A general three-step one-pot synthesis of novel (<Emphasis Type="Italic">E</Emphasis>)-6-chloro-2-(aryl/hetarylvinyl)quinoline-3-carboxylic acids

In this work, a facile and general three-step one-pot synthesis of structurally new (E)-6-chloro-2-(aryl/hetarylvinyl)quinoline-3-carboxylic acid derivatives has been achieved from easily available ethyl 6-chloro-2-(chloromethyl) quinoline-3-carboxylate and aromatic or heteroaromatic aldehydes. This strategy features simple one-pot operation, tolerance of a wide range of substituents, and good yields. Moreover, these newly synthesized compounds belong to a new class of quinoline derivatives and could be good candidates for the development of more complex quinoline compounds for use in medicinal chemistry.     

Synthesis,structural, and spectroscopic (FT-IR,NMR, and UV) Characterization of 1-(Cyclohexylmethyl)-2-(pyridin-2-yl)-1<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">d</Emphasis>]imidazole by experimental techniques and quantum chemical calculations

The title compound (II), 1-(cyclohexylmethyl)-2-(pyridin-2-yl)-1H-benzo[d]imidazole (C₁₉H₂₁N₃), was synthesized via N-alkylation of 2-(pyridin-2-yl)-1H-benzo[d]imidazole (I). Both compounds I and II were characterized by IR, NMR and UV-vis spectroscopy. Solid-state structure of compound II was determined by single-crystal X-ray diffraction technique. Furthermore, quantum chemical calculations employing density functional theory (DFT/B3LYP) method with the 6–311++G(d, p) basis set were performed for the theoretical characterization of the molecular and spectroscopic features of the compounds. Using the TD-DFT method, electronic absorption spectra of the compounds have been predicted at same level. When the obtained results were compared with the experimental findings, it is seen that theoretical results support the experimental data and a good agreement exists between them.     

Electrochemical,morphological, and spectroscopic study of poly(aniline-co-<Emphasis Type="Italic">o</Emphasis>-bromoaniline) (PA-co-<Emphasis Type="Italic">o</Emphasis>-BrA) conducting copolymer

A series of moderately conducting and soluble copolymers of poly(aniline-co-o-bromoaniline) (PA-co-o-BrA) having different compositions was obtained by in the situ copolymerization method using different concentrations of monomer units of aniline and o-bromoaniline in the feed. The physio-chemical properties of the copolymers have been studied with sophisticated instrumental techniques. The electrochemical study of the copolymers was conducted by cyclic voltammetry. The band gap of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the copolymers was evaluated by UV-vis spectroscopy. The morphological study was conducted by scanning electron microscopy and transmission electron microscopy at high magnification which shows non-uniform tubular to globular morphology of the copolymers. Surface profiles of the polymers were studied by AFM analyses, and it has confirmed the smooth surface of the copolymers while the homopolymers possesses non-uniform surfaces. The particle size distribution curve indicates that the particle sizes vary in the range of 5 to 9000 nm, and a small fraction of particles possess a size in the range of 5–10 nm.     

Structural,Spectroscopic, Antimicrobial Activity and DFT Studies on 4-Methyl-<Emphasis Type="Italic">N</Emphasis>-(4-methylphenylsulfonyl)-<Emphasis Type="Italic">N</Emphasis>-phenylbenzenesulfonamide

This study reports the structural characterization of a disulfonimide derivative, 4-methyl-N-(4-methylphenylsulfonyl)-N-phenylbenzenesulfonamide (MPBSA), using spectroscopic and quantum chemical methods. The molecule was characterized with FT-IR, ¹H ¹³C NMR and UV-Vis spectroscopies. Quantum chemical calculations of molecular geometry, vibrational wavenumbers and gauge including atomic orbital (GIAO) ¹H and ¹³C-NMR chemical shifts of the compound were carried out by using density functional method (DFT) at B3LYP/6?311++G(d,p) level of theory. Electronic absorption spectra of the compound have been computed using the time-dependent density functional theory (TD-DFT) method at the same level. A satisfactory consistency between the experimental and theoretical findings was obtained. The antimicrobial activity screening of the compound was performed on some bacteria and fungus species using microdilution method. The results showed that the title molecule have noteworthy antibacterial and antifungal activities.     

