A unique lead perrhenate crown ether complex, [Pb(12-crown-4)(H2O)(ReO4)2], exhibits an incommensurately modulated crystal structure at 101 K. In this (3 + 1)D superspace description, the ReO4- tetrahedra undergo continuous rotation. Describing their continuous rotation required introducing several constraints into the Legendre polynomials describing the displacive modulation of these atoms. At 296 K, the rotation of these tetrahedra is characterized by jumps between certain "stationary" positions. The average structure is monoclinic, P21/c with Z = 4, and can be described as comprising [Pb(C8H16O4)(ReO4)2(H2O)] ribbons. One half of the Pb2+ coordination sphere is occupied by the crown ether ligand, while the other is occupied by the oxygen atoms of water molecules and the perrhenate groups. The latter play two crystallographic roles: one bridging the PbO8 polyhedra and the other acting as a terminal ligand with a very rare monodentate (kappa 1) coordination. This is probably the reason for the nearly free rotation of these terminal ReO4 groups along the Pb-O-Re axis. The structural chemistry of lead crown ether complexes, even those with relatively simple counteranions, is expected to yield a wide variety of unique and complex structures.

Double complex salts (DCSs) of the composition [Co(NH3)6][Fe(CN)6] are a promising precursor for the preparation of catalysts for the hydrogenation of carbon oxides (CO and CO2) by Fischer–Tropsch synthesis. The specific surface area is an important parameter for catalysts. Our article investigates the influence of mechanochemical activation (MCA) on this DCS in order to determine the conditions for obtaining the largest specific surface area of the intermetallic compound, a product of the DCS thermolysis. In this work, the effect of MCA on the physicochemical properties of the DCS [Co(NH3)6][Fe(CN)6] and the products of its thermal decomposition in an argon atmosphere were investigated. It was shown that MCA leads to partial reduction of Fe+3 to Fe+2, changes in the coordination of ammonia, amorphization of the structure and a decrease in the thermal stability of DCS. Thermolysis at 650 °C of samples subjected to MCA for 10 min results in the formation of nanocrystalline intermetallic compound Co0.5Fe0.5. The results demonstrate the potential of using MCA to control the properties of functional materials based on DCS.

In this work, the effect of mechanical activation (MA) on the double complex salt (DCS) [Co(NH3)6][Fe(C2O4)3]·3H2O and its thermolysis is investigated. Mechanical activation is a promising “green chemistry” method that allows improving the physicochemical properties of the DCS [Co(NH3)6][Fe(C2O4)3]·3H2O and the products of its thermal decomposition in an argon atmosphere. The conditions of the MA process and the effect of MA and passivation on the process and kinetics of DCS thermal degradation were investigated. It was shown that due to the removal of outer-sphere coordinated water and carbonation of the DCS during MA, the number of thermal degradation stages changes. It was established that passivation at 450 °C for MA times of 0 and 10 min prevents spontaneous “combustion” of the thermal degradation products of the DCS. Optimal conditions for DCS processing were determined to be 5 min of MA and heat treatment at 450 °C without passivation. Under these conditions, the yield of the CoFe intermetallic compound reaches 82.6 wt%. This optimal combination of sample production conditions allows for a reduction in MA time and the elimination of the passivation process, making the process more cost-effective and creating conditions for optimizing the production of functional materials.

In this paper, results of studying the properties of armbrusterite, a natural heterophyllosilicate, are presented. Due to its crystal structure consisting of parallel HOH-type sheets separated by a network of large-diameter (4–6 Å) channels, this mineral is of interest as a prototype for producing novel compounds to be used as sorbents. The studies were conducted by X-ray powder diffraction and X-ray single crystal diffraction analyses, electron microscopy, and IR spectroscopy. The natural sample is shown to be able to selectively extract monovalent cations from the solution of complex composition consisting of mono- and divalent salts. Furthermore, the preliminary results of hydrothermal synthesis of an analog of this mineral are reported. It is demonstrated that the mineral can be produced under milder conditions than the known methods for synthesizing heterophyllosilicates using platinum capsules (Tuttle bombs) at 380–450 °C.

The method of obtaining functional materials almost always influences the physicochemical properties of the resulting substances. The plasma treatment of solid materials is considered to be a more energy efficient method when compared with thermal destruction. Our work is the first to treat double complex salt (DCS) [Co(NH3)6][Fe(CN)6] with different plasma discharge modes. We have demonstrated the possibility of obtaining a single-phase spinel with a CoFe2O4 structure as a result of the calcination in air of the plasma destruction product. The crystallite sizes of the obtained spinel are 40 nm, with a lattice constant 8.38 Å.

