Mössbauer and ESR study of the formation of phthalocyanineiron(II) pyridine adduct in the supercage of NaY,KY, and RbY zeolite

Phthalocyanineiron(II) (FePc) and phthalocyaninato[(2-)bispyridine]iron(II) (FePc(py)₂) synthesized in supercage of NaY, KY and RbY zeolite have been characterized by Mössbauer and ESR spectroscopy. The yield of formation of the pyridine adduct depends on the ionic radius of the alkali ions introduced into the supercage, but not on the number of iron ions trapped in the cages, suggesting that free space in the supercage was the most important factor for the formation of the FePc-py-adducts.     

Evasive Targets: Deciphering Polysemy in Mediated Humor

While polysemy has been discussed in communication studies for decades, a fundamental question has evaded systematic analysis: Which textual features make mediated texts open to multiple interpretations? Focusing on humor, we addressed this question by using a somewhat unusual point of departure–a failed intercoder reliability test. We analyzed 130 humorous forwards, of which 55 elicited disagreement between coders regarding the target of mockery and 75 were uncontroversial. Our comparative analysis yielded six textual attributes that augment polysemy in mediated humor: narrative‐valence discrepancies, unstereotypical stereotyping, debatable personality traits, self‐deprecating humor, intertextuality, and centrifugal multimodality. We demonstrate the utility of the proposed typology by analyzing public controversies stirred by humorous communication, and discuss its applicability to the study of audiences and nonhumorous genres.     

Compensation of steric demand by cation-pi interactions,cobaltocenium cations as guests in tetraurea calix[4]arene dimers

The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer. We found that the affinity of the cobaltocenium cation is higher than that of the tropylium cation (4+) and is only 2-3 times less than that of the tetraethylammoniun cation (5+). From the variable temperature 1H NMR spectra of this capsule, the free energy of activation at 298 K (deltaGdouble dagger(298K)) for the reorientation of the hydrogen bonded belt between the two parts of the dimer could be determined by total line shape analysis for the aromatic protons of the calixarene. The value of 14.3 +/- 0.2 kcal mol(-1) for the dimeric capsules of 3+ PF6- is very similar to the free activation energy found for dimeric capsules of 1 with 4+ PF6- and 5+ PF6- in C2D4Cl2. It becomes significantly lower, if PF6- is replaced by BF4-. We also found that ten times more DMSO is needed to disrupt the capsule 1 x 3+ x 1 than the corresponding 1 x 1 dimer containing benzene as guest. This demonstrates again the importance of the cation-pi interactions for the stability of such hydrogen-bonded dimeric capsules.     

Effect of copper and manganese ions on activities of laccase and peroxidases in three Pleurotus species grown on agricultural wastes

Copper (Cu²⁺) and manganese (Mn²⁺) ions influenced laccase (Lac) and peroxidase production in Pleurotus eryngii, Pleurotus ostreatus, and Pleurotus pulmonarius. In P. eryngii, the optimum Cu²⁺ concentration for Lac production was 1 mM and for peroxidases 10mM, and Mn²⁺ concentration of 5mM led to peaks of Lac and peroxidase activity. In P. ostreatus HAI 493, the highest level of Lac activity was at Cu²⁺ concentrations of 1 and 10 mM and Mn²⁺ concentration of 1mM, respectively. The absence of Cu²⁺ and Mn²⁺ caused the highest levels of peroxidase production. In P. ostreatus HAI 494, the highest level of Lac activity was at a Cu²⁺ concentration of 5 mM and at Mn²⁺ concentration of 1 mM, respectively. High levels of peroxidase activity were found in the medium without and with 1mM Cu²⁺, and at 1 and 5 mM Mn²⁺, respectively. In P. pulmonarius, the highest Lac activity was found in the presence of 5 mM Cu²⁺ and 5 mM Mn²⁺, respectively. The absence of Cu²⁺ and Mn²⁺ as well as their presence at a concentration of 1 mM led to the peaks of peroxidase activities.     

High-resolution plane-wave decomposition in an auditorium using a dual-radius scanning spherical microphone array

The spatial and temporal distribution of early reflections in an auditorium is considered important for sound perception. Previous studies presented measurement and analysis methods based on spherical microphone arrays and plane-wave decomposition that could provide information on the direction and time of arrival of early reflections. This paper presents recent results of room acoustics analysis based on a spherical microphone array, which employs high spherical harmonics order for improved spatial resolution, and a dual-radius spherical measurement array to avoid ill-conditioning at the null frequencies of the spherical Bessel function. Spatial-temporal analysis is performed to produce directional impulse responses, while analysis based on the windowed Fourier transform is employed to detect direction of arrival of individual reflections at selected frequencies. Experimental results of sound-field analysis in a real auditorium are also presented.     

