Study of chemical modifiers for the determination of chromium in biological materials by tungsten coil electrothermal atomic absorption spectrometry

The determination of Cr in digest solutions of mussels and non-fat milk powder by tungsten coil electrothermal atomic absorption spectrophotometry (TC-ETAAS) is affected by interferences. This study reports a critical evaluation of chemical modifiers that could be employed to correct these interferences. The chemical modifiers tested were: Mg [as Mg(NO₃)₂], Pd [as Pd(NO₃)₂], NH₄NO₃, ascorbic acid, and mixtures of these compounds. The less effective modifier was NH₄NO₃. The best effects, considering thermal stabilization and sensitivity, were obtained in mixtures of ascorbic acid plus Mg. Chromium was determined by TC-ETAAS in certified reference materials of mussels and non-fat milk powder, and results were comparable with those obtained by graphite furnace atomic absorption spectrophotometry (GFAAS). Received: 19 June 1998 / Revised: 11 January 1999 / Accepted: 16 January 1999     

Third- and fourth-order parametric characterization of partially coherent beams propagating throughABCD optical systems

Within the formalism of the Wigner distribution function, third- and fourth-order measurable beam parameters are proposed and their physical meaning is investigated. The general propagation law of such characteristic quantities inABCD optical systems is derived and a number of paramters are shown to be invariant under propagation inABCD devices.     

Refined solution structure of bovine pancreatic Ribonuclease A by1H NMR methods. Sidechain dynamics

An extension of the assignment of the¹H NMR spectra of bovine pancreatic Ribonuclease A has been carried out at 600 MHz covering all sidechain protons, including those belonging to long sidechain residues. Vicinal coupling constants,³ J _HNα and³ J _αβ and³ J _αβ′ have been measured with the purpose of imposing torsional constraints on the backbone ? angle as well as to introduceH _ββ′ specific assignments. On the basis of distance constraints evaluated from 1285 assigned NOEs, a first restrained molecular dynamics calculation has been carried out. The resulting root-mean-square deviation for the backbone atoms is 1.5 Å as compared to 1.8 Å for the 360 MHz NOE basis. For heavy atoms in sidechains, these numbers were, respectively, 3.0 and 2.5 Å A second calculation was carried out by introducing 37 dihedral angle constraints on backbone ?, torsions and five onX ₁ angular torsions as well as with stereospecific assignments for nearly 50 residues. Backbone and sidechain RMS deviations were, respectively, 1.2 and 2.0 Å. Sidechains have been classified in terms of their dynamical behavior aroundX ₁ after considering jointly the coupling information and that resulting from the second set of calculated structures. Results are discussed in relation to the crystal structure.     

Sn4As3 revisited: Solvothermal synthesis and crystal and electronic structure

A facile one pot method of synthesis of tin arsenide Sn₄As₃ starting from metallic tin and elemental arsenic under mild solvothermal conditions in ethylenediamine in the presence of ammonium chloride is offered. The dissolving of the tin metal in ethylenediamine and the role of NH₄Cl are discussed. The crystal structure of Sn₄As₃ has been re-determined. It is shown to crystallize in the trigonal non-centrosymmetric space group R3m, (a=4.089(1) Å, c=36.059(6) Å, Z=3), which differs from the previously reported centrosymmetric structure . The crystal structure of Sn₄As₃ consists of alternating layers of arsenic and tin atoms that are combined into seven-layer blocks and build up along the c-axis. The major structural feature is the short tin-tin distances (3.24 Å) between the adjacent blocks. The analysis of the density of states and band structure reveals that Sn₄As₃ should have metallic properties, which is in line with the previously reported experimental observations. Analysis of chemical bonding employing the electron localization function shows that only for the shortest Sn-As contacts the bonding is pairwise, while four-center bonds are formed between arsenic and tin atoms at relatively long distances (>2.85 Å). Moreover, each tin atom holds an electron lone-pair.     

MWCNT‐modified Electrode for Voltammetric Determination of Allura Red and Brilliant Blue FCF in Isotonic Sport Drinks

A fast and simple electrochemical sensor is presented for the determination of allura red and brilliant blue in isotonic sport drinks, using a glassy carbon electrode modified with multi‐walled carbon nanotubes. The electrochemical behavior of the colorants was studied by cyclic and differential pulse voltammetry in 0.1 M PBS, pH 7.0. The solution pH, the amount of nanomaterial on the surface of the electrode and the accumulation time of each colorant were optimized. Under the optimal conditions, the sensor exhibited a linear response to allura red and brilliant blue with detection limits of 7 μg L^?1 and 52 μg L^?1, respectively. The sensor was applied to the analysis of commercial isotonic sports drinks that contain individual or mixed colorants, showing good sensitivity and reproducibility. The results were compared with a chromatographic method showing that the levels of colorants are low and did not show a risk for a consumer's health.     

Determination of Cd and Pb at μg/L levels by HHPN-beam injection flame furnace-AAS

Flame-heated tubes are widespread in flame-AAS, mainly for the determination of hydride-forming elements. Instead of the introduction of gaseous compounds liquids can also be introduced continuously in such an absorption cell. With the aid of an HPLC pump the liquid is forced through a very fine nozzle, generating an aerosol beam less than 0.5?mm in diameter. This beam travels a distance of 10?cm as a “free-flying aerosol jet” into the sample introduction hole of a metal tube furnace placed in the flame. Both introduction of the entire sample and the long residence time lead to a considerable improvement in power of detection. The detection limit for 100 μL samples amounts to 7 μg/L (Pb) and to 0. 2 μg/L (Cd), which means an increase in power of detection of between one and two orders of magnitude compared to conventional flame-AAS. The relative standard deviation (100 μL sample volume, N = 10) was found to be 1.3% (signal area) for 600 μg/L Pb and to be 1.5% (signal-area) for 15 μg/L Cd. RSD values from measurements in peak-height amounted to 2.2% (Pb) and to 1.7% (Cd).     

