Electrochemical Synthesis of 3-(Sulfonyl)quinol-4-ones from -Alkynyl--(formyl)anilides and Sulfinates.

Electrolysis of -alkynyl--(formyl)anilides and sodium sulfinates on graphite electrodes delivers biologically sound 3-(sulfonyl)quinol-4-ones with moderate to good yields. The reaction is carried out in an undivided cell in the presence of silver(I) oxide with potassium iodide or sodium tetrafluoroborate as the supporting electrolyte. The reaction tolerates variously substituted anilides as well as aryl and alkyl sulfinates.

Total synthesis of the taraxacine A natural product Ag(I)-catalysed imidate-alkyne cyclization.

A domino approach towards β-carboline natural product taraxacine A and its analogues was developed. The main step relies on a silver(I) and base co-catalysed imidate-alkyne cyclization. The reaction tolerates primary and secondary alcohols, and various substitutions in the indole are possible.

Graphene Oxide/Zinc Phthalocyanine Selective Singlet Oxygen Visible-Light Nanosensor for Raman-Inactive Compounds.

A novel phthalocyanine-based hybrid nanofilm is for the first time successfully applied as an oxidative platform for surface enhanced Raman spectroscopy (SERS) sensing to fine-resolve Raman-inactive compounds. The hybrid is formed by self-assembly of zinc(II) 2,3,9,10,16,17,23,24-Octa[(3',5'-dicarboxy)-phenoxy]phthalocyaninate (ZnPc*) with the solid-supported monolayer of graphene oxide (GO) mediated by zinc acetate metal cluster. Atomic force microscopy, UV-vis and fluorescence spectroscopies confirm that this simple coordination motive in combination with molecular structure of ZnPc* prevents contact quenching of the light-excited triplet state through aromatic stacking with GO particles.

Cation-Cation Interaction in Np(V) Perchlorates and Their Electronic Absorption Spectra.

Four new Np(V) perchlorate complexes of the composition [NpO(HO)]ClO (orthorhombic) (), [(NpO)(ClO)(HO)]ClO·HO (), [(NpO)(UO)(HO)](ClO) (), and [(NpO)Cl(HO)]ClO·2HO () have been synthesized and structurally characterized. The structure of previously known monoclinic modification of NpOClO·4HO () has been determined at 100 K. The coordination environment of Np and U atoms in compounds - is pentagonal bipyramids.

Pivotal Role of the Intracellular Microenvironment in the High Photodynamic Activity of Cationic Phthalocyanines.

To investigate the influence of phthalocyanine aggregation on their photodynamic activity, a series of six cationic water-soluble zinc(II) phthalocyanines bearing from four to sixteen 4-((diethylmethylammonium)methyl)phenoxy substituents was synthesized. Depending on their structure, the phthalocyanines have different aggregation behaviors in phosphate buffer solutions ranging from fully assembled to monomeric states. Remarkably, independent of aggregation in buffer, very high photodynamic efficiencies against the tumor cell lines MCF-7 and MDA-MB-231 in the nanomolar range were found for all investigated phthalocyanine, and the IC(light) varied from 27 to 358 nM (3.

Coatings Based on Refractory Materials for Corrosion and Wear Applications.

Coatings based on refractory metals and compounds have been used in various industries since the last century due to their high thermal and heat resistance, as well as their excellent mechanical and tribological properties. Advances have made it possible to apply high-tech methods for their production, which has improved their availability and expanded their range of applications. A promising area of use of coatings based on refractory systems is the anticorrosion protection of structural materials.

Uncertainty Quantification and Flagging of Unreliable Predictions in Predicting Mass Spectrometry-Related Properties of Small Molecules Using Machine Learning.

Mass spectral identification (in particular, in metabolomics) can be refined by comparing the observed and predicted properties of molecules, such as chromatographic retention. Significant advancements have been made in predicting these values using machine learning and deep learning. Usually, model predictions do not contain any indication of the possible error (uncertainty) or only one criterion is used for this purpose.

Viral-Porphyrin Combo: Photodynamic and Oncolytic Viral Therapy for Potent Glioblastoma Treatment.

Combined viral and photodynamic therapy for oncological diseases has great potential to treat aggressive tumors such as glioblastomas. A conjugate of vesicular stomatitis virus (VSV) with protoporphyrin IX was prepared, and its oncolytic effects were studied and compared to the effects of the individual components. The VSV showed an oncolytic effect on glioblastoma cell lines T98G and LN229 at a virus titer of 10 TCID/mL.

