Heterogeneous Wide Range <Emphasis Type="Italic">pH</Emphasis>-sensing Materials Allowing Ratiometric Fluorescence Detection Based on Structurally Rigid Analogs of 2,6-distyrylpyridine

The new sensing materials based on the microsized silica gel powder with non-covalently immobilized structurally rigid analogs of 2,6-distyrylpyrydine ((3E,5E)-3,5-dibenzylidene-8-phenyl-1,2,3,5,6,7-hexahydrodicyclopenta[b,e]pyridines) were developed and tested. Most of the investigated compositions demonstrate linear ratiometric fluorescence response on pH in the physiologically important interval (pH 6–9). The compound with the greatest number of protolytic centers within the studied series demonstrated the widest pH sensitivity range, however in this case the analytical signal was the lowest. The prospects for the practical application of the investigated materials in the fiber optics sensing devices were outlined.     

Heterometallic M/Mn (M=Cu, Co, Zn) acetate complexes as precursors for binary oxides

A facile one-pot procedure, or so-called “direct synthesis,” was used to prepare the novel heterometallic complexes [M₂Mn(OAc)₆(bpy)₂], where M=Cu (1), Co (2), Zn (3), bpy=2,2′-bipyridyl, with high yields via oxidative dissolution of pure metals in a liquid phase. The complexes were characterized by an elemental analysis, single crystal X-ray diffraction method and FTIR. These complexes are proposed as precursors, whose thermal degradation may lead to the formation of solids possessing nano- to microsize levels of dispersity. The thermal behavior of the complexes obtained was studied by thermal analysis (TG/DTA/DTG) in both air and N₂ and also by TPD mass-spectrometry in vacuo. The FTIR, X-ray powder diffraction (PXRD) and thermoanalytical data were used for the identification of the solid products of thermal degradation. The morphology and microstructure of the solid residues were analyzed, using scanning electron microscopy with energy dispersive X-ray microanalysis (SEM/EDX) at mkm and sub-micro levels.     

Postsynthesis transformation of three-dimensional framework into a lamellar zeolite with modifiable architecture

Mild treatment of zeolite UTL results in degradation of its structure with preservation of the initially present dense layers connected by D4R "bridges". The lamellar product obtained through this 3D to 2D zeolite conversion has been structurally modified similar to methodologies applied to layered zeolite precursors, which show the opposite 2D to 3D zeolite transformation.     

Strong solutions and trajectory attractors to the thin-film equation with absorption

We prove local and global in time existence of non-negative weak solutions to the thin-film equation with absorption and obtain sufficient conditions for extra regularity of these solutions. Moreover, for the class of global strong solutions, we show existence of a trajectory attractor.     

Comparative solubilisation of potassium carbonate, sodium bicarbonate and sodium carbonate in hot dimethylformamide: application of cylindrical particle surface-controlled dissolution theory

A surface-controlled dissolution of cylindrical solid particles model is applied to potassium carbonate, sodium bicarbonate and sodium carbonate in dimethylformamide at elevated temperatures. Previously published data for the dissolution of potassium carbonate is interpreted assuming a cylindrical rather than a spherical shape of the particles, the former representing a closer approximation to the true shape of the particles as revealed by scanning electron microscopy. The dissolution kinetics of sodium carbonate and sodium bicarbonate in dimethylformamide at 100 degrees C were investigated via monitoring of the deprotonation of 2-cyanophenol with dissolved solid to form the 2-cyanophenolate anion that was detected with UV-visible spectroscopy. From fitting of experimental results to theory, the dissolution rate constant, k, for the dissolutions of potassium carbonate, sodium bicarbonate and sodium carbonate in dimethylformamide at 100 degrees C were found to have the values of (1.0 +/- 0.1) x 10(-7) mol cm(-2) s(-1), (5.5 +/- 0.3) x 10(-9) mol cm(-2) s(-1) and (9.7 +/- 0.8) x 10(-9) mol cm(-2) s(-1), respectively.     

Anomalous photon-assisted tunneling in graphene

We investigated the transmission of Dirac electrons through a potential barrier in the presence of circularly polarized light. An anomalous photon-assisted enhanced transmission is predicted and explained. It is demonstrated that the perfect transmission for nearly head-on collision in infinite graphene is suppressed in gapped dressed states of electrons, which is further accompanied by a shift of peaks as a function of the incident angle away from head-on collision. In addition, the perfect transmission is partially suppressed by a photon-induced gap in illuminated graphene. After the effect of rough edges of the potential barrier or impurity scattering is included, the perfect transmission with no potential barrier becomes completely suppressed and the energy range for the photon-assisted transmission is reduced at the same time.     

Passive nonlinear reshaping towards parabolic pulses in the steady-state regime in optical fibers

The passive nonlinear reshaping in normally dispersive optical fibers in the steady-state regime is studied numerically. It is found that normal dispersion and self-phase modulation are able to provide pulse reshaping towards a parabolic pulse profile at the distances exceeding the optical wave breaking length. However, as compared to the similariton formation in active fibers the resulted pulse shape in passive fibers is strongly depended on the initial pulse parameters and nonlinear and dispersive fiber properties as well. The influence of initial pulse shape, initial chirp, third-order dispersion and loss on the parabolic pulse formation is studied consistently, and estimation of practical conditions which are needed for parabolic pulses formation in a passive fiber is provided.     

Enantioselective hydrogenations with chiral titanocenes

In this review article chiral titanocenes and their application for the enantioselective hydrogenations of different unsaturated compounds are discussed, with a special emphasis on the kinetics and the practicality of the developed systems. The nature of enantioselectivity and the hydrogenation mechanisms are reviewed as well. Catalyst immobilization and the different immobilization techniques are examined.     

Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate

Plasmon assistance promotes a range of chemical transformations by decreasing their activation energies. In a common case, thermal and plasmon assistance work synergistically: higher temperature results in higher plasmon-enhanced catalysis efficiency. Herein, we report an unexpected tenfold increase in the reaction efficiency of surface plasmon-assisted Huisgen dipolar azide–alkyne cycloaddition (AAC) when the reaction mixture is cooled from room temperature to −35 °C. We attribute the observed increase in the reaction efficiency to complete plasmon-induced annihilation of the reaction barrier, prolongation of plasmon lifetime, and decreased relaxation of plasmon-excited-states under cooling. Furthermore, control quenching experiments supported by theoretical calculations indicate that plasmon-mediated substrate excitation to an electronic triplet state may play the key role in plasmon-assisted chemical transformation. Last but not least, we demonstrated the possible applicability of plasmon assistance to biological systems by AAC coupling of biotin to gold nanoparticles performed at −35 °C.

The decrease of reaction temperature can potentially lead to an increase of plasmon-assisted catalytic efficiency.