Tandem intramolecular Michael-aldol reaction as a tool for the construction of the C-ring of hexacyclinic acid

[reaction: see text] The tandem intramolecular Michael-aldol reaction was studied as a tool for the construction of the C-ring of hexacyclinic acid. By changing the reaction conditions it was possible to selectively obtain either the kinetic or the thermodynamic product. Retro-aldol reaction and subsequent epimerization provides four individual cyclopentane derivatives that can be incorporated as building blocks in natural product syntheses.     

Characteristic Attributes of Multiple Cascaded Terahertz Metasurfaces with Magnetically Tunable Subwavelength Resonators

The characteristics of multiple cascaded metasurfaces comprising H‐shaped, magnetostatically controllable, subwavelength terahertz (THz) resonators made of InAs were systematically investigated, using a commercial solver based on the finite‐integration method, for the design of tunable filters. Three configurations of the biasing magnetostatic field were compared with each other as well as with the bias‐free configuration for filtering of normally incident linearly polarized plane waves. A close study of only one metasurface was found sufficient to broadly determine the sensitivity to the direction of the magnetostatic field and the bandwidth of a stopband. Furthermore, the effects of metasurface geometry and biasing field can be considered separately for initial design purposes. All features in the transmittance spectra for the bias‐free configuration that are related to the number of cascaded metasurfaces are also observed when the biasing magnetostatic field is applied. The coupling of adjacent metasurfaces in a cascade is strongly affected by the relative permittivity and the thickness of the spacer between the two metasurfaces. The spectral locations of stopbands scale with respect to the spacer's relative permittivity, the scaling rule being different from a classical one. The stopbands are redshifted when the spacer thickness is increased, with the redshift dependent on the polarization of the incident plane wave. Inter‐metasurface coupling and inter‐resonator coupling on the same metasurface affect the spectral location of a stopband in opposite ways. On‐off type switching can be obtained by changing the orientation of magnetostatic field. The elucidated characteristics are expected to be important for not only filters but also other tunable THz devices.     

Negative rejection of ions in pressure-driven membrane processes

Negative rejections of ions in pressure-driven membrane processes can be caused by several distinct mechanisms. In a number of cases, in a final count, the phenomenon is brought about by increased concentration of an ion in the membrane phase. In the case of charged membranes, the increased concentration has to be accompanied by a weakening of electric field of filtration potential, which normally retards counter-ions and prevents the increased concentrations from manifesting themselves in negative rejections. This occurs in charge-mosaic membranes due to the so-called current circulation phenomenon or in electrolyte mixtures due to the presence of more mobile counter-ions. Negative rejections can also occur for ions whose concentration is decreased in the membrane phase. This occurs in electrolyte mixtures due to the acceleration of such ions by the electric field of diffusion potential arising because of strong rejections of other mixture components. This phenomenon is most pronounced for single-charge ions in the presence of predominant amounts of ions of higher charge of the same sign. All those mechanisms are considered within the scope of a common theoretical framework. An attempt is made of a tentative classification of mechanisms of negative rejections. An overview of available literature data is provided and it is shown that in a number of cases the published information is not sufficiently detailed for a reliable identification of the mechanisms. It is concluded that the studies of negative rejections could be a valuable membrane characterization tool but they need to be more systematic and targeted to fulfil this role.     

Fingerprint identification of volatile organic compounds in gasoline contaminated groundwater using gas chromatography differential ion mobility spectrometry

Groundwater can be contaminated when e.g. gasoline tanks leak. Due to sampling and lab analysis, groundwater monitoring is time consuming and expensive. The technologies developed for rapid on-site analysis of gasoline contaminated groundwater face the technical limitation to distinguish the gasoline from complex matrices. In the present study the fingerprint identification of volatile organic components (VOCs) in gasoline contaminated groundwater using gas chromatography (GC) differential ion mobility spectrometry (DMS) is investigated. Groundwater was spiked with five sorts of gasoline (one reformulated gasoline, gasoline without additives and three different brand gasoline collected on petrol stations) and analyzed by GC-DMS. Seven VOCs (benzene, toluene, ethyl benzene, m-xylene, p-xylene, o-xylene, 1,2,4-trimethylbenzene) were identified by GC mass spectrometry (GC-MS) as well as by GC-DMS and selected as markers. The semi-quantitative determination of the selected compounds was achieved. The limits of detection of the GC-DMS are 46.42?ng for benzene, 1.13?ng for toluene, 1.80?ng for ethylbenzene, 0.22?ng for m-xylene, 1.13?ng for p-xylene, 0.61?ng for o-xylene and 0.37?ng for 1,2,4-trimethylbenzene, respectively. These results reveal the feasibility of GC-DMS for on-site monitoring of contaminated groundwater.     

