Study of radon exhalation from the soil

The influence of meteorological parameters on radon exhalation rate was analyzed. The analyses show a significant influence of precipitation on radon exhalation rate. The highest exhalation rate was found during dry periods and the lowest during the periods of strong precipitation. We also tested two different types of detectors for the measurement of radon exhalation rate—the ionization chamber (AlphaGUARD) and the scintillation chamber of Lucas type. The exhalation rates measured by these detectors were in a good agreement. Likewise, there was an agreement in radon exhalation rates determined from short term and long term increases in radon activity concentration.     

Spectral features of substituted 9-(phenoxycarbonyl)-acridines and their protonated and methylated cation derivatives

The long-wavelength absorption of eight 9-(phenoxycarbonyl)-acridines and the 10-H-9-(phenoxycarbonyl)-acridinium and 10-methyl-9-(phenoxycarbonyl)-acridinium cations derived from them, substituted with an alkyl or trifluoroalkyl group at the benzene ring, occurs above 300 nm as the superposition of four bands. Three of these bands occupy comparable positions (expressed in nm) in all the compounds; the fourth one, however, changes position, appearing in neutral molecules as a long-wavelength shoulder below 400 nm, but in cations as an almost separate band above 400 nm. The weak fluorescence resulting from excitation within the long-wavelength absorption band is red-shifted relative to absorption, such that Stokes shifts are similar for both neutral molecules and cations. Stokes shifts tend to increase with the orientational polarisability of a medium. Computations predict that long-wavelength electronic transitions are accompanied by structural changes in molecules. They also indicate that such transitions are followed by roughly uniform electron density changes in whole molecules accompanied by small changes in their dipole moments, which accounts for the weak absorption in the long-wavelength region. The predicted radiative and non-radiative deactivation rate constants suggest the occurrence of efficient spin-orbital coupling in the molecules investigated, which is the cause of the relatively low fluorescence quantum yields. Apart from the cognitive significance of these investigations, the results demonstrate that absorption of radiation by 10-methyl-9-(phenoxycarbonyl)-acridinium cations above 400 nm may influence their chemiluminescence output.     

Wet and Dry Forms of Bacterial Cellulose Synthetized by Different Strains of <Emphasis Type="Italic">Gluconacetobacter xylinus</Emphasis> as Carriers for Yeast Immobilization

The present study aimed to explore and describe the properties of bacterial cellulose (BC) membranes obtained from three different strains of Gluconacetobacter xylinus for 72, 120, and 168 h, used as a carrier support for the immobilization of Saccharomyces cerevisiae. The experiments also included the analysis of glucose consumption and alcohol production during the fermentation process displayed by yeasts immobilized on the BC surface. The results of the present study demonstrate that the number of immobilized yeast cells is dependent on the type of cellulose-synthesizing strain, cellulose form, and duration of its synthesis. The BC in the form of wet membranes obtained after 3 days of synthesis displayed the most favorable properties as a carrier for yeast immobilization. The immobilization of yeast cells on BC, regardless of its form, increased the amount of the produced alcohol as compared to free cells. The yeast cells immobilized in BC were able to multiply on its surface during the fermentation process.     

Tandem Catalysis Utilizing Olefin Metathesis Reactions

Since olefin metathesis transformation has become a favored synthetic tool in organic synthesis, more and more distinct non‐metathetical reactions of alkylidene ruthenium complexes have been developed. Depending on the conditions applied, the same olefin metathesis catalysts can efficiently promote isomerization reactions, hydrogenation of C=C double bonds, oxidation reactions, and many others. Importantly, these transformations can be carried out in tandem with olefin metathesis reactions. Through addition of one portion of a catalyst, a tandem process provides structurally advanced products from relatively simple substrates without the need for isolation of the intermediates. These aspects not only make tandem catalysis very attractive from a practical point of view, but also open new avenues in (retro)synthetic planning. However, in the literature, the term “tandem process” is sometimes used improperly to describe other types of multi‐reaction sequences. In this Concept, a number of examples of tandem catalysis involving olefin metathesis are discussed with an emphasis on their synthetic value.     

Sustainable concepts in olefin metathesis

Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon-carbon double bonds. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions. Nevertheless, with the exception of uses in polymerization reactions, only a limited number of industrial processes use olefin metathesis. This is mainly due to difficulties associated with removing ruthenium from the final products. In this context, a number of studies have been carried out to develop procedures for the removal of the catalyst or the products of catalyst decomposition, however, none are universally attractive so far. This situation has resulted in tremendous activity in the area dealing with supported or tagged versions of homogeneous catalysts. This Review summarizes the numerous studies focused on developing cleaner ruthenium-catalyzed metathesis processes.     

Enhancement of the SPR Effect in an Optical Fiber Device Utilizing a Thin Ag Layer and a 3092A Liquid Crystal Mixture

This paper is a continuation of previous work and shows the enhancement of the surface plasmon resonance effect in a tapered optical fiber device. The study investigated liquid crystal cells containing a tapered optical fiber covered with a silver nanolayer, surrounded by a low refractive index liquid crystal in terms of the properties of light propagation in the taper structure. Silver films with a thickness of d = 10 nm were deposited on the tapered waist area. Measurements were performed at room temperature; liquid crystal steering voltage U from 0 to 200 V, with and without any amplitude modulation with a frequency of f = 5 Hz, and the wavelength λ ranged from 550 to 1200 nm. A significant influence of the initial arrangement of liquid crystals molecules on light propagation was observed. Three types of liquid crystal cells—orthogonal, parallel, and twist—were considered. During the measurements, resonant peaks were obtained—the position of which can also be controlled by the type of liquid crystal cells and the steering voltage. Based on the obtained results, the best parameters, such as highest peak’s width reduction, and the highest SNR value were received for twisted cells. In addition, the present work was compared with the previous work and showed the possibility of improving properties of the manufactured probes, and consequently, the surface plasmon resonance effect. In the presented paper, the novelty is mainly focused on the used materials as well as suitable changes in applied technological parameters. In contrast to gold, silver is characterized by different optic and dielectric properties, e.g., refractive index, extension coefficient, and permittivity, which results in changes in the light propagation and the SPR wavelengths.     