Influence of Polymer Nature on Electroadhesion.

Electroadhesive systems are promising for creating delicate robotic manipulators operating both in the natural environment and in space conditions. Using thermosetting epoxy resin, polyurethane and polyester resin as examples, the influence of the polymers' natures, potential differences and current strengths on electroadhesive interactions in polymer-polymer systems was studied. The investigations were carried out by recording the force of normal separation of substrates from electroadhesives using contact and contactless methods at various electrical parameters of the systems and their components.

Visible Light Photoredox Catalysis in the Synthesis of Phosphonate-Substituted 1,10-Phenanthrolines.

Photoredox-catalyzed phosphonylation of bromo-substituted 1,10-phenanthrolines under visible light irradiation was studied. The reaction was shown to proceed under mild conditions with Eosin Y as a photocatalyst in DMSO under blue light irradiation. It is transition-metal-free and affords the target phosphonate-substituted 1,10-phenanthrolines in moderate yields (26-51%) in 22 to 40 h.

Systematic ab initio calculation of spectroscopic constants for A-reduced rotational effective Hamiltonians of asymmetric top molecules using normal ordering of cylindrical angular momentum operators.

This research paper presents a new fundamental approach for evaluating accurate ab initio quartic, sextic, and octic centrifugal distortion parameters of A-reduced rotational effective Hamiltonians of asymmetric top molecules. In this framework, the original Watson Hamiltonian, expanded up to sextic terms of kinetic and potential energies, is subjected to a series of vibrational and rotational operator unitary transformations, leading to reduced Watson effective Hamiltonians for the equilibrium configuration, ground state, and weakly perturbed vibrationally excited states. The proposed scheme is based on a numerical-analytic implementation of the sixth-order Van Vleck operator perturbation theory with the systematic normal ordering of vibrational rising and lowering operators (a†, a) and cylindrical angular momentum operators (Jz, J+, J-).

A remarkable match of optical response in the amorphous-crystalline and zinc blende-rock salt phase pairs of GeTe.

Despite a large amount of theoretical and experimental work performed so far, the search of phase change materials (PCMs) is done with use of numerical modeling. However, it is not fully clear how and why the phase change translates into the optical contrast. In this work, we argue that a key prerequisite for a material to have a pronounced difference in optical properties between crystalline and glassy phases of PCM is the similar contrast between the observed crystalline and (may be experimentally inaccessible) parent crystalline polymorph of the glassy phase.

Odd-Numbered Ring Cluster Tc(μ-O)Cl(OOCCCl): Synthesis, Crystal Structure, and Optical and Thermal Properties.

Herein, we report a method for the preparation of the first odd homometallic and heterovalent nine-centered Tc wheel, [Tc(μ-O)Cl(OOCCl)]. The synthesized compound represents the pioneering instance of such clusters among d elements and is the fourth instance observed across all metals. The ring was synthesized by a solvothermal method in a solution of technetium acid in trichloroacetic anhydride.

Experimental and Theoretical X-ray Absorption Near Edge Structure Study of UO Systems at the U L Edge.

Uranium forms a large number of oxides and its electronic state in them is of great fundamental interest. We employ X-ray absorption spectroscopy at the U L edge to differentiate between mixed oxide phases in uranium compounds. By combining experimental XANES spectra with theoretical modeling using the FEFF code, we analyze five uranium oxides: UO, UO, UO, UO, and UO.

The (CNH)[Cu(HO)]() Structural Family: When Fluoroberyllate, Sulfate, and Selenate Are Full Analogs.

Two new organo-inorganic hybrids, (CNH)[Cu(HO)](BeF) () and (CNH)[Cu(HO)](SeO) (), were prepared via the interaction of ethylenediamine, copper fluoroberyllate or selenate, and H[BeF]/HSeO in aqueous solutions. The structures of and are similar to each other and the previously reported (CNH)[Cu(HO)](SO): monoclinic, 2/, = 5.1044(2) Å, = 11.

Difference in the Catalytic Activity of Atoms in the Corners and at the Edges of Gold Nanoparticles: Hydrogen Isotope Exchange Reaction.

