Model-based sensitivity analysis of a fluidised-bed bioreactor for mercury uptake by immobilised Pseudomonas putida cells

A model-based sensitivity analysis was performed in order to evaluate the importance of the individual operating parameters of a three-phase fluidised-bed biological reactor used for removing mercury ions from wastewater. The parameters analysed involve the immobilised biomass load (bacteria P. putida) on alginate beads, particle size, inlet flow-rate, mercury ion loads in the fed wastewater, and the solid fraction in the reactor. Predictions were generated by using pseudo-first-order, Michaelis-Menten, or pseudo-Haldane kinetic models. The results highlight the major influence of the biomass/solid load and of the liquid residence time on the reactor efficiency. Also, the resultant significant differences in the model predictions underline the importance of using a more accurate kinetic model for process design and control purposes.     

Sol–gel preparation and structural characterization of Ba2TiSi2O8 powder

Fresnoite (Ba₂TiSi₂O₈, BTS) nano-particles were successfully synthesized at a low temperature of 900?°C by a modified Pechini sol?Cgel process with starting materials of Ba(NO₃)₂, Si(OC₂H₅)₄ and Ti(OC₃H₇)₄. The structural characterization of the precursors and derived synthesized oxide powders is done by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal analysis (TG-DTG) and electron microscopy (SEM, EDX and TEM) studies. The effect of heat-treating temperature on the crystallinity of the fresnoite was investigated. Combined the XRD data and the strong FTIR peaks assigned to Ti?CO and Si?CO vibration, indicate the formation of fresnoite phase at a temperature of 900?°C. Also the nano-crystals size distribution was studied and the main diameter of nanoparticles was about 47?nm.     

Optimization of a high-performance liquid chromatography method for the analysis of complex polyphenol mixtures and application for sainfoin extracts (Onobrychis viciifolia)

A pentafluorophenylpropyl (PFP) stationary phase was tested for the simultaneous determination of several classes of phenolic compounds. The chromatographic results were compared with those obtained by using a bifunctional phase constituted of octadecyl and phenylpropyl bonded silica and three conventional C18 columns. The elution gradient was optimized with 5% formic acid and sodium acetate in combination with acetic acid as additives and methanol as solvents. For these evaluations, a complex phenolic extract of Onobrychis viciifolia (sainfoin) and test mixtures containing 54 standard substances including 2 simple phenolic compounds, 1 amino acid, 4 hydroxybenzoic acids (HBA), 6 hydroxycinnamic acids (HCA), 3 flavan-3-ols, 9 anthocyanins, 2 dihydroflavonols, 1 chalcone, 4 flavones, 1 isoflavone and 21 flavonols have been assayed. The perfluorinated column showed good resolution for the studied phenolic compounds which have the following elution order: HBA, HCA, flavan-3-ols, anthocyanins, dihydroflavonols, flavones, flavonols and isoflavones. Compared with other columns, it provides longer elution ranges for HBA, HCA and flavan-3-ols and increased retention times for all compound classes except anthocyanins which were similarly retained on a C18 column. Its selectivity is different from C18 and bifunctional phases. A high-performance liquid chromatography (HPLC) method with diode array detection (DAD) and post-column derivatization with p-dimethyl-aminocinnamic aldehyde (DMACA) has been validated for the analysis of individual phenolic compounds from a sainfoin plant extract (O. viciifolia).     

Electronic spectroscopy of the A1A' <-- X1A' system of CDF

To further investigate the Renner-Teller (RT) effect and barriers to linearity and dissociation in the simplest singlet carbene, we recorded fluorescence excitation spectra of bands involving the pure bending levels 2(n)(0) with n = 0-9 and the combination states 1(1)(0)2(n)(0) with n = 1-8 and 2(n)(0)3(1)(0) with n = 0-5 in the A(1)A'<-- X(1)A' system of CDF, in addition to some weak hot bands. The spectra were measured under jet-cooled conditions using a pulsed discharge source, and rotationally analyzed to yield precise values for the band origins and rotational constants; fluorescence lifetimes were also measured to probe for lifetime lengthening effects due to the RT interaction. The derived A state parameters are compared with previous results for CHF and with predictions of ab initio electronic structure theory. The approach to linearity in the A state is evidenced in a sharp increase in the A rotational constant with bending excitation, and a minimum in the vibrational intervals near 2(9). A fit of the vibrational intervals for the pure bending levels yields an A state barrier to linearity in good agreement both with that previously derived for CHF and ab initio predictions. From the spectra and lifetime measurements, the onset of extensive RT perturbations is found to occur at a higher energy than in CHF, consistent with the smaller A constant.     

Properties of manganite/ruthenate superlattices with ultrathin layers

The properties of manganite/ruthenate superlattices are reviewed with a specific focus on the manganite/ruthenate interface. La_0.7Sr_0.3MnO₃/SrRuO₃ and Pr_0.7Ca_0.3MnO₃/SrRuO₃ superlattices grow with a high crystalline perfection as illustrated in the figure to the right: at the interface the individual cation species can be clearly identified, interdiffusion is marginal. The superlattices show magnetization processes with an intricate interplay between magnetocrystalline anisotropy, size of the layer magnetization, spin confinement and interfacial antiferromagnetic interlayer coupling. There is further an unprecedented Curie temperature stabilization at room temperature values of the La_0.7Sr_0.3MnO₃ layers in the superlattices down to layer thicknesses of one unit cell. The magnetotransport properties, especially the Hall effect, indicate the existence of a quasi‐two‐dimensional hole gas at the La_0.7Sr_0.3MnO₃/SrRuO₃ interface; this is further supported by an analysis of cation displacements as determined from scanning transmission electron microscopy. The manganite/ruthenate interface might be considered as a model system for the study of interfacial reconstruction and charge transfer in a highly correlated ferromagnetic system.

