Effect of post-annealing in air on optical and XPS spectra of Y2O3 ceramics doped with CeO2

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Expanding excitation wavelengths for azobenzene photoswitching into the near-infrared range via endothermic triplet energy transfer

Developing azobenzene photoswitches capable of selective and efficient photoisomerization by long-wavelength excitation is an enduring challenge. Herein, rapid isomerization from the Z- to E-state of two ortho-functionalized bistable azobenzenes with near-unity photoconversion efficiency was driven by triplet energy transfer upon red and near-infrared (up to 770 nm) excitation of porphyrin photosensitizers in catalytic micromolar concentrations. We show that the process of triplet-sensitized isomerization is efficient even when the sensitizer triplet energy is substantially lower (>200 meV) than that of the azobenzene used. This makes the approach applicable for a wide variety of sensitizer-azobenzene combinations and enables the expansion of excitation wavelengths into the near-infrared spectral range. Therefore, indirect excitation via endothermic triplet energy transfer provides efficient and precise means for photoswitching upon 770 nm near-infared light illumination with no chemical modification of the azobenzene chromophore, a desirable feature in photocontrollable biomaterials.

Triplet energy transfer enables efficient Z-to-E photoswitching of azobenzenes even with near-infrared light. Ultrafast intersystem crossing of azobenzene makes the process entropy-driven and enables the use of endothermic sensitizer-azobenzene pairs.     

Role of solvent for globular proteins in solution

The properties of the solvent affect the behavior of the solution. We propose a model that accounts for the contribution of the solvent free energy to the free energy of globular proteins in solution. For the case of an attractive square-well potential, we obtain an exact mapping of the phase diagram of this model without solvent to the model that includes the solute-solvent contribution. In particular we find for appropriate choices of parameters upper critical points, lower critical points, and even closed loops with both upper and lower critical points similar to those found before [Macromolecules 36, 5843 (2003)]. In the general case of systems whose interactions are not attractive square wells, this mapping procedure can be a first approximation to understand the phase diagram in the presence of solvent. We also present simulation results for both the square-well model and a modified Lennard-Jones model.     

3-(4-Tolylazo)phenylboronic acid as the active component of polyhydroxy compounds-selective electrodes

Ionophoric, extraction, acidic and hydrophobic properties of 3-(4-tolylazo)phenylboronic acid (TAPBA) were studied. Determined K_d value equals to 36±2, pK_a equals to 8.6±0.5. TAPBA extracts dobutamine from water into chloroform and transports it across a bulk chloroform membrane. The recovery is 83% (pH=7.5), the transport rate – (6.5±0.5)×10⁻⁷ mol/h. ¹H and ¹³C NMR data confirm the formation of an 1:1 complex between arylboronic acid and catecholamine. TAPBA was used as electrode-active component of plasticized membrane electrodes with cationic and anionic responses to catecholamines and phenolic acids, respectively. For the diethyl sebacate-plasticized membrane, a slope of electrode function to dobutamine is 56±2 mV/decade; the detection limit is 1.3×10⁻⁵ mol/l; the linear range – 5×10⁻⁵–1×10⁻² mol/l; the working pH-range – 4.8–7.6; the response time – 5–10 s. ISE gives incomplete cationic function to less lipophilic catecholamines. The membrane with cationic additive shows an anionic response to caffeic acid in wide pH range.     

Sol–Gel Processed Functional Nanosized TiO2 and SiO2-Based Films for Photocatalysts and Other Applications

Titania and silica-based porous coatings have been produced via sol–gel route in the presence of pore-creating agents PEG and viscous solvent -terpineol, or template agents CTAB, as well as triblock copolimer Pluronic P123. Porous titania films were characterised by HR TEM, UV-Vis, XRD, ellipsometry, ARS methods. The dispersion of the refractive index, the porosity (32–39%) and the thickness of the samples were estimated by integrating sphere transmission and reflection spectra with 3D angular resolved light scattering. The catalytic activity of mesoporous TiO₂ and TiO₂/ZrO₂ as well as SiO₂-benzophenone films in the process of Cr^VI to Cr^III and Ag⁺ to Ag⁰ photoreduction have been studied.     

Single- and double-linkage isomerism in a six-coordinate iron porphyrin containing nitrosyl and nitro ligands

Density Functional theoretical calculations confirm the experimental observation that the low-temperature photolysis of (TPP)Fe(NO)(NO2) (as a KBr pellet) results in the generation of linkage isomers involving the axial NO and NO2 groups and suggest the possible formation of the double linkage isomer (TPP)Fe(ON)(ONO). The energy difference between the ground state (porphine)Fe(NO)(NO2) and the double-linkage isomer (porphine)Fe(ON)(ONO) is 1.57 eV, which is comparable to the 1.59 eV calculated previously for the nitrosyl-to-isonitrosyl linkage isomerism in the five-coordinate (porphine)Fe(NO) analogue.     

The first N-alkyl-N′-polyfluorohetaryl sulfur diimide

The first AlkNSNHet_F sulfur diimide 6 (Alk=adamant-1-yl, Het_F=2,3,5,6-tetrafluoropyrid-4-yl) was prepared by trapping of the corresponding alkylthiazylamide [AlkNSN]⁻3 with pentafluoropyridine, followed by X-ray structural characterization. For 6, the Z,E configuration was found. From the reaction of 3 with octafluoronaphthalene, hexafluorinated naphthothiadiazole 7 was isolated along with the parent AlkNH₂.     

Delocalizations in sigma-radical cations: the intriguing structures of ionized [n]rotanes

Highly symmetric aliphatic hydrocarbons such as D(4h)-[4]rotane do not necessarily have degenerate HOMOs. According to our predictions based on high-level computations, its radical cation should display a highly delocalized D(4h)-symmetric structure, in contrast to its Jahn-Teller distorted cousin, the radical cation of [3]rotane, which exists in two distonic localized forms with C(2v) and C(s) symmetry.     

Magnetic nanocomposites based on cyclodextrin-containing molecular tubes and iron nanoparticles

Stabilization of metallic nanoparticles may be achieved by the formation of their adducts with polymers and/or nanotubes of various chemical composition. Here, water-soluble nanotubes based on β-cyclodextrin (β-tubes) were used for entrapping of Fe nanoparticles obtained by the reduction of iron-containing precursors ([Fe₃(CO)₁₁H][Et₄N] cluster and FeSO₄). Using methods of light-scattering, viscometry, and isothermal diffusion measurements, it was shown that the adducts are associated in aqueous solutions. The presence of iron nanoparticles and the shape and size of adducts were verified by transmission electron microscopy. The adducts are long (up to 600 nm and longer), translucent associates consisting of denser walls and transparent cores. The width of nanotubes is ∼150 nm and the thickness of the wall 3–25 nm. Their magnetic properties were demonstrated by electron paramagnetic resonance method. The mechanism of self-assembly of the adducts is discussed.