin layers at the chloroform/water interface have been measured by the pendent drop and drop volume techniques. In certain intervals, the adsorption kinetics of these mixed layers was strongly influenced by the concentrations of both protein and DPPC. However, at low protein concentration, C_{β-lactoglobulin}=0.1 mg l⁻¹, the adsorption rate of mixed interfacial layers was mainly controlled by the variation of the DPPC concentration. As C_{β-lactoglobulin} was increased to 0.8 mg l⁻¹, the interfacial activity was abruptly increased, and within the concentration range of C_DPPC=10⁻⁴–10⁻⁵ mol l⁻¹, the DPPC has very little effect on the whole adsorption process. In this case, the adsorption rate of mixed layers was mainly dominated by the protein adsorption. This phenomenon also happened as the protein concentration was further increased to 3.6 mg l⁻¹. When C_DPPC>3 · 10^–5 mol l⁻¹, the adsorption behaviour was very similar to that of the pure DPPC although the protein concentration was changed. The equilibrium interfacial tensions of the mixed layers are dramatically effected by the lipid as compared to the pure protein adsorption at the same concentration. It reveals the estimation of which composition of lipid and protein decreases the interfacial tension. The combination of Brewster angle microscopy (BAM) with a conventional LB trough was applied to investigate the morphology of the mixed DPPC/β-lactoglobulin layers at the air/water interface. The mixed insoluble monolayers were produced by spreading the lipid at the water surface and the protein adsorbed from the aqueous buffer subphase. The BAM images allow to visualise the protein penetration and distribution into the DPPC monolayer on compression of the complex film. It is shown that a homogeneous distribution of β-lactoglobulin in lipid layers preferentially happens in the liquid fluid state of the monolayer while the protein can be squeezed out at higher surface pressures.     

Peracetylated α‐d‐glucopyranosyl fluoride and peracetylated α‐maltosyl fluoride

The X‐ray analyses of 2,3,4,6‐tetra‐O‐acetyl‐α‐d ‐glucopyranosyl fluoride, C₁₄H₁₉FO₉, (I), and the corresponding maltose derivative 2,3,4,6‐tetra‐O‐acetyl‐α‐d ‐glucopyranosyl‐(1→4)‐2,3,6‐tri‐O‐acetyl‐α‐d ‐glucopyranosyl fluoride, C₂₆H₃₅FO₁₇, (II), are reported. These add to the series of published α‐glycosyl halide structures; those of the peracetylated α‐glucosyl chloride [James & Hall (1969). Acta Cryst. A 25 , S196] and bromide [Takai, Watanabe, Hayashi & Watanabe (1976). Bull. Fac. Eng. Hokkaido Univ. 79 , 101–109] have been reported already. In our structures, which have been determined at 140 K, the glycopyranosyl ring appears in a regular ⁴C₁ chair conformation with all the substituents, except for the anomeric fluoride (which adopts an axial orientation), in equatorial positions. The observed bond lengths are consistent with a strong anomeric effect, viz. the C1—O5 (carbohydrate numbering) bond lengths are 1.381 (2) and 1.381 (3) Å in (I) and (II), respectively, both significantly shorter than the C5—O5 bond lengths, viz. 1.448 (2) Å in (I) and 1.444 (3) Å in (II).     

High-pressure preparation, crystal structure, and properties of the new rare-earth oxoborate β-Dy2B4O9

In this work we report about a new rare-earth oxoborate β-Dy₂B₄O₉ synthesized under high-pressure/high-temperature conditions from Dy₂O₃ and boron oxide B₂O₃ in a B₂O₃/Na₂O₂ flux with a walker-type multianvil apparatus at 8 GPa and 1000°C. Single crystal X-ray structure determination of β-Dy₂B₄O₉ revealed: , a=616.2(1) pm, b=642.8(1) pm, c=748.5(1) pm, α=102.54(1)°, β=97.08(1)°, γ=102.45(1)°, Z=2, R1=0.0151, wR₂=0.0475 (all data). The compound exhibits a new structure type which is built up from bands of linked BO₃- (Δ) and tetrahedral BO₄-groups (□). The Dy³⁺-cations are positioned in the voids between the bands. According to the conception of fundamental building blocks β-Dy₂B₄O₉ can be classified with the notation 2Δ6□:Δ3□=4□=3□Δ. Furthermore we report about temperature-resolved in situ powder diffraction measurements and IR-spectroscopic investigations on β-Dy₂B₄O₉.     

