In situ Raman and in situ XRD analysis of PdO reduction and Pd° oxidation supported on γ-Al2O3 catalyst under different atmospheres

Reduction of Pd° and decomposition of palladium oxide supported on γ-alumina were studied at atmospheric pressure under different atmospheres (H(2), CH(4), He) over a 4 wt% Pd/Al(2)O(3) catalyst (mean palladium particle size: 5 nm with 50% of small particles of size below 5 nm). During temperature programmed tests (reduction, decomposition and oxidation) the crystal domain behaviour of the PdO/Pd° phase was evaluated by in situ Raman spectroscopy and in situ XRD analysis. Under H(2)/N(2), the reduction of small PdO particles (<5 nm) occurs at room temperature, whereas reduction of larger particles (>5 nm) starts at 100 °C and is achieved at 150 °C. Subsequent oxidation in O(2)/N(2) leads to reoxidation of small crystal domain at ambient temperature while oxidation of large particles starts at 300 °C. Under CH(4)/N(2), the small particle reduction occurs between 240 and 250 °C while large particle reduction is fast and occurs between 280 and 290 °C. Subsequent reoxidation of the catalyst reduced in CH(4)/N(2) shows that small and large particle oxidation of Pd° starts also at 300 °C. Under He, no small particle decomposition is observed probably due to strong interactions between particles and support whereas large particle reduction occurs between 700 and 750 °C. After thermal decomposition under He, the oxidation starts at 300 °C. Thus, the reduction phenomenon (small and large crystal domain) depends on the nature of the reducing agent (H(2), CH(4), He). However, whatever the reduction or decomposition treatment or the crystal domain, Pd° oxidation starts at 300 °C and is completed only at temperatures higher than 550 °C. Under lean conditions, with or without water, the palladium consists of reduced sites of palladium (Pd°, Pd(δ+) with δ < 2 or PdO(x) with x < 1) randomly distributed on palladium particles.     

Nonextensive statistical effects in the quark-gluon plasma formation at relativistic heavy-ion collisions energies

We investigate the relativistic equation of state of hadronic matter and quark-gluon plasma at finite temperature and baryon density in the framework of the non-extensive statistical mechanics, characterized by power-law quantum distributions. We impose the Gibbs conditions on the global conservation of baryon number, electric charge and strangeness number. For the hadronic phase, we study an extended relativistic mean-field theoretical model with the inclusion of strange particles (hyperons and mesons). For the quark sector, we employ an extended MIT-Bag model. In this context we focus on the relevance of non-extensive effects in the presence of strange matter.     

N^N^C platinum(II) and palladium(II) cyclometallates of 6,6′-diphenyl-2,2′-bipyridine, L: Crystal and molecular structure of [Pd(L-H)Cl]

Reaction of K₂[PtCl₄] or Na₂[PdCl₄] with 6,6′-diphenyl-2,2′-bipyridine, L, gives the cyclometallated species [Pt(L-H)Cl], 1, and [Pd(L-H)Cl], 2, respectively, where L-H is a terdentate N^N^C anionic ligand originated by direct activation of a C(sp²)-H bond. The crystal structure of 2 has been solved by X-ray diffraction and compared to that of the analogous complex [Pd(L′-H)Cl] L′ = 6-phenyl-2,2′-bipyridine. The second phenyl ring in 2 entails a considerable distortion of the coordination around the metal. A similar distortion is also to be expected in the analogous compound 1, due to the almost equal covalent radii of palladium(II) and platinum(II).From the complexes 1 and 2 the chloride can be displaced with AgBF₄ and substituted by CO or PPh₃ to give the corresponding cationic species. By reaction of 1 with Na[BH₄] substitution of H⁻ for Cl⁻ can be achieved: the rare hydrido complex [Pt(L-H)H], stabilized only by nitrogen ligands, was isolated in the solid state and fully characterized in solution. It is noteworthy that in the case of the 6-phenyl-2,2′-bipyridine the analogous terminal hydride [Pd(L′-H)H] is unstable. In platinum chemistry the reaction of 6-substituted 2,2′-bipyridines is known to give either N^N^C or N′^C(3) rollover cyclometallation, depending on the nature of the metal precursor. In the case of 6,6′-Ph₂-2,2′-bipy cyclometallation was also shown to undergo multiple C-H activation giving the C^N^C pincer complex [Pt(L-2H)(DMSO)]. The latter species can be related to complex 1: indeed its reaction with HCl produces complex 1 and [Pt(L-H)(DMSO)Cl], a rollover species with a pendant phenyl substituent.     

