Formation of mononuclear rhodium(III) sulfates: <Superscript>103</Superscript>Rh and <Superscript>17</Superscript>O NMR study

It was shown that the monomeric rhodium sulfate complexes [Rh(H₂O)₄(SO₄)]⁺, trans-[Rh(H₂O)₂(SO₄)₂]^?, cis-[Rh(H₂O)₂(SO₄)₂]^?, and [Rh(SO₄)₃]^3? were not predominant forms in aqueous solutions. The ¹⁰³Rh NMR chemical shifts of the complexes were assigned, and the conditions for their formation in solutions, concentration parameters, and acidity at which the fraction of the monomers was maximal were determined. The constants of formation of the complexes and ion pair (IP) were estimated: K _IP = 8 ± 3.5, K ₁ ≈ 8, K _2trans ≈ 1, K _2cis ≈ 1, and K ₃ ≈ 2.     

Microwave-assisted solvent-free synthesis and luminescence properties of 2-substituted-4,5-di(2-furyl)-1<Emphasis Type="Italic">H</Emphasis>-imidazoles

A solvent-free microwave-assisted method for the synthesis of 2-substituted-4,5-di(2-furyl)-1H-imidazoles was developed. Imidazoles with moderate to good yields were produced by condensation of furil with aldehydes over acidic alumina impregnated with ammonium acetate, and they were characterized by FT-IR, HRMS, ¹H NMR and ¹³C NMR spectroscopy. Crystal structure of 2,4,5-tri-2-furyl-1H-imidazole (I) in the orthorhombic space group Pbca was reported, which showed more coplanarity than the reported crystal structure of I in the monoclinic space group Cc. Moreover, their luminescent properties were investigated. It was found that the organic small molecule compounds synthesized possess higher fluorescence quantum efficiency (up to 0.508) in a 0.1 M H₂SO₄ aqueous solution dissolved in 0.5 mL of CH₃OH; along with higher stability; also the emission of some compounds synthesized in the solution was sensitive to the polarity of the solvents.     

<Emphasis Type="Italic">N</Emphasis>-allyl and <Emphasis Type="Italic">N</Emphasis>-propargyl trifluoromethanesulfonimides. Theoretical analysis

Tautomers of N-allyl- and N-propargyl-substituted trifluoromethanesulfonimides (CF₃SO₂)₂NR (R = CH₂CH=CH₂, Z/E-CH=CHMe, CH₂C≡CH, CH=CH=CH₂, C≡CCH₂) were calculated by the DFT (B3LYP, wB97XD, PBE1PBE), MP2, and CBS-QB3 methods. The results were compared with the theoretical data for the corresponding amines and amides NHRR¹ (R¹ = H, CF₃SO₂). It was shown that there is no conjugation between the nitrogen atom and C=C bond and that conjugation exists with the C≡C bond with electron density displacement toward the nitrogen atom. The calculations of anions derived from N-allyl- and N-propargyl-trifluoromethanesulfonimides revealed the possibility of their rearrangement with elimination of trifluoromethanesulfinate anion and formation of its H-complex with N-(prop-2-en-1-ylidene)trifluoromethanesulfonamide or N-(prop-2-yn-1-ylidene)trifluoromethanesulfonamide.     

Direct electrochemistry and electrocatalysis of cytochrome <Emphasis Type="Italic">c</Emphasis> based on dandelion-like Bi<Subscript>2</Subscript>S<Subscript>3</Subscript> nanoflowers

The direct electrochemistry and electrocatalysis of cytochrome c (Cyt c) based on dandelion-like bismuth sulfide (d-Bi₂S₃) nanoflowers have been developed. The morphologies and composition of the d-Bi₂S₃ were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS). Then, the electrochemical behaviors of Cyt c immobilized within the d-Bi₂S₃/chitosan film and its electrocatalytic ability toward hydrogen peroxide (H₂O₂) reduction were investigated by cyclic voltammetry. The electron transfer rate constant was estimated to be 13.1 s^?1, suggesting that a fast direct electron transfer was realized. The prepared Cyt c/d-Bi₂S₃/chitosan nanobiocomposite-modified electrode possessed excellent electrocatalytic ability toward H₂O₂ reduction that showed linearity in the range from 0.5 μM to 1.56 mM with a correlation coefficient of 0.9993. The detection limit was 0.2 μM on signal-to-noise ratio of 3. In addition, the d-Bi₂S₃ nanoflowers may be also applied to direct electron transfer of other redox proteins.     

