An Easy Synthesis of Monofluorinated Derivatives of Pyrroles from β-Fluoro-β-Nitrostyrenes

The catalyst-free conjugate addition of pyrroles to β-Fluoro-β-nitrostyrenes was investigated. The reaction was found to proceed under solvent-free conditions to form 2-(2-Fluoro-2-nitro-1-arylethyl)-1H-pyrroles. The effectiveness of this approach was demonstrated through the preparation of a series of the target products in a quantitative yield. The kinetics of a conjugate addition of pyrrole was studied in detail to reveal the substituent effect and activation parameters of the reaction. The subsequent base-induced elimination of nitrous acid afforded a series of novel 2-(2-Fluoro-1-arylvinyl)-1H-pyrroles prepared in up to an 85% isolated yield. The two-step sequence herein proposed is an indispensable alternative to a direct reaction with elusive and unstable 1-Fluoroacetylenes.     

Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure,Electrochemical Properties,and Antiradical Activity

A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh₃, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph₃SbBr₂ in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1–3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the “catechol/o-semiquinone” redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical.     

Design and Synthesis of New 5-aryl-4-Arylethynyl-1H-1,2,3-triazoles with Valuable Photophysical and Biological Properties

Cu-catalyzed 1,3-dipolar cycloaddition of methyl 2-azidoacetate to iodobuta-1,3-diynes and subsequent Suzuki-Miyaura cross-coupling were used to synthesize new triazoles derivatives: 5-aryl-4-arylethynyl-1H-1,2,3-triazoles. Investigation of their optical properties by using UV absorption and fluorescence emission spectroscopies revealed that all molecules possess fluorescence properties with the values of the Stokes shift more than 100 nm. The photophysical behavior of the two most promising triazoles in polar and non-polar solvents was also studied.     

Topological transition in coated wire medium

Employing nonlocal homogenization approach, we investigate the properties of a metamaterial consisting of parallel metallic wires with dielectric coating. We demonstrate that manipulation of dielectric contrast between wire dielectric shell and host material at fixed frequency results in dynamic switching of metamaterial dispersion regime from elliptic to the hyperbolic one, i.e. the topological transition takes place. It is proved that such transition can be induced by the variation of the metamaterial temperature. Our findings thus pave a way to the implementation of a tunable ‘elliptic‐hyperbolic’ metamaterial.     

Nonlinear spectral-spatial control and localization of supercontinuum radiation

We present the first observation of spatiospectral control and localization of supercontinuum light through the nonlinear interaction of spectral components in extended periodic structures. We use an array of optical waveguides in a LiNbO3 crystal and employ the interplay between diffraction and nonlinearity to dynamically control the output spectrum of the supercontinuum radiation. This effect presents an efficient scheme for optically tunable spectral filtering of supercontinua.     

4T split TEM volume head and knee coils for improved sensitivity and patient accessibility

Split RF coils offer improved patient access by eliminating the need for the coil to be slid over the region of interest. For unshielded birdcage coils, the presence of end ring currents necessitates a direct electrical connection between two halves of the coil. For high-field (>3T) shielded birdcage coils, both the shield and the coil must be split and reliably connected electrically. This problem can be circumvented by the use of split TEM volume coils. Since the elements of a TEM coil are coupled inductively, no direct electrical connection between the halves is necessary. In this work we demonstrate that the effects of splitting the shield for head and knee TEMs can be compensated for, and performance retained. For the knee, the improved access allowed the coil diameter to be reduced, enhancing the sensitivity by 15-20%.     

Highly dispersive large mode area photonic bandgap fiber

An all-silica photonic bandgap fiber composed of a low-index core surrounded by alternating high- and low-index rings allows us to achieve a large mode area (500 microm(2)) and large chromatic dispersion. Sharp resonances from the even Bragg mode to odd ring modes theoretically lead to 20,000 ps/(nm km) chromatic dispersion when large bends are applied. By nature, sharp resonances are sensitive to inhomogeneities along the fiber length. Under experimental conditions, the resonances are broadened and the dispersion coefficient is decreased to 1000 ps/(nm km). However, to the best of our knowledge, this is the largest dispersion coefficient reported using a large mode area fiber.     

Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes

Tunable electron-accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π-conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π-extended molecules functionalized with P-cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation-anion interactions, which can drastically change physical behavior of these two-component systems.     

A Molecular Photosensitizer in a Porous Block Copolymer Matrix-Implications for the Design of Photocatalytically Active Membranes

Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.