A conversion electron Mössbauer study on the photolysis of europium/III/ oxalate

The¹⁵¹Eu Mössbauer spectra were measured of surface-oxidized europium/II/ sulfate with the γ-ray transmission- and conversion electron technique. The comparison of such spectra demonstrated that the change in the oxidation state of trace amounts of europium induced by surface reactions could be characterized by the conversion electron Mössbauer technique. The photochemical reduction of europium/III/ oxalate to a Eu/II/species after irradiation with a low-pressure mercury lamp was demonstrated by means of this technique as well as ESR.     

Mössbauer spectroscopic study of frozen solutions of57Co using a specially designed cryostat for time differential coincidence emission Mössbauer spectroscopy of237Np

Experiments on the⁵⁷Fe Mössbauer effect in frozen solutions were carried out in order to demonstrate the capabilities of a cryostat which was developed for the emission Mössbauer spectroscopy of²³⁷Np. We confirmed the existence of an aliovalent state of⁵⁷Fe in the temperature range from 5.5 to 35 K. However, the relative amounts of Fe(II) and Fe(III) in the frozen matrix were almost constant for the temperature range from 5.5 to 150 K. The design, operation and capabilities of the cryostat are also described.     

A Gel‐Based Model of Selective Cell Motility: Implications for Cell Sorting,Diagnostics, and Screening

The ability to precisely control cell‐loaded material systems is essential for in vitro testing of novel therapeutics poised to advance to clinic. In this report, unique patterns of cell migration are devised into an in vitro gel‐in‐gel model for the purpose of obtaining cell response data to potentially therapeutic chemical agonists. The model consists of co‐cultures in a cell‐loaded microgel invading an acellular “sorting” gel. Material properties including biophysical and chemical compositions of the sorting gel are carefully controlled to guide a desired cell‐specific behavior, leading to massive tumor cell invasion by amoeboid migration mechanisms. Optical transparency enables straightforward and high‐throughput measurements of outgrowth response in the presence of either chemical and photoradiation therapy. Important dosing and drug sensitivity information are obtained with the gel‐in‐gel model using no more than a light microscope, without further need for arduous genomic or proteomic screening of the tissue samples.     

Self-assembled ionophores from isoguanosine: diffusion NMR spectroscopy clarifies cation's and anion's influence on supramolecular structure

Cation-templated self-assembly of the lipophilic isoguanosine (isoG 1) with different monovalent cations (M(+)=Li(+), Na(+), K(+), NH(4) (+), and Cs(+)) was studied in solvents of different polarity by using diffusion NMR spectroscopy. Previous studies that did not use diffusion NMR techniques concluded that isoG 1 forms both pentamers (isoG 1)(5)M(+) and decamers (isoG 1)(10)M(+) in the presence of alkali-metal cations. The present diffusion NMR studies demonstrate, however, that isoG 1 does not form (isoG 1)(5)M(+) pentamers. In fact, the diffusion NMR data indicates that both doubly charged decamers of formula (isoG 1)(10)2 M(+) and singly charged decamers, (isoG 1)(10)M(+), are formed with lithium, sodium, potassium, and ammonium tetraphenylborate salts (LiB(Ph)(4), KB(Ph)(4), NaB(Ph)(4) and NH(4)B(Ph)(4)), depending on the isoG 1:salt stoichiometry of the solution. In the presence of CsB(Ph)(4), isoG 1 affords only the singly charged decamers (isoG 1)(10)Cs(+). By monitoring the diffusion coefficient of the B(Ph)(4) (-) ion in the different mixtures of solvents, we also concluded that the anion is more strongly associated to the doubly charged decamers (isoG 1)(10)2 M(+) than to the singly charged decamers (isoG 1)(10)M(+). The (isoG 1)(10)2 M(+) species can, however, exist in solution without the mediation of the anion. This last conclusion was supported by the finding that the doubly charged decamers (isoG 1)(10)2 M(+) also prevail in 1:1 CD(3)CN:CDCl(3), a solvent mixture in which the B(Ph)(4) (-) ion does not interact significantly with the self-assembled complex. These diffusion measurements, which have provided new and improved structural information about these decameric isoG 1 assemblies, demonstrate the utility of combining diffusion NMR techniques with conventional NMR methods in seeking to characterize labile, multicomponent, supramolecular systems in solution, especially those with high symmetry.