Metal-free boron carbonitride (BCN) has attracted considerable interest for photoelectrochemical water splitting applications. However, its utility is limited by inadequate charge carrier transport, serious charge recombination and suboptimal surface catalytic activity. Herein, we propose a novel boron carbon (BCx) tuning layer strategy to address these limitations. By employing an integrated one-stop approach, BCN nanowalls are vertically grown on BCx film surfaces via plasma-enhanced chemical vapor deposition (PECVD) for fabrication photoelectrodes. Experimental analyses and band structure studies confirm that the BCx tuning layer not only promotes the formation of vertically aligned BCN nanowall arrays, but also serves as an efficient electron transfer pathway for photogenerated electrons. This inhibits charge recombination and enhances charge separation, thereby making more holes available as active sites for photoelectrochemical reactions. Consequently, the BCN/BCx photoanode achieves a water oxidation photocurrent of 0.82 mA cm(-2) at 1.23 V, a 4.6 times improvement over pristine BCN. Furthermore, the BCN/BCx photoanode demonstrates remarkable stability, maintaining a steady photocurrent under continuous illumination for 100 h. This innovative tuning layer strategy offers promising prospects for advanced applications in catalysis, sensors, transistors and beyond.

This article explores the application of high-power impulse magnetron sputtering (HPIMS) with an additional discharge generated by a small anode to synthesize titanium dioxide coatings. The effect of resputtering on film porosity is examined. The films were annealed at 500°C in air and nitrogen to obtain the crystalline anatase phase. The effect of the additional discharge on the charged particle current to the substrate is examined. Differences in coating porosity are identified. The dimensions of the coherent scattering region (CSR) were measured and found to be comparable to the film thickness. Microstress and Urbach energy values were also calculated, and an analysis of the correlation between these parameters for porous coatings was performed.

The phase formation in the Hf1–xTixO2 and Zr1–xTixO2 (x = 0–1) thin films obtained by atomic layer deposition has been systematically investigated. The elemental composition, long-range order, and short-range atomic structure of the as-deposited and vacuum-annealed (700–900°C) films were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, Raman and IR spectroscopy. The results show that the crystallization behavior is highly dependent on the Ti content (x) and post-deposition annealing. As-deposited films are predominantly amorphous for 0.13 < x < 0.875, while binary and lightly alloyed oxides (x ≈ 0 or x ≈ 1) are polycrystalline. Annealing induces crystallization into distinct phase regions: solid solutions based on HfO2 or ZrO2 phases at low x, orthorhombic HfTiO4 or ZrTiO4 titanates at intermediate x = 0.25–0.5, mixtures of titanates with TiO2 phases at x = 0.67–0.75 and anatase-based solid solutions at higher x. IR spectroscopy demonstrates the presence of the bands characteristic of TiO2 phases (anatase, rutile) across a wide concentration range. This study elucidates the non-equilibrium phase evolution in ALD-grown Hf–Ti–O and Zr–Ti–O films, highlighting the critical influence of composition and thermal treatment on the resulting structure.

The speciation of Ag+ in DMSO remains a challenging question due to the formation of equilibrated polynuclear species of unknown nature. This contribution illustrates a possible presence of [Ag4(µ2-DMSO)6(DMSO)2]4+ polynuclear moiety as a component of Ag+ speciation in DMSO solution. This cation was isolated in the solid state by the assist of [SiW12O40]4– as a counter anion. The dried crystals of [Ag4(µ2-DMSO)6(DMSO)2][SiW12O40]·3DMSO·0.7H2O (1) have been characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), FT-IR and TGA. Argentophilic interactions in the cation were studied by quantum-chemical calculations, revealing non-uniform Ag–O interaction of the “central” DMSO ligand with three closest surrounding Ag atoms. The solutions of 1 in CH3CN were studied by high performance liquid chromatography coupled with ICP (HPLC-ICP-AES) and electrochemistry. The results indicate that the [Ag4(µ2-DMSO)6(DMSO)2]4+ complex undergoes speciation in the solution with the formation of several silver containing species, whose chromatographic indication is possible owing to slow exchange kinetics between DMSO and CH3CN ligands. Such mixed ligand complexes are quite unusial and need further characterization.

