Building a second-opinion tool for classical polygraph.

Classical polygraph screenings are routinely used by critical businesses such as banking, law enforcement agencies, and federal governments. A major concern of scientific communities is that screenings are prone to errors. However, screening errors are not only due to the method, but also due to human (polygraph examiner) error. Here we show application of machine learning (ML) to detect examiner errors. From an ML perspective, we trained an error detection model in the absence of labeled errors. From a practical perspective, we devised and tested successfully a second-opinion tool to find human errors in examiners' conclusions, thus reducing subjectivity of polygraph screenings. We report novel features that uplift the model's accuracy, and experimental results on whether people lie differently on different topics. We anticipate our results to be a step towards rethinking classical polygraph practices.

Novel D-A-π-A1 Type Organic Sensitizers from 4,7-Dibromobenzo[d][1,2,3]thiadiazole and Indoline Donors for Dye-Sensitized Solar Cells.

Two novel D-A-π-A1 metal-free organic dyes of the KEA series containing benzo[d][1,2,3]thiadiazole (isoBT) internal acceptor, indoline donors fused with cyclopentane or cyclohexane rings (D), a thiophene as a π-spacer, and a cyanoacrylate as an anchor part were synthesized. Monoarylation of 4,7-dibromobenzo[d][1,2,3]thiadiazole by Suzuki-Miyamura cross-coupling reaction showed that in the case of indoline and carbazole donors, the reaction was non-selective, i.e., two monosubstituted derivatives were isolated in each case, whereas only one mono-isomer was formed with phenyl- and 2-thienylboronic acids. This was explained by the fact that heterocyclic indoline and carbazole fragments are much stronger donor groups compared to thiophene and benzene, as confirmed by cyclic voltammetry measurements and calculation of HOMO energies of indoline, carbazole, thiophene and benzene molecules. The structure of monoaryl(hetaryl) derivatives was strictly proven by NMR spectroscopy and X-ray diffraction. The optical and photovoltaic properties observed for the KEA dyes showed that these compounds are promising for the creation of solar cells. A comparison with symmetrical benzo[c][1,2,3]thiadiazole dyes WS-2 and MAX114 showed that the asymmetric nature of benzo[d][1,2,3]thiadiazole KEA dyes leads to a hypsochromic shift of the ICT band in comparison with the corresponding benzo[c][1,2,5]thiadiazole isomers. KEA dyes have a narrow HOMO-LUMO gap of 1.5-1.6 eV. Amongst these dyes, KEA321 recorded the best power efficiency (PCE), i.e., 5.17%, which is superior to the corresponding symmetrical benzo[c][1,2,3]thiadiazole dyes WS-2 and MAX114 (5.07 and 4.90%).

ROS-generation and cellular uptake behavior of amino-silica nanoparticles arisen from their uploading by both iron-oxides and hexamolybdenum clusters.

The present work introduces combination of superparamagnetic iron oxides (SPIONs) and hexamolybdenum cluster ([{Mo6I8}I6]2-) units within amino-decorated silica nanoparticles (SNs) as promising design of the hybrid SNs as efficient cellular contrast and therapeutic agents. The heating generated by SNs doped with SPIONs (Fe3O4@SNs) under alternating magnetic field is characterized by high specific absorption rate (SAR = 446 W/g). The cluster units deposition onto both Fe3O4@SNs and "empty" silica nanoparticles (SNs) results in Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6] with red cluster-centered luminescence and ability to generate reactive oxygen species (ROS) under the irradiation. The monitoring of spin-trapped ROS by ESR spectroscopy technique indicates that the ROS-generation decreases in time for SNs[{Mo6I8}I6] and [{Mo6I8}I6]2- in aqueous solutions, while it remains constant for Fe3O4@SNs[{Mo6I8}I6]. The cytotoxicity is low for both Fe3O4@SNs[{Mo6I8}I6] and SNs[{Mo6I8}I6], while the flow cytometry indicates preferable cellular uptake of the former versus the latter type of the nanoparticles. Moreover, entering into nucleus along with cytoplasm differentiates the intracellular distribution of Fe3O4@SNs[{Mo6I8}I6] from that of SNs[{Mo6I8}I6], which remain in the cell cytoplasm only. The exceptional behavior of Fe3O4@SNs[{Mo6I8}I6] is explained by residual amounts of iron ions at the silica surface.

