Principal component analysis and cluster analysis for the characterisation of marbles by capillary electrophoresis

Chemical characterisation has been carried out on 25 quarry marbles collected from Marmara, Aegean and Thrace regions of Turkey. Ten elements were determined by capillary electrophoresis (CE). Principal component analysis and cluster analysis techniques were utilised to define grouping of different marble samples. These techniques showed that the analysed marbles were differentiable mainly by provenance. Experimental conditions such as pH, applied voltage and concentration of α-hydroxyisobutyric acid (HIBA) were optimised to achieve the best separation of metal ions using central composite design. The optimum pH 3.7, applied voltage 15 kV and concentration of HIBA 10 mM were found to provide the best separation for all metal ions investigated.     

Sintering behavior and apatite formation of diopside prepared by coprecipitation process

Sintering behavior and bioactivity of diopside, CaMgSi₂O₆, prepared by a coprecipitation process were examined for its biomedical applicability. As-prepared powder was synthesized by adding aqueous ammonia to an ethanol solution containing Ca(NO₃)₂·4H₂O, Mg(NO₃)₂·6H₂O, and Si(OC₂H₅)₄ and characterized by means of TG–DTA, XRD, and TG–MS. The dried powder was X-ray amorphous and crystallized into diopside at 845.5 °C. The glass network formation by SiO₄ tetrahedra was almost completed below 800 °C. The bioactivity of the diopside prepared by sintering the compressed powder at 1100 °C for 2 h was evaluated by immersion of the sintered body in a simulated body fluid (SBF) at 36.5 °C. Leaf-like apatite particles were found to be formed on the surface of the sintered body and grew with passage of soaking time. This apatite-forming behavior in the SBF is related to the dissolution of Ca(II) ions from the sintered body in the early stage of immersion. Thus, diopside prepared by the coprecipitation process using the metal alkoxide and the metal salts was found to have an apatite-forming ability.     

Water oxidation with inhomogeneous metal-silicon interfaces

Silicon (Si) is a prime candidate for manufacturing water-splitting photoelectrochemical cells, however, the stability of this material remains a serious bottleneck. This is particularly true for the photoanode, subject to severe deactivation mechanisms. So far, thin film homogeneity has been the paradigm in the quest for stable and efficient Si-based photoanodes, which involved the use of vapor deposition methods to produce conformal thin films ensuring Si protection and efficient catalysis during operation. Conversely, recent reports on n-Si/metal thin film junctions have highlighted the benefits of the junction heterogeneity, generated in situ. In addition, results obtained from n-Si photoanodes partially covered with discontinuous films of Co and Ni nanoparticles lately suggested that homogeneity is not a prerequisite to reach efficiency and stability. Such findings may open new protection routes for Si-based photoanodes, breaking with classical strategies and allowing the use of liquid phase modification methods such as electrodeposition.     

Fluorescence emission control and switching of oxymethylcrowned spirobenzopyrans by metal ion

Oxymethylcrowned spirobenzopyran 1 and pyrenylspirobenzopyran 2 were synthesized, and fluorescence emission of their corresponding merocyanine form was examined in the presence of metal ions. For 2, fluorescence emission derived from the pyrene moiety was completely quenched by photoinduced electron transfer (PET) of the nitrogen atom when the merocyanine form was not produced, namely, without metal ions. However, when 2 was converted to the merocyanine form by the complexation of its crown ether with a metal ion, fluorescence resonance energy transfer (FRET) from the pyrene to the merocyanine moieties took place to produce fluorescence emission. This result demonstrates that the spirobenzopyran isomerization can function as a fluorescence emission switch. Fluorescence quantum yield measurement for 1 and 2 showed that fluorescence emission depends on the binding metal ion in which the fluorescence quantum yield generally increased with the increase of metal ion radius.     

