Nucleophilic Reactivity of Hydroxide and Hydroperoxide Ions in Aqueous-Alcoholic Media and of HCO<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ion in Water

Nucleophilic reactivity of hydroxide and hydroperoxide ions toward ethyl 4-nitrophenyl ethylphosphonate, diethyl 4-nitrophenyl phosphate, 4-nitrophenyl 4-toluenesulfonate, and 4-nitrophenyl dimethylcarbamate in the system H₂O₂-KOH was studied in aqueous-alcoholic solutions at 25°C. The rate of reactions of both anions with ethyl 4-nitrophenyl ethylphosphonate, diethyl 4-nitrophenyl phosphate, and 4-nitrophenyl dimethylcarbamate and of hydroxide ion with 4-nitrophenyl 4-toluenesulfonate increases with rise in the fraction of the alcohol in mixtures of water with isopropyl and tert-butyl alcohols, while the reaction rate of hydroperoxide ion with 4-nitrophenyl 4-toluenesulfonate decreases. The rate of reactions of both anions with all the above substrates in mixtures of water with ethylene glycol decreases as the fraction of the latter rises. The apparent rate of the reaction of ethyl 4-nitrophenyl ethylphosphonate with anionic nucleophiles in the system H₂O₂-HO^?-HCO ₃ ^? in water at pH 8.5 almost does not depend on the concentration of ammonium hydrogen carbonate up to a value of 1 M, and it increases when the NH₄HCO₃ concentration exceeds 1 M. Mixtures of water with the lower monohydric alcohols were recommended for use as components of H₂O₂-HO^?-HCO ₃ ^? systems for oxidative decomposition of ecotoxicants.     

Heterometallic titanium–gold complexes inhibit renal cancer cells in vitro and in vivo

Following recent work on heterometallic titanocene–gold complexes as potential chemotherapeutics for renal cancer, we report here on the synthesis, characterization and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = S–C₆H₄–COO^–) bound to gold(i)-phosphane fragments through a thiolate group [(η-C₅H₅)₂TiMe(μ-mba)Au(PR₃)]. The compounds are more stable in physiological media than those previously reported and are highly cytotoxic against human cancer renal cell lines. We describe here preliminary mechanistic data involving studies on the interaction of selected compounds with plasmid (pBR322) DNA used as a model nucleic acid, and with selected protein kinases from a panel of 35 protein kinases having oncological interest. Preliminary mechanistic studies in Caki-1 renal cells indicate that the cytotoxic and anti-migration effects of the most active compound 5 [(η-C₅H₅)₂TiMe(μ-mba)Au(PPh₃)] involve inhibition of thioredoxin reductase and loss of expression of protein kinases that drive cell migration (AKT, p90-RSK, and MAPKAPK3). The co-localization of both titanium and gold metals (1 : 1 ratio) in Caki-1 renal cells was demonstrated for 5 indicating the robustness of the heterometallic compound in vitro. Two compounds were selected for further in vivo studies on mice based on their selectivity in vitro against renal cancer cell lines when compared to non-tumorigenic human kidney cell lines (HEK-293T and RPTC) and the favourable preliminary toxicity profile in C57BL/6 mice. Evaluation of Caki-1 xenografts in NOD.CB17-Prkdc SCID/J mice showed an impressive tumor reduction (67%) after treatment for 28 days (3 mg per kg per every other day) with heterometallic compound 5 as compared with the previously described [(η-C₅H₅)₂Ti{OC(O)-4-C₆H₄-P(Ph₂)AuCl}₂] 3 which was non-inhibitory. These findings indicate that structural modifications on the ligand scaffold affect the in vivo efficacy of this class of compounds.     

