Oxidative degradation of nitrogen-containing organic compounds: vaccum-ultraviolet (VUV) photolysis of aqueous solutions of 3-amino 5-methylisoxazole

The oxidative degradation of 3-amino 5-methyl isoxazole initiated by the VUV photolysis of water at 172 nm has been studied. Mineralization of CO₂, H₂O, NO ₃ ^– and NH ₄ ⁺ is more efficient when reductive conditions (argon saturated solutions) are favoured. Formation of compounds which cannot be completely oxidised to CO₂ is observed. Experiments performed under strictly oxidative conditions show higher yields of these inert compounds and, hence, incomplete mineralization. Cyanide was formed in concentrations lower than 5×10^–5 mol/l. In alkaline aqueous solutions, cyanide is completely transformed into CO ₃ ^2– , NH ₄ ⁺ and NO ₃ ^– during the irradiation time needed to mineralize the isoxazole. Therefore, cyanide does not present a potential risk for the use of the VUV photolysis for isoxazole degradation. Similarly, organic nitrogen is converted into both, NO ₃ ^– and NH ₄ ⁺ . The relative concentrations of the two ions depend on total irradiation time, oxygen saturation and reactor geometry. A sequence of reactions is proposed and discussed.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Muonium formation in xenon and argon up to 60 atmospheres

Results of muon polarization studies in xenon and argon up to 60 atm are reported. In argon for pressures up to 10 atm, the muon polarization is best explained by an epithermalcharge exchange model. Above this pressure, the decrease inP _D and increase inP _L are ascribed to charge neutralization and spin exchange reactions, respectively, in the radiolysis track. Measurements with Xe/He mixtures with a xenon pressure of 1 atm indicate that the lost polarization in the pure xenon at this pressure is due to inefficient moderation of the muon. As the pressure in pure xenon is increased above 10 atm, we find thatP _L remains roughly constant andP _D begins to increase. The lost fraction may be due to the formation of a XeMu Van der Waals type complex, whileP _D is ascribed to XeMu⁺ formation. This suggests that spur processes appear to be less important in xenon than in argon.     

Influence of the anode material on an argon arc

The interaction between the arc and the anode was experimentally studied by means of a transferred arc burning in argon with copper, iron, or steel anodes. Depending on the rate of anode cooling, a stable plasma was obtained just above the anode, established either in pure argon (strong cooling) or in a mixture of argon with metal vapor. Temperature and metal concentration fields were deduced from spectroscopic measurements. Two important results were reached: the arc radius near the anode depends on the nature of the electrode, even without anode erosion; and the presence of metal vapor leads to a cooling of the plasma. The same arc configurations were theoretically simulated by a two-dimensional model. The comparison between experimental and numerical results allows a large proportion of the observed phenomena to be interpreted, in spite of partial discrepancies between predicted and measured values. The dimension of the arc root at the anode depends on the thermal conductivity of the solid metal, whereas the cooling effect due to metal vapor in the plasma is explained by the increases of electrical conductivity and of radiative losses in the presence of the vapor     

Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films

We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La_0.7Ca_0.3MnO₃ (LCMO) and YBa₂Cu₃O_7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO₃ (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on the LAO (control) and LCMO side of the substrate. Critical current, I _c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed that while the control side showed a J _c of ∼ 2 × 10⁶ A/cm², the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J _c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of J _c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length has been quantified. A control experiment carried out with LaNiO₃ deposited by PLD on YBCO did not show any evidence of self-injection.     

A General Alternative Procedure for Solving Negative Degree of Difficulty Problems in Geometric Programming

The degree of difficulty is an important concept in classical geometric programming theory. The dual problem is often infeasible when the degree of difficulty is negative and little has been published on this topic. In this paper, an alternative procedure is developed to find the optimal solution for the posynomial geometric programming problem with a negative degree of difficulty. First an equivalent problem was constructed with a positive degree of difficulty and the general posynomial geometric programming problem was solved using an original method previously developed by the authors. This method avoids the difficulty of non-differentiability of the dual objective function in the classical methods classified as dual. It also avoids the problem that appears when the feasible region for the dual problem is formed by an inconsistent system of linear equations.     

Direct determination of molybdenum in mineral waters by atomic absorption spectrometry with electrothermal atomization

A new method for the direct determination of molybdenum by ETA-AAS in mineral waters without prior separation or concentration is proposed. With careful control of the graphite furnace conditions selective volatilization of the salt matrix is successfully attained. The possible spectroscopic interference due to common metals as well as the reproducibility, precision and repeatability of the method has been studied and the molybdenum content of 21 mineral waters measured.     

Regioselective Acceptorless Dehydrogenative Coupling of N‐Heterocycles toward Functionalized Quinolines,Phenanthrolines, and Indoles

A new strategy has been developed for the oxidant‐ and base‐free dehydrogenative coupling of N‐heterocycles at mild conditions. Under the action of an iridium catalyst, N‐heterocycles undergo multiple sp³ C? H activation steps, generating a nucleophilic enamine that reacts in situ with various electrophiles to give highly functionalized products. The dehydrogenative coupling can be cascaded with Friedel–Crafts addition, resulting in a double functionalization of the N‐heterocycles.     

Rational Design of a Humanized Glucagon‐Like Peptide‐1 Receptor Agonist Antibody

Bovine antibody BLV1H12 possesses a unique “stalk–knob” architecture in its ultralong heavy chain CDR3, allowing substitutions of the “knob” domain with protein agonists to generate functional antibody chimeras. We have generated a humanized glucagon‐like peptide‐1 (GLP‐1) receptor agonist antibody by first introducing a coiled‐coil “stalk” into CDR3H of the antibody herceptin. Exendin‐4 (Ex‐4), a GLP‐1 receptor agonist, was then fused to the engineered stalk with flexible linkers, and a Factor Xa cleavage site was inserted immediately in front of Ex‐4 to allow release of the N‐terminus of the fused peptide. The resulting clipped herceptin–Ex‐4 fusion protein is more potent in vitro in activating GLP‐1 receptors than the Ex‐4 peptide. The clipped herceptin–Ex‐4 has an extended plasma half‐life of approximately four days and sustained control of blood glucose levels for more than a week in mice. This work provides a novel approach to the development of human or humanized agonist antibodies as therapeutics.     

Supercritical fluid chromatography with photodiode array detection for pesticide analysis in papaya and avocado samples

To improve the analysis of pesticides in complex food matrices with economic importance, alternative chromatographic techniques, such as supercritical fluid chromatography, can be used. Supercritical fluid chromatography has barely been applied for pesticide analysis in food matrices. In this paper, an analytical method using supercritical fluid chromatography coupled to a photodiode array detection has been established for the first time for the quantification of pesticides in papaya and avocado. The extraction of methyl parathion, atrazine, ametryn, carbofuran, and carbaryl was performed through the quick, easy, cheap, effective, rugged, and safe methodology. The method was validated using papaya and avocado samples. For papaya, the correlation coefficient values were higher than 0.99; limits of detection and quantification ranged from 130–380 and 220–640 μg/kg, respectively; recovery values ranged from 72.8–94.6%; precision was lower than 3%. For avocado, limit of detection values were ?450 μg/kg; precision was lower than 11%; recoveries ranged from 50.0–94.2%. Method feasibility was tested for lime, banana, mango, and melon samples. Our results demonstrate that the proposed method is applicable to methyl parathion, atrazine, ametryn, and carbaryl, toxics pesticides used worldwide. The methodology presented in this work could be applicable to other fruits.