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Three (4,4′-((1E,1′E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (–HC=CH–) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about −5.39 eV (SAI1 and SAI2) and −5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about −3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO–LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500–1700 cm−1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C=N)–TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm−2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes. [ABSTRACT FROM AUTHOR]

A new piperazine imine, (7E)-N-((4-((E)-(4-hexadecylphenylimino)methyl) piperazin-1-yl)methylene)-4-dodecylbenzenamine, has been synthesized by the condensation of 1,4-piperazinedicarboxaldehyde with 4- hexadecylaniline. The imine was characterized by cyclic voltammetry, Fourier transform middle-infrared absorption spectroscopy and X-ray diffraction. Thermal properties of imine was analyzed by differential scanning calorimetry method during first and second heating scan at 10 and 20 °C/min. Texture of imine was investigated by polarized optical microscopy and atomic force microscopy. Furthermore, imine was blended with titanium dioxide in anatase form and fully characterized by the same methods. Piperazine imine and its mixture with titanium dioxide exhibited only a transition from crystal to isotropic state. Imine exhibits two-step reduction wave attributed to one-electron transfer in each step as was found by cyclic voltammetry. Both titanium dioxide and poly(3-hexylthiophene) change the electrochemical properties of piperazine imine, however, in different ways. Studied imine blended with titanium dioxide exhibited higher value of energy band gap than pure piperazine imine and lower Eg than pure poly(3-hexylthiophene). [ABSTRACT FROM AUTHOR]

The aim of our study was to analyze the influence of various concentrations of γ-Fe2O3 nanoparticles on the physical properties of the liquid crystalline ferroelectric SmC* phase, as well as to check the effect of introducing nanoparticles in the LC matrix on their properties in the prepared five nanocomposites. UV-vis spectroscopy showed that the admixture reduced the absorption of nanocomposites in the UV range, additional absorption bands appeared, and all nanocomposites were transparent in the range of 500–850 nm. The molecular dynamics in particular phases of the nanocomposites were investigated by the dielectric spectroscopy method, and it was found that nanoparticles caused a significant increase in the dielectric constant at low frequencies, a strong modification of the dielectric processes in the SmC* phase, and the emergence of new relaxation processes for the highest dopant concentrations. SQUID magnetometry allowed us to determine the magnetic nature of the nanoparticles used, and to show that the blocked state of nanoparticles was preserved in nanocomposites (hysteresis loops were also registered in the ferroelectric SmC* phase). The dependence of the coercive field on the admixture concentration and the widening of the hysteresis loop in nanocomposites in relation to pure nanoparticles were also found. In turn, the FT-MIR spectroscopy method was used to check the influence of the impurity concentration on the formation/disappearance or modification of the absorption bands, and the modification of both the FWHM and the maximum positions for the four selected vibrations in the MIR range, as well as the discontinuous behavior of these parameters at the phase transitions, were found. [ABSTRACT FROM AUTHOR]

Five crystalline phases of [Co(NH3)6](BF4)3 were identified by adiabatic calorimetry. Two phase transitions at Tc1(II→I) = 271.7K and Tc2(111 → II) = 152.2K are accompanied by large entropy changes (8.4 and 6.5 J K1 mol1, respectively), whereas two additional transitions at Tc3(IV → III) = 67.4K and Tc4(V→IV) = 48.9K are accompanied by small entropy changes (0.31 and 0.15 J K-1 mol-1, respectively). X-ray single-crystal diffraction at 293 K demonstrates that phase I is cubic (Z= 4) and that two types of anions exist with different types of orientational disorder. In phase II, at 200 K, which is also a cubic system (Z=32), five anions (out of 12) become ordered, and three cations (out of four) are deformed to give a lower symmetry. This is attributed to the orientational ordering of the anions triggered by NH-F hydrogen-bonding interactions. Further ordering of the anions and the symmetry reduction of the crystal occurred at Tc2, but the structure of phase III still remained cubic. The energies required to reorient an ordered anion in the crystal lattice of phases II and III were estimated from the excess heat capacity, demonstrating that the NH... F hydrogen-bonding interactions in this compound are considerably weaker than the NH...O interactions in an isostructural compound, [Co(NH3)6](ClO4)3. [ABSTRACT FROM AUTHOR]