Electronically driven phase transitions in a quasi-one-dimensional adsorbate system

A quasi-1D system is prepared using the Pt(110) surface as a template. The electronic surface resonance structure is studied by angle-resolved photoemission spectroscopy for the clean surface as well as for different Bromine coverages. A Fermi surface mapping reveals saddle points at the Fermi level in the interior of the surface Brillouin zone. Correspondingly, a maximum in the static response function χ(q, 0) at the connecting vector q is expected. With 1/2G_x < q < 2/3G_x one observes indeed a 3-fold periodicity around defects and a 2-fold periodicity at low temperature for Θ_Br = 0.5 ML. Cooling of a defect-free c(2×2)-Br/Pt(110) preparation counter-intuitively results in a loss of long-range order. Motivated by DFT calculations this is attributed to an anomalous order-order phase transition into the (2×1) phase accompanied by intense, strongly anisotropic fluctuations within a temperature range of ~200 K. The peculiar behaviour is rationalised in terms of a competition between inter-adsorbate repulsion and an adsorbate triggered 2k_F interaction in the substrate.     

Metal–Organic Framework‐Activated Carbon Composite Materials for the Removal of Ammonia from Contaminated Airstreams

Metal–organic frameworks (MOFs) are a class of porous materials that show promise in the removal of toxic industrial chemicals (TICs) from contaminated airstreams, though their development for this application has so far been hindered by issues of water stability and the wide availability and low cost of traditionally used activated carbons. Here a series of three MOF‐activated carbon composite materials with different MOF to carbon ratios are prepared by growing STAM‐17‐OEt crystals inside the commercially available BPL activated carbon. The composite materials display excellent water stability and increased uptake of ammonia gas when compared to unimpregnated carbon. Such properties make these composites very promising in the fields of air purification and personal protective equipment.     

Damage effects of γ-radiation on lipid bilayers

Summary The lipid composition of multi-lamellar vesicles of 1,2-dipalmitoyl-sn-glycero-3-phosphorylcholine exposed to¹³⁷Cs γ-rays depends on the absorbed dose. In fact,³¹P and¹H NMR analysis shows that four new molecular species are formed during the irradiation:a) 1-palmitoyl-sn-glycero-3-phosphorylcholine,b) 2-palmitoyl-sn-glycero-3-phosphorylcholine,c) glycerophosphorylcholine andd) free palmitic acid. Neglecting the speciesc), that is present only at high dose and in very small amount, the behaviour of molar fractionvs. dose is sublinear fora) andb), while ford) it is almost linear over all the dose range examined. The molecular and structural damage consequences onto the multi-lamellar vesicles, evidentiated by spin-labelling and DSC techniques, are discussed. It is clearly shown in particular, that the behaviour of the main transition does not depend on the concentration of the lysolecithins, but rather on that of the free palmitic acid, the role of which had previously been entirely neglected. The authors of this paper have agreed to not receive the proofs for correction.     

On a class of stochastic differential equations used in quantum optics

Stochastic differential equations for processes with values in Hilbert spaces are now largely used in the quantum theory of open systems. In this work we present a class of such equations and discuss their main properties; moreover, we explain how they are derived from purely quantum mechanical models, where the dynamics is represented by a unitary evolution in a Hilbert space, and how they are related to the theory of continual measurements. An essential tool is an isomorphism between the bosonic Fock space and the Wiener space, which allows to connect certain quantum objects with probabilistic ones.     

Simultaneous determination of ten amphetamine designer drugs in human whole blood by capillary electrophoresis with diode array detection

In recent years, a number of new designer drugs have entered the illicit drug market. The methylenedioxyderivatives of amphetamine represent the largest group of designer drugs. This paper describes a method for screening for and simultaneously quantifying 10 2,5-methylenedioxy-derivatives of amphetamine and phenethylamine in human whole blood, using capillary electrophoresis (CE) with diode array detection (DAD). Using an aqueous pH 2.5 phosphate buffer, CE analysis gave peaks with good symmetry and reproducible migration times. Under these experimental conditions, the 10 amphetamines were resolved in 15 min and without interference from biological matrices (blood). Their identification by migration time was confirmed by their UV spectra recorded with a DAD (190-350 nm). The main advantages of the present method lie in its simplicity, clean and reliable extraction from human whole blood and simultaneous detection and quantification by CE-DAD. The applicability of the method was demonstrated by analysis of in vivo rat blood samples. The method was validated according to international guidelines.