The Influence of Dopant Concentration on Optical-Electrical Features of Quantum Dot-Sensitized Solar Cell

In this study, TiO₂/CdS/Cd_xCu_1−xSe, TiO₂/CdS/Cd_xMn_1−xSe, and TiO₂/CdS/Cd_xAg_2−2xSe thin films were synthesized by chemical bath deposition for the fabrication of photoanode in quantum-dot-sensitized solar cells. As a result, the structural properties of the thin films have been studied by X-ray diffraction, which confirmed the zinc Blende structure in the samples. The optical films were researched by their experimental absorption spectra with different doping concentrations. Those results were combined with the Tauc correlation to estimate the absorption density, the band gap energy, valence band and conduction band positions, steepness parameter, and electron–phonon interaction. Furthermore, the electrical features, electrochemical impedance spectrum and photocurrent density curves were carried out. The result was used to explain the enhancing performance efficiency.     

Fast and continuous chemical isolation of short-lived isotopes of Hf,Ta and W as homologs of elements 104, 105 and 106

Some short-lived isotopes of Hf, Ta and W, synthesized at the U-400 cyclotron of JINR-Dubna, have been isolated using a previously elaborated fast continuous method of chemical isolation of element 104 from nuclear reaction products. The products were transported by a NaCl aerosol jet, from the irradiated targets to a separation device in which Hf, Ta and W were isolated by using three coupled ion-exchange columns.     

Sterically congested uranyl complexes with seven-coordination of the UO2 unit: the peculiar ligation mode of nitrate in [UO2(NO3)2(Rbtp)] complexes

Addition of 1 or 2 molar equiv of Rbtp [Rbtp = 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine; R = Me, Pr ( n )] to UO 2(OTf) 2 in anhydrous acetonitrile gave the neutral compounds [UO 2(OTf) 2(Rbtp)] [R = Me ( 1), ( n )Pr ( 2)] and the cationic complexes [UO 2(Rbtp) 2][OTf] 2 [R = Me ( 3), Pr ( n ) ( 4)], respectively. No equilibrium between the mono and bis(Rbtp) complexes or between [UO 2(Rbtp) 2][OTf] 2 and free Rbtp in acetonitrile was detected by NMR spectroscopy. The crystal structures of 1 and 3 resemble those of their terpyridine analogues, and 3 is another example of a uranyl complex with the uranium atom in the unusual rhombohedral environment. In the presence of 1 molar equiv of Rbtp in acetonitrile, UO 2(NO 3) 2 was in equilibrium with [UO 2(NO 3) 2(Rbtp)] and the formation of the bis adduct was not observed, even with an excess of Rbtp. The X-ray crystal structures of [UO 2(NO 3) 2(Rbtp)] [R = Me ( 5), Pr ( n ) ( 6)] reveal a particular coordination geometry with seven coordinating atoms around the UO 2 fragment. The large steric crowding in the equatorial girdle forces the bidentate nitrate ligands to be almost perpendicular to the mean equatorial plane, inducing bending of the UO 2 fragment. The dinuclear oxo compound [U(CyMe 4btbp) 2(mu-O)UO 2(NO 3) 3][OTf] ( 7), which was obtained fortuitously from a 1:2:1 mixture of U(OTf) 4, CyMe 4btbp, and UO 2(NO 3) 2 [CyMe 4btbp = 6,6'-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2'-bipyridine] is a very rare example of a mixed valence complex involving covalently bound U (IV) and U (VI) ions; its crystal structure also exhibits a seven coordinate uranyl moiety, with one bidentate nitrate group almost parallel to the UO 2 fragment. The distinct structural features of [UO 2(kappa (2)-NO 3) 2(Mebtp)], with its high coordination number and a noticeable bending of the UO 2 fragment, and of [UO 2(kappa (2)-NO 3)(kappa (1)-NO 3)(terpy)], which displays a classical geometry, were analyzed by Density Functional Theory, considering the bonding energy components and the molecular orbitals involved in the interaction between the uranyl, nitrate, and Mebtp or terpy moieties. The unusual geometry of the Mebtp derivative with the seven coordinating atoms around the UO 2 fragment was found very stable. In both the Mebtp and terpy complexes, the origin of the interaction appears to be primarily steric (Pauli repulsion and electrostatic); this term represents 62-63% of the total bonding energy while the orbital term contributes to about 37-38%.     

Simultaneous Determination of Paracetamol,Ibuprofen, and Caffeine in Tablets by Molecular Absorption Spectroscopy Combined with Classical Least Square Method

In this paper, the classical least-squares (CLS) method with molecular absorption spectrophotometric measurement was used to determine simultaneously paracetamol (PAR), ibuprofen (IBU), and caffeine (CAF) in tablets. The absorbance spectra of the standard solutions and samples were measured over a wavelength from 220 to 300 nm with a 0.5 nm step. The concentration of PAR, IBU, and CAF in the sample solutions was calculated by using Visual Basic for Applications (VBA) and a program called CLS-Excel written in Microsoft Excel 2016. The method and the CLS-Excel program were tested on mixed standard laboratory samples with different PAR, IBU, and CAF concentration ratios, and they showed only small errors and a satisfying repeatability. An analytical procedure for tablets containing PAR, IBU, and CAF was developed. The reliability of the procedure was proved via the recovery and repeatability of the analysis results with an actual tablet sample and by comparing the mean contents of active substances in the tablets obtained from the analytical procedure with the HPLC method. The procedure is simple with a reduced cost compared with the HPLC standard method.     

