Complete supramolecular self-assembled adlayer on a silicon surface at room temperature

The engineering of a complete adlayer of organic nanolines by supramolecular self-assembly has been achieved for the first time on a silicon-based surface at room temperature and has been studied by scanning tunneling microscopy. This complete adlayer has been successfully obtained thanks to the combination of a specific Si(111)-B square root 3x square root 3R30 degrees semiconductive surface and of strong hydrogen bonds between a pair of dipolar molecules.     

Local atomic structures of single-component metallic glasses

In this study we examine the structural properties of single-component metallic glasses of aluminum. We use a molecular dynamics simulation based on semi-empirical many-body potential, derived from the embedded atom method (EAM). The radial distribution function (RDF), common neighbors analysis method (CNA), coordination number analysis (CN) and Voronoi tessellation are used to characterize the metal’s local structure during the heating and cooling (quenching). The simulation results reveal that the melting temperature depends on the heating rate. In addition, atomic visualization shows that the structure of aluminum after fast quenching is in a glassy state, confirmed quantitatively by the splitting of the second peak of the radial distribution function, and by the appearance of icosahedral clusters observed via CNA technique. On the other hand, the Wendt-Abraham parameters are calculated to determine the glass transition temperature (T_g), which depends strongly on the cooling rate; it increases while the cooling rate increases. On the basis of CN analysis and Voronoi tessellation, we demonstrate that the transition from the Al liquid to glassy state is mainly due to the formation of distorted and perfect icosahedral clusters.     

Performance characteristics of an ion chromatographic method for the quantitation of citrate and phosphate in pharmaceutical solutions

The performance of an ion chromatographic method for measuring citrate and phosphate in pharmaceutical solutions is evaluated. Performance characteristics examined include accuracy, precision, specificity, response linearity, robustness, and the ability to meet system suitability criteria. In general, the method is found to be robust within reasonable deviations from its specified operating conditions. Analytical accuracy is typically 100 +/- 3%, and short-term precision is not more than 1.5% relative standard deviation. The instrument response is linear over a range of 50% to 150% of the standard preparation target concentrations (12 mg/L for phosphate and 20 mg/L for citrate), and the results obtained using a single-point standard versus a calibration curve are essentially equivalent. A small analytical bias is observed and ascribed to the relative purity of the differing salts, used as raw materials in tested finished products and as reference standards in the analytical method. The assay is specific in that no phosphate or citrate peaks are observed in a variety of method-related solutions and matrix blanks (with and without autoclaving). The assay with manual preparation of the eluents is sensitive to the composition of the eluent in the sense that the eluent must be effectively degassed and protected from CO(2) ingress during use. In order for the assay to perform effectively, extensive system equilibration and conditioning is required. However, a properly conditioned and equilibrated system can be used to test a number of samples via chromatographic runs that include many (> 50) injections.     

Effect of zeolite structure on the selective catalytic reduction of NO with ammonia over Mn-Fe supported on ZSM-5, BEA,MOR and FER

A series of catalysts based on Mn-Fe loaded zeolites was prepared by impregnation and their activity in the selective catalytic reduction of NO with ammonia (NH₃-SCR) was investigated. The highest catalytic conversion was recorded for MnFe-ZSM-5 (MnFe-Z), followed by MnFe-BEA (MnFe-B) and MnFe-MOR (MnFe-M), while MnFe-FER (MnFe-F) showed a very poor activity over the entire temperature range. In order to evidence a correlation between the structure and acidity of the zeolites and NO conversion, the prepared samples were characterized by various techniques (ICP-AES, N₂ physisorption at 77 K, XRD, ²⁷NMR, Raman, FTIR spectroscopy of adsorbed ammonia, H₂-TPR, DRS UV–Vis, EPR and XPS). The superior catalytic activity of MnFe-Z at low temperature is attributed to the abundance of Mn⁴⁺ concentration as revealed by XPS, the highest NH₃-L/NH₄⁺ ratio indicative of the contribution of metals in generating Lewis acidic centers as evidenced by IR-NH3, and the better reducibility of manganese and iron on ZSM-5 which increases the kinetics for red-ox cycles as confirmed in TPR analysis. Fe₃Mn₃O₈ mixed oxide phase is also detected by XRD and XPS and can be associated with the high reducibility of MnFe-Z which generates a high oxidation ability favoring NO to NO₂ oxidation. Raman spectroscopy was also used to confirm the existence of a strong synergy between metals and ZSM-5 support revealed by the shift in the signal position and the decrease in band intensities. The results showed that the zeolite framework and acidity generate catalysts with different textural and structural properties which influence the metal dispersion and speciation and hence influence the catalytic performances.