Structural Characterization of a Novel Antioxidant Pigment Produced by a Photochromogenic <Emphasis Type="Italic">Microbacterium oxydans</Emphasis> Strain

The Microbacteriaceae family, such as Microbacterium, is well known for its ability to produce carotenoid-type pigments, but little has been published on the structure of such pigments. Here, we isolated the yellow pigment that is responsible for the yellowish color of a Microbacterium oxydans strain isolated from a decomposing stump of a resinous tree. The pigment, which is synthesized when the bacterium is grown under light, was purified and characterized using several spectroscopic analyses, such as ultraviolet-visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FTIR), ¹H and ¹³C nuclear magnetic resonance (¹H NMR, ¹³C NMR), and high-resolution mass spectrometry (HRMS). From these analysis, a molecular formula (C₂₇H₄₂O₂) and a chemical structure (8-hydroxymethyl-2,4,12-trimethyl-14-(2,6,6-trimethyl-cyclohex-2-enyl)-teradeca-3,7,9,11,13-pentan-2-ol) were deduced. The chemical properties of the pigment, such as aqueous stability at different pH, stability in different organic solvents, and antioxidant capacity, are also reported. Together, these data and previous studies have resulted in the identification of a new antioxidant pigment produced by M. oxydans. To the best of our knowledge, this is the first thorough investigation of this carotenoid-like pigment in the Microbacterium genera.     

X-ray study of rhodium(III) sulfates

Compounds with compositions [Rh(H₂O)₆]₂(SO₄)₃·4H₂O (I), (H₃O)[Rh(H₂O)₆](SO₄)₂ (II), [Rh(H₂O)₅OH](SO₄)·0.5H₂O (III), and [Rh(H₂O)₆]₂(SO₄)·(H₂SO₄) _x ·5H₂O (IV) have been studied. The crystal structures of II, III, and IV were determined. All compounds crystallized in the monoclinic crystal system. Crystal data for II: a = 7.279(2) Å, b = 10.512(7) Å, c = 15.806(3) Å, β = 96.71(3)°, space group P2₁/n, Z = 2, d _calc = 2.334 g/cm³; III: a = 20.433(4) Å, b = 7.820(2) c = 11.215(2) Å, β = 114.14(1)°, space group C2/c, Z = 8, d _calc = 2.559 g/cm³; IV: a = 6.2250(4 Å), b = 27.0270(12) Å, c = 7.2674(5) Å, β = 97.04(3)°, space group P2₁/c, Z = 4, d _calc = 2.143 g/cm³. The compounds were studied by IR spectroscopy and powder X-ray diffraction. All of the isolated crystalline phases are sparingly soluble in ethanol and well soluble in water.     

Performance and characterisation of CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript>-WO<Subscript>3</Subscript> catalysts for selective catalytic reduction of NO with NH<Subscript>3</Subscript>

Ce-Ti-W-O _x catalysts were prepared and applied to the NH₃-selective catalytic reduction (SCR) reaction. The experimental results showed that the Ce-Ti-W-O _x catalyst prepared by the hydrothermal method exhibited higher NO conversion than those synthesised via the sol-gel and impregnating methods, while the optimal content of WO₃ and molar ratio of Ce/Ti were 20 mass % and 4: 6, respectively. Under these conditions, the catalyst exhibited the highest level of catalytic activity (the NO conversion reached values higher than 90 %) across a wide temperature range of 225–450°C, with a range of gas hourly space velocity (GHSV) of 40000–140000 h^?1. The catalyst also exhibited good resistance to H₂O and SO₂. The influences of morphology, phase structure, and surface properties on the catalytic performance were investigated by N₂ adsorption-desorption measurement, XRD, XPS, H₂-TPR, and SEM. It was found that the high efficiency of NO removal was due to the large BET surface area, the amorphous surface species, the change to element valence states, and the strong interaction between Ce, Ti, and W.     