Template Controlled Synthesis (TCS) of size-controlled metal nanoclusters: preparation of nanostructured metals supported by inorganic supports

Strictly size-controlled metal nanoclusters of palladium(0) and gold(0) can be easily formed in the organic component of an organic-inorganic composite between a gel-type resin (DV44) and silica. To this purpose, silica is impregnated at incipient wetness with a solution of the required co-monomers (N,N-dimethylacrylamide, 4-vinylpyridine and N,N′-methylene-bis-acrylamide), which are co-polymerized to give the composite. The silica-supported polymeric framework is then loaded with palladium(II) or gold(III) precursors. Their chemical reduction with aqueous solutions of sodium boronhydride yields the metal nanoclusters. Their size is controlled by the nanomorphology of the polymeric framework, which acts as a template during the nanocluster growth (Template Controlled Synthesis). Upon thermal decomposition of the polymeric template at 600°C under nitrogen, the nanostructured metals are deposited onto the silica surface. In the case of palladium the final step occurs with retention of the original size of the nanoclusters.     

Energetics and bonding in beryllium metallized carbon clusters

Small carbon clusters C, C₂ and C₃ metallized with beryllium were studied by first principles within the hybrid density functional approach with generalized gradient correction. Cluster isomer structures for the ground state and several excited states where systematically calculated for C_xBe_y with x = 1–3 and y = 1–4 including the vibrational analysis of all states. Ionization potentials and electron affinities are calculated for the ground state cluster isomers. The thermal stability of the ground state isomers was verified within the harmonic approximation of the Helmholtz free energy up to temperatures of about 1000 K. Within the family of clusters studied, C₂Be₃ undergoes a solid-like structural transition at about 260 K changing from a planar structure at low temperatures to a linear isomer at high temperatures.     

The synthesis and structure of a chiral 1D aluminophosphate chain compound: d-Co(en)3[AlP2O8]·6.5H2O

A new chiral one-dimensional (1D) aluminophosphate chain compound [d-Co(en)₃][AlP₂O₈]·6.5H₂O (designated AlPO-CJ22) has been hydrothermally synthesized by using the optically pure d-Co(en)₃I₃ complex as the template. Single-crystal structural analysis reveals that its structure is built up from alternating connection of AlO₄ and PO₂(=O₂) tetrahedra to form corner-shared Al₂P₂ four-membered ring (4-MR) chains. The d-Co(en)₃³⁺ complex cations extended along the 2₁ screw axis interact with the inorganic chains through hydrogen-bonds of N?O atoms in a helical fashion. Optical rotation measurement shows that AlPO-CJ22 is chiral as with d-Co(en)₃³⁺ complex cations. Crystal data: orthorhombic, I2₁2₁2₁, , , , Z=8, R₁=0.067, wR₂=0.1291, and Flack parameter: −0.02(3). CCDC number: 254179.     

Photooxidation of Ethylbenzene with TiO<Subscript>2</Subscript> and Metal Coated TiO<Subscript>2</Subscript> and its Kinetics

Summary. Photooxidation of ethylbenzene with oxygen to give ethylbenzene hydroperoxide has been achieved in a stirred photochemical reactor that was cooled by a water system by irradiation with a 400W high-pressure mercury lamp and using TiO₂ powder and metal coated TiO₂. The effects of the amount of copper or silver coated on TiO₂ and of the temperature on the rate of oxidation have been investigated. It is suggested that thermal cleavage of the O–O bond and photochemically generated singlet oxygen should be considered as the initiating step in a radical chain mechanism. An optimum loading of 6% Ag or 4–5% Cu was observed for photooxidation of ethylbenzene.     

Thermochemistry of adducts of some transition metals(II) bromides with pyridine N-oxide

The compounds [MBr₂(pyNO)_n] (where M: Mn, Fe, Co, Ni, Cu or Zn; pyNO is pyridine N-oxide and n=2, 3 or 6) were synthesized and characterized by melting points, elemental analysis, thermal analysis and electronic and IR spectroscopy. The enthalpies of dissolution of the adducts, metal(II) bromides and pyNo in methanol were measured and by using thermochemical cycles, the following thermochemical parameters for the adducts have been determined: the standard enthalpies for the Lewis acid/base reactions (Δ_rH^θ), the standard enthalpies of formation (Δ_fH^θ), the standard enthalpies of decomposition (Δ_DH^θ), the lattice standard enthalpies (Δ_MH^θ) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ_rH^θ(g)). The mean bond dissociation enthalpies of the M(II)-oxygen bonds () have been estimated.