Dye-sensitized solar cells based on composite solid polymer electrolytes

The ionic conductivity of polymer electrolytes and their interfacial contact with dye-attached TiO2 particles were enhanced markedly by the addition of amorphous oligomer into polymer electrolytes, resulting in very high overall energy conversion efficiency.     

Investigations on the conditional kinetic and thermodynamic stability of aquatic humic substance-metal complexes by means of EDTA exchange, ultrafiltration and atomic spectrometry

The conditional metal availability and the kinetic stability of humic substance-metal species in humic-rich waters (e.g. bog water) was characterized by means of EDTA exchange. For this purpose a combined procedure consisting of time-controlled ligand exchange by EDTA, species differentiation by a fast single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods (e.g. AAS, ICP-OES, TXRF) was developed. The kinetics and the yield of the EDTA exchange served as operational parameters for assessing the kinetic stability and EDTA availability of HS-metal species, respectively. Considerable fractions of natural HS-metal species studied were shown to be EDTA-inert (e.g. 31% of the total Fe, 44% of the total Al) even after long reaction times (48 h), in contrast to artificial ones formed in solutions of isolated HS. Moreover, the conditional thermodynamic stability of HS-metal complexes formed by successive loading of an aquatic reference HS (HO14) with a number of heavy metal ions (e.g. Cr(III), Cu(II), Fe(III), Mn(II), Zn(II)) was also evaluated discriminating the free metal concentrations by means of TF-UF. In addition, from the loading isotherms obtained conditional complexation capacities could be derived for the studied HS exhibiting the order Fe(III)>Cu(II)>Cr(III)>Co(II)>Mn(II).     

On the mechanism of reorientational and structural relaxation in supercooled liquids: the role of border dynamics and cooperativity

Molecular dynamics simulation and analysis based upon the many-body potential energy landscape (PEL) are employed to characterize single molecule reorientation and structural relaxation, and their interrelation, in deeply supercooled liquid CS(2). The rotational mechanism changes from small-step Debye diffusion to sudden large angle reorientation (SLAR) as the temperature falls below the mode-coupling temperature T(c). The onset of SLAR is explained in terms of the PEL; it is an essential feature of low-T rotational dynamics, along with the related phenomena of dynamic heterogeneity and the bifurcation of slow and fast relaxation processes. A long trajectory in which the system is initially trapped in a low energy local minimum, and eventually escapes, is followed in detail, both on the PEL and in real space. During the trapped period, "return" dynamics occurs, always leading back to the trap. Structural relaxation is identified with irreversible escape to a new trap. These processes lead to weak and strong SLAR, respectively; strong SLAR is a clear signal of structural relaxation. Return dynamics involves small groups of two to four molecules, while a string-like structure composed of all the active groups participates in the escape. It is proposed that, rather than simple, nearly instantaneous, one-dimensional barrier crossings, relaxation involves activation of the system to the complex, multidimensional region on the borders of the basins of attraction of the minima for an extended period.     

Volumetric determination of the U/O ratio in uranium oxides

A method is given for determining the general formula UO(2+x), of sintered uranium dioxide pellets and uranium dioxide powders. Uranium(VI) is reduced by titration with iron(II) ammonium sulphate, after which the total amount of uranium is oxidized by titration with potassium dichromate. The end-points of both titrations are detected electrometrically. Determination of x in the range 0.0001-1.00 is possible.     

The weakly bound He-HCCCN complex: high-resolution microwave spectra and intermolecular potential-energy surface

Rotational spectra of the weakly bound He-HCCCN and He-DCCCN van der Waals complexes were observed using a pulsed-nozzle Fourier-transform microwave spectrometer in the 7-26-GHz frequency region. Nuclear quadrupole hyperfine structures due to the 14N and D nuclei (both with nuclear-spin quantum number I = 1) were resolved and assigned. Both strong a and weaker b-type transitions were observed and the assigned transitions were used to fit the parameters of a distortable asymmetric rotor model. The dimers are floppy, near T-shaped complexes. Three intermolecular potential-energy surfaces were calculated using the coupled-cluster method with single and double excitations and noniterative inclusion of triple excitations. Bound-state rotational energy levels supported by these surfaces were determined. The quality of the potential-energy surfaces was assessed by comparing the experimental and calculated transition frequencies and also the corresponding spectroscopic parameters. Simple scaling of the surfaces improved both the transition frequencies and spectroscopic constants. Five other recently reported surfaces [O. Akin-Ojo, R. Bukowski, and K. Szalewicz, J. Chem. Phys. 119, 8379 (2003)], calculated using a variety of methods, and their agreement with spectroscopic properties of He-HCCCN are discussed.     