Synthesis,structural, spectral,thermal and comparative biological activity studies of [V<Subscript>2</Subscript>O<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]

The hydrothermal reaction of a mixture of V₂O₅, VCl₃, 2,5-pyridinedicarboxylic acid and diluted H₂SO₄ for 68 h at 180°C gives a blue colored solution which yields prismatic blue crystals of IV ₂ ^IV O₂(SO₄)₂(H₂O)₆] (1) in 32% yield (based on V). Complex 1 was investigated by means of elemental analysis (C, H and S), TGA, FT-IR, manganometric titration, Single Crystal X-ray Diffraction Methods and also comparative antimicrobial activities. Crystal data for the compound: monoclinic space group P2₁/c and unit cell parameters are a = 7.3850(12) Å, b = 7.3990(7) Å, c = 12.229(2) Å, β = 108.976(12)° and Z = 2. Although structure of 1 as a natural mineral has been previously determined, this work covers new preparation method and full characterization of 1 along with comparison of antibacterial activity between 1 and the commercial vanadium(IV) oxide sulfate hydrate compounds, VOSO₄ · xH₂O (Riedel-de Haën and Alfa Aesar brand names). 1 was evaluated for the antimicrobial activity against gram-positive, gram-negative bacteria, yeasts and mould compared with the commercial VOSO₄ · xH₂O compounds. 1 showed weak activity against bacteria Bacillus cereus, Nocardia asteroides and yeast Candida albicans. A good antimicrobial activity was recorded against Cirtobacter freundii (15 mm). There are only a few reproducible well-defined vanadium(IV) starting materials to use for exploring the synthesis of new materials. VCl₄, VO(acac)₂, VOSO₄ · xH₂O and [V(IV)OSO₄(H₂O)₄] · SO₄ · [H₂N(C₂H₄)₂NH₂] are common starting materials for such applications. In addition to these compounds, 1 can be used as an oxovanadium precursor.     

A new high-spin iron(III) bis(aqua) complex with the <Emphasis Type="Italic">meso</Emphasis>-tetra(para-chlorophenyl)porphyrin: X-ray crystallography,Hirshfeld surface analysis,magnetic, EPR and electrochemical properties

Chemical preparation of the bis(aqua) iron(III) metalloporphyrin [Fe^III(TClPP)(H₂O)₂](SO₃CF₃)·2(Pnz)·3/4(C₆H₁₂)·2H₂O (TClPP?=?TClPP?=?5,10,15,20-tetra(para-chlorophenyl)porphyrinato and Pnz?=?phenazine) coordination complex (I) was made. The crystal structure of (I) was determined by X-ray single-crystal diffraction and elucidated by Hirshfeld surface approach. Magnetic, spectroscopic and electrochemical properties were also reported and discussed. The mean equatorial distance (Fe–Np) between the iron(III) atom and porphyrin nitrogen atoms is appropriate to a high-spin (S?=?5/2) iron(III) complex. The high-spin state is also confirmed by both magnetic and electron paramagnetic resonance (EPR) spectroscopy data. The repetitive building unit of the crystal structure provides [Fe^III(TClPP)(H₂O)₂]⁺ ion complexes, two non-coordinated Pnz molecules and two water molecules which are interconnected by O–H···O/N/Cl, C–H···O/F/Cl hydrogen bonds, and by C–X···π, C–H···π and π–π stacking intermolecular contacts, forming a 3D supramolecular network. The role and nature of these intermolecular interactions were quantitatively analysed by 3D Hirshfeld surface analysis and associated 2D fingerprint plots. Cyclic voltammetry measurements indicate a one-electron reversible reduction wave with an E_1/2 (Fe(III)/Fe(II) half-potential value of ?0.24 V, which confirms the high-spin S?=?5/2 state of the studied complex.     

