Correlation of singlet-triplet gaps for aryl carbenes calculated by MINDO/3, MNDO,AM1, and PM3 with Hammett-type substituent constants

Heats of formation, atomic charges, and geometries of some 110 structures involving substituted singlet and triplet phenyl and 4,4-dimethyl-1,4-dihydronaphthalene carbenes and the corresponding diazomethanes were calculated by MINDO/3, MNDO, AM1, and PM3 semiempirical molecular orbital methods. The singlet-triplet gaps for AM1 and PM3 calculations for the para derivatives in both systems have been successfully correlated with Brown σ⁺ constants. Good correlations with σ⁺ were found for the charges on the carbenic centers of the singlets as well as with the energy barrier for rotation of the aryl group about the C-C single bond in substituted singlet phenylcarbenes. Comparisons of these results with experimental data indicate that AM1 and PM3 are much better than MNDO and MINDO/3 in predicting the intrinsic substituent effects in singlet carbenes.     

In vitro antibiofilm activity of the freshwater bryozoan Hyalinella punctata: a case study of Pseudomonas aeruginosa PAO1

The antibiofilm and possible antiquorum sensing effects against the strain Pseudomonas aeruginosa PAO1 of five crude extracts of the freshwater bryozoan Hyalinella punctata (Hancock, 1850) were evaluated in vitro for the first time. H. punctata ethyl acetate extract (HpEtAc) exhibited the highest antibiofilm activity reducing the biofilm formation of P. aeruginosa PAO1 in the range of 80.63–88.13%. While all tested extracts reduced the twitching motility of the aforementioned bacterial strain, HpEtAc showed to be the most effective. Finally, at a concentration of 0.5 MIC, the same extract mostly inhibited the production of pyocyanin by P. aeruginosa PAO1 (71.53%). In comparison both with the positive controls used (streptomycin and ampicillin, 67.13 and 69.77%, respectively), HpEtAc was found to inhibit pyocyanin in a higher extent. An extensive chemical characterisation of this particular extract may result in isolation and identification of novel lead compounds targeting P. aeruginosa, an opportunistic human pathogen.     

Proton shuffling in acid/base‐catalyzed enolizations: a computational study

Enolization of acetaldehyde catalyzed by the combined action of a general base (ammonia) and a general acid (formic acid) was examined by density functional theory at the B3LYP/6‐311 + G(3df,2p) level while manipulating distance relationships among the reactants. Computations were carried out in the gas phase, in the presence of four water molecules, and with a dielectric constant of 78.4. Enolization involves an early transition state where general‐base catalysis is more developed than general‐acid catalysis. Although formic acid does not promote enolization by itself, it does facilitate α‐proton transfer from acetaldehyde to the general base by several orders of magnitude. Formic acid accomplishes this feat via a hydrogen bond at a van der Waals distance to the carbonyl oxygen as opposed to forming a low‐barrier hydrogen bond. A low‐barrier hydrogen bond would indeed be capable of accelerating the enolization were it not for the energy cost of generating it. Formic acid may also facilitate enolization by internal solvation of the ammonium ion that is partially formed in the transition state via carbon‐to‐nitrogen proton transfer. General‐base catalysis by trimethylamine, which is out of position to coordinate with the formic acid carboxyl, actually has lower activation energy than that of ammonia catalysis, possibly owing to basicity/shielding effects. Computations also demonstrate that the proton removed by the ammonia nitrogen remains on the nitrogen throughout rather than being transferred via low‐energy rotation processes and secondary proton transfers to an oxygen atom of formic acid or the enol itself. Finally, stepwise and concerted mechanisms for enolizations have been proposed in the literature, with experimental evidence being provided for both. The concerted/non‐concerted disagreement seems to stem from the continuum of organic mechanisms that Nature bestows onto organic chemistry. Thus, acid/base catalysis varies from stepwise at one extreme to synchronous at the other extreme with an infinite number of concerted mechanisms in between. Since the degree of concertedness undoubtedly depends upon the particular acid, base, substrate, and solvent, disparate enolization models are to be expected. Copyright © 2012 John Wiley & Sons, Ltd.     