The goal of this work is to investigate the catalytic activities of low-coordination atoms located in gold nanoparticles. Gold nanoparticles with sizes from 0.7 to 40 nm deposited on γ-AlO were used as a catalyst.

Local Stress in Cylindrically Curved Lipid Membrane: Insights into Local Versus Global Lateral Fluidity Models.

Lipid membranes, which are fundamental to cellular function, undergo various mechanical deformations. Accurate modeling of these processes necessitates a thorough understanding of membrane elasticity. The lateral shear modulus, a critical parameter describing membrane resistance to lateral stresses, remains elusive due to the membrane's fluid nature.

Effect of Silver Nanoparticle Size on Antibacterial Activity.

The ubiquitous use of products containing AgNPs results in the entry of nanoparticles into the environment. Both nanoparticles and Ag released upon their oxidative dissolution have a toxic effect on living microorganisms. The antibacterial activity of spherical silver nanoparticles of 10.

Surface potentials of conductors in electrolyte solutions.

When we place conducting bodies in electrolyte solutions, their surface potential Φs appears to be much smaller in magnitude than the applied one Φ0 and normally does not obey the classical electrostatic boundary condition of a constant potential expected for conductors. In this paper, we demonstrate that an explanation of these observations can be obtained by postulating that diffuse ions condense at the "wall" due to the reduced permittivity of a solvent. For small values of Φ0, the surface potential responds linearly.

The Identity Algorithm: How the Most Popular Electron Ionization Mass Spectral Library Search Engine Actually Works.

The Identity algorithm implemented in the MS Search (NIST) software is widely used for library searches of gas chromatography/mass spectrometry data against electron ionization mass spectral databases. It has been available to researchers since 1993, with the release of MS Search 1.5a.

Proton irradiation Of GaO Schottky diodes and NiO/GaO heterojunctions.

p-NiO/n-GaO heterojunction (HJ) diodes exhibit much larger changes in their properties upon 1.1 MeV proton irradiation than Schottky diodes (SDs) prepared on the same material. In p-NiO/GaO HJ diodes, the narrow region adjacent to the HJ boundary is found to contain a high density of relatively deep centers with levels near E-0.

Pivotal role of Tc NMR spectroscopy in solid-state and molecular chemistry.

The radioelement Technetium (element 43) pertains to various domains including the nuclear enterprise (i.e., spent nuclear fuel (SNF) reprocessing and nuclear waste remediation) and nuclear medicine (i.

Crystallographic models of ribbons and ribbon-based J-aggregate nanotubes from the geometry of tube ends.

Self-assembly into tubular structures typically proceeds by helical winding of ribbon intermediates, however, only the central parts of the tubes, that retain no information on the ribbon geometry, have received attention so far. We propose the procedure of establishing the crystal structure of ribbons and ribbon-based tubes on the basis of crystallographic analysis of the tube-end geometry, where the terminal parts of the ribbons fold and form characteristic mono/bilayer polygonal shapes. The terminal parts of flattened J-aggregate nanotubes of trimethine cyanine dye were clearly resolved in electron microscopy and atomic force microscopy images, and the original parallelogram shape of ribbons was reconstructed and interpreted as a two-dimensional [1-10]/[010] facetted crystal with inclined molecular π-stacks parallel to the long ribbon side.

Formation of Superhydrophobic Coatings Based on Dispersion Compositions of Hexyl Methacrylate Copolymers with Glycidyl Methacrylate and Silica Nanoparticles.

In the last decade, the task of developing environmentally friendly and cost-effective methods for obtaining stable superhydrophobic coatings has become topical. In this study, we examined the effect of the concentrations of filler and polymer binder on the hydrophobic properties and surface roughness of composite coatings made from organic-aqueous compositions based on hexyl methacrylate (HMA) and glycidyl methacrylate (GMA) copolymers. Silicon dioxide nanoparticles were used as a filler.

Effect of Surface Polymeric Organosilicon Nanolayers on the Electrochemical and Corrosion Behavior of Copper.

The formation of polymeric self-organizing organosilicon surface nanolayers on copper occuring as a result of modification of the metal surface with organosilane-based formulations has been studied. The anticorrosive effect of such surface layers in corrosive chloride-containing electrolytes as well as in artificial and natural atmospheres has been studied in detail. It has been found that the maximum protective effect is observed at a thickness of 3.