Kinetics of Na|CF<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and Li|CF<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> systems

Properties of CF _x /Li and CF _x /Na cells were examined while using galvanostatic charging/discharging, electrochemical impedance spectroscopy and scanning electron microscopy (SEM). The capacity during the first cycle was as high as ca. 1000 mAh g^?1. Such an electrode is suitable for primary CF _x /Li and CF _x /Na batteries. SEM images of CF _x cathode showed that during discharging it was transformed into amorphous carbon and LiF or NaF crystals (of diameter of ca. 5–20 μm). These systems (C?+?LiF or C?+?NaF) cannot be reversibly converted back into CF _x /Li or CF _x /Na, respectively. Exchange current densities are between 10^?7 Acm^?2 and 10^?9 Acm^?2 when working with LiPF₆ and NaPF₆ electrolytes (1.12?×?10^?7 Acm^?2 and 6.82?×?10^?9 Acm^?2, respectively). Those values are low and indicate that the charge transfer process may be the rate-determining step. Activation energies for the charge transfer process were 57 and 72 kJ mol^?1 for CF _x /LiPF₆ and CF _x /NaPF₆ systems, respectively. Higher activation energy barrier for the CF/Na⁺?+?e^??→?C?+?NaF reaction results in lower observed exchange current density in comparison to the system with lithium ions.     

BiVO<Subscript>4</Subscript>-NPs: an efficient nano-catalyst for the synthesis of biscoumarins,bis(indolyl)methanes and 3,4-dihydropyrimidin-2(1<Emphasis Type="Italic">H</Emphasis>)-ones (thiones) derivatives

BiVO₄-NPs can be used as an efficient and reusable nano-catalyst for the promotion of the synthesis of biscoumarins, bis(indolyl)methanes and 3,4-dihydropyrimidin-2(1H)-ones (thiones) derivatives. The structures of the products were characterized by IR, ¹H NMR and ¹³C NMR spectroscopy and comparison with the authentic samples. Easy work-up procedure, excellent yields, short reaction times and reusability of the catalyst are some advantages of this work. In addition, in this article and for the first time, the preparation of 3,4-dihydropyrimidin-2(1H)-ones and -thiones from the protected derivatives of aldehydes including oximes, semicarbazones and 1,1-diacetates is reported.     

Structure of hexaaquamagnesium (II) bis(4-<Emphasis Type="Italic">p</Emphasis>-aminobenzenesulfamido-2,6-dimethoxypyrimidinate) pentahydrate

The X-ray analysis of a single crystal of Mg(C₁₂H₁₃N₄O₄S)₂·11H₂O, where (C₁₂H₁₃N₄O₄S)^? is the anion of 4-p-aminobenzenesulfamido-2,6-dimethoxypyrimidine (sulfadimethoxine) is carried out. Unit cell parameters are: a = 19.753(4) Å, b = 34.031(7) Å, c = 13.859(3) Å; β = 125.37(3)°, C2/c, Z = 8, R(F) = 0.042. The structure is built of [Mg(OH₂)₆]²⁺, (C₁₂H₁₃N₄O₄S)^?, and water molecules and corresponds to the formula [Mg(OH₂)₆](C₁₂H₁₃N₄O₄S)₂·5H₂O. The IR bands of ν_asymSO₂ and ν_symSO₂ are bathochromically shifted as a result of their participation in hydrogen bonding, and not because of any direct coordination of sulfadimethoxinate anion to the complexing atom through oxygen.     

