A structural study of new tetrakis(1H-pyrazol-1-yl)methanes

Tetrakis(1H-pyrazol-1-yl)methanes are very rare compounds of which only two are known: the unsubstituted 1 obtained classically by Hückel in 1937 from carbon tetrachloride and prepared again several times and the 3,5-dimethyl substituted 2 obtained serendipitously by Pombeiro in 2009. We have now extended this group to include four new derivatives 8, 9, 11 and 12 bearing methyl groups. The X-ray crystal structure of the four compounds has been determined. They have been studied by NMR both in solution (¹H, ¹³C, ¹⁵N) and in the solid state (¹³C and ¹⁵N). DFT calculations of the six compounds (geometries, energies and absolute shieldings) have been used to discuss the experimental observations.     

Neobavaisoflavone May Modulate the Activity of Topoisomerase Inhibitors towards U-87 MG Cells: An In Vitro Study

Despite many advances in therapy, glioblastoma (GB) is still characterized by its poor prognosis. The main reason for this is unsuccessful treatment, which slightly extends the duration of remission; thus, new regimens are needed. One of many types of chemotherapeutics that are being investigated in this field is topoisomerase inhibitors, mainly in combination therapy with other drugs. On the other hand, the search for new anti-cancer substances continues. Neobavaisoflavone (NBIF) is a natural compound isolated from Psoralea corylifolia L., which possesses anti-oxidant, anti-inflammatory, and anti-cancer properties. The aim of this study was to evaluate the effect of NBIF in human U-87 MG glioblastoma cells in comparison to normal human NHA astrocytes, and to examine if it influences the activity of irinotecan, etoposide, and doxorubicin in this in vitro model. We demonstrated that NBIF decreases U-87 MG cells viability in a dose-dependent manner. Furthermore, we found that it inhibits cell growth and causes glutathione (GSH) depletion more intensely in U-87 MG cells than in astrocytes. This study also provides, for the first time, evidence of the potentialization of the doxorubicin effect by NBIF, which was shown by the reduction in the viability in U-87 MG cells.     

Aggregation and micellization of sodium dodecyl sulfate in the presence of Ce(III) at different temperatures: a conductometric study

Aggregation properties of sodium dodecyl sulfate (SDS) in the presence of cerium(III) chloride, at various temperatures (298.15-323.15 K) have been measured by the electrical conductance technique. The experimental data on aqueous solutions as a function of SDS concentration show the presence of two inflexion points indicating the presence of two distinct interaction mechanisms: the first, occurring at SDS concentrations below the critical micelle concentration of the pure surfactant, which can be explained by the formation of aggregates between dodecyl sulfate (DS-) and Ce(III), while the second one, at SDS concentrations around the critical micelle concentration (cmc) of the pure surfactant which is due to the SDS micellization. The aggregation between DS- and Ce(III) was confirmed by static light scattering. The binding ratio of DS-/Ce(III) changes from 6 to 4, shows a slight dependence on the Ce(III) concentration and is independent of the temperature. The thermodynamic micellization parameters, Gibbs energy, enthalpy and entropy of micellization were calculated on the basis of the experimental data for the aggregation concentration, and the degree of counterion dissociation of the micelles. The SDS micellization is energetically favoured by increasing either the concentration of CeCl3 or the temperature. Such behaviour is clearly dominated by a decrease of the micellization (exothermic) enthalpy. The entropy of micellization approaches zero as the cerium(III) chloride concentration and temperature increase.     

Composition operators on Hardy spaces on Lavrentiev domains

For any simply connected domain , we prove that a Littlewood type inequality is necessary for boundedness of composition operators on , , whenever the symbols are finitely-valent. Moreover, the corresponding ``little-oh' condition is also necessary for the compactness. Nevertheless, it is shown that such an inequality is not sufficient for characterizing bounded composition operators even induced by univalent symbols. Furthermore, such inequality is no longer necessary if we drop the extra assumption on the symbol of being finitely-valent. In particular, this solves a question posed by Shapiro and Smith (2003). Finally, we show a striking link between the geometry of the underlying domain and the symbol inducing the composition operator in , and in this sense, we relate both facts characterizing bounded and compact composition operators whenever is a Lavrentiev domain.

