A new approach for fluorine determination by solid sampling graphite furnace molecular absorption spectrometry

This work deals with the determination of fluorine by solid sampling graphite furnace molecular absorption spectrometry. The molecular absorbance of aluminum monofluoride (AlF), which is produced in the vapor phase in the presence of Al³⁺, is measured at 227.5 nm, a non-resonant platinum line. A conventional graphite furnace program has been used with pyrolysis and vaporization temperatures of 800 and 2300 °C, respectively. Solutions of Ba²⁺ and Al³⁺ have been used to avoid fluorine losses during the pyrolysis stage and to produce AlF in the vaporization stage, respectively. Certified coal and alumina samples were analyzed using aqueous standards for calibration. The agreement between the found concentration and the certified value, or the value obtained by another method ranged from 92 to 105%, with a relative standard deviation less than 8.5%. The limit of detection and the characteristic mass was 0.17 μg g^− 1 and 205 pg, respectively.     

Determination of copper in medicinal plants used as dietary supplements by atomic absorption spectrometry with direct flame solid analysis

An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g⁻¹ if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS.     

Anthill Earth as a Gold Occurrence Indicator,and Gold Determination by Solid Sampling Flame Atomic Absorption Spectrometry

With the aim of avoiding cumbersome sample treatment, we present a device for the introduction of solid soil samples into AAS-flames for gold determination, as well as the proposition of earth from anthills as a gold occurrence indicator. A previous ground sample of anthill earth (0.50 mg) was weighed directly into a small recipient of polyethylene which was then connected to a sampling boronsilicate glass chamber. The sample was carried by an airflow (5 L min⁻¹) to a quartz cell positioned between the burner top and the optical beam. The generated atomic vapor produced a transient signal which was totally integrated in three seconds. The performance was compared with conventional flame atomic absorption spectrometry after proper sample digestion. No significant differences were observed between both procedures (mean deviation ±1.90%), and a LOQ of 0.03 μg Au was achieved using the proposed method. The anthill earth was found to be very suitable for indication of gold occurrence in soils and related materials.     

Phase-field approach to fracture for finite-deformation contact problems

The present contribution deals with a variationally consistent Mortar contact algorithm applied to a phase-field fracture approach for finite deformations, see [4]. A phase-field approach to fracture allows for the numerical simulation of complex fracture patterns for three dimensional problems, extended recently to finite deformations (see [2] for more details). In a nutshell, the phase-field approach relies on a regularization of the sharp (fracture-) interface. In order to improve the accuracy, a fourth-order Cahn-Hilliard phase-field equation is considered, requiring global C¹ continuity (see [1]), which will be dealt with using an isogeometrical analysis (IGA) framework. Additionally, a newly developed hierarchical refinement scheme is applied to resolve for local physical phenomena e.g. the contact zone (see [3] for more details). The Mortar method is a modern and very accurate numerical method to implement contact boundaries. This approach can be extended in a straightforward manner to transient phase-field fracture problems. The performance of the proposed methods will be examined in a representative numerical example. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical and Experimental Analysis of Protoporphyrin IX Photodegradation Using Multi-Wavelength Light Sources

Photodynamic procedures have been used in many applications, ranging from cancer treatment to microorganism inactivation. Photodynamic reactions start with the activation of a photosensitizing molecule with light, leading to the production of cytotoxic molecules that promote cell death. However, establishing the correct light and photosensitizer dosimetry for a broadband light source remains challenging. In this study, we proposed a theoretical mathematical model for the photodegradation of protoporphyrin IX (PpIX), when irradiated by multi-wavelength light sources. The theoretical model predicts the experimental photobleaching (temporal change in PpIX concentration) of PpIX for different light sources. We showed that photobleaching occurs independently of the light source wavelengths but instead depends only on the number of absorbed photons. The model presented here can be used as an important mathematical approach to better understand current photodynamic therapy protocols and help achieve optimization of the doses delivered.     