Five crystalline phases of [Co(NH3)6](BF4)3 were identified by adiabatic calorimetry. Two phase transitions at Tc1(II→I) = 271.7K and Tc2(111 → II) = 152.2K are accompanied by large entropy changes (8.4 and 6.5 J K1 mol1, respectively), whereas two additional transitions at Tc3(IV → III) = 67.4K and Tc4(V→IV) = 48.9K are accompanied by small entropy changes (0.31 and 0.15 J K-1 mol-1, respectively). X-ray single-crystal diffraction at 293 K demonstrates that phase I is cubic (Z= 4) and that two types of anions exist with different types of orientational disorder. In phase II, at 200 K, which is also a cubic system (Z=32), five anions (out of 12) become ordered, and three cations (out of four) are deformed to give a lower symmetry. This is attributed to the orientational ordering of the anions triggered by NH-F hydrogen-bonding interactions. Further ordering of the anions and the symmetry reduction of the crystal occurred at Tc2, but the structure of phase III still remained cubic. The energies required to reorient an ordered anion in the crystal lattice of phases II and III were estimated from the excess heat capacity, demonstrating that the NH... F hydrogen-bonding interactions in this compound are considerably weaker than the NH...O interactions in an isostructural compound, [Co(NH3)6](ClO4)3. [ABSTRACT FROM AUTHOR]

Abstract: [Co(NH3)6](ClO4)3 was investigated by neutron scattering methods in the temperature range of 20–290K. Neutron powder diffraction revealed that the crystal structure does not change at the T C2 and T C3 phase transitions. High temperature phases are orientationally disordered. QENS study showed that NH3 ligands perform rapid reorientational motion around their 3-fold axes in a wide temperature range. However, below T C3 some excess of elastic scattering is observed, which can be explained by the assumption that only half of the NH3 groups reorient fast enough to contribute to the QENS broadening, whereas the remaining NH3 groups reorient more slowly. The activation energy for NH3 jumps, estimated from the temperature dependence of QENS broadening, is small but comparable with the results obtained for other hexaammine complexes. Quantum chemical calculation, carried out on the basis of DFT for isolated [Co(NH3)6]3+ cation and anion, and experimental (IR,RS,IINS) spectra are in good agreement. [Copyright &y& Elsevier]

Abstract: Two phase transitions – one sharp at T 1 =247.4K and the other very broad at T 2 ∼135K – were observed for [Cr(OS(CH3)2)6](BF4)3 by adiabatic calorimetry. They are of the order–disorder type, and their transition entropies are 28.4 and 8.3JK−1 mol−1, respectively. IR absorption and Raman scattering spectroscopy measurements revealed distinct changes in the molecular dynamics of both CH3 groups and BF4 − anions at T 1 and reduced symmetry of the [Cr(OS(CH3)2)6]3+ complex cations and OS(CH3)2 ligands below T 2. The spectral width of an IR and Raman active band associated with the δ as(FBF)F 2 mode yielded an activation energy (E a)∼9kJmol−1 for the reorientation of BF4 − anions, which is comparable with that obtained for other coordination compounds with BF4 − anions. [Copyright &y& Elsevier]

Abstract: Two phase transitions were found in solid [Al(OS(CH3)2)6](NO3)3 at T C1 =343.1K by differential scanning calorimetry and at T C2 =34.3K by adiabatic calorimetry. The transition at T C1 is accompanied by large thermal hysteresis (ca. 30K) and a large entropy change (76JK−1 mol−1), suggesting an order–disorder-type transition, whereas that at T C2 has a considerably smaller entropy change (3.4JK−1 mol−1). The phase behavior of the deuterated compound is essentially the same. IR and Raman spectra reveal a reduction in symmetry below T C1 and a change in the reorientational dynamics of CH3 groups and NO3 − anions, indicating that the highest temperature phase is orientationally disordered. The transition at T C2 can be explained by a librational soft-mode theory and all complex cations change their orientation in a cooperative manner. [Copyright &y& Elsevier]

