Comparative study of catalytic activity of Pd loaded hydroxyapatite and fluoroapatite in butan-2-ol conversion and methane oxidation

Palladium loaded calcium-hydroxyapatite, Pd(z)/CaHAp, and calcium-fluoroapatite, Pd(z)/CaFAp, were synthesised and characterised by TEM, XRD, IR and UV–vis–NIR spectroscopies. Introduction of palladium does not change the structure of CaHAp and CaFAp. The average size of PdO particles was found to be around 4–5 nm on Pd(1)/CaHAp but larger (6–7 nm) on Pd(1)/CaFap. The acid–base properties of the supports and of the catalysts were studied using butan-2-ol conversion. On CaHAp and CaFAp, the butenes yield (dehydration reaction) is very low either in the absence or in the presence of oxygen. The methyl ethyl ketone yield (dehydrogenation reaction) is significant only in the presence of oxygen and higher over CaFAp. Conversely, the performances of Pd(z)/CaHAp are better than those of Pd(z)/CaFAp below 180 °C. Above 180 °C, buta-2-ol combustion is favoured on Pd/CaHAp but not on Pd/CaFAp.

In methane oxidation, Pd(z)/CaHAp showed also a much larger activity than Pd(z)/CaFAp. On 2 wt% Pd loaded CaHAp, the methane oxidation reaches a conversion of almost 100% at 350 °C, which is comparable with the performance of conventional Pd/Al₂O₃ catalysts. The reducibility of PdO under methane–oxygen mixtures is lower on Pd(z)/CaHAp. For both reactions, the lower activity of Pd(z)/CaFAp is related to its higher acidity, resulting from the substitution of OH⁻ by F⁻, and to the larger PdO particle size.     

Synthesis of novel heterobimetallic complexes of platinum(II) bridged by the mixed phosphine-phosphine oxide ligands Ph2P(CH2)2P(O)Ph2

Summary The mixed phosphine-phosphine oxides Ph₂P(CH₂)_n-P(O)Ph₂ (n = 1 or 2) react with K₂PtCl₄ to give cis-{PtCl₂- ¹-Ph₂P(CH₂) _n P(O)Ph₂]₂}. Treatment of the latter (n = 2) with transition metal chlorides MCl₂·nH₂O, or with Me₂SnCl₂, SnCl₄·5H₂O, Th(NO₃)₄·xH₂O or UO₂(NO₃)₂· 6H₂O, gives novel heterobimetallic complexes identified as cis-{PtCl₂[-Ph₂P(CH₂)₂P(O)Ph₂]₂MX₂}·nH₂O. Attempts to prepare similar heterobimetallic complexes using the starting complexes {PtX₂[ ¹-Ph₂PCH₂P(O)-Ph₂]₂} (X = C1), cis- or CN, trans-] were unsuccessful. Possible reasons for this are discussed.     

A new characterization of periodic oscillations in periodic difference equations

In this paper, we characterize periodic solutions of p-periodic difference equations. We classify the periods into multiples of p and nonmultiples of p. We show that the elements of the set of multiples of p follow the well-known Sharkovsky’s ordering multiplied by p. On the other hand, we show that the elements of the set Γ_p of nonmultiples of p are independent in their existence. Moreover, we show the existence of a p-periodic difference equation with infinite Γ_p-set in which the maps are defined on a compact domain and agree exactly on a countable set. Based on the proposed classification, we give a refinement of Sharkovsky’s theorem for periodic difference equations.     

Syntheses, characterization, biological activity and fluorescence properties of bis-(salicylaldehyde)-1,3-propylenediimine Schiff base ligand and its lanthanide complexes

Eight new lanthanide metal complexes [LnL(NO(3))(2)]NO(3) {Ln(III) = Nd, Dy, Sm, Pr, Gd, Tb, La and Er, L = bis-(salicyladehyde)-1,3-propylenediimine Schiff base ligand} were prepared. These complexes were characterized by elemental analysis, thermogravimetric analysis (TGA), molar conductivity measurements and spectral studies ((1)H NMR, FT-IR, UV-vis, and luminescence). The Schiff base ligand coordinates to Ln(III) ion in a tetra-dentate manner through the phenolic oxygen and azomethine nitrogen atoms. The coordination number of eight is achieved by involving two bi-dentate nitrate groups in the coordination sphere. Sm, Tb and Dy complexes exhibit the characteristic luminescence emissions of the central metal ions attributed to efficient energy transfer from the ligand to the metal center. Most of the complexes exhibit antibacterial activity against a number of pathogenic bacteria.     

Synthesis of alpha-keto-imides via oxidation of ynamides

A de novo preparation of alpha-keto-imides via ynamide oxidation is described. With a number of alkyne oxidation conditions screened, a highly efficient RuO2-NaIO4 mediated oxidation and a DMDO oxidation have been identified to tolerate a wide range of ynamide types. In addition to accessing a wide variety of alpha-keto-imides, the RuO2-NaIO4 protocol provides a novel entry to the vicinal tricarbonyl motif via oxidation of push-pull ynamides, and imido acylsilanes from silyl-substituted ynamides. Chemoselective oxidation of ynamides containing olefins can be achieved by using DMDO, while the RuO2-NaIO4 protocol is not effective. These studies provide further support for the synthetic utility of ynamides.     

A stereoselective intramolecular halo-etherification of chiral enamides in the synthesis of halogenated cyclic ethers

A stereoselective halo-etherification of chiral enamides is described here. This work provides an approach to halogen containing cyclic ethers and reveals further mechanistic insights to the chemistry of chiral enamides.     

Structural,luminescence and biological studies of trivalent lanthanide complexes with N,N′-bis(2-hydroxynaphthylmethylidene)-1,3-propanediamine Schiff base ligand

New eight lanthanide metal complexes were prepared. These complexes were characterized by elemental analysis, molar conductivity measurements, spectral analysis (¹H NMR, FT-IR, UV–vis), luminescence and thermal gravimetric analysis. All Ln(III) complexes were 1:1 electrolytes as established by their molar conductivities. The microanalysis and spectroscopic analysis revealed eight-coordinated environments around lanthanide ions with two nitrate ligands behaving in a bidentate manner. The other four positions were found to be occupied with tetradentate L_III ligand. Tb–L_III and Sm–L_III complexes exhibited characteristic luminescence emissions of the central metal ions and this was attributed to efficient energy transfer from the ligand to the metal center. The L_III and Ln–L_III complexes showed antibacterial activity against a number of pathogenic bacteria.