Structure and Dynamic Rearrangements of the Pt2dba3 and Pd2dba3 Complexes in Solution.

Although the tris(dibenzylideneacetone)diplatinum complex (Pt2dba3) is an important source of Pt(0) used in catalysis and materials science, its structure has not yet been fully elucidated. A thorough study of the three-dimensional structure of Pt2dba3 and its dynamic behavior in solution was carried out using NMR spectroscopy methods at a high field (600 MHz) and molecular modeling. The complex was shown to contain three dba ligands in the s-cis,s-trans, s-trans,s-cis, and s-trans,s-trans conformations, which are uniformly oriented around the Pt2 backbone. In solution, the Pt2dba3 and Pd2dba3 complexes undergo rapid dynamic rearrangements, as evidenced by the exchange between the signals of the olefin protons of various dba ligands in the EXSY NMR spectra. According to the experimental measurements, the activation energies of the rearrangements were estimated to be 19.9 ± 0.2 and 17.9 ± 0.2 kcal/mol for the platinum and palladium complexes, respectively. Three possible mechanisms for this chemical exchange process were considered within the framework of DFT calculations. According to the calculated data, M2dba3 complexes undergo fluxional isomerization involving successive rotations of the dihedral angles formed by the carbonyl group and the C═C bond. Dissociation of dba ligands does not occur within these processes.

"3-in-1" Hybrid Biocatalysts: Association of Yeast Cells Immobilized in a Sol-Gel Matrix for Determining Sewage Pollution.

This study presents a novel ″3-in-1″ hybrid biocatalyst design that combines the individual efficiency of microorganisms while avoiding negative interactions between them. Yeast cells of Ogataea polymorpha VKM Y-2559, Blastobotrys adeninivorans VKM Y-2677, and Debaryomyces hansenii VKM Y-2482 were immobilized in an organosilicon material by using the sol-gel method, resulting in a hybrid biocatalyst. The catalytic activity of the immobilized microorganism mixture was evaluated by employing it as the bioreceptor element of a biosensor. Optical and scanning electron microscopies were used to examine the morphology of the biohybrid material. Elemental distribution analysis confirmed the encapsulation of yeast cells in a matrix composed of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) (85 and 15 vol %, respectively). The resulting heterogeneous biocatalyst exhibited excellent performance in determining the biochemical oxygen demand (BOD) index in real surface water samples, with a sensitivity coefficient of 50 ± 3 × 10-3·min-1, a concentration range of 0.3-31 mg/L, long-term stability for 25 days, and a relative standard deviation of 3.8%. These findings demonstrate the potential of the developed hybrid biocatalyst for effective pollution monitoring and wastewater treatment applications.

Laser-Ablative Synthesis of Silicon-Iron Composite Nanoparticles for Theranostic Applications.

The combination of photothermal and magnetic functionalities in one biocompatible nanoformulation forms an attractive basis for developing multifunctional agents for biomedical theranostics. Here, we report the fabrication of silicon-iron (Si-Fe) composite nanoparticles (NPs) for theranostic applications by using a method of femtosecond laser ablation in acetone from a mixed target combining silicon and iron. The NPs were then transferred to water for subsequent biological use. From structural analyses, it was shown that the formed Si-Fe NPs have a spherical shape and sizes ranging from 5 to 150 nm, with the presence of two characteristic maxima around 20 nm and 90 nm in the size distribution. They are mostly composed of silicon with the presence of a significant iron silicide content and iron oxide inclusions. Our studies also show that the NPs exhibit magnetic properties due to the presence of iron ions in their composition, which makes the formation of contrast in magnetic resonance imaging (MRI) possible, as it is verified by magnetic resonance relaxometry at the proton resonance frequency. In addition, the Si-Fe NPs are characterized by strong optical absorption in the window of relative transparency of bio-tissue (650-950 nm). Benefiting from such absorption, the Si-Fe NPs provide strong photoheating in their aqueous suspensions under continuous wave laser excitation at 808 nm. The NP-induced photoheating is described by a photothermal conversion efficiency of 33-42%, which is approximately 3.0-3.3 times larger than that for pure laser-synthesized Si NPs, and it is explained by the presence of iron silicide in the NP composition. Combining the strong photothermal effect and MRI functionality, the synthesized Si-Fe NPs promise a major advancement of modalities for cancer theranostics, including MRI-guided photothermal therapy and surgery.