Characterization of tri-o-methylcellulose by one- and two-dimensional NMR methods

Tri-O-methylcellulose was prepared from partially O-methylated cellulose and its chemical shifts (¹H and ¹³C), and proton coupling constants were assigned using the following NMR methods: (1) One-dimensional ¹H and ¹³C spectra of the title compound were used to assign functional groups and to compare with literature data; (2) double quantum filtered proton–proton correlation spectroscopy (¹H, ¹H DQF-COSY) was used to assign the chemical shifts of the network of 7 protons in the anhydroglucose portion of the repeat unit; (3) the heteronuclear single-quantum coherence (HSQC) spectrum was used to establish connectivities between the bonded protons and carbons; (4) the heteronuclear multiple-bond correlation (HMBC) spectrum was used to connect the hydrogens of the methyl ethers to their respective sugar carbons; (5) the combination of HSQC and HMBC spectra was used to assign the ¹³C shifts of the methyl ethers; (6) all spectra were used in combination to verify the assigned chemical shifts; (7) first-order proton coupling constants data (J_H,H in Hz) were obtained from the resolution-enhanced proton spectra. The NMR spectra of tri-O-methylcellulose and other cellulose ethers do not resemble the spectra of similarly substituted cellobioses. Although the ¹H and ¹³C shifts and coupling constants of 2,3,6-tri-O-methylcellulose closely resemble those of methyl tetra-O-methyl-β-D -glucoside, there are differences with regard to the chemical shifts and the order of appearances of the resonating nuclei of the methyl ether appendages and the proton at position 4 in the pyranose ring. H4 in tri-O-methylcellulose is deshielded by the acetal system comprising the β-1→4 linkage, and it resonates downfield. H4 in the permethylated glucoside is not as deshielded by the equitorial O-methyl group at C4, and it resonates upfield. The order of appearance of the ¹H and ¹³C resonances in the spectra of the tri-O-methylcellulose repeat unit (from upfield to downfield) are H2 < H3 < H5 < H6a < H3a < H2a < pro R H6B < H4 < pro S H6A ≪ H1 and C6a < C3a < C2a < C6 < C5 < C4 < C2 < C3 ≪ C1, respectively. Close examination of the pyranose ring coupling constants of the repeat unit in tri-O-methylcellulose supports the ⁴C₁ arrangement of the glucopyranose ring. Examination of the proton coupling constants about the C5-C6 bond (J_5,6A and J_5,6B) in the nuclear Overhauser effect difference spectra revealed that the C6 O-methyl group is predominantly in the gauche gauche conformation about the C5-C6 bond for the polymer in solution. © 1999 John Wiley & Sons, Inc.* J Polym Sci A: Polym Chem 37: 4019–4032, 1999     

Random quantum operations

We define a natural ensemble of trace preserving, completely positive quantum maps and present algorithms to generate them at random. Spectral properties of the superoperator Φ associated with a given quantum map are investigated and a quantum analogue of the Frobenius-Perron theorem is proved. We derive a general formula for the density of eigenvalues of Φ and show the connection with the Ginibre ensemble of real non-symmetric random matrices. Numerical investigations of the spectral gap imply that a generic state of the system iterated several times by a fixed generic map converges exponentially to an invariant state.     

9‐(2,6‐Dichloro­phen­oxycarbonyl)‐10‐methyl­acridinium trifluoro­methane­sulfonate and its precursor 2,6‐dichloro­phenyl acridine‐9‐carboxyl­ate

The title compounds, C₂₁H₁₄Cl₂NO₂⁺·CF₃O₃S⁻, (I), and C₂₀H₁₁Cl₂NO₂, (II), form triclinic crystals. Adjacent cations of (I) are oriented either parallel or antiparallel; in the latter case, they are related by a centre of symmetry. Together with the CF₃SO₃⁻ anions, the antiparallel‐oriented cations of (I) form layers in which the mol­ecules are linked via a network of C—H·O and π–π inter­actions (between the benzene rings). These layers, in turn, are linked via a network of multidirectional π–π inter­actions between the acridine rings, and the whole lattice is stabilized by electrostatic inter­actions between ions. Adjacent mol­ecules of (II) are oriented either parallel or antiparallel; in the latter case, they are related by a centre of symmetry. Parallel‐oriented mol­ecules are arranged in chains stabilized via C—H·Cl inter­actions. These chains are oriented either parallel or antiparallel and are stabilized, in the latter case, via multidirectional π–π inter­actions and more generally via dispersive inter­actions. Acridine and independent benzene moieties lie parallel in the lattices of (I) and (II), and are mutually oriented at an angle of 33.4 (2)° in (I) and 9.3 (2)° in (II).     

Aqueous olefin metathesis

According to popular belief, oxygen and water are the natural enemies of organometallic reactions and therefore must be excluded rigorously from the reaction vessel. This belief is founded in the case of the highly reactive nucleophilic metal alkylidene complexes that were used in early catalytic olefin metathesis. However, owing to the high stability of the ruthenium carbene complexes introduced by Grubbs, metathesis in water has become reality.