The aim of this paper is to show, by systematic studies, the influence of γ-Fe2O3 nanoparticles on the physical parameters of the liquid crystalline matrix, exhibiting a ferroelectric phase in a wide temperature range. The detailed research was carried out by using diffraction (PXRD), microscopic (OM, SEM, FCPM, POM), thermal (DSC), optical (TLI), electric and spectroscopic (FTIR) methods. We show that even the smallest concentration of γ-Fe2O3 nanoparticles largely modifies the parameters of the ferroelectric SmC* phase, such as spontaneous polarization, switching time, tilt angle, rotational viscosity, dispersion anchoring energy coefficient and helix pitch. The admixture also causes a significant reduction in the temperature of phase transitions, broadening the SmA* phase at the expense of the SmC* phase and strong streaking of the texture. We present and explain the non-monotonic modification of these parameters with an increase in the nanoparticle concentration. The influence of oleic acid admixture on these parameters is also widely discussed. We have shown that certain parameters of organic-metal nanocomposites can be controlled by the appropriate amount of metal admixture. [ABSTRACT FROM AUTHOR]

The main goal of this paper was to study the dielectric properties of hybrid binary and ternary composites based on biodegradable polymer Ecoflex®, single walled carbon nanotubes (SWCN), and liquid crystalline 4′-pentyl-4-biphenylcarbonitrile (5CB) compound. The obtained results were compared with other created analogically to Ecoflex®, hybrid layers based on biodegradable polymers such as L,D-polylactide (L,D-PLA) and polycaprolactone (PCL). Frequency domain dielectric spectroscopy (FDDS) results were analyzed taking into consideration the amount of SWCN, frequency, and temperature. For pure Ecoflex®, two relaxation processes (α and β) were identified. It was shown that the SWCN admixture (in the weight ratio 10:0.01) did not change the properties of the Ecoflex® layer, while in the case of PCL and L,D-PLA, the layers became conductive. The dielectric constant increased with an increase in the content of SWCN in the Ecoflex® matrix and the conductive behavior was not visible, even for the greatest concentration (10:0.06 weight ratio). In the case of the Ecoflex® polymer matrix, the conduction relaxation process at a frequency ca. several kilohertz appeared and became stronger with an increase in the SWCN admixture in the matrix. Addition of oleic acid to the polymer matrix had a smaller effect on the increase in the dielectric response than the addition of liquid crystal 5CB. Fourier transform infrared (FTIR) results revealed that the molecular structure and chemical character of the Ecoflex® and PCL matrixes remained unchanged upon the addition of SWCN or 5CB in a weight ratio of 10:0.01 and 10:1, respectively, while molecular interactions appeared between L,D-PLA and 5CB. Moreover, adding oleic acid to pure Ecoflex® as well as the binary and ternary hybrid layers with SWCN and/or 5CB in a weight ratio of Ecoflex®:oleic acid equal to 10:0.3 did not have an influence on the chemical bonding of these materials. [ABSTRACT FROM AUTHOR]

Although Poland is one of the leading recipients of the waste stream in the European Union (EU), it is at the same time below the average in terms of efficiency of their use/utilization. The adopted technological solutions cause waste processing rates to be relatively low in Poland. As a result, the report of the Early Warning and Response System (EWRS) of the EU indicated Poland as one of the 14 countries of the EU which are at risk in terms of possibility of achieving 50% recycling of waste. This article discusses the implemented technological solutions, and shows the profitability of the investment and the values of the process heat demand both for extractor and reactor. The experimental part analyzed the composition of the input and output of the process and compared it to the required fuel specifications. Attention was drawn to the need to improve the recycling process in order to increase the quality of manufactured fuel components. As potential ways of solving the problem of low fuel quality, cleaning the sorted reaction mass from solid particles and extending the technological line with a distillation column have been proposed. The recommended direction of improvement of the technology is also the optimization of the process of the reactor's purification and removal of contaminants. [ABSTRACT FROM AUTHOR]