Consolidation of blended powders by severe plastic deformation to form amorphous metal matrix composites

Warm equal channel angular extrusion (ECAE) in 90° tooling is used to consolidate Vitreloy 106a plus tungsten powders. A fully dense amorphous matrix composite showing good infiltration of the amorphous phase in between crystalline particles and uniform consolidation is achieved after one ECAE extrusion in the supercooled liquid temperature region of the amorphous phase. The results demonstrate that ECAE appears to be a viable processing method for producing bulk metallic glass matrix-crystalline particle composites.     

Synthesis of Terpenoid-Like Bischalcones from α- and β-Ionones and Their Biological Activities

Ionone-based terpenoid-like bischalcones (3a–h and 4a–h) were synthesized from the reaction of α- and/or β-ionones with aldehyde derivatives in excellent yields. The antibacterial activities of synthesized compounds were screened against human pathogenic micro-organisms by employing the disk-diffusion technique.     

Properties of an organosilicon nanophase generated in a poly(amide imide) matrix by the sol‐gel technique

Poly(amide imide) (PAI) nanocomposites prepared by the in situ generation of crosslinked organosilicon nanophase (ON) through the sol‐gel process were characterized by wide‐angle and small‐angle X‐ray diffraction, thermogravimetric analysis, dynamic mechanical analysis and kinetics of water uptake. It was concluded that the polymer nanocomposite (PNC) were likely to possess a complex morphology on the nanoscale characterized by co‐existence of two mixed nanophases of different compositions. At low methyl triethoxysilane (MTS) contents the fractal‐like organization of paracrystalline nano‐domains of PAI chain fragments is destroyed by the randomly distributed ON particles, whereas on the increase of MTS content the spatial correlations between ON particles become stronger, giving rise to their own fractal‐like structure. The higher values of small‐angle X‐ray scattering (SAXS) invariant, apparent water diffusivity and limiting water uptake for the PNC compared to the pristine PAI were assumed to reflect the loose inner structures of PAI‐rich and ON‐rich nanophases, respectively. Copyright © 2005 John Wiley & Sons, Ltd.     

Boundedness of Sublinear Operators and Commutators on Generalized Morrey Spaces

In this paper the authors study the boundedness for a large class of sublinear operators \({T_{\alpha}, \alpha \in [0,n)}\) generated by Calderón–Zygmund operators (α = 0) and generated by Riesz potential operator (α > 0) on generalized Morrey spaces \({M_{p,\varphi}}\) . As an application of the above result, the boundeness of the commutator of sublinear operators \({T_{b,\alpha}, \alpha \in [0,n)}\) on generalized Morrey spaces is also obtained. In the case \({b \in BMO}\) and T _b,α is a sublinear operator, we find the sufficient conditions on the pair \({(\varphi_1,\varphi_2)}\) which ensures the boundedness of the operators \({T_{b,\alpha}, \alpha \in [0,n)}\) from one generalized Morrey space \({M_{p,\varphi_1}}\) to another \({M_{q,\varphi_2}}\) with 1/p ? 1/q = α/n. In all the cases the conditions for the boundedness are given in terms of Zygmund-type integral inequalities on \({(\varphi_1,\varphi_2)}\) , which do not assume any assumption on monotonicity of \({\varphi_1, \, \varphi_2}\) in r. Conditions of these theorems are satisfied by many important operators in analysis, in particular, Littlewood–Paley operator, Marcinkiewicz operator and Bochner–Riesz operator.     

Forward and reverse bias current-voltage characteristics of Au/n-Si Schottky barrier diodes with and without SnO2 insulator layer

The effects of interfacial insulator layer, interface states (N_ss) and series resistance (R_s) on the electrical characteristics of Au/n-Si structures have been investigated using forward and reverse bias current-voltage (I-V) characteristics at room temperature. Therefore, Au/n-Si Schottky barrier diodes (SBDs) were fabricated as SBDs with and without insulator SnO₂ layer to explain the effect of insulator layer on main electrical parameters. The values of ideality factor (n), R_s and barrier height (Φ_Bo) were calculated from ln(I) vs. V plots and Cheung methods. The energy density distribution profile of the interface states was obtained from the forward bias I-V data by taking bias dependence of ideality factor, effective barrier height (Φ_e) and R_s into account for MS and MIS SBDs. It was found that N_ss values increase from at about mid-gap energy of Si to bottom of conductance band edge of both SBDs and the MIS SBD’s N_ss values are 5-10 times lower than those of MS SBD’s. An apparent exponential increase from the mid-gap towards the bottom of conductance band is observed for both SBDs’ (MS and MIS) interface states obtained without taking R_s into account.