Crystal structure of volatile sodium beta-diketonates with bulky ligands tmhd and mtmhd was studied by X-ray diffraction (tmhd= 2,2,6,6-tetramethyl-heptane-3,5-dionate; mtmhd= 2,2-dimethyl-6-methoxy-6-methyl-heptane-3,5-dionate. Na(tmhd) (1) was established to be polymeric in solid state, featuring highly coordinationdeficient environment of Na atoms by O atoms with the coordination number amounting to 4 and 5. Methoxy-substituted analog Na(mtmhd) (2) forms crystals comprising hexanuclear molecules with all oxygen atoms engaged in coordination with sodium atoms. The thermal properties of the compounds were studied by vacuum sublimation and TGA. Heterometallic Na-Ni complexes were prepared by cocrystallisation of the sodium complexes with Ni(SB), where SB: acacen = N,N'-ethylenebis(acetylacetoniminate), CH3acacen = N,N'-propylenebis(acetylacetoniminate). [Ni(acacen)Na(tmhd)]2 (3) and [(Ni(CH3acacen))2(Na(tmhd))3] (4) were isolated and their crystal structure was determined by X-ray diffraction. It was established that compounds 3 and 4 are volatile and sublime when heated in vacuum. Preliminary results of chemical vapour deposition of Na-Ni-O films using 3 are discussed.

This contribution reports a new route to silver(I) based coordination polymers (CPs) with dicarboxylate linkers and pyridines (py-R) as auxiliary ligands. First of all, silver(I) terephthalate ([Ag2C6H4(COO)2]n, 1), silver(I) maleate ([Ag2C2H2(COO)2]n, 2) and silver(I) malate ([Ag2C2H3(OH)(COO)2]n, 3) were prepared. Next, they were dissolved in neat pyridine or picoline. Colorless crystals of CPs formulated as [Ag2(4-Me-py)3C6H4(COO)2]n (4), [Ag2(2-Me-py)4C6H4(COO)2]n (5) and molecular complex [Ag4(2-Me-py)6C2H2(COO)22] (6) were isolated from the solutions. Addition of 4,4’-bipyridine (bpy) into the solution of silver(I) malate in pyridine produced crystals of a two-dimensional coordination polymer formulated as [Ag2(bpy)2C2H3(OH)(COO)2]n·2nH2O (7). Both 4 and [Ag2(2-Me-py)4C6H4(COO)2]n (5) are luminescent with a blue-green emission.

Graphene oxide (GO) is used for sorption preconcentration of heavy metals (HMs) from aqueous solutions, where the influence of the matrix is insignificant, or from biological samples, but existing methods are mainly aimed at determining one or a few analytes. However, for complete information of the state of the organism and the environment, it is advisable to perform multi-element analysis of samples. In this paper, the method of urine analysis including preconcentration of heavy metals (HMs) and other analytes from solutions on the graphene oxide and analysis of analyte concentrates by inductively coupled plasma mass spectrometry (ICP-MS) and optical emission spectrometry (ICP-OES) is developed. GO was obtained from graphite oxide by microwave radiation influence. The microwave digestion method was used for the urine sample preparation to eliminate the interfering influence of the sample matrix organic compounds, after which sorption preconcentration of analytes on GO was performed. The use of sorption preconcentration allows to improve limits of detection (LODs) of analytes by 3-60 times comparing to ICP-MS and ICP-OES analysis of urine samples. The LODs of Bi, Cd, Ce, Cu, Dy, Er, Eu, Gd, Ho, In, Lu, Nd, Pb, Pr, Sc, Sm, Tb, Tm, Y, Yb and Zn from 0.3 to 2000 ng L-1 are achieved. Accuracy of developed method was confirmed by << spike >> experiment. The developed method was applied to analysis of real urine samples. The results of analysis by ICP-MS and ICP-OES with preconcentration of analytes and without preconcentration were in good agreement. The future applications include development of methods of multielement analysis of other biological fluids, for example blood or saliva, using of graphene oxide materials with nitrogen-containing functional groups for increasing of the sorption capacity, employment electrothermal vaporisation or ultrasonic nebulisation for introduction of analyte concentrates into the ICP after sorption preconcentration.

Crystals of copper bis(heptafluorodimethyloctanedionate) (Cu(fod)2) have been grown by evaporation of solvent from solutions. Crystals of monoclinic syngony (I) have been obtained from toluene, while crystals of monoclinic (I) and triclinic (II) syngony have been obtained from acetonitrile. Crystallographic data: P21/c, a = 13.1863 (6), b = 9.8118 (4), c = 10.6997 (6), β = 113.633(2)° for I; 1̅ , a = 10.7941(12), b = 11.4759(14), c = 12.5263(13), α = 115.350(4)°, β = 102.957(4)°, γ = 100.999(4)° for II. Crystal packings I and II have the same structure of molecules. Crystal structures I and II are molecular and consist of discrete Cu(fod)2 molecules. Temperature dependences for saturated vapor pressure have been obtained by flow method for liquid and crystalline (phase I) Cu(fod)2 in the range 314–393 K. Thermal stability of the compound is determined, thermodynamic parameters of sublimation and evaporation have been established.

