Polymethylated [Fe(η6-arene)2]2+ dications: methyl-group rearrangements and application of the EINS mechanism

Reactions between the methylated arenes ArMe(n) [where ArMe(n) = C(6)Me(n)H((6-n)), and n = 1-6] and FeCl(2) in heptane at 90 °C in the presence of anhydrous AlCl(3) give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMe(n))(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl(3)/mesitylene and AlCl(3)/durene reactions in the absence of FeCl(2) (90 °C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMe(n) / FeCl(2) /AlCl(3) reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%. The pure compounds are characterised by (1)H NMR spectroscopy and electrospray-ionization mass-spectrometry (ESI-MS), and the structures of [Fe(m-xylene)(2)][PF(6)](2) and [Fe(durene)(2)][PF(6)](2) are established by single-crystal X-ray diffraction analyses.     

Electronic and vibrational transition moment directions in 7-dimethylamino-3-methyl-N-methyl-d3-4-phenylethynylcarbostyril

We report the synthesis and photophysical characterization of 7-dimethylamino-3-methyl-N-methyl-d(3)-4-phenylethynylcarbostyril, a chromophore of interest as a rotator in surface-mounted molecular rotors. Measurement of UV-vis absorption and fluorescence spectra, steady state fluorescence and excitation anisotropy, and linear dichroism in the IR and UV-vis permitted a determination of absolute vibrational and electronic transition moment directions in this previously unreported chromophore. The first singlet-singlet absorption and fluorescence are polarized perpendicular to the axle of the rotator. Density functional theory calculations of electronic excitation and vibrational frequencies gave results in very good agreement with those observed. Calculated IR transition moment directions showed rather poor agreement with experiment.     

Crystallization products of risedronate with carbohydrates and their substituted derivatives

The gastrointestinal absorption of bisphosphonates is in general only about 1%. To address this problem mixtures of risedronate monosodium salt with twelve varied sugar alcohols, furanoses, pyranoses and eight gluco-, manno- and galactopyranoside derivatives as counterions were designed in an effort to prepare co-crystals/new entities with improved intestinal absorption. Crystalline forms were generated by means of kinetically and/or thermodynamically controlled crystallization processes. One hundred and fifty-two prepared samples were screened by means of FT-NIR and FT-Raman spectroscopy. No co-crystal was prepared, but noteworthy results were obtained. A new solid phase of risedronate monosodium salt generated in the presence of phenyl-β-d-galactopyranoside under thermodynamically controlled crystallization conditions was found and also characterized using solid state NMR spectroscopy, X-ray powder diffraction and differential scanning calorimetry. This new polymorph was named as form P. Interactions between risedronate monosodium salt and both carbohydrates were confirmed by means of molecular dynamics simulation. In the present study the relationships between the chemical structures of the studied compounds required for crystalline form change are discussed.     

Comparison of various easy-to-use procedures for extraction of phenols from apricot fruits

Phenols are broadly distributed in the plant kingdom and are the most abundant secondary metabolites of plants. Plant polyphenols have drawn increasing attention due to their potential antioxidant properties and their marked effects in the prevention of various oxidative stress associated diseases such as cancer. The objective of this study was to investigate a suitable method for determination of protocatechuic acid, 4-aminobenzoic acid, chlorogenic acid, caffeic acid, vanillin, p-coumaric acid, rutin, ferulic acid, quercetin, resveratrol and quercitrin from apricot samples. A high-performance liquid chromatograph with electrochemical and UV detectors was used. The method was optimized in respect to both the separation selectivity of individual phenolic compounds and the maximum sensitivity with the electrochemical detection. The lowest limits of detection (3 S/N) using UV detection were estimated for ferulic acid (3 μM), quercitrin (4 μM) and quercetin (4 μM). Using electrochemical detection values of 27 nM, 40 nM and 37 nM were achieved for ferulic acid, quercitrin and quercetin, respectively. It follows from the acquired results that the coulometric detection under a universal potential of 600 mV is more suitable and sensitive for polyphenols determination than UV detection at a universal wavelength of 260 nm. Subsequently, we tested the influence of solvent composition, vortexing and sonication on separation efficiency. Our results showed that a combination of water, acetone and methanol in 20:20:60 ratio was the most effective for p-aminobenzoic acid, chlorgenic acid, caffeic acid, protocatechuic acid, ferulic acid, rutin, resveratrol and quercetin, in comparison with other solvents. On the other hand, vortexing at 4 °C produced the highest yield. Moreover, we tested the contents of individual polyphenols in the apricot cultivars Mamaria, Mold and LE-1075. The major phenolic compounds were chlorgenic acid and rutin. Chlorgenic acid was found in amounts of 2,302 mg/100 g in cultivar LE-1075, 546 mg/100 g in cultivar Mamaria and 129 mg/100 g in cultivar Mold. Generally, the cultivar LE-1075 produced the highest polyphenol content values, contrary to Mold, which compared to cultivar LE-1075 was quite poor from the point of view of the phenolics content.     

