Solid solutions between β-Ca3(PO4)2 and sodium-containing whitlockite

Mixtures of CaHPO₄, CaCO₃, and Na₂CO₃ were heated at 870°C under steam or under dry CO₂ until phase composition and weight were constant. According to chemical analysis and X-ray diffractometry the stability field of the β-Ca₃(PO₄)₂ phase is limited by the molar P/Ca ratio of 0.664 ± 0.003 and 0.675 ± 0.010 irrespective of the partial water vapour pressure. A continuous series of solid solutions was found between β-Ca₃(PO₄)₂ and a new whitlockite with the composition Ca₁₀Na(PO₄)₇. The IR spectrum of these solid solutions shows that the point symmetry of the PO₄ groups and their environment increases with increasing sodium content. This is in agreement with data published about the structure of β-Ca₃(PO₄)₂ and whitlockite. The composition of these solid solutions suggests that Na⁺ ions can replace H⁺ ions in the whitlockite structure. Carbonate and pyrophosphate ions are not incorporated in these whitlockites.     

Structure and microstructure of epitaxial Sr n Fe n O3 n −1 films

Thin films of SrFeO_{3??? x} (0?≤?x?≤?0.5) (SFO) grown on a (LaAlO₃)_0.3 (SrAl_0.5Ta_0.5O₃)_0.7 (LSAT) substrate by pulsed laser deposition have been structurally investigated by electron diffraction and high resolution transmission electron microscopy for different post-deposition oxygen treatments. During the deposition and post-growth oxidation, the oxygen-reduced SFO films accept extra oxygen along the tetrahedral layers to minimize the elastic strain energy. The oxidation process stops at a concentration SFO_2.875 and/or SFO_2.75 because a zero misfit with the LSAT substrate is reached. A possible growth mechanism and phase transition mechanism are suggested. The non-oxidized films exhibit twin boundaries having a local perovskite-type structure with a nominal composition close to SFO₃.     

Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism

The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd⁰(PPh₃)₂] (generated from [Pd⁰(PPh₃)₄]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented S_NAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies.     

Enhanced ethanol sensing properties of WO3 modified TiO2 nanorods

Pristine and WO₃ decorated TiO₂ nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO₂ NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO₂ NRs and thermally oxidised to obtain WO₃ nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO₂ NRs with WO₃.     

Flowerlike hybrid horseradish peroxidase nanobiocatalyst for the polymerization of guaiacol

In this study, the catalytic activity and stability of flowerlike hybrid horseradish peroxidase (HRP) nanobiocatalyst (HRP-Cu ²⁺ ) obtained from Cu ²⁺ ions and HRP enzyme in the polymerization reaction of guaiacol were analyzed. We demonstrated that HRP-Cu ²⁺ and hydrogen peroxide (H ₂ O ₂ ) initiator showed significantly increased catalytic activity and stability on the polymerization of guaiacol compared to that of free HRP enzyme. Poly(guaiacol) was observed with quite high yields (88%) and molecular weights (38,000 g/mol) under pH 7.4 phosphate-buffered saline (PBS) conditions at 60 °C with 5 weight% of HRP-Cu ²⁺ loading. HRP-Cu ²⁺ also shows very high thermal stability and works even at 70 °C reaction temperature; free HRP enzyme denatures at that temperature. Furthermore, HRP-Cu ²⁺ provided considerable repeated use and showed some degree of catalytic activity, even after the fourth recycle, in the polymerization of guaiacol.     

Chemical composition,antimicrobial, and lipase enzyme activity of essential oil and solvent extracts from Serapias orientalis subsp. orientalis

The volatile components of essential oil (EO), SPME, and SPME of solvent extracts ( n -hexane, methanol, and water) obtained from fresh Serapias orientalis subsp. orientalis ( Soo ) were analyzed by GC-FID/MS. EO of Soo gave 11 compounds in the percentage of 99.97%; capronaldehyde (37.01%), 2-( E )-hexenal (23.19%), and n -nonanal (19.05%) were found to be major constituents. SPME GC-FID/MS analyses of fresh plant and solvent extracts of Soo revealed 7, 12, 7, and 4 compounds within the range of 99.7% to 99.9%. Limonene (76.5%, 41.7%, and 61.3%) was the major compound in SPMEs of the n -hexane and methanol extracts. α -Methoxy- p -cresol (52.9%) was the main component in its water extract. The antimicrobial activity of EO and the solvent extracts of Soo were screened against 9microorganisms. EO showed the best activity against Mycobacterium smegmatis , with 79.5 µg/mL MIC value. The n -hexane, methanol, and water extracts were the most active against the Staphylococcus aureus within the range of 81.25–125.0 µg/mL (MIC). IC ₅₀ values for the lipase enzyme inhibitory activity of EO and solvent extracts ( n -hexane, methanol, and water) were determined to be 59.87 µg/mL, 64.03 µg/mL, 101.91 µg/mL, and 121.24 µg/mL, respectively.     

Isolation from pig liver microsomes, identification by electrospray tandem mass spectrometry and in vitro immunosuppressive activity of a rapamycin tris-epoxide metabolite

It was demonstrated that rapamycin is metabolized in vitro by pig liver microsomes under the influence of the cytochrome P450-dependent mixed function oxygenase system to a rapamycin tris-epoxide metabolite, as demonstrated by electrospray tandem mass spectrometry. The in vitro immunosuppressive activity of this metabolite was found to be lower than that of rapamycin, probably because the rapamycin effector sector was structurally modified. The effector region of rapamycin was recognized to include the conjugated double bonds of this compound and metabolic reactions affecting this region may change the binding affinity of the rapamycin-FKBP binary complex towards another pharmacological receptor bound to the binary complex. Moreover, metabolic modifications in the effector region are probably able to induce a change in the binding affinities of the rapamycin-FKBP binary complex, including the pipecolic acid moiety and the lactone function of the parent drug.     

1H and31P ENDOR of the isotropic CO2 − signal atg=2.0007 in the EPR spectra of precipitated carbonated apatites

The isotropic EPR signal atg=2.0007 in X-irradiated carbonated apatites, precipitated from aquaeous solutions and dried at 25°C, is investigated with Electron Nuclear Double Resonance (ENDOR). The²³Na,³¹P and¹H ENDOR results indicate that the precursor of this radical is most probably located in an aqueous phase entrapped between the crystallites (the so-called occluded water). Other experimental features, such as the correlation between the appearance of the signal in the EPR spectrum and the presence of some residual (adsorbed and/or occluded) water in the sample seem to strengthen our hypothesis.