[Ni(ND3)6](ClO4)2 has three solid phases between 100 and 300 K. The phase transitions temperatures at heating (TC1h=164.1 K and TC2h=145.1 K) are shifted, as compared to the non-deuterated compound, towards the lower temperature of ca. 8 and 5 K, respectively. The ClO4- anions perform fast, picosecond, isotropic reorientation with the activation energy of 6.6 kJ mol-1, which abruptly slow down at TC1c phase transition, during sample cooling. The ND3 ligands perform fast uniaxial reorientation around the Ni–N bond in all three detected phases, with the effective activation energy of 2.9 kJ mol-1. The reorientational motion of ND3 is only slightly distorted at the TC1 phase transition due to the dynamical orientational order–disorder process of anions. The low value of the activation energy for the ND3 reorientation suggests that this reorientation undergoes the translation–rotation coupling, which makes the barrier to the rotation of the ammonia ligands not constant but fluctuating. The phase polymorphism and the dynamics of the molecular reorientations of the title compound are similar but not quite identical with these of the [Ni(NH3)6](ClO4)2. [Copyright &y& Elsevier]

Abstract: Four crystalline phases of the coordination compound [Ru(NH3)6](BF4)3 are identified by adiabatic calorimetry. Three phase transitions, one at T C3(IV→III)=30.7K, the second at T C2(III→II)=91.7K (both accompanied by comparable entropy changes 3.0 and 3.1JK−1 mol−1, respectively) and the third at T C1(II→I)=241.6K (accompanied by an entropy change of 8.1JK−1 mol−1) were discovered. X-ray single crystal diffraction (at 293K) demonstrates that phase I is a highly dynamic disordered cubic phase (, No. 225) with two types of anions differing in a degree of disorder. In phase II (at 170K) the structure remains cubic (, No. 206), with two different types of cations and four different types of anions. Splitting of certain IR bands connected with NH3 ligands at the observed phase transitions suggests a lowering of the symmetry of the [Ru(NH3)6]3+ complex cation. Both NH3 ligands and anions perform fast reorientations (τ R ≈10−12 s), which are significantly slowed down below the phase transition at T C3. 1H NMR studies led to estimate the values of the activation energy of NH3 ligands reorientation in the phases II and I as equal to ∼8kJmol−1. In phase I the whole hexammineruthenium(III) cations reorientation as a tumbling process can be noticed. The activation energy value of this motion is ∼24kJmol−1. 19F NMR studies give the values of the activation energy of anions reorientation as ∼6kJmol−1. Above the phase transition temperature half of anions perform a tumbling motion with E a ≈8kJmol−1. [Copyright &y& Elsevier]

The aim of our study was to analyze the influence of various concentrations of γ -Fe 2 O 3 nanoparticles on the physical properties of the liquid crystalline ferroelectric SmC* phase, as well as to check the effect of introducing nanoparticles in the LC matrix on their properties in the prepared five nanocomposites. UV-vis spectroscopy showed that the admixture reduced the absorption of nanocomposites in the UV range, additional absorption bands appeared, and all nanocomposites were transparent in the range of 500-850 nm. The molecular dynamics in particular phases of the nanocomposites were investigated by the dielectric spectroscopy method, and it was found that nanoparticles caused a significant increase in the dielectric constant at low frequencies, a strong modification of the dielectric processes in the SmC* phase, and the emergence of new relaxation processes for the highest dopant concentrations. SQUID magnetometry allowed us to determine the magnetic nature of the nanoparticles used, and to show that the blocked state of nanoparticles was preserved in nanocomposites (hysteresis loops were also registered in the ferroelectric SmC* phase). The dependence of the coercive field on the admixture concentration and the widening of the hysteresis loop in nanocomposites in relation to pure nanoparticles were also found. In turn, the FT-MIR spectroscopy method was used to check the influence of the impurity concentration on the formation/disappearance or modification of the absorption bands, and the modification of both the FWHM and the maximum positions for the four selected vibrations in the MIR range, as well as the discontinuous behavior of these parameters at the phase transitions, were found.

