Determination of Trace Amounts of Palladium(II) by Solid-Phase Spectrophotometry

A simple and sensitive method for solid-phase spectrophotometric determination of palladium(II) at µgL^–1 level based on the reaction product of Pd²⁺ with disodium 1-nitroso-2-hydroxynaphthalene-3,6-disulphonate (Nitroso R salt) previously immobilized on Dowex 1×1 anion exchanger has been developed. The experimental factors (wavelength, pH, amount of resin, concentration of Pd²⁺ solution, volume of solution sample, equilibration time) were optimized. The advantages of this procedure as opposed to solution methods are discussed. The results obtained with synthetic solutions clearly indicate the suitability of the proposed method for real samples analysis.     

Merging homogeneous catalysis with biocatalysis; papain as hydrogenation catalyst

Papain, modified at Cys-25 with a monodentate phosphite ligand and complexed with Rh(COD)2BF4, is an active catalyst in the hydrogenation of methyl 2-acetamidoacrylate.     

Enantioselective RH-catalyzed hydrogenation of enol acetates and enol carbamates with monodentate phosphoramidites

[reaction: see text] Monodentate phosphoramidites, in particular PipPhos and its octahydro analogue, are excellent ligands for the rhodium-catalyzed asymmetric hydrogenation of aromatic enol acetates, enol carbamates, and 2-dienol carbamates up to 98% ee. These latter substrates were hydrogenated selectively to the carbamates of the allyl alcohol.     

Effect of dye aggregation on triarylmethane-mediated photoinduced damage of hexokinase and DNA

The observation that enhanced mitochondrial membrane potential is a prevalent cancer cell phenotype has provided the conceptual basis for the development of mitochondrial targeting as a novel therapeutic strategy for both chemo- and photochemotherapy of neoplastic diseases. Cationic triarylmethane (TAM(+)) dyes represent a series of photosensitizers whose phototoxic effects develop at least in part at the mitochondrial level. In this report we describe how the molecular structure of four representative TAM(+) dyes (Crystal Violet, Ethyl Violet, Victoria blue R, and Victoria pure blue BO) affects their efficiency as mediators of the photoinduced inactivation of two model mitochondrial targets, hexokinase (HK) and DNA. Our results have indicated that TAM(+) dyes efficiently bind to HK and DNA in aqueous media both as dye monomers and aggregates, with the degree of aggregation increasing with increasing the lipophilic character of the photosensitizer. The efficiency with which HK and DNA are damaged upon 532 nm photolysis of biopolymer-TAM(+) complexes was found to decrease upon increasing the degree of dye aggregation over these macromolecular templates. Comparative experiments carried out both in water and in D(2)O, and in air-equilibrated and nitrogen-purged samples have also indicated that, at least when Crystal Violet is used as the photosensitizer, the mechanism of macromolecular damage does not require the involvement of molecular oxygen to operate. This finding makes Crystal Violet a potential candidate for use in photochemotherapy of hypoxic or poorly perfused tumor areas.     

The influence of temperature and photoinitiator concentration on photoinitiated polymerization of diacrylate monomer

The behavior of p-methoxybenzoyldiphenylphosphine oxide, previously synthesized, as a photoinitiator for the polymerization of diacrylate monomer, in the presence of 3% (w/w) tertiary amine (triethyl amine) as synergist additive, was studied. The influence of temperature in the range 30–90°C at 3% (w/w) photoinitiator concentration and the influence of the photoinitiator concentration in the range 0.5–3.5% (w/w) at 30°C was investigated by differential scanning photocalorimetry (photo-DSC). In all experiments the photopolymerization was performed at constant light intensity (3 mW cm⁻²). The maximum conversion was obtained at temperature of 90°C at 3% (w/w) photoinitiator concentration and 3% (w/w) triethyl amine. The optimal concentration of photoinitiator to obtain maximum conversion was 3% (w/w), at 30°C. No thermal polymerization occurred at higher temperature.     

Site‐Specific Substitution Preferences in the Solid Solutions Li12Si7–xGex,Li12–yNaySi7, Na7LiSi8–zGez,and Li3NaSi6–vGev

The mixed silicide‐germanides Li₁₂Si_7–xGe_x, Na₇LiSi_8–zGe_z, and Li₃NaSi_6–vGe_v which could serve as potential precursors for Si_1–xGe_x materials were synthesized and characterized by X‐ray diffraction methods. The full solid solution series Li₁₂Si_7–xGe_x (0 ≤ x ≤ 7) is easily accessible from the elements and features preferential occupation of the more negatively charged crystallographic tetrel positions by Ge, which is the more electronegative element. In case of Na₇LiSi_8–zGe_z a broad solid solution range of 1.3 ≤ x ≤ 8 is available but the ternary silicide Na₇LiSi₈ could not be obtained by the tested methods of synthesis. The solubility of Ge in Li₃NaSi_6–vGe_v is highly limited to a maximum of v ≈ 0.5, and again the formally more negatively charged tetrel positions are preferred by Ge. Additionally, the two crystallographic Li positions in Li₁₂Si₇ with unusually large displacement parameters can be partially substituted by Na in Li_12–yNa_ySi₇ with 0 ≤ y ≤ 0.6. The statistical mixing of Li and Na in this solid solution contrasts the typical ordering of Li and Na in most ternary tetrelides.     