Chemical isolation of element 106 from aqueous solutions according to model experiments with short-lived tungsten isotopes

The short-lived isotopes of W and their descendants have been isolated from the products of the bombardment of¹⁴⁴Sm with²⁴Mg by a fast continuous ion-exchange method, using HF solution media. The feasibility of this method for isolation of element 106 is discussed.     

Autoxidation of 4-amorphen-11-ol and the biogenesis of nor- and seco-amorphane sesquiterpenes from fabiana imbricata

Photooxidation of 4-amorphen-11-ol (1), recently reported as one of the major sesquiterpene natural products from the medicinal plant Fabiana imbricata, results in three allylic hydroperoxides 6, 9 and 10, which are expected from the “ene-type” reaction of molecular oxygen with the tri-substituted double bond in 1. The tertiary allylic hydroperoxide 6 undergoes carbon-carbon bond cleavage and a second autoxidation reaction to yield the more highly oxygenated seco-amorphane 11 under very mild conditions. In acid, this compound may then undergo either a second carbon-carbon bond cleavage reaction to yield nor-sesquiterpenes 2 and 3 (reported as bona fide natural products from F. imbricata, or cyclize to the sesquiterpene peroxofabianane (5), which is a presumed precursor to the natural product fabianane (4). Some mechanistic investigations concerning the two chemical processes: viz:- carbon-carbon bond cleavage and autoxidation which would account for the formation of natural products 2, 3 and 4 from 1 are reported. Tertiary allylic hydroperoxide 32, which lacks the 11-hydroxyl functional group present in 1 undergoes only C-4/C-5 carbon-carbon bond cleavage under more forcing conditions, suggesting a role for this functional group in assisting the autoxidation reactions of 4-amorphen-11-ol.     

Comprehensive two-dimensional gas chromatography for enhanced analysis of naphthas: new column combination involving permethylated cyclodextrin in the second dimension

A new column association using comprehensive two-dimensional gas chromatography for the detailed molecular analysis of hydrocarbon mixtures is reported in this paper. In order to compare the impact of two different secondary columns, a novel column combination relying on a GC x 2GC system was used. This system is based on a non-polar first column (PONA) combined with both a permethylated beta-cyclodextrin (beta-Dex 120) stationary phase and a polysilphenylensiloxane (BPX 50) in the second dimension. Compared to BPX 50 stationary phase, the implementation of beta-cyclodextrin columns as the second dimension was found to improve the resolution between paraffins and naphthenes in the naphtha range but not in the middle distillate range. Attempts to improve the results and to understand the interaction mechanism remained unsuccessful. Therefore, the benefits of the beta-Dex 120-column are only demonstrated on heavy naphtha cut for the quantitation of hydrocarbons.     

New guaianolides from Berlandiera Pumila and B. Texana,and the X-ray crystal structure of pumilin

The isolation and structure determination of two new guaianolides, pumilin and its 2,3-epoxide, from Berlandiera pumila and B. texana are reported. The structure of pumilin was determined from nmr and mass spectral data, and from an X-ray single crystal study; the structure of the epoxide was found by comparison of nmr spectra. Pumilin is shown to be a Δ¹⁽¹⁰⁾-cis-guaianolide with a cyclopentenone ring attached to C1 and C5, and an α-methylene-γ-lactone ring trans-fused to C6 and C7. The absolute configuration was inferred from spectral considerations and knowledge of previous structural determinations. The cd spectrum of pumilin exhibits a negative Cotton effect, and the lactone chromophore has left-handed chirality. The cyclo-heptene ring is in the chair configuration, with the lactone a half-chair and the cyclopentenone essentially planar. Crystals are orthorhombic, a = 7.065, b = 13.652, c = 19.586 Å, space group P2₁2₁2₁, Z = 4, and the final R value is 3.9%. The crystal structure is strengthened by an O···O hydrogen bond linking the molecules into infinite chains.     

Homoleptic Zincate‐Promoted Room‐Temperature Halogen–Metal Exchange of Bromopyridines

Homoleptic lithium tri‐ and tetraalkyl zincates were reacted with a set of bromopyridines. Efficient and chemoselective bromine–metal exchanges were realized at room temperature with a substoichiometric amount of nBu₄ZnLi₂?TMEDA reagent (1/3 equiv; TMEDA=N,N,N′,N′‐tetramethylethylenediamine). This reactivity contrasted with that of tBu₄ZnLi₂?TMEDA, which was inefficient below one equivalent. DFT calculations allowed us to rationalize the formation of N???Li stabilized polypyridyl zincates in the reaction. The one‐pot difunctionalization of dibromopyridines was also realized using the reagent stoichiometrically. The direct creation of C? Zn bonds in bromopyridines enabled us to perform efficient Negishi‐type cross‐couplings.