Complex compounds are under close scrutiny by scientists as precursors, which are needed to produce functional materials. When the thermolysis method of double complex salts is used on an industrial scale, the most detailed information on the thermal decomposition, including the kinetics of decomposition, is required. The kinetics of pyrolysis, solid, and gaseous products of [Co(NH3)6][Fe(C2O4)3]∙2H2O (I) and [Co(en)3][Fe(C2O4)3] (II) (en—ethylenediamine) thermolysis were studied in this work. The solid products of thermal decomposition were studied using scanning electron microscopy and elemental analysis, and the specific surface area (8 and 71 m2/g, respectively) was measured. It was determined that a double complex salt (DCS) with a coordinated en has a higher thermal stability than with NH3 due to the chelation effect.

Single crystals of a novel silver borate nitrate, Ag-12(B9O18)(NO3)(3) (1), were produced as a byproduct upon preparation of Ag3B6O10(NO3). 1 is hexagonal, (P6(3)/m, a = 11.2896(3) & Aring;, c = 11.6693(3) & Aring;); its structure exhibits just a second example of unique [B9O18](9-) nonaborate anions [9B:6 Delta 3 square:3(<2 Delta square>-)<3 square>] which can be described as three triborate groups linked in a large cycle. As commonly observed among silver borates, the Ag+ cations exhibit strongly anharmonic vibrations which were described using Gram-Chariler series up to 4th order. 1 is characterized by single-crystal X-ray diffraction, variable-temperature powder X-ray diffraction, IR, Raman, and UV-vis-NIR spectroscopy, complex thermal analysis, and DFT calculations. The thermal expansion of 1 is slightly anisotropic (alpha(a) = 15.0, alpha(c) = 17.7 x 10(-6) degrees C-1 at 200 degrees C). Upon heating, the compound decomposes with formation of metallic silver and another borate, AgBO2, which could be earlier prepared only at high oxygen pressure.

New silver-based representatives of the larderellite and veatchite families, Ag2B10O14(OH)4 center dot H2O (1) and Ag2B5O8(OH)center dot H2O (2) respectively, have been prepared using a soft hydrothermal synthetic approach inside a sealed silica tube. Both structures are built of the pentaborate groups yet exhibit various dimensionality: 2D for 1 and 1D for 2. The silver atoms in 1 exhibit noticeable anharmonicity approximated using Gram-Charlie approach. 1 was additionally characterized by thermal analysis, high-temperature X-ray powder diffraction and IR spectroscopy. Thermal expansion of 1 is strongly anisotropic (alpha 11 = 38, alpha 22 = -13, alpha 33 = 14 x 10-6 degrees C- 1) which is related with the hinge mechanism of the larderellite chains from corner-sharing pentaborate groups. Topology and complexity analysis of these compounds within the larderellite and veatchite families is presented.

Extensive searches for new monovalent metal borates as promising nonlinear optical materials continuously provide new exciting results. Attempts to add the iodine end-member of the acentric Na3B4O7X family resulted in a compound with a complex twofold monoclinic superstructure, Na17B24O42I5. As for the lighter-halide analogies, its crystal structure is formed by a 12B:infinity(3)[3(4:2 Delta + 2T)] framework of B4O9 tetraborate groups, 4B:2 Delta 2 square:=, yet the guest metal- halide sublattice is less dense and contains 5 NaI per 6 Na2B4O7 formula units, most likely due to the large size of the iodide ion. Upon heating in the presence of excess NaI, Na17B24O42I5 converts into a simple hexagonal Na3B4O7I structure, completely analogous to Na3B4O7Br, which exists above 444 degrees C.

Purple crystals of ethylenediammonium cobalt bis(hydrogen phosphite) dichloride were produced from an aqueous solution containing ethylenediamine, cobalt chloride, and phosphorous acid. The new compound is monoclinic, P 2 1 / c , a = 8.6665(3) Å, b = 7.2866(2) Å, c = 9.7300(3) Å, β = 112.726(3); V = 566.74(3) Å 3 , Z = 2. The 2D structure comprised ethylenediammonium cations sandwiched between the [Co(HPHO 3 ) 2 Cl 2 ] 2− layers. The latter are built of trans -CoO 4 Cl 2 octahedra linked by hydrogen-bonded dimers of hydrophosphite ions, (HPHO 3 ) 2 2− . The new compound is a complete structural analog of the recently reported (C 2 N 2 H 10 )[Co(HSeO 3 ) 2 Cl 2 ] and isostructural analogs with other transition metal dications; it is, in fact, the first representative of a new “layered hydrophosphite” family. Its structure provides yet another illustration of essential similarities in the crystal chemistry of selenites and phosphites, including protonated species, wherein the lone pair of Se IV and the nearly nonpolar P–H enhance formation of loose and/or open-framework structural architectures.