Structure and conductivity in CeNb<Subscript>3</Subscript>O<Subscript>9-δ</Subscript>

Abstract  In the search of new materials for solid oxide fuel cells, a study of the structure and electrical conductivity of Mg-doped and nominally pure CeNb₃O_9-δ was undertaken. This material exhibits an orthorhombic crystal structure as determined by Rietveld refinement. Through a combined study of 4-point DC and AC impedance spectroscopy, it was determined that the material presents oxygen ion conductivity, electron conductivity and electron-hole conductivity according to the partial pressure of oxygen and temperature in agreement with a simple defect chemistry model. Finally, some experiments seem to indicate the presence of proton conduction. Graphical Abstract        

Trends in formation and stability of homo- and heteroligand <Emphasis Type="Italic">d</Emphasis>-metal complexes with 2,2′-dipyrrolylmethenes in dimethylformamide

The reactions of symmetric and nonsymmetric alkyl-substituted 2,2′-dipyrrolylmethenes with Cu(II), Ni(II), Co(II), Zn(II), Cd(II), and Hg(II) acetates in dimethylformamide solutions at 298.15 K were studied. The formation of hetero- and homoligand complexes was observed in the systems studied depending on the concentration conditions and the nature of the complexing metal. The stepped and complete constants of formation for metal complexes were determined. The key trends of the influence of the metal and ligand nature on the stabilization of the complexes were established.     

Primary photophysical and photochemical processes upon UV excitation of PtBr<Subscript>6</Subscript><Superscript>2–</Superscript> and PtCl<Subscript>6</Subscript><Superscript>2–</Superscript> complexes in water and methanol

Primary photophysical and photochemical processes were studied for Pt^IVBr₆ ^2– and Pt^IVCl₆ ^2– complexes in water and methanol by ultrafast kinetic spectroscopy upon excitation in the band region of charge transfer from the ligand-centered group π-orbitals to the e_g*-orbital of Pt^IV complex anion (LMCT bands). The data obtained earlier upon excitation in the region of d—d bands were compared. Irrespective of the excitation wavelength, the photochemical properties of complexes are caused by the reactions of intermediates proceeding in the picosecond time range. These intermediates were identified as Pt^IVBr₅ ^– upon photolysis of Pt^IVBr₆ ^2– and, presumably, the Adamson radical pair [Pt^IIICl₅ ^2–(C _4v )...Cl?] upon photolysis of Pt^IVCl₆ ^2–. The difference in the exciting light wavelengths has an impact only on the first step of these processes, i.e., transition from the Franck—Condon excited state to intermediates.     

Ionic mobility in β-PbF<Subscript>2</Subscript> doped by yttrium and lanthanum fluorides

NMR (¹⁹F, ²⁰⁷Pb) and impedance spectroscopy methods are used to investigate the ionic mobility and conductivity in solid solutions of (1 ? x)PbF₂ ? xMF₃ (where M is Y³⁺ and La³⁺) at 0.05 ≤ x ≤ 0.1. The factors determining the form of ionic movement in these systems and its energy in a range of temperatures from 170 K to 500 K are considered and analyzed. It is found that the solid solutions studied can be related to the class of superionic conductors: their σ value is 2·10^?3 ? 5·10^?3 S/cm at temperatures above 470 K, and the activation energy does not exceed 0.52–0.58 eV.     

Evaluation of bias,precision, and systematic errors in proficiency testing of Cl<Superscript>−</Superscript> and Cu concentration in water

The proficiency testing exercise was conducted to assess the quality of water testing in several laboratories in India. The 11 participants from all over India gathered at one place and attended the workshop organized at NEERI, Nagpur. The test samples were analyzed for Cl⁻ (Chloride) and Cu (Copper) concentration in water. The objective of the study was to determine bias and precision among participants for the analysis of Cl⁻ and Cu concentration. Statistical analysis indicated that most of the measurement results were overestimating the Cl⁻ concentration and underestimating the Cu concentration. The presence of systematic error identified the need for further improvement in determining the Cu concentration in water by the participants.     

