Influence of oxidation time on semiconductive behaviour of thermally grown oxide films on AISI 304L

The oxide films formed on AISI 304L stainless steel at 300 °C in the oxidation time range between 2 and 4 h have been studied by photoelectrochemistry. Photocurrents were investigated as a function of the wavelength of the incident light and the electrode potential. The investigation allowed the determination of the semiconductive properties of the oxides. The oxide films showed n-type behaviour. A duplex structure of the oxide films has been suggested on the basis of the photocurrent spectra, with an internal oxide layer having an optical gap (E_g2 = 2.16-2.3 eV) depending on the applied potential and oxidation time, higher to that of the external oxide layer (E_g1 ≈ 1.9 eV). Significant variations in the amplitude of the photocurrent were detected as a function of the applied potential and the oxidation time.     

Alcohol uncaging with fluorescence reporting: evaluation of o-acetoxyphenyl methyloxazolone precursors

This paper evaluates a series of photolabile protecting groups with built-in fluorescence reporting. They rely on readily available o-acetoxyphenyl methyloxazolones as activated precursors. Alcohol substrates are easily caged. The resulting photoactivable esters exhibit large one- and two-photon uncaging cross sections. The alcohol substrates are quantitatively released in a 1:1 molar ratio with a strongly fluorescent coumarin coproduct that serves as a reporter to quantify substrate delivery.     

A theoretical study of medium effects on the structure of the glycine analogue aminomethylphosphonic acid

alpha-Aminophosphonic acids are analogues of natural alpha-aminoacids and very promising agents for use in various pharmaceutical applications. However, in contrast to the numerous theoretical investigations on the structure of natural alpha-aminoacids, only very few studies on alpha-aminophosphonic acids have been performed. In the present work, we report a detailed investigation of the simplest compound, the glycine analogue aminomethylphosphonic acid (AMPA), by means of quantum mechanical calculations at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) and MP2/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) levels. We focus on the structure of the neutral species looking at the evolution of non-ionized and ionized forms from gas phase to non-polar solvents and aqueous media. Continuum and discrete-continuum solvent models have been employed to account for the effects of the environment. The discussion is centered on: (1) the geometry and relative stability of possible conformers in gas phase and aqueous solution, (2) the free energy of tautomerization in different media, (3) the role of hydrogen bonds in liquid water, and (4) the free energy of transfer from water to a hydrophobic solvent such as cyclohexane. Systematic comparison between AMPA and Gly is performed. Though both systems exhibit many similarities, some important differences have also been found that may be explained, at least in part, by the higher acidity of phosphonic acids compared to carboxylic acids. In particular, in solvents lacking hydrogen-bond formation capability, Gly derivatives should mainly exist as non-ionized molecules while the equivalent AMPA derivatives should adopt a zwitterionic structure in media with dielectric constant above 10. This might have significant environmental or biological consequences that will need to be addressed.     

Magnetic properties and giant magnetoresistance in electrodeposited Co–Ag granular films

Small cobalt particles embedded in a silver matrix have been prepared using the electrodeposition technique. The size of the clusters is controlled by the deposition potential and the Co growth time. Structural, magnetic and magneto-transport properties of Co–Ag samples have been investigated as a function of the Co concentration between 2 and 40 at% cobalt. Superparamagnetic behavior is evidenced for the low contents of cobalt while long-range magnetic order appears at higher Co concentrations. The particles size has been determined from magnetic properties and from the X-ray diffraction technique, and varies between 3.5 and 9 nm. Magnetoresistance passes through a maximum as a function of the cobalt concentration. A maximum of ∼4% GMR is obtained at room temperature while GMR reaches a value of 14% at 10 K.     

Analytical kinetic study of steel corrosion inhibition by Na3PO4 in synthetic concrete solutions

The inhibitory effect of sodium phosphate Na₃PO₄ has been studied previously by gravimetric measurements, and the maximum efficiency was recorded at a concentration of 7.5 × 10⁻³ mol/L, it reached more than 70% in synthetic concrete pore solution. The influence of immersion time on this optimal concentration was followed by the same gravimetric method; the results obtained show that the inhibitory efficiency decreases slightly with time. In addition, two other parameters that condition the kinetics of corrosion inhibition have been treated, which are the pH of the initial time and final time solution as well as the variation of temperature on the evolution of the inhibitory efficiencies. The increase in temperature slightly decreases inhibitory efficiencies. It is found that the efficiency of sodium phosphate at 25°C reached a value of 69.28% for the optimum concentration of 7.5 × 10⁻³. While at 35 and 45°C, it attained 68.08% and 63.31%, respectively, for the same concentration. The thermodynamic study reveals that the adsorption of the inhibitory molecules on the metal surface follows the Langmuir adsorption model and that is a physical adsorption.     

Controlled assembly of covalent and supramolecular chemical modules: from engineering of complex structures to high-performance chromatography

A biological approach to generating complex behaviors in chemistry is described. It is suggested theoretically that the assembly of modules composed of chemical reactions or molecular structures under appropriate external constraints can lead to features typical of the biological world like autocatalysis, kinetic proofreading, or oriented molecular motion. This approach may account for the primitive steps of molecular evolution and, in addition, it can find useful applications in chemistry such as high-performance chromatography.