Interfacial uploading of luminescent hexamolybdenum cluster units onto amino-decorated silica nanoparticles as new design of nanomaterial for cellular imaging and photodynamic therapy.

The present work introduces a facile synthetic route to embed phosphorescent K2[{Mo6I8}I6] and (nBu4N)2[{Mo6I8}(CH3COO)6] clusters (C) onto silica-water interface of amino-decorated silica nanoparticles (SNs, 60 ±â€¯6 nm). The assembled C-SNs gain in the luminescence intensity, which remains stable within three months after their assembly. High uptake capacity of the clusters (8700 of K2[{Mo6I8}I6] and 6500 of (nBu4N)2[{Mo6I8}(CH3COO)6] per the each nanoparticle) derives from ionic self-assembly and coordination bonds between the cluster complexes and ionic (amino- and siloxy-) groups at the silica surface. The coordination via amino- or siloxy-groups restricts aquation and hydrolysis of the embedded clusters, in comparison with the parent K2[{Mo6I8}I6] and (nBu4N)2[{Mo6I8}(CH3COO)6. High potential of the assembled nanoparticles in the ROS generation was revealed by EPR measurements facilitated by spin trapping. The high positive charge and convenient colloid stability of the assembled C-SNs hybrids are the prerequisite for their efficient cellular uptake, which is exemplified in the work by MCF-7 cell line. The measured dark and photoinduced cytotoxicity of the C-SNs hybrids reveals significant photodynamic therapy effect on the MCF-7 cancer cell line versus the normal cells. This effect is entirely due to the embedded clusters and is dependent on the chemical composition of the cluster.

Fused 1,2,3-Thiaselenazoles Synthesized from 1,2,3-Dithiazoles through Selective Chalcogen Exchange.

A new approach to the synthesis of fused 1,2,3-thiaselenazoles-rare five-membered heterocycles that contain two different chalcogens-from the corresponding 1,2,3-dithiazoles and SeO2 was accomplished by selective exchange of S and Se atoms. The fused carbo- and heterocyclic units were indene, naphthalenone, cyclohexadienone, cyclopentadiene, benzoannulene, and benzoxazine. The molecular structures of two of the thiaselenadiazole products and one of the dithiazole precursors were confirmed by single-crystal X-ray diffraction. The reaction is highly solvent selective; it only takes place in solvents that contain a C=O group (e.g., DMF or tetramethylurea). According to DFT calculations, the reaction is thermodynamically favorable. Based on the DFT calculations and 77 Se NMR spectroscopy, two tentative mechanisms that feature isomeric transition states and intermediates are suggested for the reaction via ring-opening addition of SeO2 to the S-X dithiazole bond (X=N or S). The DFT-calculated first adiabatic electron affinities of the compounds were chalcogen independent and positive in all cases, which assumes formation of thermodynamically stable radical anions (RAs). These calculated RAs featured either normal or abnormal elongation of the S1-X2 (X=S or Se) bond relative to their neutral precursors and possessed π* or σ* SOMOs, respectively.

First tellurium-containing phthalocyanine analogues: strong effect of tellurium on spectral, redox and conductivity properties of porphyrazines with annulated chalcogenodiazole ring(s).

The first tellurium-containing phthalocyanine analogues have been prepared and spectroscopically characterised: the Mg(II) complex of tetra(1,2,5-telluradiazolo)porphyrazine and a low-symmetry tert-butyl substituted Mg(II) tribenzoporphyrazine with one fused 1,2,5-telluradiazole ring. It was observed that the introduction of Te atom(s) reduces the energy of the Q-transition, facilitates the reduction of the macrocycle and strongly increases the conductivity of thin films.