Hyperconjugation versus back bonding in AH3−nXn species (A = Si and Ge; X = F,Cl and Br; and n = 1, 2 and 3)

In this research two competing phenomena, back bonding and hyperconjugation, have been investigated based on Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analyses for radical AH_3?nX_n species, where A = Si and Ge, and n = 1, 2 and 3. It is demonstrated in this article that both above phenomena will be occurred significantly, while back bonding is the only event in analogous compounds with carbon and hyperconjugation is rather negligible. It was also found that only one back bonding with the help of keyword $CHOOSE in NBO analysis can be found in this type of compounds with reasonable structure, while it can be sometimes detected in AH_3?nX_n without using keyword $CHOOSE. It is also shown that there is always an increase in bond length in comparison with reference molecules in mentioned species due to existing hyperconjugation, while if the central atom is carbon, we have always a decrease of bond length due to only having back bonding. Additionally, from AIM point of view, the delocalization indices for α-spin (majority spin) is more than β-spin (minority spin) in radical species for molecules without back bonding, while the situation in our compounds is quite reverse, which can be attributed to the π back bonding in the β-spin electrons.     

Intercalation and dynamics of hydrated Fe<Superscript>2+</Superscript> in the vermiculites from Santa Olalla and Ojén

Although the intercalation of Fe³⁺ into layered phyllosicilicates—especially into smectites—attracted much attention in the past two decades, the information about Fe²⁺ loaded phyllosilicates is sparse. Here we present an investigation of the Fe²⁺ exchanged vermiculites from Santa Olalla and Ojén (Andalusia, Spain) by means of Mössbauer spectroscopy. The room temperature Mössbauer spectra are very similar to those of the starting compounds (Na forms) except for a decrease of the contribution of structural Fe³⁺ and a concomitant increase of the contribution of Fe²⁺ sites, indicating an internal redox process. The extent of this redox reaction is different for the two vermiculites. Thus, the intercalated Fe²⁺ acts as an electron mediator from the external medium to the structural Fe³⁺ ions. A new component attributable to intercalated Fe²⁺ is practically invisible in the room temperature Mössbauer spectra, but increases strongly and continuously during cooling to 4.2 K, where it is the dominant feature of the Mössbauer patterns. At 4.2 K, its quadruple splitting amounts to 3.31 mm/s, which is in excellent agreement with the quadrupole slitting of Fe²⁺ coordinated to six water molecules in a highly symmetric octahedral arrangement. The strong decrease of the Mössbauer–Lamb factor of this component with increasing temperature indicates a weak bonding of the Fe²⁺ in the interlayer space.     

Luminescence and long-lasting afterglow in Mn<Superscript>2+</Superscript> and Eu<Superscript>3+</Superscript> co-doped ZnO–GeO<Subscript>2</Subscript> glasses and glass ceramics prepared by sol–gel method

To develop new fluorescent and afterglow materials, Mn²⁺ and Eu³⁺ co-doped ZnO–GeO₂ glasses and glass ceramics were prepared by a sol–gel method and their optical properties were investigated by measuring luminescence, excitation and afterglow spectra, and luminescence quantum yield (QY). Under UV irradiation at 254 nm, some glasses and all of the glass ceramics showed green luminescence peaking at 534 nm due to the ⁴T₁ → ⁶A₁ transition of tetrahedrally coordinated Mn²⁺ ions. The strongest luminescence was observed in a glass ceramic of 0.1MnO–0.3Eu₂O₃–25ZnO–75GeO₂ heat treated at 900 °C, with QY of 49.8%. All of the green-luminescent glasses and glass ceramics showed green afterglow, and the afterglow lasting for more than 60 min was obtained in a glass ceramic heat treated at 900 °C. It is considered that the Eu³⁺ ions may behave as electron trapping centers to be associated with the occurrence of the green afterglow due to the Mn²⁺ ions in the co-doped system.     