Crystals of the first new organo-inorganic hybrid borate based on potassium crown ether complex, [K(C12H24O6)B5O6(OH)(4)](H2O) (1), have been produced from aqueous solutions and characterized by single-crystal X-ray diffraction. 1 crystalizes is orthorhombic system, Pnma, a = 10.1684(3) & Aring;, b = 11.6289(3) & Aring;, c = 21.2247(6) & Aring;, V = 2509.76(12) & Aring;(3), R-obs = 0.059. The structure of 1 consists of molecular [K(C12H24O6)B5O6(OH)(4)](0) complexes, common for crown ether complexes but yet not among borates, with a very rare monodentate coordination of the common pentaborate anion(1-). The molecular complexes are linked into weak chains via hydrogen bonding to outer-sphere water molecules. Hirshfeld surfaces analysis and complexity measurement of 1 were performed. Perspectives of borate structures containing crown ether complexes as templates are briefly outlined.

A composite material based on electrospinning printed polyhydroxybutyrate fibers impregnated with brushite cement containing Zn substitution was developed for bone implant applications. Powder X-ray Diffraction (PXRD), Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy were applied for materials characterization. Soaking the composite in Ringer's solution led to the transformation of brushite into apatite phase, accompanied by the morphology changes of the material. The bending strength of the composite material was measured to be 3.1 ± 0.5 MPa. NCTC mouse fibroblast cells were used to demonstrate by means of the MTT test that the developed material was not cytotoxic. The behavior of the human dental pulp stem cells on the surface of the composite material investigated by the direct contact method was similar to the control. It was found that the developed Zn containing composite material possessed antibacterial properties, as testified by microbiology investigations against bacteria strains of Escherichia coli and Staphylococcus aureus. Thus, the developed composite material is promising for the treatment of damaged tissues with bacterial infection complications.

Purple crystals of ethylenediammonium cobalt bis(hydrogen phosphite) dichloride were produced from an aqueous solution containing ethylenediamine, cobalt chloride, and phosphorous acid. The new compound is monoclinic, P21/c, a = 8.6665(3) Å, b = 7.2866(2) Å, c = 9.7300(3) Å, β = 112.726(3); V = 566.74(3) Å3, Z = 2. The 2D structure comprised ethylenediammonium cations sandwiched between the [Co(HPHO3)2Cl2]2− layers. The latter are built of trans-CoO4Cl2 octahedra linked by hydrogen-bonded dimers of hydrophosphite ions, (HPHO3)22−. The new compound is a complete structural analog of the recently reported (C2N2H10)[Co(HSeO3)2Cl2] and isostructural analogs with other transition metal dications; it is, in fact, the first representative of a new “layered hydrophosphite” family. Its structure provides yet another illustration of essential similarities in the crystal chemistry of selenites and phosphites, including protonated species, wherein the lone pair of SeIV and the nearly nonpolar P–H enhance formation of loose and/or open-framework structural architectures.

An alternative approach for the currently used replacement therapy in dentistry is to apply materials that restore tooth tissue. Among them, composites, based on biopolymers with calcium phosphates, and cells can be applied. In the present work, a composite based on polyvinylpyrrolidone (PVP) and alginate (Alg) with carbonate hydroxyapatite (CHA) was prepared and characterized. The composite was investigated by X-ray diffraction, infrared spectroscopy, electron paramagnetic resonance (EPR) and scanning electron microscopy methods, and the microstructure, porosity, and swelling properties of the material were described. In vitro studies included the MTT test using mouse fibroblasts, and adhesion and survivability tests with human dental pulp stem cells (DPSC). The mineral component of the composite corresponded to CHA with an admixture of amorphous calcium phosphate. The presence of a bond between the polymer matrix and CHA particles was shown by EPR. The structure of the material was represented by micro- (30–190 μm) and nano-pores (average 8.71 ± 4.15 nm). The swelling measurements attested that CHA addition increased the polymer matrix hydrophilicity by 200%. In vitro studies demonstrated the biocompatibility of PVP-Alg-CHA (95 ± 5% cell viability), and DPSC located inside the pores. It was concluded that the PVP-Alg-CHA porous composite is promising for dentistry applications.

Reducing the amount of CO2 in the atmosphere is a very important task. Therefore, the development and search for new approaches to the synthesis of catalytic systems, allowing for the catalytic conversion of CO2 into valuable products, is an urgent task. In this work, the catalyst was obtained by the thermolysis of a double complex compound. In this regard, kinetic studies of the parameters of the thermolysis process of double complex salts-[Co(NH)3]6][Fe(CN)6] were additionally determined using isoconversion and model approaches of non-isothermal kinetics. The catalyst was studied using various physicochemical methods—X-ray diffraction (XRD), infrared (IR)-spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). It was shown that, at the stage of catalyst preparation, the formation of a CoFe alloy occurred, while the surface mainly consisted of carbon in sp2-hybridization, and the metals existed in the form of spinel CoFe2O4. It was shown that catalysts based on bimetallic salts were active in the process of hydrogenation of carbon dioxide without a pre-activation stage (CO2 conversion reached 28%, with a specific activity of 4.0 µmolCO2/gMe·s). It was established that it was possible to change the selectivity of the carbon dioxide hydrogenation process by pre-treating the catalyst with hydrogen (selectivity for methane formation in the presence of an unreduced catalyst is 46.4–68.0%, whereas in the presence of a reduced catalyst it is 5.1–16.5%).