Insight on spectral,thermal and biological behaviour of some Cu(II) complexes with saturated pentaazamacrocyclic ligands bearing amino acid residues

Journal of Thermal Analysis and Calorimetry - A novel series of Cu(II) complexes with formula M(HLn)(ClO4)2·mH2O [HLn: 13-membered pentaazamacrocyclic ligand resulted from condensation of...     

Experimental Investigations of AlMg3 Components with Polyurethane and Graphene Oxide Nanosheets Composite Coatings,after Accelerated UV-Aging

The use of graphene (Gr) and its derivates graphene oxide (GO) showed that these materials are good candidates to enhance the properties of polyurethane (PU) coatings, especially the anticorrosion ones since graphene absorbs most of the light and provides hydrophobicity for repelling water. An important aspect of these multifunctional materials is that all these improvements can be realized even at very low filler loadings in the polymer matrix. In this work, an ultrasound cavitation technique was used for the proper dispersion of GO nanosheets (GON) in polyurethane (PU) resin to obtain a composite coating to protect the AlMg3 substrate. The addition of GON considerably improved the physical properties of coatings, as demonstrated by electrochemical impedance spectroscopy (EIS) analysis, promising improved anticorrosion performance after accelerated UV-ageing. Computational methods and Differential Scanning Calorimetry (DSC) measurements showed that GON facilitates the formation of additional bonds and stabilizes the PU structures during the ultraviolet (UV) exposure and aggressive attack of corrosive species. Limiting oxygen index (LOI) data reveal a slow burning behaviour of PU-GON coatings during UV exposure, which is better than PU alone.     

Thermal behavior of aminotrimethoxysilanphosphonate functionalized onto styrene-divinylbenzene copolymer

Abstract

The chlorometylated styrene–divinylbenzene copolymer with different percent of divinylbenzene (code: S-6.7 DVB, S-12DVB, and S-15DVB) was functionalized with 3-hydroxybenzaldehyde for obtaining intermediated polymers. The aminotrimethoxysilanphosphonate groups were grafted by one-pot reactions in tetrahydrofuran using three components: polymers grafted with aldehyde groups (code: CHO-6.7, CHO-12, and CHO-15), 3-aminopropyltrimethoxysilane, diethylphosphite. The aminotrimethoxysilanphosphonate groups functionalized onto styrene-(6.7, 12, and 15%) divinylbenzene copolymer (code: PAF-6.7, PAF-12, and PAF-15) and evolution of the reaction were evidenced by FT-IR spectroscopy and porous structure by N₂ adsorption-desorption, SEM microscopy. The thermal behavior of aldehydes and materials: PAF-6.7, PAF-12, and PAF-15 are different than initial polymer supports.     

Structure and Bonding of La2NiBi

La₂NiBi was synthesized by heating a cold pressed pellet of the elements in a sealed and evacuated silica tube at 1070 K. The structure was determined via powder and single crystal X‐ray diffraction. La₂NiBi crystallizes orthorhombically, in the space group Pnma: a = 838.88(6), b = 455.61(11), c = 1210.4(2) pm and V = 0.46261(14) nm³ (wR = 0.1002, 1001 F² values, 26 variables, Z = 4). La₂NiBi represents a higher congener of La₂NiSb and adopts a ternary ordered version of the Bi₃Ni structure type. Similar to La₂NiSb, the nickel atoms form infinite zigzag chains (259 pm Ni–Ni) with trigonal‐prismatic lanthanum coordination. One rectangular face of the lanthanum prism is capped by a bismuth atom (333.08–364.74 pm La–Bi, 281.18 pm Ni–Bi). These zigzag chains run along the b axis. DFT based band structure calculations and DOS representations suggest metallic behavior. This was confirmed via temperature dependent impedance spectroscopic measurements. A Seebeck coefficient of –10 μV · K^–1 in the temperature range up to 873 K substantiates this finding. Thermal analyses show that the compound is stable up to 873 K under inert gas conditions and degrades at higher temperatures. The magnetic measurements show almost no grain boundary nickel impurities characterizing La₂NiBi as a weak Pauli paramagnet.