Sol–gel preparation and white up-conversion luminescence in rare-earth doped PbF<Subscript>2</Subscript> nanocrystals dissolved in silica glass

89.5(SiO₂)10(PbF₂)0.5(REF₃) silicate glasses have been prepared using room temperature sol–gel processing of Si(OCH₂CH₃)₄, Pb(CH₃COO)₂·3H₂O, RE(CH₃COO)₃·nH₂O and trifluoroacetic acid as a fluorinating agent, where RE stands for rare-earth ions, such as Yb³⁺, Er³⁺, Ho³⁺, Tm³⁺, or combinations of those ions. On heat treatment of these glasses at about 300–400 °C, the rare-earth doped spherical PbF₂ nanocrystals precipitate within SiO₂ glass matrix providing transparent nano-structured glass–ceramics, while the diameter of the nanocrystals can be set in the range from 5 to 25 nm by varying time and temperature of the heat treatment. The structural and photoluminescence studies confirm the incorporation of rare-earth ions into the PbF₂ nanocrystals and white and tuneable colour up-conversion luminescence has been detected in case of Yb³⁺-Er³⁺-Tm³⁺ and Yb³⁺-Ho³⁺-Tm³⁺ co-doped nanocrystals by varying dopant ratio and pump power.     

Development of electrochemistry in Bosnia and Herzegovina — historical perspective

Journal of Solid State Electrochemistry - The aim of this paper is considering a brief historical perspective and overview of recent ideas and directions in electrochemistry in Bosnia and...     

Measuring <Superscript>226</Superscript>Ra and <Superscript>232</Superscript>Th activity in soil and vegetation samples using a method of double γ-coincidences

A coincidence method for measuring radium and thorium activity has been developed using the PRIPYAT-2M gamma-ray coincidence spectrometer, with six NaI(Tl) detectors and registration geometry close to 4π. It was tested by measuring soil samples from the Northern region of Montenegro, as well as vegetation samples from the same region. The results showed a good agreement with ones obtained by the HPGe spectrometer.     

Synthesis of Coenzyme Q<Subscript>10</Subscript> and β-carotene by Yeasts Isolated from Antarctic Soil and Lichen in Response to Ultraviolet and Visible Radiations

The effect of different doses of visible (Vis), ultraviolet-А (UVA), and mixed light (UVA + Vis) upon coenzyme Q₁₀ (CoQ₁₀) and β-carotene synthesis and biomass yield by the Sporobolomyces salmonicolor AL₁, Cryptococcus albidus AS₅₅, Cryptococcus laurentii AS₅₆, and C. laurentii AS₅₈ strains isolated from Antarctic samples was investigated. The β-carotene concentration in the red strain biomass increased by 52% under irradiation with 11 J/cm² Vis, and the CoQ₁₀ concentration rose by 37% in relation to the control quantity obtained through dark cultivation. Under irradiation with 6 J/cm² UVA, the S. salmonicolor AL₁ strain synthesized 15% more β-carotene; C. albidus AS₅₅, 22%; C. laurentii AS₅₆, 44%; and C. laurentii AS₅₈, 35% in relation to the control quantity. Irradiation with a low UVА + Vis dose significantly stimulated β-carotene biosynthesis by the strains of the Cryptococcus genus (87%, 138%, and 100%), whereas S. salmonicolor AL₁ increased the β-carotene content to a smaller degree (55%). Higher doses of all three irradiation types inhibited β-carotene accumulation. Vis suppressed CoQ₁₀ biosynthesis in the Cryptococcus strains, whereas UVА and UVА + Vis inhibited it in all four strains. The S. salmonicolor AL₁ strain pre-treated with 0.02 J/cm² UVA synthesized twice as much CoQ₁₀ and β-carotene when cultivated in the presence of Vis light in an 11-J/cm² dose.     

Bond energies and the enthalpies of formation of mono- and polyradicals in nitroakanes 3. Nitroalkanes C<Subscript>4</Subscript>–C<Subscript>7</Subscript>

Based on the experimentally determined values and published data, the enthalpies of formation of nitroalkanes C₄–C₇ in the standard state and in the gas phase were recommended. The dissociation energies of bonds in these compounds were determined taking into account the enthalpies of atomization and the energies of nonvalent interactions of nitro groups with one another. The calculated values were compared with the available thermal decomposition kinetic data. The dissociation energies of bonds in C₄–C₇ nitroalkane radicals were also calculated using the enthalpies of atomization and the energies of nonvalent interactions of nitro groups. Regularities of changes in the bond dissociation energies of nitroalkanes C₁–C₇ and their radicals are established.     