Trifluoromethylation of [AuF3(SIMes)]: Preparation and Characterization of [Au(CF3)xF3−x(SIMes)] (x=1–3) Complexes

Trifluoromethylation of [AuF₃(SIMes)] with the Ruppert–Prakash reagent TMSCF₃ in the presence of CsF yields the product series [Au(CF₃)_xF_3−x(SIMes)] (x=1–3). The degree of trifluoromethylation is solvent dependent and the ratio of the species can be controlled by varying the stoichiometry of the reaction, as evidenced from the ¹⁹F NMR spectra of the corresponding reaction mixtures. The molecular structures in the solid state of trans-[Au(CF₃)F₂(SIMes)] and [Au(CF₃)₃(SIMes)] are presented, together with a selective route for the synthesis of the latter complex. Correlation of the calculated SIMes affinity with the carbene carbon chemical shift in the ¹³C NMR spectrum reveals that trans-[Au(CF₃)F₂(SIMes)] and [Au(CF₃)₃(SIMes)] nicely follow the trend in Lewis acidities of related organo gold(III) complexes. Furthermore, a new correlation between the Au−C_carbene bond length of the molecular structure in the solid state and the chemical shift of the carbene carbon in the ¹³C NMR spectrum is presented.     

M?ssbauer analysis of high-energy mechanical-milled sand fraction of a magnetic soil developing on basalt

A sample of the coarse sand fraction from the soil material of the A-horizon (0?C0.2 m from the soil surface) of a dusky red magnetic Oxisol was submitted to high-energy mechanical milling for different times. This assay aimed mainly at (a) monitoring the individualization of strongly aggregated mineral particles, and (b) measuring the effect of the milling pressure on the mineralogy changes of the material. These data are also intended to experimentally subside any physical model describing the mechanical behavior of the superficial soil layer that is subjected to intensive machine management, in agriculture fields. Powder X-ray data reveal that some mineralogical phases, notably gibbsite, disappear soon after the first few hours milling. The 298 K-transmission Mössbauer spectrum for the non-milled sand sample shows a qualitatively typical pattern for the sand fraction of basalt derived soils, with magnetically ordered sextets, assignable mainly to hematite and maghemite, and an intense central (super)paramagnetic Fe^3?+? doublet. For the milled samples, spectra revealed progressive spectral reduction of the magnetic hyperfine structure, with concomitant increase of relative subspectral areas due to (super)paramagnetic phases, as the milling time increased. This result is consistent with the reduction of measured saturation magnetization, from 4.96(8) J T^???1 kg^???1, for the non-milled sample, to 3.26(7) J T^???1 kg^???1, for the sample milled for 8 hours.     

Cadmium determination in biological samples by direct solid sampling flame atomic absorption spectrometry

A direct solid sampling flame atomic absorption spectrometric procedure for trace determination of cadmium in biological samples has been developed. Test samples (0.05–2.00 mg) were ground and weighed into small polyethylene vials, which were connected to the device for solid sample introduction into a conventional air/acetylene flame. Test samples were carried as a dry aerosol to a quartz cell, placed between the burner and the optical path, which had a perpendicular entrance and a slit in the upper part. The atomic vapor generated in the flame produced a transient signal that was totally integrated within 1 s. The effect of operating conditions and the extent of grinding on the analytical signal were evaluated. Background signals were always low and a characteristic mass of 0.29 ng Cd was obtained. Calibration was performed using different masses of solid certified reference materials. Results obtained for certified and in-house reference materials were typically within the 95% confidence interval of the certified and/or reference value, and the precision, expressed as relative standard deviation, was between 3.8 and 6.7%. The proposed system is simple and it might be adapted to conventional atomic absorption spectrometers allowing the determination of Cd in more than 80 test samples per hour, excluding weighing.     

1JNH values show that N1...N3 hydrogen bonds are stronger in dsRNA A:U than dsDNA A:T base pairs

Here, we show that 1JNH values are on average 0.4 Hz less negative for double-stranded RNA A:U than for DNA A:T base pairs, which, according to existing theory, suggests that RNA N1...N3 hydrogen bond distances are about 0.02 A shorter than those of DNA. Also, there is a statistically relevant trend between 1JNH and 2hDelta13C2 values, which supports the original hypothesis that 2hDelta13C2 values are also sensitive to hydrogen bond distances. Finally, a context dependence is observed for these values, which suggests that hydrogen-bonding and base-stacking interactions are coupled.