Directly Oxidized Chemiluminescence of 2-Substituted-4,5-di(2-Furyl)-1<Emphasis Type="Italic">H</Emphasis> -Imidazole by Acidic Potassium Permanganate and its Analytical Application for Determination of Albumin

In the paper, 2,4,5-tri(2-furyl)-1H-imidazole (TFI) and 2-phenyl-4,5-di(2-furyl)-1H-imidazole (PDFI), were chosen to investigate chemiluminescence (CL) properties of 2-substituted-4,5-di(2-furyl)-1H-imidazoles. The directly oxidized CL of analytes by potassium permanganate (KMnO₄) was in detail studied. The KMnO₄ could directly oxidize TFI/PDFI to produce strong CL emission in acidic solution. The effects of experimental conditions were investigated. Under the optimal conditions, the effect of albumin on the TFI/PDFI-KMnO₄ system was investigated. It was found that the addition of albumin into the system could induce enhancement of CL signal, and the enhanced CL intensity is linearly related to the logarithm of concentration of albumin. Based on this study, a novel CL method has been developed for the determination of albumin with high sensitivity and good selectivity. The method was applied to the determination of albumin in human serum samples, and the results were in agreement with those obtained by the bromcresol green (BCG) method. The relative errors for the analytical results were from −5.8% to 4.2%. These new phenomena would further enable people to exploit more CL analytical application of the heterocyclic imidazole derivatives.     

Asymmetric hydrogenation of (<Emphasis Type="Italic">E</Emphasis>)-dimethyl-2-acetamido-2-phenylvinylphosphonate in supercritical carbon dioxide in the presence of metal complex catalysts with phosphite-type ligands

Asymmetric hydrogenation of (E)-dimethyl-2-acetamido-2-phenylvinylphosphonate was performed in CH₂Cl₂ and supercritical carbon dioxide with the participation of Rh and Ir complexes with chiral phosphite-type ligands. Iridium catalysts dissolved in supercritical CO₂ allow high enantioselectivity (up to 98.5% ee) and conversion to be obtained. Rhodium catalysts yield exclusively racemic reaction products.     

Geometric frustrations in magnetically diluted complex oxides Li<Emphasis Type="Italic">M</Emphasis>O<Subscript>2</Subscript> (<Emphasis Type="Italic">M</Emphasis> = Sc,Ga, 3<Emphasis Type="Italic">d</Emphasis> elements)

The effect of local environment of a transition-element atom on the properties of bulk ceramics has been investigated by the example of complex oxides LiMO₂ (M = Sc, Ga, Fe, Co, Ni). It is found that the anomalies in the magnetic properties of all systems studied are due to the presence of nanoclusters of transition-element atoms and the magnetic and geometric frustrations related to the nanocluster formation.     

The role of specific features of the electronic structure in electrical resistivity of band ferromagnets Co<Subscript>2</Subscript>Fe<Emphasis Type="Italic">Z</Emphasis> (<Emphasis Type="Italic">Z</Emphasis> = Al,Si, Ga,Ge, In,Sn, Sb)

The electrical resistivity ρ(T) of the band ferromagnets Co₂FeZ (where Z = Al, Si, Ga, Ge, In, Sn, and Sb are s- and p-elements of Mendeleev’s Periodic Table) has been investigated in the temperature range 4.2 K < T < 1100 K. It has been shown that the dependences ρ(T) of these alloys in a magnetically ordered state at temperatures T < T _C are predominantly determined by the specific features of the electronic spectrum in the vicinity of the Fermi level. The processes of charge carrier scattering affect the behavior of the electrical resistivity ρ(T) only in the vicinity of the Curie temperature T _C and above, as well as in the low-temperature range (at T ? T _C).     

Spin dynamics and phase transitions in quasi-2D antiferromagnets <Emphasis Type="Italic">R</Emphasis><Subscript>2</Subscript>CuO<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis>=Pr,Nd, Sm,Eu, Gd)

The spin and lattice dynamics of the R₂CuO₄ quasi-2D antiferromagnetic crystals (R=Pr, Nd, Sm, Eu, Gd) were studied in the millimeter-range electromagnetic wave band. Strong variations of the absorption coefficient were observed to occur at temperatures T≈T₀. Absorption lines of electrical nature due to lattice dynamics were also revealed near the T₀ temperatures. The observed anomalies are assumed to originate from phase transitions at T≈T₀, which entail changes in the structural and magnetic properties.     

Low-temperature anomaly of the magnetization in alloys (Pr,Dy,<Emphasis Type="Italic">M</Emphasis>)<Subscript>2</Subscript>(Fe,Co)<Subscript>14</Subscript>B (<Emphasis Type="Italic">M</Emphasis> = Gd,Sm, Nd)

It has been found that temperature dependences of the saturation magnetization of sintered hard magnetic (Pr,Dy,M)₂(Fe,Co)₁₄B (M = Gd, Sm, Nd) alloys demonstrate an increase at a temperature lower than a critical temperature (150 K for Sm and Nd and 70 K for Gd). An additive of copper does not influence the critical temperature. It has been assumed that there is a low-temperature phase in which cobalt is replaced with boron that diffuses from the (Pr,Dy,Gd)(Fe,Co)₄B phase to the near-surface region of grains of the main magnetic (Pr,Dy,Gd)₂(Fe,Co)₁₄B phase.     

