Optical spectra of anionic boron cluster compounds and their utilization for photometric detection

The article presents first collection of UV-vis absorption spectra of purely synthetic boron cluster compounds. Single-cage compounds have at least 11 cluster atoms; cobaltadicarboranes consists of 2 substituted 11-vertex bis(dicarbollide) clusters sandwiching the central cobalt atom. Spectrum of any of 18 investigated compounds has absorption maximum between 200 and 210 nm; its molar extinction coefficient is of the order of 10(3)-10(4)L/molcm. Second maximum exists in a spectrum of a single-cage compound if its exo-skeletal substituent absorbs UV-light above 200 nm. Spectra of cobaltadicarbaboranes both bridged and unbridged have pronounced second maxima between 270 and 300 nm. Their molar extinction coefficients range from 10(4) to 10(5)L/molcm. First light absorption minimum is close to 254 nm in spectra with two and more absorption maxima. Several correlations are derived between structure of investigated compounds and their UV-vis absorption spectra.     

On-line preconcentration of perfluorooctanoic acid and perfluorooctanesulfonic acid by nonaqueous capillary electrophoresis

Separation of major environmental pollutants as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) by capillary electrophoresis is reported for the first time. It is not possible to resolve the solutes in an aqueous media. However, the use of methanol and acetonitrile as the background electrolyte (BGE) solvents allowed their rapid separation in an uncoated capillary. A major effort was put into BGE optimization in respect to both separation efficiency and detection for further on‐line preconcentration. 5 mmol.L^?1 naphthalene‐1‐sulfonic acid and 10 mmol.L^?1 triethylamine dissolved in ACN/MeOH (50:50 v/v) provided best separation and detection conditions. Next, the large‐volume sample stacking and the field‐amplified sample injection were applied and compared. Large‐volume sample stacking improved limits of detection (LODs) with regard to the standard injection by 69 times for PFOA and 143 times for PFOS with LODs of 280 and 230 nmol.L^?1, respectively. Field‐amplified sample injection improved LODs 624 times for PFOAand 806 times for PFOS with LODs 31 and 40 nmol.L^?1, respectively. Both preconcentration methods showed repeatabilities of migration times less than 1.2% RSD intraday and 6.6% RSD interday. The method was applied on PFOA and PFOS analysis in a sample of river water treated with solid‐phase extraction, which further improved LOD toward 5.6 × 10^?10 mol.L^?1 for PFOS and 6.4 × 10^?10 mol.L^?1 for PFOA and allows the method to be used for river water contamination screening or decomposition studies.     

Bivalent and other solutions of fuzzy relational equations via linguistic hedges

We show that the well-known results regarding solutions of fuzzy relational equations and their systems can easily be generalized to obtain criteria regarding constrained solutions such as solutions which are crisp relations. When the constraint is empty, constrained solutions are ordinary solutions. The generalization is obtained by employing intensifying and relaxing linguistic hedges, conceived in this paper as certain unary functions on the scale of truth degrees. One aim of the paper is to highlight the problem of constrained solutions and to demonstrate that this problem naturally appears when identifying unknown relations. The other is to emphasize the role of linguistic hedges as constraints.     

Thionin-sensitized intrazeolite photooxygenation of trisubstituted alkenes: substituent effects on the regioselectivity as probed through isotopic labeling

The regioselectivity for the intrazeolite photooxygenation of several trisubstituted alkenes with geminal dimethyl groups was examined. The length of the alkyl chain at the lone position was varied, and as end groups, the phenyl or the cyclohexyl functionalities were chosen. The general trend for all alkenes is a significant increase of the reactivity at the twin position compared to the photooxygenation in solution. For the cyclohexyl-substituted alkenes, it was found that the regioselectivity is nearly independent of the alkyl chain length. However, for the phenyl-substituted alkenes, the ene reactivity of the allylic methylene hydrogen atoms at the lone position and the twix/twin regioselectivity depend significantly on the distance of the phenyl group from the double bond. These trends are discussed in terms of cation-pi interactions and conformational effects. Intramolecular and intermolecular isotope effects in the intrazeolite photooxygenation of deuterium-labeled alkenes suggest that a perepoxide-type intermediate is formed in the rate-determining step. Type I photooxygenation that involves reaction of the radical cations of the alkenes with superoxide ion are unlikely.     