Structural-dimensional effects and their application in the &quot;core—nanoshell&quot; systems synthesized by the molecular layering

In connection with the development of nanotechnology in the last 15—20 years, the method of molecular layering (ML), created in the middle of the last century in the USSR, has attracted increasing attention. The features of structural-dimensional effects in the products obtained by new chemical nanotechnology and promising directions of their practical application in "core—nanoshell" compositions are considered in the review. In accordance with the synthetic capabilities of the ML method, the functional properties of the "core—nanoshell" type materials are affected by the "monolayer effect" and the substrate shielding effect, as well as the multicomponent nature of the system, and mutual structural coordination effect of the substrate and the build-up nanolayer. The review presents theoretical and experimental data on the application of the observed effects in the creation of shell pigments and fillers, modified sorbents, catalytic membrane reactors, nanodoped ceramic materials, polymers, quartz fibers with adjustable optical characteristics, electrets, etc.     

Comparison of the Active Species in the RF and Microwave Flowing Discharges of N<Subscript>2</Subscript> and Ar–20 %N<Subscript>2</Subscript>

We report a detailed comparison between RF and microwave (HF) plasmas of N₂ and Ar–20 %N₂ as well as in the corresponding afterglows by comparing densities of active species at nearly the same discharge conditions of tube diameter (5–6 mm), gas pressure (6–8 Torr), flow rate (0.6–1.0 slm) and applied power (50–150 W). The analysis reveals an interesting difference between the two cases; the length of the RF plasma (~25 cm) is measured to be much longer than that of HF (6 cm). This ensures a much longer residence time (10^?2 s) of the active species in the N₂ RF plasma [compared to that (10^?3 s) of HF], providing a condition for an efficient vibrational excitation of N₂(X, v) by (V–V) climbing-up processes, making the RF plasma more vibrationally excited than the HF one. As a result of high V–V plasma excitation in RF, the densities of the vibrationally excited N₂(X, v > 13) molecules are higher in the RF afterglow than in the HF afterglow. Destruction of N₂(X, v) due to the tube wall is estimated to be very similar between the two system as can be inferred from the γ_v destruction probability of N₂(X, v > 3–13) on the tube wall (2–3 × 10^?3 for both cases) obtained from a comparison between the density of N₂(X, v > 3–9) in the plasmas to that of the N₂(X, v > 13) in the long afterglows. Interestingly enough, densities of N-atoms and N₂(A) metastable molecules in the afterglow regions, however, are measured to be very similar with each other. The measured lower density of N₂ ⁺ ions than expected in the HF afterglow is rationalized from a high oxygen impurity in our HF setup since N₂ ⁺ ions are very sensitive to oxygen impurity .     

On the nature of phase conversions and transformations in porous system in hydrothermal processing of χ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> into boehmite

Study of the influence exerted by conditions of hydrothermal treatment of χ-Al₂O₃ on the phase composition and porous system parameters of the resulting products at T = 150–200°C and P = 0.5–1.5 MPa demonstrated the products formed in hydrothermal treatment of χ-Al₂O₃ are the bayerite and boehmite phases formed simultaneously in parallel pathways. Bayerite crystals have a needle-like shape and length of about 10 nm. 3D boehmite crystals are formed as parallelepipeds with edge size exceeding 200 nm in an alkaline medium at pH 8.0–9.2 and as 2D particles having the shape of rhombic plates with edge size of 80–500 nm and thickness of 20–100 nm at Ph 4.0–6.0. The crystallization of coarse boehmite particles favors formation of coarse mesopores and a low-porous system. A full phase transition of χ-Al₂O₃ to boehmite occurs at 180–200°C in 180–240 min.