Specific features of the electrical resistivity of half-metallic ferromagnets Co<Subscript>2</Subscript> <Emphasis Type="Italic">Me</Emphasis>Al (<Emphasis Type="Italic">Me</Emphasis> = Ti,V, Cr,Mn, Fe)

The transport properties of half-metallic ferromagnetic Heusler alloys Co₂MeAl (Me = Ti, V, Cr, Mn, Fe are transition 3d metals) have been measured in the temperature range of 4–900 K. The specific features of the behavior of the resistivity have been considered in the framework of the two-current model of conductivity that takes into account the existence of the energy gap in the electronic spectra of the alloys near the Fermi level of one of electron subbands that differs in the spin direction.     

Micro-Raman spectroscopic investigation of NiSi films formed on BF<Subscript>2</Subscript><Superscript>+</Superscript>-, B<Superscript>+</Superscript>- and non-implanted (100)Si substrates

The micro-Raman spectroscopic technique was used to investigate vibrational properties of NiSi thin films formed on three different (100)Si substrates: non-implanted, 20 keV BF₂⁺-implanted, and 20 keV B⁺-implanted. Raman measurements were also performed on NiSi powder to identify various phonon modes associated with different selection rules of group theory. It was found that the Raman peaks for NiSi thin films formed on the BF₂⁺-implanted substrate were broader and shifted to lower frequencies compared to those for films formed on the other substrates. The broadening of the Raman peaks for these films, which also exhibit much improved thermal stability, is attributed to the small grains that probably result from the segregation of fluorine to grain boundaries and interfaces. It is further proposed that grain boundary segregation influences the stress in the silicide film, resulting in shifts in phonon peak positions. PACS 78.30.Am; 74.25.Kc; 68.35.Dv; 68.55.Ln; 66.30.Jt     

Structural study,intermolecular interactions in view of X-ray and Hirshfeld surface analysis,DSC characterization,and electrical properties of <Emphasis Type="Italic">bis</Emphasis>-(4-benzylpyridinium) tetrabromozincate

The synthesis and crystal structure of the bis-(4-benzylpyridinium) tetrabromozincate(II) “(4-BP)₂[ZnBr₄]” salt are reported in the present paper. After an X-ray investigation, it has been shown that the title compound belongs to the centrosymmetric monoclinic system at 296 K, in the space group P2₁/n with the following lattice parameters a = 15.0764(8) Å, b = 22.5575(12) Å, c = 16.0739(9) Å, and β = 93.887(3)°. The FT-IR and Raman spectra confirm the presence of both cationic and anionic parts. The crystal packing is governed by an extensive network: N–H…Br, (N: pyridinium), C–H…Br hydrogen bonds, π…π, and C–H…π stacking between identical 4-BP (aromatic–aromatic), in which they may be effective in the stabilization of the crystal structure. Moreover, Hirshfeld surface analysis was used for visually analyzing intermolecular interactions in crystal structures. The phase transitions at T = 323 K have been confirmed by the differential scanning calorimetry. The electrical technique was measured in the 209 Hz–5-MHz frequency range and 298–393-K temperature intervals. The evolution of the dielectric constant as a function of frequency and temperature proved the presence of a first-order phase transition at 323 K.

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Calculation of the optical spectra of the copper(I) complex with triphenylphosphine,iodine, and 3-pyridine-2-yl-5-phenyl-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole by the DFT method

The IR and UV spectra of the [CuIL(PPh₃)] complex (PPh₃ = triphenylphosphine, L = 3-pyridine- 2-yl-5-phenyl-1Н-1,2,4-triazole) have been analyzed in detail within the density functional theory (DFT) and its time-dependent version TD DFT. The standard functional B3LYP and sets of basis orbitals 6-311G(d,p) and Lanl2DZ are used for the atoms of the elements of periods I and II and for the iodine atom, respectively. The calculated IR spectra of the complex and free ligands coincide with the observed IR bands, due to which one can completely interpret all normal modes and confirm X-ray diffraction (XRD) data. Particular attention is paid to the structure of excited triplet (Т ₁) state in order to explain the role of copper and iodine ions in the formation of photo- and electroluminescence spectra. It is shown that the equilibrium Т ₁ state undergoes structural relaxation after the vertical excitation and significantly changes its electronic nature and the charge transfer structure.     

Localized excitation effects in (E,E)-2,5-<Emphasis Type="Italic">bis</Emphasis>[2-(4-N,N-dipropylaminophenyl) ethylenyl]-3,6-dimethylpyrazine and generation of its different forms in solution

Dipole moments of (E,E)-2,5-bis[2-(4-N,N-dipropylaminophenyl)ethylenyl]-3,6-dimethylpyrazine (VS365) quadrupolar dye in 1,4-dioxane and cyclohexane in addition to its instantaneous fluorescence spectra and fluorescence lifetimes in dichloromethane (pure and with added trifluoroacetic acid) were measured. Quantumchemical calculations show that the π − π conjugated system is localized in the flattest part of the molecule due to disorder in the ground-state geometry of the dye molecule and that this part is the one responsible for light absorption. The effect of localized excitation of the dye causes a considerable change in its dipole moment Δ^aμ. Various fluorescent forms of the dye that feature considerably spaced emission spectra and different fluorescence lifetimes originate by adding trifluoroacetic acid to the solution of oligophenylenevinylene in dichloromethane.     