Effects of lutetium doping on the X-ray-excited luminescence properties of the tungstate Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Lu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>WO<Subscript>4</Subscript>

Polycrystalline samples in the lutetium-doped zinc tungstate system Zn_1?x Lu _x WO₄ with 0 ≤ x ≤ 0.08 were synthesized using the coprecipitation method followed by thermal treatment at 1000 °C during 4 h. The polycrystalline samples were characterized by X-ray diffraction analysis, scanning electron microscopy (SEM), infrared spectroscopy, and luminescence analysis under X-ray excitation. Rietveld analyses were performed. The variation of the wolframite structure cell parameters in the range 0 ≤ x ≤ 0.05 were congruent with substitution of Zn²⁺ by Lu³⁺. SEM micrographs of the obtained samples presented improved crystallization with morphology depending on the lutetium fraction. The luminescence spectra obtained under X-ray excitation (E < 40 keV) were in the blue–green region, and their intensity increased with x up to x = 0.05. The differences in the intensities of the X-ray luminescence spectra could be related to additional cation vacancies resulting from substitution of Zn²⁺ by Lu³⁺.     

NiMoW/P-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Hydrotreating Catalysts: Influence of the Mo/W Ratio on the Hydrodesulfurization and Hydrogenation Activity

A series of NiMoW/P-Al₂O₃ catalysts with different Mo/W ratios (sample containing Mo only, Mo/W = 2: 1, Mo/W = 1: 1, Mo/W = 1: 2, and sample containing W only; P₂O₅ content of the support 2.0 wt %) were synthesized. The precursors of the active phase were the heteropoly acids H₃PMo₁₂O₄₀?nH₂O and H₃PW₁₂O₄₀?nH₂O, and also nickel citrate. The sulfide phase in the samples was studied by high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy; the catalytic activity of the samples in dibenzothiophene hydrodesulfurization and naphthalene hydrogenation was determined. For the dibenzothiophene hydrogenolysis in the presence of quinoline and naphthalene (content in the model mixture, wt %: dibenzothiophene 0.3, naphthalene 1.5, and quinoline 0.5), k_HDS for different samples is in the range 17.6–42.5 h^–1 at 275°C and 24.6–45.9 h^–1 at 300°C. For the naphthalene hydrogenation, k_HYD varies from 0.79 to 1.89 h^–1 at 275°C and from 0.91 to 3.78 h^–1 at 300°C. The sample based on molybdenum showed the highest activity in hydrogenation and hydrodesulfurization.     

Synthesis,structure, and properties of M<Subscript>3</Subscript>VO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> (M = Rb,Cs)

Vanadium(V) complexes of general composition M₃VO₂(SO₄)₂ (M = Rb, Cs) were synthesized by a solid-state route. The individuality of the synthesized compounds was proved by X-ray and neutron diffraction, vibrational spectroscopy, and microscopic analysis. The X-ray diffraction patterns of M₃VO₂(SO₄)₂ were indexed to fit the monoclinic system (space group P2/c, Z = 4) with the following unit cell parameters: a = 11.6487(2) Å, b = 8.4469(2) Å, c = 12.1110(2) Å, β = 109.483(1)°, V = 1123.43 ų (Rb); a = 12.0546(3) Å b = 8.7706(2) Å, c = 12.6496(3) Å, β = 109.843(2)°, V = 1257.99 ų (Cs). In the crystal structure of M₃VO₂(SO₄)₂, [VO₂(SO₄)₂]^3? complex anions can be discerned in which the vanadium atom is surrounded by five oxygen atoms: two oxygen atoms form short terminal V–O bonds, and three oxygen atoms are from the two sulfato groups, one of which acts as a monodentate ligand and the other acts as a bidentate chelating ligand.     

Synthesis,Structure, and Antiproliferative Activity of <Emphasis Type="Italic">trans</Emphasis>-Palladium(II) Complexes with Tetrazol-2-ylacetic Acid Derivatives

A series of trans-palladium(II) complexes (trans-[PdCl₂L₂], L = ethyl 5-R-2H-tetrazol-2-ylacetate, 5-R-2H-tetrazol-2-ylacetamides, R = Me, Ph) has been synthesized, and their structure has been proved by ¹H and ¹³C–{¹H} NMR and high-resolution mass spectra and X-ray analysis. Antiproliferative activity of the synthesized complexes has been determined, and the mechanism of their interaction with DNA has been studied by UV and CD spectroscopy.     