Synthesis and low-order optical nonlinearities of colloidal HgSe quantum dots in the visible and near infrared ranges.

We synthesize colloidal HgSe quantum dots and characterize their nonlinear refraction and nonlinear absorption using a Nd:YAG laser and its second harmonic. The 7.5 nm quantum dots were synthesized using the hot-injection method. The nonlinear absorption (ß = 9×10-7 cm W-1) and negative nonlinear refraction (γ = -5×10-12 cm2 W-1) coefficients of colloidal quantum dots were determined using the 10 ns, 532 nm laser radiation. The joint influence of above processes was realized at a higher intensity of probe pulses. In the case of 10 ns, 1064 nm radiation, only negative nonlinear refraction dominated during z-scans of these quantum dots. The studies of optical limiting using two laser sources demonstrated the effectiveness of this process at 532 nm. The role of nonlinear scattering is analyzed. We discuss the mechanisms responsible for the nonlinear refraction processes in colloidal HgSe quantum dots.

Diamidophosphites from ß-hydroxyamides: readily assembled ligands for Pd-catalyzed asymmetric allylic substitution.

Two groups of modular chiral diamidophosphite ligands were easily synthesised from accessible N-Boc-amino alcohols and pseudodipeptides. The reaction of these compounds with [Pd(allyl)Cl]2 in the presence of AgBF4 yielded complexes [Pd(allyl)(L)2]BF4. In addition, metallochelates [Pd(allyl)(L)]BF4 with (S)-methioninol-based P,S-bidentate ligands were prepared. The structures of the novel ligands and complexes were elucidated by means of 2D-NMR and were confirmed by single-crystal X-ray diffraction, as well as by DFT calculations. Asymmetric inducers of this type exhibited high enantioselectivities in the Pd-mediated allylic substitution of (E)-1,3-diphenylallyl ethyl carbonate with CH2(CO2Me)2 (up to 98% ee) and (CH2)4NH (up to 92% ee). Ee values of up to 86% and 73% were obtained in the Pd-catalyzed allylic alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate and ethyl 2-oxocyclopentane-1-carboxylate, respectively. The effects of the structural modules, such as the nature of the phosphorus-containing ring or exocyclic substituent, on the catalytic activity and enantioselectivity were investigated.

Stilbene derivative as a photosensitive compound to control the excitability of neonatal rat cardiomyocytes.

Substances that can be used as photosensitizers for cardiac tissue are very helpful in modeling various excitation patterns in a cardiac tissue culture and may have prospective use in the temporary and permanent ablation of unwanted excitation sources in the heart.The aim of the present work is to study the effect of stilbene derivative c-TAB (2- {4- [(E) -2- (4-ethoxyphenyl) vinyl] phenoxy} ethyl) trimethylammonium bromide) on the cardiomyocyte layers and voltage-gated ion channels in cardiac cells. C-TAB is a structural analog to AzoTAB, reported previously as a photoswitch for cardiac and neural cells, in which the azobenzene moiety is replaced by a stilbene grouping. Such a replacement makes c-TAB less toxic to living cells. c-TAB has been shown to successfully inhibit excitation in cardiac cells in both trans- and cis- forms. The excitation inhibition of cardiac cells under c-TAB is reversible and can be overturned easily by washing out the c-TAB; however, not by light illumination. The irradiation of cardiac cells with near-UV, when the trans- form of c-TAB is applied, changes reversible inhibition to a permanent one that cannot be overturned by a washout.