Oriented confined water induced by cationic lipids

We report on attenuated total reflection Fourier-transform infrared (ATR FTIR) spectroscopic measurements on oriented lipid multilayers of N,N-dimethyl-N,N-dioctadecyl-ammonium halides (DODAX, X = F, Cl, Br, I). The main goal of this study is the investigation of the structure and spectroscopic properties of water absorbed to these model membranes. Intensities of the water stretch absorptions were used to determine the amount of bound water. At high water activity, DODAF membranes bind ~11 water molecules/lipid while DODAC and DODAB adsorb 1-2 water/lipid and DODAI was hydrophobic. By adjustment of DODAF hydration to ~2 water molecules, stretching absorptions from water of the first hydration shell were accessible for the fluoride, chloride, and bromide analogs. The polarized measurements demonstrate highly confined and oriented water with infrared (IR) order parameters ranging from 0.2 to -0.4. Resolved IR water band components are attributed to different hydrogen-bonded populations. Complementary molecular dynamics simulations of DODAB strongly support the existence of differently hydrogen-bonded and oriented water within DODAB multilayers. A combination of both techniques was used for an assignment of water stretch band components to structures. The described cationic lipid systems are a prototype for a bottom-up approach to understand the IR spectroscopy of structured water at biological interfaces since they permit a defined increase of hydrophilic water-anionic interactions leading to extended water networks at membranes.     

Molecular order and dynamic mechanical behavior of polyurethanes based on liquid crystalline diol

Synthesis of the liquid crystalline (LC) diol 6,6′-[ethylenebis(l,4-phenylene-oxy)]-dihexanol (I) is described. The structure of polyurethanes prepared from diol I and 4,4′-methylenedi(phenyl isocyanate) (MDI), 4,4′-methylenedi(cyclohexyl isocyanate) (HMDI), or 2(4)-methyl-l,3-phenylene diisocyanate (TDI) at 1:1 molar ratios of isocyanate and hydroxy groups is studied by dynamic mechanical spectroscopy, differential scanning calorimetry (DSC), polarizing microscopy, and x-ray scattering. The polymer prepared from HMDI and the diol (I/HMDI) shows, on cooling, thermal behavior typical of amorphous polymers. A frequency-temperature superposition could be applied to the mechanical data, and the horizontal shift factor satisfied the Williams-Landel-Ferry (WLF) equation. A more-complex thermal behavior was found for I/HMDI polymer during subsequent heating; above 70°C, the formation of an ordered structure takes place, and this structure melts at about 120°C. Complex thermal behavior is exhibited by I/TDI polymer. On cooling its melt, the polymer forms a nematic phase at about 80°C, which freezes into the LC glassy state. On heating, the mesophase melts, and. subsequently, a better-ordered smectic phase is formed at 95°C, which melts at 120°C. This structure buildup is accompanied by a rapid increase in storage modulus G′, and the sample shows thermorheologically complex mechanical behavior. The polymer formed from the diol and MDI (I/MDI) exhibits a most-complex thermal behavior. On cooling and heating, four transitions can be detected in its thermal mechanical behavior, and the structure of the polymer is strongly dependent on its thermal history.     

Spin–orbit coupling in biradicals. 5. Zero-field splitting in triplet dimethylnitrenium,dimethylphosphenium and dimethylarsenium cations

The spin dipole–spin dipole and spin–orbit coupling contributions to the zero-field splitting parameters D and E of [CH₃–N–CH₃]⁺, [CH₃–P–CH₃]⁺, and [CH₃–As–CH₃]⁺ have been calculated from CASSCF(14,14)/cc-pVTZ wave functions and the Breit–Pauli Hamiltonian at T₁ B3LYP/cc-pVTZ optimized geometries. The spin–orbit coupling contributions represent a minor correction for the dimethylnitrenium cation, which has a triplet ground state. They dominate the spin–spin terms by an order of magnitude in the dimethylphosphenium cation and by more than two orders of magnitude in the dimethylarsenium cation, both of which have a singlet ground state. The properties of all these biradicaloids follow expectations based on the simple algebraic 2-in-2 model of biradical structure.