Structural characterization of a mixed-ligand complex of copper(II) with 1,10-phenanthroline and the <Emphasis Type="Italic">m</Emphasis>-aminobenzoate ion

A new copper(II) complex of 1,10-phenanthroline (C1₂H₈N₂) and the meta-aminobenzoate ion (m-amb; C₇H₆NO ₂ ^? ), having the formula Cu(C₁₂H₈N₂)(C₇H₆NO₂)Cl?0.5H₂O, is prepared and characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. The structure is built up from monomeric units in which the coordination environment around the metal ion is a square plane arising from a bidentate 1,10-phenanthroline molecule, a monodentate m-amb anion, and a chloride ion. A very long (Cu–N = 2.856(5) Å) bond to the nitrogen atom of an adjacent m-amb ion generates [101] polymeric chains in the crystal. The crystal structure is consolidated by N–H???O and O–H???O hydrogen bonds and C–H???O, C–H???Cl, and aromatic π–π stacking interactions. Crystal data: C₁₉H₁₅ClCuN₃O_2.5, M _r = 424.33, monoclinic, P2₁/n (No. 14), a = 9.8200(5) Å, b = 10.9291(7) Å, c = 16.3803(9) Å, β = 105.293(3)°, V = 1695.74(17) ų, Z = 4, R(F) = 0.043, wR(F ²) = 0.122.     

Structure and proton-donating ability of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(2-phenylacetyl)methanesulfonamide

According to the data of quantum-chemical calculations and IR spectroscopy the trifluoro-N-(2-phenylacetyl)methanesulfonamide CF₃SO₂NHC(O)CH₂Ph in the isolated state and in inert media exists in the form of two conformers with the syn- and antiperiplanar orientation of the C=O and N-H bonds. Its self-associates in the CCl₄ solution and in molecular crystals constitute cyclic dimers formed by the NH···O=S bonds and chain dimers with the NH···O=C bonds. As a hydrogen bond donor, trifluoro-N-(2-phenylacetyl)methanesulfonamide is stronger than N-methyltrifluoromethanesulfonamide. Its pK _a in methanol is 5.45, that is 5 pK units lower than for amides CF₃SO₂NHR and 2 pK units higher than for imide (CF₃SO₂)₂NH.     

Thermal behavior of quinoline <Emphasis Type="Italic">N</Emphasis>-oxide hydrates and deuterohydrate

Spectral and thermochemical investigation of physicochemical properties of quinoline N-oxide crystallohydrates with H₂O and D₂O is carried out. Quinoline N-oxide is established to form with H₂O a stable dihydrate where two water molecules are energetically not equal. Complete dehydration of quinoline N-oxide occurs when temperature reaches 150°C. With accounting for the obtained thermochenical data, quinoline N-oxide and its mono- and dihydrates are isolated in the individual state and their IR spectra are registered and considered. It is established that at boiling quinoline N-oxide in D₂O proceeds chemical reaction affording isoindoline-1,3-dione (phthalimide). The product is identified by elemental analysis and ¹H NMR and IR spectroscopy. The band assignment in the IR spectra of quinoline N-oxide, phthalimide and of the complex of the latter with D₂O is based on the quantum-chemical DFT calculations.     

Specific Features of the Structure of Chelate Complexes of <Emphasis Type="Italic">N</Emphasis>-Thiocarbamoylamidophosphates with Zn(II) and Cd(II) Cations

The reaction of potassium salts of N-thiocarbamoylamidophosphates RC(S)NHP(O)(OPr-i)₂X [X = PhNH, p-MeOPhNH, p-BrPhNH, i-PrNH, t-BuNH, Et₂N, C₅H10N, OC₄H₈N, C₆H₁₁NH] with Zn(II) cation gives complexes of the composition Zn(L-O,S)₂. The Cd(II) complexes could not be isolated under analogous conditions because of their hydrolytic lability. The reaction of thioureas (X = PhNH, p-MeOPhNH) with Cd(II) acetate in DMF provides stable solvato complexes of the composition Cd(DMF)₂L₂. The structure of the resulting compounds was studied by means of IR, ¹H, and ³¹P NMR spectroscopy and EI and ESI mass spectrometry.