Ferrous cysteinate nanoparticles in the form of hexagonal nanoplates up to 20 nm thick have been synthesized in aerobic conditions. Their size has been confirmed by scanning electron microscopy. Their composition, investigated using atomic emission spectroscopy with inductively coupled plasma (ICP-AES), CHNS analysis, and IR spectroscopy, has coincided with the known complex Na2Fe(cyst)2·H2O (cyst being the cysteine fragment –SCH2СН(NН2)СОО–). Using X-ray photoelectron spectroscopy (XPS) and powder X-ray diffraction (XRD), the chemical transformations of the compound obtained under the action of air oxygen and moisture have been studied. Under these conditions, the Fe2+(cyst)(H2O)1.5 complex has been formed.

One of the major limitations of anti-cancer drug is their poor selectivity and high toxicity. Present study is aimed overcoming these difficulties by development targeted drug delivery systems. Drug delivery systems were synthesized based on magnetite nanoparticles with grafted poly(2-vinylpyridine) from their pre-modified surface with 3-(trimethoxysilyl)propyl methacrylate. Physical and chemical properties of synthesized samples were examined by FTIR, XRD, VSM, EDA, Mössbauer spectroscopy. 5-FU release from nanocarriers was estimated using UV-Vis spectroscopy.

Diabetes is one of the global healthcare problems requiring the development of reliable and accurate devices for monitoring blood glucose levels. In this study, a non-enzymatic sensor based on a modified poly(ethylene terephthalate) track-etched membrane (PET TeMs) was developed for the electrochemical detection of glucose. For the first time, membrane modification using mercaptopropyltrimethoxysilane (MPTMS) was applied to improve the adhesion of gold nanostructures and enhance the efficiency of the gold electroless deposition process. The modification significantly increased the sensor real surface area to 0.91±0.25 cm². Voltammetric measurements showed a linear dependence between the current density and glucose concentration in the range of 0.1 to 16 mM, with a detection limit of 0.058 mM for PET TeMs/MPTMS@Au sensors. The developed sensors demonstrate good sensitivity and high stability, broadening their potential application in biosensing.

New complexes of magnesium with asymmetric fluorinated β-diketones are synthesized: pentafluoropropionyl (Hpfpac, 6,6,6,5,5-pentafluorohexane-2,4-dione) and heptafluorobutyrylacetone (Hhfbac, 7,7,7,6,6,5,5-heptafluoroheptane-2,4-dione). The [Mg(H2O)(EtOH)(pfpac)2] 1 and [Mg(H2O)2(hfbac)2]·H2O 2 phases are characterized by a number of methods. The structures of crystals of 1, 2, and [Mg(EtOH)2(hfbac)2] 3 are determined by the single crystal X-ray diffraction analysis. Magnesium atoms have a distorted octahedral environment, and neutral ligands are in the trans-position. Molecules are involved in systems of OH⋯Odik hydrogen bonds, forming layers (2) or chains (1, 3). A relative evaluation shows that 2 is more volatile than 1. Structures of molecules and packing characters are compared with those of a series of related β-diketonate complexes. The effect of an increase in the ligand perfluoroalkyl chain (L = tfac, trifluoroacetylacetonate ion), including isoformular [Mg(H2O)2(L)2]·H2O, is shown.

The crystal structure of new isostructural complex Tb(thd)3 (1), Ho(thd)3 (2) (sp. gr. Pmn21) and Tb(thd)3 (3), Dy (thd)3 (4), Er(thd)3 (5), Yb(thd)3 (6) (sp. gr. Pna21) are determined. The crystal structures of 1-6 are molecular and consist of discrete monomeric Ln(thd)3 molecules (Ln = Tb, Ho, Dy, Er, Yb). The samples of Ln(thd)3 in the solid state have been investigated over the temperature range from 120 to 300 K using differential scanning calorimetry. DSC curves Ln(thd)3 exhibit a single endothermic peak of the crystal-to-crystal reversible phase transition. First-order phase transition is accompanied by an abrupt change in the volume of the unit cell. The quantum chemical calculations allow one to conclude that the electronic structures of the three modifications for Tb tris-2,2,6,6-tetramethylheptane-2,4-dionates are some different. It has been shown that for Tb(III) complexes with thd-ligands the modification I is energetically more stable.