Photochemistry of HI on argon and water nanoparticles: hydronium radical generation in HI·(H2O)n

Photochemistry of HI molecules on large Ar(n) and (H(2)O)(n), n ～ 100-500, clusters was investigated after excitation with 243 nm and 193 nm laser radiation. The measured H-fragment kinetic energy distributions pointed to a completely different photodissociation mechanism of HI on water than on argon clusters. Distinct features corresponding to the fragment caging (slow fragments) and direct exit (fast fragments) were observed in the spectra from HI photodissociation on Ar(n) clusters. On the other hand, the fast fragments were entirely missing in the spectrum from HI·(H(2)O)(n) and the slow-fragment part of the spectrum had a different shape from HI·Ar(n). The HI·(H(2)O)(n) spectrum was interpreted in terms of the acidic dissociation of HI on (H(2)O)(n) in the ground state, and hydronium radical H(3)O formation following the UV excitation of the ionically dissociated species into states of a charge-transfer-to-solvent character. The H(3)O generation was proved by experiments with deuterated species DI and D(2)O. The experiment was complemented by ab initio calculations of structures and absorption spectra for small HI·(H(2)O)(n) clusters, n = 0-5, supporting the proposed model.     

Synthesis and evaluation of antitrypanosomal activity of some thiosemicarbazide derivatives of 1-butyl-6-fluoro-7-morpholino-4-oxo-1,4-dihydroquinoline-3-carboxylic acid

The synthesis of thiosemicarbazide of 1-butyl-6-fluoro-7-morpholino-4-oxo-1,4-dihydroquinoline-3-carboxylic acid as well as its heterocyclic derivatives – 1,3,4-thiadiazole and 1,2,4-triazole are described; the modification of proper 1,2,4-triazole derivative by maleimides is also presented. Spectral properties of the prepared compounds and X-ray analysis for the selected compounds were studied. For the compounds antitrypanosomal potential and the toxicity were determined.     

Thermoelectric energy conversion in layered structures with strained Ge quantum dots grown on Si surfaces

The efficiency of the energy conversion devices depends in many ways on the materials used and various emerging cost-effective nanomaterials have promised huge potentials in highly efficient energy conversion. Here we show that thermoelectric voltage can be enhanced by a factor of 3 using layer-cake growth of Ge quantum dots through thermal oxidation of SiGe layers stacked in SiO₂/Si₃N₄ multilayer structure. The key to achieving this behavior has been to strain the Ge/Si interface by Ge dots migrating to Si substrate. Calculations taking into account the carrier trapping in the dot with a quantum transmission into the neighboring dot show satisfactory agreement with experiments above ≈200 K. The results may be of interest for improving the functionality of thermoelectric devices based on Ge/Si.     

Two-color vector solitons in nonlocal media

We investigate the interaction between two beams differing in wavelength and the properties of dual-frequency spatial solitons in nonlocal birefringent reorientational media. We report the first experimental observations of anisotropic nonlocal vector solitons in unbiased nematic liquid crystals. Model and simulations, based on the paraxiality along the Poynting vectors, include joint walk-off and breathing.     

Anisotropic Nucleation,Growth and Ripening under Stirring—A Phenomenological Model

The anisotropic formation of elongated metal-oxide aggregates in water under intensive stirring is analyzed. It is treated in terms of anisotropic ballistically mediated aggregation kinetics in open systems. The basic kinetic equations describing the stages of homogeneous nucleation, independent growth, and ripening of the aggregates are formulated for the open system under the external influence with the stirring intensity as the main parameter governing the process. The most significant elongation of the aggregates is shown to evolve at the ripening stage.