Flow analysis-vapor phase generation-Fourier transform infrared (FA-VPG-FTIR) spectrometric determination of nitrite

In this work, the coupling between flow analysis (FA)–vapor phase generation (VPG) and Fourier transform infrared spectrometry (FTIR) has been proposed as a novel and alternative strategy for the determination of nitrite. The analyte was transformed into the gaseous nitric oxide (NO) by on-line reaction with potassium iodide (KI) or ascorbic acid in acidic medium. The gaseous NO generated was transported by means of a N₂ gas carrier stream inside the IR gas cell and the corresponding FTIR spectrum was acquired in a continuous mode. The absorbance at 1876 cm⁻¹, corrected by a baseline established between 1879 and 1872 cm⁻¹ at a nominal resolution of 2 cm⁻¹, was selected as a measurement criterion. The effect of different spectroscopic and flow analysis experimental parameters, such as nominal resolution, number of scans, reducing agent and its concentration, acidic medium, reagents and sample flow rates, and the carrier gas flow rate on the analytical signal, and then in the figures of merit were initially evaluated by using a standard short path length (10 cm) IR gas cell. The optimization of the system was carried out by the univariate method. The main aims of this study were: (i) to investigate the on-line generation of gaseous nitric oxide in a continuous flow system, and (ii) the use of Fourier transform infrared spectrometry as an alternative and selective detector for the determination of nitrite. The proposed method was initially tested and applied for the determination of nitrite in samples with very high concentration of nitrite, such as frankfurters.     

Insertion reactions of [M(SR)3(PMe2Ph)2] with CS2 (M = Ru, Os; R = C6F4H-4, C6F5). X-ray structures of [Ru(S2CSC6F4H-4)2(PMe2Ph)2], trans-thiolates [M(SR)2(S2CSR)(PMe2Ph)2] (M = Ru; R = C6F5 and M = Os; R = C6F4H-4), and trans-thiolate-phosphine [Os(SC6F5)2(S2CSC6F5)(PMe2Ph)2

Reactions of [M(SR)(3)(PMe(2)Ph)(2)] (M = Ru, Os; R = C(6)F(4)H-4, C(6)F(5)) with CS(2) in acetone afford [Ru(S(2)CSR)(2)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 1; C(6)F(5), 3) and trans-thiolates [Ru(SR)(2)(S(2)CSR)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 2; C(6)F(5), 4) or the isomers trans-thiolates [Os(SR)(2)(S(2)CSR)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 5; C(6)F(5), 7) and trans-thiolate-phosphine [Os(SR)(2)(S(2)CSR)(PMe(2)Ph)(2)] (R = C(6)F(4)H-4, 6; C(6)F(5), 8) through processes involving CS(2) insertion into M-SR bonds. The ruthenium(III) complexes [Ru(SR)(3)(PMe(2)Ph)(2)] react with CS(2) to give the diamagnetic thiolate-thioxanthato ruthenium(II) and the paramagnetic ruthenium(III) complexes while osmium(III) complexes [Os(SR)(3)(PMe(2)Ph)(2)] react to give the paramagnetic thiolate-thioxanthato osmium(III) isomers. The single-crystal X-ray diffraction studies of 1, 4, 5, and 8 show distorted octahedral structures. (31)P [(1)H] and (19)F NMR studies show that the solution structures of 1 and 3 are consistent with the solid-state structure of 1.     

Von Neumann Regularity and Quadratic Conorms in JB^＊-triples and C^＊-algebras

We revise the notion of von Neumann regularity in JB^＊-triples by finding a new characterisation in terms of the range of the quadratic operator Q（a）. We introduce the quadratic conorm of an element a in a JB^＊-triple as the minimum reduced modulus of the mapping Q（a）. It is shown that the quadratic conorm of a coincides with the infimum of the squares of the points in the triple spectrum of a. It is established that a contractive bijection between JBW^＊-triples is a triple isomorphism if, and only if, it preserves quadratic conorms. The continuity of the quadratic conorm and the generalized inverse are discussed. Some applications to C^＊-algebras and von Neumann algebras are also studied.     

Size exclusion chromatography with dual-beam refractive index gradient detection of polystyrene samples

Non-aqueous size exclusion chromatography (SEC) of polystyrenes (as model analytes) is examined using the microscale molar mass sensor (μ-MMS) for detection. The μ-MMS is combined with SEC to demonstrate this simultaneously universal and molar mass selective detection method for polymer characterization. The μ-MMS is based on measuring the refractive index gradient (RIG) at two positions (upstream and downstream) within a T-shaped microfluidic channel. The RIG is produced from a sample stream (eluting analytes in the mobile phase) merging with a mobile phase stream (mobile phase only). The magnitude of the RIG is measured as a probe beam deflection angle and is related to analyte diffusion coefficient, the time allowed for analyte diffusion from the sample stream toward the mobile phase stream, and the bulk phase analyte refractive index difference relative to the mobile phase. Thus, two deflection angles are measured simultaneously, the upstream angle and the downstream angle. An angle ratio is calculated by dividing the downstream angle by the upstream angle. The μ-MMS was found to extend the useful molar mass calibration range of the SEC system (nominally limited by the total exclusion and total permeation regions from ∼100,000 g/mol to ∼800 g/mol), to a range of 3,114,000-162 g/mol. The injected concentration LOD (based on 3 s statistics) was 2 ppm for the upstream detection position. The point-by-point time-dependent ratio, termed a ‘ratiogram’, is demonstrated for resolved and overlapped peaks. Within detector band broadening produces some anomalies in the ratiogram shapes, but with highly overlapped distributions of peaks this problem is diminished. Ratiogram plots are converted to molar mass as a function of time, demonstrating the utility of SEC/μ-MMS to examine a complex polymer mixture.     

Numerical Properties of Shifted Tridiagonal LU Factorizations

In this paper, we consider shifted tridiagonal matrices. We prove that the standard algorithm to compute the LU factorization in this situation is mixed forward-backward stable and, therefore, componentwise forward stable. Moreover, we give a formula to compute the corresponding condition number in O(n) flops. This research has been partially supported by Dirección General de Investigación (Ministerio de Ciencia y Tecnología) of Spain through grants BFM2003-06335-C03-02 and MTM2006-06671 as well as by the Postdoctoral Fellowship EX2004-0658 provided by Ministerio de Educación y Ciencia of Spain.     

Syntheses,characterization, and biological evaluation of new zinc-and gold-chloroquine diphosphate complexes

Antimalarial drugs such as chloroquine are beneficial agents in systemic lupus and rheumatoid arthritis. In this work, two new chloroquine diphosphate (CQDP) complexes containing Zn(II) and Au(III) of formula Zn(CQDP)(NO₃)₂ (1) and Au(CQDP)Cl₃ (2), respectively, were synthesized and characterized by physico-chemical and spectroscopic methods. To examine their possible anti-inflammatory properties, the new derivatives were tested in the range from 1 to 100 μM on the respiratory burst of isolated human neutrophils (PMNs) as well as in whole blood. In isolated PMNs, complex 1 inhibited the isoluminol-enhanced chemiluminescence (IL-CL) only at the highest concentration tested, whereas in the whole blood assay, 10 μM of this complex was sufficient to significantly inhibit the luminol-enhanced chemiluminescence (L-CL). On the contrary, complex 2 dose-dependently inhibited the IL-CL but affected the L-CL only at 100 μM. In conclusion, both complexes are more active than CQDP and may be useful for future treatment of diseases resulting from exacerbated neutrophil functions.