Carbon-13 magnetic resonance spectra of quaternary ammonium salts derived from enamino ketones

¹³C magnetic resonance spectra of nine quaternary ammonium salts of the general formula R¹C¹(O)C²H?C³HNR₃⁴Cl (where R¹, R⁴ = alkyl) were obtained and compared with those of the parent amino compounds. The chemical shift differences between these two classes of compounds are qualitatively accounted for by π-electron density changes. Steric effects and hyperconjugation of the alkyl substituents are also discussed.     

Negative emotions boost user activity at BBC forum

We present an empirical study of user activity in online BBC discussion forums, measured by the number of posts written by individual debaters and the average sentiment of these posts. Nearly 2.5 million posts from over 18 thousand users were investigated. Scale-free distributions were observed for activity in individual discussion threads as well as for overall activity. The number of unique users in a thread normalized by the thread length decays with thread length, suggesting that thread life is sustained by mutual discussions rather than by independent comments. Automatic sentiment analysis shows that most posts contain negative emotions and the most active users in individual threads express predominantly negative sentiments. It follows that the average emotion of longer threads is more negative and that threads can be sustained by negative comments. An agent-based computer simulation model has been used to reproduce several essential characteristics of the analyzed system. The model stresses the role of discussions between users, especially emotionally laden quarrels between supporters of opposite opinions, and represents many observed statistics of the forum.     

A mean-value theorem and its applications

For a function f defined in an interval I, satisfying the conditions ensuring the existence and uniqueness of the Lagrange mean L[f], we prove that there exists a unique two variable mean M[f] such that

     

Synthesis and optoelectronic properties of hexahydroxylated 10-O-R-substituted anthracenes via a new modification of the Friedel-Crafts reaction using O-protected ortho-acetal diarylmethanols

A new modification of the Friedel-Crafts type intramolecular cyclization involving O-protected ortho-acetal diarylmethanols as a new type of reactant, was carried out for the first time in a medium containing a large amount of water at room temperature and enabled synthesis of a series of electron-rich, hexahydroxylated 10-O-R-substituted anthracenes, where R is an alkyl (Me, nBu, n-C(16)H(33)) or arylalkyl group (CH(2)Ph, CH(2)-2-Napht, CH(2)C(6)H(4)CH(2)OAr) and also evaluation of their electronic and optoelectronic properties in solution, crystal, and solid thin film. In this transformation, a central 10-O-R-substituted benzene ring was formed, fused to rings originating from two independent aromatic aldehydes. The reaction proceeded via two identified mechanisms involving acetal and/or free aldehyde groups. The acid sensitive acetal and dibenzyl alkoxy functions have never been used together in the intramolecular Friedel-Crafts type cyclization. The new compounds revealed deep blue fluorescence and quantum yields in solution around 0.3. The electrical properties investigated for thin films obtained by vacuum deposition on glass were 10-O-R-substituent dependent and showed much faster transient current decay in the case of the 10-O-CH(2)Ph derivative than for the material with a 10-O-Me substituent (the lifetime of charge carriers was 25 times shorter in this case). The AFM images of thin films, Stokes shifts, and X-ray analysis of π-stacking interactions in crystals of the new materials have been also obtained.     

Core-modified hexaphyrin: synthesis and characterization of 31,34-disilahexaphyrinoid

Condensation of 16-silatripyrrane with pentafluorobenzaldehyde under catalytic conditions followed by DDQ oxidation leads to 31,34-disilahexaphyrinoid--a four times reduced derivative of 31,34-disilahexaphyrin which contains two built-in silole units flanked by four tetrahedrally hybridized meso carbons. In the preferred folded macrocyclic conformation the silole rings remain perpendicular to each other. The steric hindrance of bulky substituents at silicon atoms and β-positions of siloles prevented aromatization. Only one meso diastereomer (5S, 15S, 20R, 30R) has been isolated and subsequently identified by 1D and 2D NMR techniques. The density functional theory (DFT) has been applied to model the molecular structure of 31,34-disilahexaphyrinoid consistent with constraints imposed by NOE experiments. The total energies calculated at the B3LYP/6-31G**//B3LYP/6-31G** level for four feasible meso diastereomers clearly demonstrated the energetic preference for the meso diastereomer (5S, 15S, 20R, 30R).     

Density outbursts in a food web model with a closed nutrient cycle

A spatial three level food web model with a closed nutrient cycle is presented and analyzed via Monte Carlo simulations. The food web consists of three trophic levels. The basal level species (called resources  , R$R$) corresponds to primary producers in real ecosystems. The species at an intermediate level (consumers  , C$C$) relates to herbivores. It feeds on the resources. The consumers themselves constitute food for the top level species (predators  , P$P$), which corresponds to carnivores. The remains of the consumers and predators (detritus  , D$D$) provide nutrient for the resources. The time evolution of the model reveals two asymptotic states: an absorbing one with all species being extinct, and a coexisting one, in which concentrations of all species are non-zero. There are two possible ways for the system to reach the absorbing state. In some cases the densities increase very quickly at the beginning of a simulation and then decline slowly and almost monotonically. In others, well pronounced peaks in the R$R$, C$C$ and D$D$ densities appear regularly before the extinction. Those peaks correspond to density outbursts (waves) traveling through the system. We investigate the mechanisms leading to the waves. In particular, we show that the percolation of the detritus (i.e. the accumulation of nutrients) is necessary for the emergence of the waves. Moreover, our results corroborate the hypothesis that top-level predators play an essential role in maintaining the stability of a food web (top-down control).     

Simplified kinetic calibration of solid-phase microextraction for in vivo pharmacokinetics

Solid-phase microextraction (SPME) has been demonstrated to be useful for in vivo sampling in pharmacokinetic studies. In this study, a single time-point kinetic calibration for in vivo dynamic monitoring was developed by simplification of the laborious multiple time-point kinetic calibration, based on the independent desorption kinetics of the preloaded standards from SPME fibers with the changing analyte concentrations. The theoretical foundation and practical application conditions, such as the replicate numbers, the optimal time-point for desorption, and the sampling time, were systematically investigated. Furthermore, the feasibility of using regular standards rather than deuterated ones for the kinetic calibration was justified by comparing to the data obtained using the deuterated standards. All the methods were verified by in vitro and in vivo experiments. The results from in vivo SPME were validated by the blood drawing and chemical assay. These simplified calibration methods improved the quantitative applications of SPME for dynamic monitoring and in vivo sampling, enhance the multiplexing capability and automatic potentials for high throughput analysis, and decrease expenses on reagents and instruments.     

Optical characterization of bubbly flows with a near-critical-angle scattering technique

The newly developed critical angle refractometry and sizing technique (CARS) allows simultaneous and instantaneous characterization of the local size distribution and the relative refractive index (i.e. composition) of a cloud of bubbles. The paper presents the recent improvement of this technique by comparison of different light scattering models and inversion procedures. Experimental results carried in various air/water and air/water-ethanol bubbly flows clearly demonstrate the efficiency and the potential of this technique.