Relaxation dynamics in glycerol-water mixtures: I. Glycerol-rich mixtures

We discuss the relaxation dynamics of glycerol-water mixtures, as studied by dielectric spectroscopy in the frequency range from 1 Hz to 250 MHz and at temperatures between 173 and 323 K. The experimental results obtained for the glycerol-rich mixtures suggest that the main dielectric relaxation process, as well as the so-called high-frequency "excess wing" (EW) and dc conductivity, follow the same temperature dependence. This result indicates that all of these processes are induced by the same molecular origin. A new phenomenological function is proposed to describe the whole dielectric spectrum in the covered frequency range, and some possible mechanisms of dielectric behaviors through the dc conductivity, the main relaxation process, and the EW are discussed.     

Synthesis and structural characterisation of a novel tris-methylene bridged compound (NO) 4Fe2 Se(μ-CH2)3

The tris-methylene bridged compound (NO)₄Fe₂Se(μ-CH₂)₃ has been isolated. It has been characterised by IR and ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups.     

Influence of localized excited states on the transition moment directions of charge transfer complex absorptions

The influence of localized excited (LE) states on the spectroscopy of charge transfer (CT) complexes has been examined for a series of complexes formed between methyl-substituted benzene donors and 1,2,4,5-tetracyanobenzene as acceptor in 1,2-dichloroethane and octanenitrile solvents. A molecular orbital model was used to describe the appearance of multiple CT absorption bands that occur in the spectra of these complexes. The influence of LE states in these CT absorptions was explored using time-resolved linear dichroism spectroscopy where the direction of the CT transition moment vector (TMV) was used to probe the magnitude of intensity borrowing. The TMV directions for each of the observed CT transitions within the absorption spectra were determined for several complexes. In some cases, the observed CT transitions were interpreted as being pure CT transitions; in others the observed transitions are influenced significantly by a LE transition. The correlation between the TMV directions and the transition energy suggests that the magnitude of intensity borrowing is influenced not only by the energy difference between the CT and LE transitions but also by the specific character of the transitions under consideration.     

Obtusin,a unique bromine-containing polycyclic ketal from the red marine alga Laurenciaobtusa

The structure of a unique bromine-containing ketal, obtusin ($\text{1}$), has been determined by spectral and X-ray crystallographic techniques. Obtusin is a natural component of the Mediteranean red alga $\text{Laurencia}$$\text{obtusa}$.     

Deprotection of Thioacetals Using K2S2O8/[bmim]Br as a Mild and Efficient Reagent under Solvent-Free Conditions

Summary. A straightforward and effective procedure for the deprotection of thioacetals to the corresponding carbonyl compounds using potassium persulfate and the ionic liquid [bmim]Br under solvent-free conditions is reported. A variety of aliphatic and aromatic 1,3-dithiolanes or 1,3-dithanes was deprotected to the corresponding carbonyl derivatives by this procedure.     

Spectroscopy and quantum chemical modeling reveal a predominant contribution of excitonic interactions to the bathochromic shift in alpha-crustacyanin, the blue carotenoprotein in the carapace of the lobster Homarus gammarus

To resolve the molecular basis of the coloration mechanism of alpha-crustacyanin, we used (13)C-labeled astaxanthins as chromophores for solid-state (13)C NMR and resonance Raman spectroscopy of [6,6',7,7']-(13)C(4) alpha-crustacyanin and [8,8',9,9',10,10',11,11',20,20']-(13)C(10) alpha-crustacyanin. We complement the experimental data with time-dependent density functional theory calculations on several models based on the structural information available for beta-crustacyanin. The data rule out major changes and strong polarization effects in the ground-state electron density of astaxanthin upon binding to the protein. Conformational changes in the chromophore and hydrogen-bond interactions between the astaxanthin and the protein can account only for about one-third of the total bathochromic shift in alpha-crustacyanin. The exciton coupling due to the proximity of two astaxanthin chromophores is found to be large, suggesting that aggregation effects in the protein represent the primary source of the color change.     

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O) n − and (NH3) n −

The photodetachment spectra of (H₂O) _n ^=2?69/? and (NH₃) _n ^=41?1100/? have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly withn ^?1/3, extrapolating to a VDE (n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.     

The stereochemistry of guggulsterol-1

The steroechemistry of guggulsterol-1, a component of the exudate of $\text{Commiphora}$$\text{mukul}$, is shown to be 20(R), 22(R)($\text{3}$).     

Stereoselective formation of glycosyl sulfoxides and their subsequent equilibration: ring inversion of an alpha-xylopyranosyl sulfoxide dependent on the configuration at sulfur

A series of four S-allyl D-thiopyranosides, alpha- and beta-manno and xylo, were oxidized with MCPBA at low temperature to give seven of the eight possible sulfoxides, whose configuration at sulfur was determined either directly by X-ray crystallography or by correlation with closely related structures. For the axial thioglycosides oxidation leads very predominantly to the (R)(S)-diastereomer in the xylo series and exclusively so in the manno series; the configuration at C2 is of little importance in determining the stereoselectivity of oxidation of axial thioglycopyranosides. In the equatorial series the configuration at C2 has a significant effect on the outcome of the reaction as, although both series favored the (S)(S)-sulfoxide, selectivity was significantly higher in the case of the beta-mannoside than of the beta-xyloside. The two alpha-xylo sulfoxides have different conformations of the pyranoside ring with the (R)(S)-isomer adopting the (1)C(4) chair and the (S)(S)-diastereomer the (4)C(1). Each pair of diastereomeric sulfoxides was thermally equilibrated in C(6)D(6) and in CD(3)OD. In the mannose series the kinetic isomers are also thermodynamically preferred. In the xylose series, on the other hand, the nature of the thermodynamic isomer in both the alpha- and beta-anomers is a function of solvent with a switch observed on going from C(6)D(6) to CD(3)OD. The results are rationalized in terms of the exo-anomeric effect, steric shielding provided by H3 and H5 in the axial series, the interaction of the C2-O2 and sulfoxide dipoles, and increased steric interactions on hydrogen bonding of the sulfoxides to CD(3)OD.     

SrInGe and EuInGe: new Zintl phases with an unusual anionic network derived from the ThSi(2) structure

Two new isostructural Zintl phases, EuInGe and SrInGe, are obtained from high-temperature reactions of the pure elements in welded Ta tubes. Both ternary phases crystallize in a new structure type in space group Pnma (No. 62), with a = 4.921(1) A, b = 3.9865(9) A, and c = 16.004(3) A for EuInGe; and a = 5.021(1) A, b = 4.0455(9) A, and c = 16.188(4) A for SrInGe. The crystal structures established by single-crystal X-ray diffraction feature zigzag chains of 3-bonded Ge atoms and puckered layers of 4-bonded In atoms. The two structural units are linked into an anionic network with channels composed of 5-membered and 7-membered rings. The channels are filled by the respective divalent cations. The chemical bonding of the anionic [InGe](2)(-) network, derived from a one-electron oxidative distortion of the alpha-ThSi(2) structure, is explained using extended-Hückel band structure calculations. Magnetic measurements indicate that EuInGe exhibits Curie-Weiss paramagnetic behavior above 35 K and antiferromagnetic behavior below 35 K. The calculated effective moment, mu(eff) = 8.11 mu(B), of EuInGe and the diamagnetic behavior of SrInGe are consistent with the oxidation states of Eu(II) and Sr(II), respectively.