     

Formation and Structural Characterization of Metal Complexes derived from Thiosalicylic Acid

The formation and structural aspects of some metal complexes of thiosalicylic acid (TSA) were studied. The μ‐bridging tetra‐coordinated Ru complex, [Ru(C₆H₄(CO₂)(μ‐S)(H₂O)]₂ ( 1 ) was formed by hydrothermal reaction of TSA with RuCl₃. The complexes [M(dtdb)(phen)(H₂O)]_n ( 2 – 4 ) (M = Zn^II, Co^II, Ni^II, dtdb = 2,2′‐dithiodibenzoate anion, phen = 1,10‐phenanthroline) were obtained by the slow diffusion technique and the in situ S–S bond formation was confirmed by elemental, spectral and X‐ray analysis. Reaction of TSA with CuCl₂ and 2,2′‐bipyridine (bipy) under the slow diffusion technique yielded the dimer [Cu(tdb)(bipy)] ( 5 ) (tdb = thiodibenzoic acid), where the in situ generation of 2,2′‐thiodibenzoic acid was observed.     

Structural studies of NaPO3-MoO3 glasses by solid-state nuclear magnetic resonance and Raman spectroscopy

Vitreous samples were prepared in the (100 - x)% NaPO(3)-x% MoO(3) (0 相似文献   

Absorption and Emission Sensitivity of 2‐(2′‐Hydroxyphenyl)benzoxazole to Solvents and Impurities

2‐(2′‐Hydroxyphenyl)benzoxazole (HBO) is known for undergoing intramolecular proton transfer in the excited state to result in the emission of its tautomer. A minor long‐wavelength absorption band in the range 370–420 nm has been reported in highly polar solvents such as dimethylsulfoxide (DMSO). However, the nature of this species has not been entirely clarified. In this work, we provide evidence that this long‐wavelength absorption band might have been caused by base or metal salt impurities that are introduced into the spectral sample during solvent transport using glass Pasteur pipettes. The contamination by base or metal salt could be avoided by using borosilicate glass syringes or nonglass pipettes in sample handling. Quantum chemical calculations conclude that solvent‐mediated deprotonation is too energetically costly to occur without the aid of a base of an adequate strength. In the presence of such a base, the deprotonation of HBO and its effect on emission are investigated in dichloromethane and DMSO, the latter of which facilitates deprotonation much more readily than the former. Finally, the absorption and emission spectra of HBO in 13 solvents are reported, from which it is concluded that ESIPT is hindered in polar solvents that are also strong hydrogen bond acceptors.     

Design of new organic superacids with fused and isolated pyrrole and cyclopentadiene rings and assessment of effect of –BX2 (X = H,F, Cl,CN) substituents on the acidity enhancement: A DFT analysis

New classes of organic Brønsted acids were designed with pyrrole and cyclopentadiene scaffolds, and their acidity was assessed theoretically by the B3LYP/6-311++G(d,p) method. The hydrogen atom of NH group in pyrrole was substituted by an –BX₂ (X = H, F, Cl, CN, CF₃). The boron atom stabilizes the conjugated bases by interaction with the center of negative charge after deprotonation. The acidity of the compounds was promoted by substitution of the hydrogen atoms of the rings with CN moiety as a strong electron withdrawing group. Also, after deprotonation, delocalization of the negative charge in both pyrrole and cyclopentadiene rings causes stability of the conjugated bases and consequently enhances the acidity. The charge delocalization in the neutral acids and their conjugated bases was compared using nucleus-independent chemical shift index. Enthalpies and Gibbs free energies of deprotonation in gas phase, ∆H_acid and ∆G_acid, were used as a measure of acidity. Both compounds with isolated and fused pyrrole and cyclopentadiene rings were investigated and it was found that the formers are more acidic. Using these strategies, several acids and superacids with wide range of acidity with ∆G_acid values of 244 to 328 kcal mol⁻¹ were obtained.     

Comparison of the thermal performances of two nanofluids at low temperature in a plate heat exchanger

The objective of this study is to compare experimentally the thermal performances of two types of commercial nanofluids. The first is composed of oxides of alumina (γAl₂O₃) dispersed in water and the second one is aqueous suspensions of nanotubes of carbons (CNTs). The viscosity of the nanofluids is measured as a function of the temperature between 2 and 10 °C. An experimental device, containing three thermal buckles controlled in temperature and greatly instrumented permits to study the thermal convective transfers. The evolution of the convective coefficient permits to study the convective thermal transfers. The evolution of the convective coefficient is presented according to the Reynolds number, at low temperature from 0 to 10 °C and for the two aforementioned nanofluids. An assessment of the pressure drops in the circuit as well as of the powers of the circulator and outputs is dealt with.