     

Luminescent Solar Concentrators Based on Renewable Polyester Matrices

This study reports for the first time the use of bio‐based alternatives for PMMA as host matrix for luminescent solar concentrators (LSCs). Notably, two types of renewable polyesters were synthesized in varying molar ratios via a two‐step melt‐polycondensation reaction with dibutyl tin oxide as catalyst. The first is a homopolymer of diethyl 2,3:4,5‐di‐O‐methylene galactarate (GxMe) and isosorbide (IGPn), and the second is a random copolymer of GxMe with 1,3‐propanediol and dimethyl terephthalate (GTPn). The two polyesters were found to be optically transparent, totally amorphous with a T_g higher than 45 °C and temperature resistance comparable to PMMA. Lumogen Red (LR) and an aggregation‐induced emission (AIE) fluorophore, TPETPAFN, were utilized as fluorophores and the derived thin polymer films (25 μm) were found highly homogeneous, especially for those prepared from GTPn, possibly due to the presence of compatibilizing terephthalate units in the matrix composition and the higher molecular weight. The spectroscopic characterization and the optical efficiency determination (η_opt) evidenced LSCs performances similar or superior to those collected from LR/PMMA thin films. Noteworthy, η_opt of 7.7 % and 7.1 % were recorded for the GTPn‐based matrix containing LR and TPETPAFN, respectively, thus definitely supporting the bio‐based polyesters as renewable and highly fluorophore‐compatible matrices for high‐performance LSCs.     

Transmission Electron Microscopy Study on the Formation of Al<Subscript>18</Subscript>B<Subscript>4</Subscript>O<Subscript>33</Subscript> Whiskers

The aim of this paper is to report the results of a systematic high-resolution transmission electron microscopy study on Al₁₈B₄O₃₃. The fluxing agent method permits the formation of needle-shaped whiskers of Al₁₈B₄O₃₃, having sub-micron thickness with a tendency to come and fuse together. Amounts of 25% and 50% K₂SO₄, K₂CO₃ or KCl were used liked fluxing agents. Using this method, the optimum temperature for the synthesised compound was found to be 1000°C. The investigation techniques were X-ray diffraction and electron microscopy.     

Luminescent cyclometallated platinum(II) complexes with N-benzoyl thiourea derivatives as ancillary ligands

A series of cyclometallated 2-phenylpyridine Pt(II) complexes having N-benzoyl thiourea derivatives as ancillary ligands were prepared and characterised by elemental analysis, IR and UV–Vis spectroscopy, ¹H and ¹³C NMR spectroscopy as well as by X-ray diffraction on single-crystal. All complexes were obtained as a single isomer with N atom of the 2-phenylpyridine ligand and S atom of the N-benzoyl thiourea derivatives coordinated in trans positions to the platinum metal as evidenced by using X-ray crystallography and NMR spectroscopy. All Pt(II) complexes show good luminescence properties at room temperature, both in dichloromethane solution and in solid state.     

Two‐Step Spin Transition in a 1D FeII 1,2,4‐Triazole Chain Compound

A thermochromic 1D spin crossover coordination (SCO) polymer [Fe(βAlatrz)₃](BF₄)₂ ? 2 H₂O ( 1? 2 H₂O), whose precursor βAlatrz, (1,2,4‐triazol‐4‐yl‐propionate) has been tailored from a β‐amino acid ester is investigated in detail by a set of superconducting quantum interference device (SQUID), ⁵⁷Fe Mössbauer, differential scanning calorimetry, infrared, and Raman measurements. An hysteretic abrupt two‐step spin crossover (T_1/2^↓=230 K and T_1/2^↑=235 K, and T_1/2^↓=172 K and T_1/2^↑=188 K, respectively) is registered for the first time for a 1,2,4‐triazole‐based Fe^II 1D coordination polymer. The two‐step SCO configuration is observed in a 1:2 ratio of low‐spin/high‐spin in the intermediate phase for a 1D chain. The origin of the stepwise transition was attributed to a distribution of chains of different lengths in 1? 2 H₂O after First Order Reversal Curves (FORC) analyses. A detailed DFT analysis allowed us to propose the normal mode assignment of the Raman peaks in the low‐spin and high‐spin states of 1? 2 H₂O. Vibrational spectra of 1? 2 H₂O reveal that the BF₄^? anions and water molecules play no significant role on the vibrational properties of the [Fe(βAlatrz)₃]²⁺ polymeric chains, although non‐coordinated water molecules have a dramatic influence on the emergence of a step in the spin transition curve. The dehydrated material [Fe(βAlatrz)₃](BF₄)₂ ( 1 ) reveals indeed a significantly different magnetic behavior with a one‐step SCO which was also investigated.