The ZrO2–HfO2 oxide films are prepared by pulsed chemical vapor deposition using volatile organometallic precursors. It is shown that the morphology, thickness, and uniformity of the resulting coatings are affected by the mode of reaction space organization. A 360 nm thick oxide coating is obtained by introducing the precursor vapor and the reactant gas into the reactor through an earlier elaborated system of separate reaction components supply. The atomic force microscopy data show that the resulting surface is almost smooth and has an arithmetic average roughness of a few nanometers. Current-voltage and capacitance-voltage characteristics of the obtained ZrO2–HfO2 oxide coatings are studied. It is noted that the breakdown electric field is almost independent of the oxide coating thickness (0.1-0.48 MV/cm) in the interval of 225-325 nm. The breakdown electric field increases as the oxide film thickness increases from 325 nm to 360 nm. The dependence of the dielectric constant on the oxide film thickness is determined from the measured capacitance-voltage characteristics of the obtained ZrO2–HfO2 films. It is shown that this dependence depends linearly on the film thickness.

Two novel bismuth(III) iodide complexes (1,3,4-MePy)[BiI4] (1) and (3-Br-1-MePy)[BiI4] (2)) were synthesized by the reaction of iodides of corresponding cations with BiI3 in organic solvents. Crystal structures of the compounds were determined by single crystal X-ray diffraction. For both complexes, the thermal stability was studied, and the optical band gap values were experimentally estimated.

In this work, approaches to the formation of multifunctional film heterostructures based on noble metals for the modification of the surface of implant materials (titanium alloy TiAl6V4 and carbon-fiber-reinforced polyetheretherketone CFR-PEEK) are developed. Such heterostructures consist of continuous layers of platinum (Pt) or iridium (Ir) and antibacterial components on their surface, namely silver (nanoparticles or discontinuous films) and gold (nanoparticles). Chemical or physical gas-phase deposition methods were used for their preparation. The influence of the concentration and form of the antibacterial component on the antibacterial activity and in vivo biocompatibility of the film structures was evaluated for the first time. Differences in the dynamics of silver dissolution depending on Ag concentration in the sample and the type of bottom surface (the noble metal layer = Ir, Pt or TiAl6V4) surfaces allowed us to better understand the nature of the antibacterial action against Staphylococcus aureus and Pseudomonas aeruginosa (S. aureus and P. aeruginosa) of Ag/M heterostructures. From in vivo histological studies using rats, the best biocompatibility was shown by the Ag/M heterostructure with a prolonged release of the low fraction of antibacterial component (Ag).

As potential precursors for the synthesis of fluoroperovskites, a family of heavy alkali metal (MI = K, Cs) fluorinated β-diketonates were prepared and characterized by elemental analysis, IR, and powder-XRD. The crystal structures of the new six complexes, MI(β-dikF)(H2O)X, X = 0 or 1, were also determined. The structural diversity of this poorly explored class of complexes was discussed, including the preferred types of cation polyhedra and the ligand coordination modes, and the thermal properties of the metal β-diketonates were studied by TG–DTA in an inert (He) atmosphere. The data obtained allowed us to reveal the effect of the metal cation and the terminal substituent on the structural and thermal features of this family of complexes.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

New magnesium complexes [Mg(H2O)2(ofhac)2] 1 and [Mg(tmeda)(ofhac)2] 2 (ofhac =  $$\text{C}{{\text{F}}_{\text{3}}}\text{C(O)}$$ $$\text{CHC(O)}{{\text{C}}_{\text{2}}}\text{F}_{5}^{-}$$ , tmeda = N,N,N′,N′-tetramethylethylenediamine) with a 1,1,1,2,2,6,6,6-octafluorohexane-3,5-dionate ligand are prepared. The composition of these compounds is confirmed by elemental analysis and IR spectroscopy, the structure is determined by XRD. The coordination environment of magnesium is distorted octahedral in both complexes. The ofhac ligands are coordinated in the bidentate-cyclic mode; the lengths of Mg–O bonds are similar and vary within 2.033(14)-2.063(18) Å. The aqua ligands in 1 occupy cis positions (d(Mg–O) = 2.0511(18) Å, θ(O–Mg–O) = 85.0(1)°) and participate in the system of O–H…O and O–H…F hydrogen bonds forming a chain packing. The tmeda ligand in 2 performs a chelating function (d(Mg–N) = 2.212(4) Å, θ(N–Mg–N) = 81.0(6)°). The dependence of the structure and the thermal properties of the complexes on the size of the fluorinated substituent (C2F5 instead of CF3) is estimated by comparing the complex with its analogues bearing 1,1,1,5,5,5-hexafluoro-2,4-pentadionate ligands. The crystal structures of [Mg(H2O)2(L)2] are homeotypic; the analogues of [Mg(tmeda)(L)2] crystallize in different space groups. The absence of trans isomers in [Mg(H2O)2(L)2] is confirmed by powder XRD. The thermogravimetry experiments in flowing helium and sublimation tests in vacuum showed that complexes with the ofhac ligand are more volatile. Introducing a C2F5 groups into the ligand also decreases the melting point of the compounds, more significantly for aqua complexes.