Studies on the constituents of bulbs of the orchid <Emphasis Type="Italic">Prosthechea michuacana</Emphasis> and antioxidant activity

Bioassay-guided fractionation of the chloroform extract of bulbs of the orchid P. michuacana was used to determine the chemical identity of bioactive constituents. The use of DPPH assay led to the isolation of two new lanostane triterpenoids 3a-acetoxy, 24-hydroxy-24-methyl-5a-lanosta-9(11),25-diene (1) and 3a-acetoxy, 24-hydroxy-24-methyl-5a-lanosta-9(11)ene (2), a new stilbene a-a'-dihydro,3',5',2-trimethoxy-3-hydroxy4-acetyl-4'-isopentenylstilbene (3), the phenanthrene 4,6,7-trihydroxy-2-methoxy-8-(methylbut-2enyl)phenanthrene-1,1'-4',6',7'-trihydroxy-2'-methoxy-8'-(methylbut-2'-enyl)phenanthrene (4), one new abietane-type diterpene 12-hydroxy-3{,7{,18a-triacetoxy-8,11,13-abietatriene (5), together with gigantol (6), a known compound. The compounds were identified by spectral analysis and comparison with spectroscopic data reported in the literature. Compounds 3, 4, 5, and 6 showed DPPH and ABTS radical-scavenging and anti-lipid peroxidation activities, but none of the isolated triterpenes showed promising antioxidant activity.     

Determination of cadmium in hair and blood by tungsten coil electrothermal atomic absorption spectrometry with chemical modifiers

Three chemical modifiers ((NH(4))(2)HPO(4), NH(4)H(2)PO(4), and Pd as Pd(NO(3))(2)) were evaluated for the determination of Cd in acid-digested solutions of hair and blood using electrothermal atomic absorption spectrometry in a tungsten coil atomizer (TCA). All modifiers caused some thermal stabilization of Cd when compared to the behavior observed in nitric acid medium. The best effects were observed in 15 mug ml(-)(1) Pd medium; the characteristic mass of Cd was 0.3 pg and the method detection limits were 0.009 mug g(-)(1) in hair and 0.2 mug l(-)(1) in blood. In addition to a slight thermal stabilization effect, Pd also increased the sensitivity for Cd by ca. 40% and the tungsten coil lifetime by 20% (i.e. from 300 to 360 heating cycles), reduced background signals, and eliminated condensed phase interferences caused by concomitants. The accuracy (3.2% as mean relative error in the Pd modifier) was checked for the determination of Cd in acid-digested solutions of certified reference materials of human hair and blood and by recoveries of Cd in spiked hair and blood samples by both TCA and a graphite furnace procedure. All results obtained in chemical modifiers are in agreement at a 95% confidence level.     

Study of the surface chemistry and morphology of single walled carbon nanotube-magnetite composites

The study of the morphologies of the single walled carbon nanotube (SWCNT), magnetite nanoparticles (MNP), and the composite based on them was carried with combined X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). These techniques together with thermogravimetric analyses (TGA) and diffuse reflectance infrared transform spectroscopy (DRIFTS) confirmed the production of pure single phases, and that the composite material consisted of MNP attached to the outer surface of the SWCNT. The Mössbauer spectroscopy (MS) research showed the presence of a large quantity of Lewis acid sites in the highly dispersed magnetite particles supported on the SWCNT outer surface. The DRIFTS carbon dioxide adsorption study of the composites revealed significant adsorption of carbon dioxide, fundamentally in the Lewis acid sites. Then, the Lewis acid sites were observed to be catalytically active. Further, the electron exchange between the Lewis acid sites and the basic or amphoteric adsorbed molecules could influence the magnetic properties of the magnetite. Consequently, together with this first ever use of MS in the study of Lewis acid sites, this investigation revealed the potential of the composites for catalytic and sensors applications.     

Phosphorylation of Thr9 Affects the Folding Landscape of the N-Terminal Segment of Human AGT Enhancing Protein Aggregation of Disease-Causing Mutants

The mutations G170R and I244T are the most common disease cause in primary hyperoxaluria type I (PH1). These mutations cause the misfolding of the AGT protein in the minor allele AGT-LM that contains the P11L polymorphism, which may affect the folding of the N-terminal segment (NTT-AGT). The NTT-AGT is phosphorylated at T9, although the role of this event in PH1 is unknown. In this work, phosphorylation of T9 was mimicked by introducing the T9E mutation in the NTT-AGT peptide and the full-length protein. The NTT-AGT conformational landscape was studied by circular dichroism, NMR, and statistical mechanical methods. Functional and stability effects on the full-length AGT protein were characterized by spectroscopic methods. The T9E and P11L mutations together reshaped the conformational landscape of the isolated NTT-AGT peptide by stabilizing ordered conformations. In the context of the full-length AGT protein, the T9E mutation had no effect on the overall AGT function or conformation, but enhanced aggregation of the minor allele (LM) protein and synergized with the mutations G170R and I244T. Our findings indicate that phosphorylation of T9 may affect the conformation of the NTT-AGT and synergize with PH1-causing mutations to promote aggregation in a genotype-specific manner. Phosphorylation should be considered a novel regulatory mechanism in PH1 pathogenesis.