A new entry to the isogeissoschizoid skeleton

[reaction: see text] The tetracyclic isogeissoschizoid skeleton has been prepared by a novel route that involves the ozonolysis and double reductive amination of a cyclopentene, a nickel-catalyzed cyclization, and a late-stage Fischer indole synthesis.     

Kinetic spectrophotometric determination of hydrocortisone acetate in a pharmaceutical preparation by use of partial least-squares regression

A kinetic spectrophotometric method for the determination of hydrocortisone acetate based on its condensation with isonicotinic acid hydrazide is proposed. The method is applied to the determination of hydrocortisone acetate in a commercially available pharmaceutical preparation, presented as a pomade, that also contains another corticosteroid and additional active compounds. The operating procedure involves dissolving the pomade in chloroform and the addition of the reagent solution directly to the cuvette, in this way avoiding the previous extraction of analytes from the insoluble pomade matrix required by the alternative HPLC procedure. Calibration is performed by partial least-squares regression, using absorbance or first derivative spectra values recorded each minute during the first 30 min of reaction. Use of first derivative spectra overcomes possible scattered light problems produced by excipients precipitating, and produced slightly better results than absorbance data. The relative standard deviation obtained for 11 replicates analysed on different days was approx. 1.5%. The proposed method improves both accuracy and precision of the classical initial rate method and the precision of the HPLC procedure.     

Characterisation of fatty acids in biological oil samples using comprehensive multidimensional gas chromatography

Comprehensive multidimensional gas chromatography can adequately resolve very complex mixtures of analytes such as the fatty acid mixtures which are contained in, e.g., fish and vegetable oils. Well-ordered patterns are obtained in the two-dimensional separation plane which can be used to tentatively identify peaks when no standard is available. The technique which can also be used for quantification, i.e., quantitative ratio analysis, should be especially useful for fingerprinting purposes. Unravelling the composition of complex mixtures such as fish oils appears to be highly rewarding.     

The influence of complexing agents on the effectiveness of electrochemical masking with anionic surfactants in anodic stripping voltammetry

The influence of sodium dodecyl sulphate, sodium dodecyl sulphonate and sodium stearinate on the anodic stripping peaks of Tl(I), Pb(II), Cd(II), Cu(II) and In(III) was investigated. The supporting electrolytes were 0.5M sodium sulphate solution, 0.2M citrate solution (pH 3.7, 4.6 and 7.3), 0.5M tartrate solution (pH 4.4) and 0.1M solution of EDTA (pH 4.4). The composition of complex compounds forming in a solution under experimental conditions was defined. The conditions of ion reduction of metals on hanging mercury electrode during the electrolytical deposition were investigated. The investigation included an analysis of voltammetric curves of the metal ions. The obtained results suggest that "electrochemical masking" is much stronger in electrolytes containing a complexing agent than in the sodium sulphate solution. The influence of the complexing agent may not be explained in terms of the interaction between the form of the complex and the charge of the adsorbed surfactant particles; rather the complexing process is connected with indirect inhibition, i.e., by decreasing the rate of charge transfer reaction.     

A spectrophotometric and polarographic investigation of three new cyclohexene-substituted benzodiazepines

Three recently introduced benzodiazepine derivatives, tetrazepam (I), nortetrazepam (II) and menitrazepam (III) have been subjected to spectral and polarographic investigation. From the ultraviolet spectral data their pK(a)-values have been determined: 4.28 (I), 4.3 (II) and 3.5 (III). From the polarographic measurements it can be concluded that in I and II the 4,5 CN double bond is reduced with 2 electrons. For the first time for the benzodiazepine series it has been observed that in slightly alkaline solutions this process takes place in two separate 1-electron steps. In III, first the aromatic nitro group is reduced to a hydroxylamine group, then at more negative potentials the CN double bond is also reduced; its reduction wave mostly coalesces with that for the 6-electron reduction of the nitro group to an amino group. A differential pulse polarographic method is presented, for the determination of I, II, III at concentrations as low as 10(-7)M.