Solvatochromism,Preferential Solvation of 2,3-Bis(Chloromethyl)-1,4-Anthraquinone in Binary Mixtures and the Molecular Recognition Towards <Emphasis Type="Italic">p</Emphasis>-Tert-Butyl-Calix[4]arene

Optical absorption and fluorescence emission spectra of 2,3-bis(chloromethyl)-1,4-anthraquinone (DCMAQ) in single solvents namely, carbon tetrachloride, acetonitrile, chloroform, propan-2-ol and its binary mixtures [carbon tetrachloride/chloroform, chloroform/acetonitrile, chloroform/propan-2-ol] have been investigated. The preferential solvation of DCMAQ in above mixtures has been studied by monitoring the absorption and fluorescence spectra of DCMAQ. The spectral features indicate that DCMAQ is preferentially solvated by CHCl₃ in the above mixtures. This can be elucidated from the local mole fraction, non-linearity in transition energy plot, preferential solvation index (δ _s2) and (f ₂/f ₁) values. Molecular recognition properties of p-tert-butylcalix[4]arene (tBC) to DCMAQ via hydrogen bonding and π–π interaction were sensed successfully on the basis of absorption and fluorescence emission spectroscopies, by which the stoichiometry ratio and the binding constant of the tBC–DCMAQ complex were determined.     

Preparation,thermal expansion,chemical compatibility,electrical conductivity and polarization of A2−αA′αMO4 (A = Pr,Sm; A′ = Sr; M = Mn,Ni; α = 0.3, 0.6) as a new cathode for SOFC

A_2−αA′_αMO₄ (A = Pr, Sm, A′ = Sr, M = Ni, Mn) with K₂NiF₄-type structure were synthesized by solid reaction. Their chemical stability, electrical conductivity and thermal expansion behavior as well as cathodic polarization were investigated in relation to the cathode of SOFC. The results showed that A_2−αA′_αMO₄ exhibited a low reactivity with yttria stabilized zirconia (YSZ) electrolyte. The thermal expansion coefficient (TEC) values were changed with the ionic radius of A. The specific conductivities of the nickelates were higher than those of manganites. While the nickelates showed a lower cathodic polarization in comparison with manganites.     

Multicomponent <Emphasis Type="Italic">n</Emphasis>-(Bi,Sb)<Subscript>2</Subscript>(Te,Se,S)<Subscript>3</Subscript> solid solutions with different atomic substitutions in the Bi and Te sublattices

The thermoelectric properties of n-Bi_{2 ? x} Sb _x Te_{3 ? y ? z} Se _y S _z solid solutions are studied in the temperature range 300–550 K. It is shown that an increase in the parameter β determining the figure-of-merit Z of the material is observed in compositions with the optimally related effective mass of the density of states m/m ₀, the carrier mobility μ₀, and the lattice thermal conductivity κ _L . Within the temperature range 300–350 K, the parameter β and the figure-of-merit Z are found to increase in solid solutions with substitutions in both bismuth telluride sublattices Bi → Sb and Te → Se, S (x = 0.16, y = z = 0.12) for optimum electron concentrations. An increase in the electron concentration and substitutions of atoms only in the tellurium sublattice bring about an increase in the β parameter and the value of Z at higher temperatures. Within the range 350–450 K, the parameters β and Z are observed to increase in a solid solution with a low content of substituted atoms in the tellurium sublattice Te → Se, S for y = z = 0.09 and, at higher temperatures up to 550 K, in compositions with tellurium substituted by selenium only, with increasing content of substituted atoms.     

The effect of temperature and pressure on the heat conductivity of TlSbC<Stack><Subscript>2</Subscript><Superscript>VI</Superscript></Stack> (<Emphasis Type="Italic">C</Emphasis><Superscript>VI</Superscript> → S,Se, Te)

The effect of temperature and pressure on heat conductivity of ternary compounds TiSbC ₂^VI (C ^VI → S, Se, Te) in the solid and liquid states in a temperature range of 300–800 K, as well as under the pressure up to 0.35 GPa in a temperature range of 275–450 K, is studied. The dependence of heat conductivity on average atomic weight under the S → Se → Te transition is found. Analysis of the experimental data makes it possible to attribute TlSbS₂ to the class of substances exhibiting semiconductor-semiconductor melting behavior.