Selectivity of Chemical Conversions: Do Light‐Driven Photoelectrocatalytic Processes Hold Special Promise?

One of the great challenges in chemistry is the development of innovative catalytic processes. In this context, significant opportunities are currently opening up for technologies based on electrocatalysis and photoelectrocatalysis, as these can drive various valuable catalytic redox transformations under very mild conditions. However, many catalytic processes lead to various different products of different value, and the technological attractiveness of catalytic processes depends to a large extent on their selectivity towards a specific desired product. In this Viewpoint, I propose and explore the idea that, due to the distinct features of interfacial energetics at illuminated semiconductors, light‐driven photoelectrocatalytic processes at well‐designed semiconductors represent a particularly attractive platform for the development of highly efficient systems for selective catalytic conversions. The investigations of selectivity and synthetic aspects of photoelectrocatalysis should gain momentum, especially as they also promise commercially viable applications on a more immediate time scale as compared to, for example, the light‐driven production of hydrogen.     

Dynamics of flow near a separation point

Dynamical behavior of a boundary layer separation is studied using the experimental approach. The dynamical nature of the phenomenon is demonstrated on a simple case of a flat–plate boundary layer in adverse pressure gradient. The Time–Resolved PIV technique was utilized for monitoring instantaneous structure of the separation region and its time development. Distinctive coherent structures and their dynamical behavior were identified using the Proper Orthogonal Decomposition method. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Control of a boundary layer separation

The results of experimental study on a boundary layer separation control are given in the paper. The boundary layer on a flat wall is subjected to adverse pressure gradient. The active control strategy evolving a synthetic jet has been applied. The separation process is investigated using TR-PIV method. Dynamical aspects of the phenomenon are analyzed in details. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural analogues of quinoline alkaloids: Straightforward route to [1,3]dioxolo[4,5-c]quinolines with antibacterial properties

Compounds bearing [1,3]dioxolo-quinoline scaffolds have been found in quinoline-based natural products; the only exception is the [1,3]dioxolo[4,5-c]quinoline moiety with a rare occurrence in both natural and synthetic derivatives. In this article, we report the preparation of diversely substituted and functionalized [1,3]dioxolo[4,5-c]quinolines using [1,3]dioxolo[4,5-c]quinoline-4-carbaldehyde (DQC) as the common intermediate. DQC was synthesized on a large scale from anthranilic acid and chloroacetone as the starting materials, with the rearrangement of acetonyl-anthranilate as the key step. The developed method allows for the simple preparation of [1,3]dioxolo[4,5-c]quinolines with various C2 substituents on the quinoline scaffold. Additionally, the synthetic route was successfully applied to the preparation of 3-hydroxyquinoline-4(1H)-ones. The target compounds were tested against representative Gram-positive/negative bacteria, and two derivatives exhibited submicromolar minimum inhibitory concentrations against Micrococcus luteus.     

Influence of substituents on selectivity and efficiency of chiral separations of anions containing single nido-7,8-dicarbaundecaborane cluster with alpha-cyclodextrin

In background electrolyte (BGE) with the optimal methanol concentration of 30% (v/v), the ion with -NCS group bonded to a cluster boron atom exhibits the strongest interaction with alpha-cyclodextrin and the highest separation selectivity. Interaction of ions with alkyl or thioalkyl group weakens with the increasing substituent size. The ion with phenyl group exhibits the weakest interaction. Bonding of a group to boron atom weakens the ion interaction with alpha-cyclodextrin. Second substituent further weakens the interaction with alpha-cyclodextrin. Separation efficiency is lower at the presence of alpha-cyclodextrin than at its absence. This separation efficiency loss, amounts up to 90%.