Unimolecular rearrangement of α-silylcarbenium ions. An ab initio study

The unimolecular rearrangements of hydrogen, methyl and phenyl groups at the Si atom in α-silylcarbenium ions have been investigated using an ab initio molecular orbital method. MP2/6–31 + G^*//HF/6–31G^* calculations predict that all three groups migrate from the Si to an adjacent C_α with no energy barrier. Thus, the silicenium ion is the only stable species in each potential energy surface. The conformation of the benzylsilicenium ion, (C₆H₅)CH₂−SiH₂⁺, indicates that the phenyl ring is significantly bent toward the silyl cationic center in order to interact with the vacant 3p(Si⁺) orbital. In contrast to MP2 results, Hartree-Fuck calculations (both HF/3–21G^* and HF/6–31G^* levels) predict small energy barriers for 1,2-migrations of H and Me (1.4 kcal mol⁻¹ for H migration, and 1.5 kcal mol⁻¹ for Me migration, respectively, at the HF/6–31G^* level). This difference provides convincing evidence that the incorporation of electron correlation is of particular importance in describing the potential energy surface for the rearrangement of α-silylcarbenium ions to silicenium ions. The results of the calculations have also been applied to the possible rearrangement mechanism of α-chlorosilanes to chlorosilanes, assuming that the experimental conditions are favorable toward the generation of ionic species. Various factors which may govern the migratory aptitudes of various R groups, i.e. (1) activation energies, (2) overall reaction energies and (3) the conformational preference of reactants have been investigated. The calculated activation energy obtained, namely the energy for the generation of the silicenium ion and the C⁻¹ ion from an α-chlorosilane, is consistent with the experimental migratory aptitude in the gas phase observed in mass spectrometers.     

Substoichiometric TiCl4-mediated vicinal difunctionalization of α,β-acetylenic ketones for the synthesis of β-halo Baylis–Hillman olefins

A substoichiometric amount of titanium tetrachloride was found to be effective to promote and participate in the tandem α-hydroxyalkylation/β-chlorination of α,β-acetylenic ketones in the presence of (n-Bu)₄NI. This method provides the concise synthesis of (E)-β-halo Baylis–Hillman adducts. No β-iodo products were detected when using this combination of halogen sources. The reaction process involves 1,4-addition of chloro anion released from TiCl₄ onto α,β-acetylenic ketones to give TiCl₃–allenolate intermediates followed by the titanium Lewis acid-promoted carbonyl addition. Modest to good yields (53–77%) and excellent E/Z stereoselectivity (>95%) have been obtained for 10 examples.     

Mass spectra of some α-substituted phenyl-α,α′-dimethoxyl ketones and their derivatives

The mass spectra of some α-substituted phenyl-α,α′-dimethoxyl ketones (compounds 1) and their 2,4-dinitrophenylhydrazones (compounds 2) and semicarbazones (compounds 3) have been studied. The characteristic fragments at m/z (M ? 73) from compounds 1, m/z (M ? 253) from compounds 2 and m/z (M ? 130) from compounds 3 are abundant and proposed to be [ArCROCH₃]⁺. Fragmentations yielding [M⁺ ? 49] from compounds 2 are abnormal and probably involve the methoxyl and nitro groups. The intense peak at m/z 130 due to [CH₃OCH₂CNNHCONH₂]⁺ from compounds 3 corresponds to α-cleavage of the molecular ion. Some other fragments from these new compounds are interpreted in this paper.     

H NMR of the α,α′-bipyridine and o-phenanthroline adducts of n-butyltin trichloride

¹H NMR spectra of the α,α′-bipyridine adduct of n-BuSnCl₃ indicated the non-equivalence of the two pyridine rings. In particular the signals of the proton on the carbon atom adjacent to the two nitrogen atoms were widely separated. Similar spectral behavior was observed in the o-phenanthroline adduct. These adducts therefore are concluded to have the n-butyl group lying on the N---Sn---N plane of the hexacoordinated complexes. The configurational rearrangement of these adducts was markedly accelerated in the presence of excess n-BuSnCl₃.