Treatment-resistant mood disorders, including both major depressive disorder (MDD) and bipolar disorder (BD), are challenging to treat, as limited interventions exist. Ketamine exhibits an antidepressive effect in treatment-resistant depression. Abnormal copper levels might be associated with symptoms of depression. Impulsivity is related to measures of depression, both in MDD and in BD. The aim of this paper is to explore the associations between blood copper levels and impulsivity in patients who are treatment-resistant, in the course of treatment-resistant mood disorders. The paper does not support evidence for the link between copper concentrations and impulsivity outcomes in the course of short-term ketamine treatment., Competing Interests: Conflict of Interest: Jakub Słupski has received research support from Actavis, Eli Lilly, Minerva, Sunovion, Celon. Wieslaw Jerzy Cubała has received research support from Actavis, Alkermes, Allergan, Angelini, Auspex, Biogen, Bristol-Myers Squibb, Celon, Cephalon, Eli Lilly, Ferrier, Forest Laboratories, Gedeon Richter, GW Pharmaceuticals, Janssen, KCR, Lundbeck, Orion, Otsuka, Sanofi, and Servier; he has served on speakers’ bureaus for Adamed, Angelini, AstraZeneca, Bristol-Myers Squibb, Celon, GlaxoSmithKline, Janssen, Krka, Lekam, Lundbeck, Novartis, Orion, Pfizer, Polfa Tarchomin, Sanofi, Servier, and Zentiva; and he has served as a consultant for Celon, GW Pharmaceuticals, Janssen, KCR, Quintiles, and Roche. Natalia Górska has received research support from Actavis, Eli Lilly, Minerva, Sunovion, Celon. Anita Słupska: none to declare. Maria Gałuszko-Węgielnik has received research support from Alkermes, Biogen, Janssen, KCR, Otsuka, and Servier., (2021 authors.)

Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

The effect of the presence of titanium dioxide in two new imines, ( E , E )-(butane-1,4-diyl)bis(oxybutane-4,1-diyl) bis(4-{[(benzo[ d ][1,3]thiazol-2-yl)methylidene]amino}benzoate) (SP1) and ( E )- N -[(benzo[ d ][1,3]thiazol-2-yl)methylidene]-4-dodecylaniline (SP2), on the properties and stability of imine:TiO 2 composites for organic device applications were examined. The investigated titanium dioxide (in anatase form, obtained via the sol-gel method) exhibited a surface area of 59.5 m 2 /g according to Brunauer-Emmett-Teller theory, and its structure is a combination of both meso- and microporous. The average pore diameter calculated by the Barrett-Joyner-Halenda method was 6.2 nm and the cumulative volume of pores was 0.117 m 3 /g. The imine SP1 exhibited columnar organization (Col), while SP2 revealed a hexagonal columnar crystalline phase (Col hk ). The imine:TiO 2 mixtures in various weight ratio (3:0, 3:1, 3:2, 3:3) showed a lower energy gap and HOMO-LUMO energy levels compared to pure TiO 2 . This implies that TiO 2 provides not only a larger surface area for sensitizer adsorption and good electron collection, but also causes a shift of the imine energy levels resulting from intermolecular interaction. Also the temperature of the phase transition was slightly affected with the increase of TiO 2 concentration in imine-based composites. The changes observed in the Fourier transform middle-infrared absorption (FT-MIR) spectra confirmed the significant influence of TiO 2 on structural properties of both investigated imines. Similar interactions of oxygen vacancies existing on the TiO 2 surface with SP1 and SP2 were observed. The imine:TiO 2 mixtures showed good air stability and reusability, which demonstrates its potential for organic device applications.