     

On-Surface Synthesis and Real-Space Visualization of Aromatic P3N3

On-surface synthesis is at the verge of emerging as the method of choice for the generation and visualization of unstable or unconventional molecules, which could not be obtained via traditional synthetic methods. A case in point is the on-surface synthesis of the structurally elusive cyclotriphosphazene (P₃N₃), an inorganic aromatic analogue of benzene. Here, we report the preparation of this fleetingly existing species on Cu(111) and Au(111) surfaces at 5.2 K through molecular manipulation with unprecedented precision, i.e., voltage pulse-induced sextuple dechlorination of an ultra-small (about 6 Å) hexachlorophosphazene P₃N₃Cl₆ precursor by the tip of a scanning probe microscope. Real-space atomic-level imaging of cyclotriphosphazene reveals its planar D_3h-symmetric ring structure. Furthermore, this demasking strategy has been expanded to generate cyclotriphosphazene from a hexaazide precursor P₃N₂₁ via a different stimulation method (photolysis) for complementary measurements by matrix isolation infrared and ultraviolet spectroscopy.     

An electrochemical study into the interaction between complement-derived peptides and DOPC mono- and bilayers

Electrochemical methods employing the hanging mercury drop electrode were used to study the interaction between variants of the complement-derived antimicrobial peptide CNY21 (CNYITELRRQH ARASHLGLAR) and dioleoyl phosphatidylcholine (DOPC) monolayers. Capacitance potential and impedance measurements showed that the CNY21 analogues investigated interact with DOPC monolayers coating the mercury drop. Increasing the peptide hydrophobicity by substituting the two histidine residues with leucine resulted in a deeper peptide penetration into the hydrophobic region of the DOPC monolayer, indicated by an increase in the dielectric constant of the lipid monolayer (Deltaepsilon = 2.0 after 15 min interaction). Increasing the peptide net charge from +3 to +5 by replacing the histidines by lysines, on the other hand, arrests the peptide in the lipid head group region. Reduction of electroactive ions (Tl+, Pb2+, Cd2+, and Eu3+) at the monolayer-coated electrode was employed to further characterize the types of defects induced by the peptides. All peptides studied permeabilize the monolayer to Tl+ to an appreciable extent, but this effect is more pronounced for the more hydrophobic peptide (CNY21L), which also allows penetration of larger ions and ions of higher valency. The results for the various ions indicate that charge repulsion rather than ion size is the determining factor for cation penetration through peptide-induced defects in the DOPC monolayer. The effects obtained for monolayers were compared to results obtained with bilayers from liposome leakage and circular dichroism studies for unilamellar DOPC vesicles, and in situ ellipsometry for supported DOPC bilayers. Trends in peptide-induced liposome leakage were similar to peptide effects on electrochemical impedance and permeability of electroactive ions for the monolayer system, demonstrating that formation of transmembrane pores alone does not constitute the mechanism of action for the peptides investigated. Instead, our results point to the importance of local packing defects in the lipid membrane in close proximity to the adsorbed peptide molecules.     

Perchlorination of Coronene Enhances its Propensity for Self‐Assembly on Graphene

Providing a quantitative understanding of the thermodynamics involved in molecular adsorption and self‐assembly at a nanostructured carbon material is of fundamental importance and finds outstanding applications in the graphene era. Here, we study the effect of edge perchlorination of coronene, which is a prototypical polyaromatic hydrocarbon, on the binding affinity for the basal planes of graphite. First, by comparing the desorption barrier of hydrogenated versus perchlorinated coronene measured by temperature‐programmed desorption, we quantify the enhancement of the strength of physisorption at the single‐molecule level though chlorine substitution. Then, by a thermodynamic analysis of the corresponding monolayers based on force‐field calculations and statistical mechanics, we show that perchlorination decreases the free energy of self‐assembly, not only enthalpically (by enhancing the strength of surface binding), but also entropically (by decreasing the surface concentration). The functional advantage of a chemically modulated 2D self‐assembly is demonstrated in the context of the molecule‐assisted liquid‐phase exfoliation of graphite into graphene.     

Investigation studies involving sound absorbing parameters of roadside screen panels subjected to aging in simulated conditions

The paper presents the results of investigation studies involving the impact of atmospheric factors on sound-absorbing parameters of roadside acoustic screen panels. The research studies comprised the aging test consisting of 1000 cycles in simulated conditions, sound absorption measurements and surface morphology tests, using the SEM scanning method. The simulation of aging consisted of 100 or 150 cycles at a time. Then, the panels were investigated in the reverberation chamber to define their sound-absorbing properties. The process was repeated until 1000 cycles were completed. Basing on the carried out tests, a statistical linear model was worked out which was used to estimate the value of a single number sound absorption coefficient after successive aging cycles. The optimality of the model was demonstrated by means of a statistical test confirming normal distribution of random residuals. For the research studies, we employed an innovative structural design of panels for which aging characteristics were obtained. Basing on the obtained results and on the statistical analysis, the prospects to maintain acoustic properties of the panels during their service life was estimated.