β-Tricalcium phosphate (β-TCP) is widely used as bone implant material. It has been observed that doping the β-TCP structure with certain cations can help in combating bacteria and pathogenic microorganisms. Previous literature investigations have focused on tricalcium phosphate structures with silver, copper, zinc, and iron cations. However, there are limited studies available on the biological properties of β-TCP containing nickel and cobalt ions. In this work, Ca10.5−xNix(PO4)7 and Ca10.5−xCox(PO4)7 solid solutions with the β-Ca3(PO4)2 structure were synthesized by a high-temperature solid-state reaction. Structural studies revealed the β-TCP structure becomes saturated at 9.5 mol/% for Co2+ or Ni2+ ions. Beyond this saturation point, Ni2+ and Co2+ ions form impurity phases after complete occupying of the octahedral M5 site. The incorporation of these ions into the β-TCP crystal structure delays the phase transition to the α-TCP phase and stabilizes the structure as the temperature increases. Biocompatibility tests conducted on adipose tissue-derived mesenchymal stem cells (aMSC) using the (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) (MTT) assay showed that all prepared samples did not exhibit cytotoxic effects. Furthermore, there was no inhibition of cell differentiation into the osteogenic lineage. Antibacterial properties were studied on the C. albicans fungus and on E. coli, E. faecalis, S. aureus, and P. aeruginosa bacteria strains. The Ni- and Co-doped β-TCP series exhibited varying degrees of bacterial growth inhibition depending on the doping ion concentration and the specific bacteria strain or fungus. The combination of antibacterial activity and cell-friendly properties makes these phosphates promising candidates for anti-infection bone substitute materials.

Chamaenerion angustifolium (L.) Scop. is one of the promising sources of biologically active compounds and a valuable industrial crop. Recently, green extraction methods have become more topical. One of them is the application of deep eutectic solvents (DESs). The aim of this work was the synthesis and characterization of DES consisting of glycerin or propylene glycol with malonic, malic, or citric acids, evaluation of their effectiveness for extracting useful substances from C. angustifolium during ultrasonic extraction, description of kinetics, and optimization of extraction conditions. DESs were obtained and characterized with FTIR. Their effectiveness in the process of ultrasound-assisted extraction of biologically active substances from C. angustifolium was estimated. Kinetic parameters describing the dependence of the total phenolic, flavonoids, and antioxidant content, free radical scavenging of DPPH, and concentration of flavonoid aglycons (myricetin, quercetin, and kaempferol) via time in the range of 5–60 min at 45 °C are obtained. Extraction conditions were optimized with the Box–Behnken design of experiment. The results of this work make it possible to expand the scope of DES applications and serve the development of C. angustifolium processing methods.

Chamaenerion angustifolium (L.) Scop. (fireweed) is a perennial herbaceous plant of the Onagraceae family widely used in folk and scientific medicine. It is a promising source of bioactive components. One of the modern trends in extraction is the use of natural deep eutectic solvents (NADESs) combined with ultrasound-assisted extraction (UAE). However, works devoted to the extraction of biologically active substances from C. angustifolium using NADESs are scarce. The aim of this work is a comprehensive study of UAE of bioactive components from C. angustifolium using NADESs based on choline chloride and malonic, malic, tartaric, and citric acids. The antioxidative properties, total phenols, and flavonoids content were estimated for NADES-based extracts. The reference solvents were water and 90% v/v ethanol. Volatile extracted components were identified using GC-MS. The kinetics of the UAE were studied at 45 °C for 20–180 min with water added to 30 wt% NADES. The power of the ultrasound was 120 W, and the frequency was 40 kHz. It was found that NADES choline chloride + citric acid is more effective for the extraction of bioactive components. For this, NADES UAE conditions were optimized following a Box–Behnken design of the experiment and a response surface methodology. The temperature ranged from 30 to 60 °C, the time of extraction ranged from 20 to 60, and the addition of water ranged from 30 to 70 wt%. We established the optimal extraction conditions: temperature 58 °C, time of extraction 35 min, and 70 wt% water. The obtained results expand the knowledge about the use of NADES for the extraction of biologically active compounds from cheap and available plant raw materials.