Measurement of Stark broadening of Mn I and Mn II spectral lines in plasmas used for Laser-Induced Breakdown Spectroscopy

We present measurements of the Stark broadening of several Mn lines in the conditions of typical laser-induced plasmas. Single-and double-pulse Laser-Induced Breakdown spectroscopy (LIBS) configurations are studied on a series of Fe–Mn alloy samples with Mn concentration ranging from 6% to 30%. The effects of self-absorption on the measured line broadenings are discussed in detail. In particular, the experimental results evidence that self-absorption is much higher in laser-induced plasmas generated with double pulses, compared to the case of single pulse. After measurement of the electron density, the Stark coefficients of several neutral and ionic Mn lines are derived through the measure of the broadening in conditions of optically thin plasma. The results obtained for singly ionized Mn lines are compared with the theoretical and experimental data present in the literature. For the first time, experimental measurements of the Stark coefficient for several neutral Mn lines are also presented.     

On the conformational memory in the photodissociation of formic acid

The photodissociation of formic acid at 248 and 193 nm was investigated by classical trajectory and RRKM calculations using an interpolated potential energy surface, iteratively constructed using the B3LYP/aug-cc-pVDZ level of calculation. Several sampling schemes in the ground electronic state were employed to explore the possibility of conformational memory in formic acid. The CO/CO2 branching ratios obtained from trajectories initiated at the cis and at the trans conformers are almost identical to each other and in very good accordance with the RRKM results. In addition, when a specific initial excitation that simulates more rigorously the internal conversion process is used, the calculated branching ratio does not vary with respect to those obtained from cis and trans initializations. This result is at odds with the idea of conformational memory in the ground state proposed recently for the interpretation of the experimental results. It was also found that the calculated CO vibrational distributions after dissociation of the parent molecule at 248 nm are in agreement with the experimental available data.     

Coupling of ultrasonic nebulization to flame furnace atomic absorption spectrometry—new possibilities for trace element determination

The use of ultrasonic nebulization (USN) with desolvation system for sample introduction in flame atomic absorption spectrometry (F AAS) and flame furnace atomic absorption spectrometry (FF AAS) with a nickel tube is described. Polytetrafluorethylene (PTFE) adaptors were built to replace the pneumatic nebulizer for USN-F AAS measurements. For USN-FF AAS analysis, an alumina injector allowed the direct introduction of the dry aerosol into the nickel tube. The analytical performance of both systems is shown for Ag, Bi, Cd, Cr, Cu, Mn, Pb, Sb, Se, Tl and Zn. The results demonstrate that a sensitivity gain of up to 39 times can be achieved using USN-FF AAS, mainly due to the increase in residence time and to the absence of dilution of the analyte by the flame gases, as the atomization takes place inside the nickel tube. However, elements that require higher atomization temperatures, such as Cr and Mn, are more efficiently determined using USN-F AAS. To evaluate the accuracy of the proposed methods for the determination of trace elements, five certified reference samples were analyzed, and good agreement was, in general, achieved between certified and determined values at a 95% confidence level. The relative standard deviation was frequently below 5%, demonstrating good precision, particularly for USN-FF AAS. In this sense, coupling of USN with F AAS and especially with FF AAS has proved to be simple, safe, with high precision and good accuracy, also maintaining some of the most important features of F AAS, such as the high analytical frequency and the low running cost.     

Evaluation of uncertainty sources associated with toxic trace element concentrations in rice

Todays and tomorrows globalized world requires the acceptance of each others capabilities, competence and metrological traceability of measurements to the International System of Units and thus mutual acceptance of quantitative results. Therefore, mutually and publicly recognized standards and certificates are needed at national and international levels. An important step to attain this ambitious goal is to intensify regional metrological collaboration. The exercises of interlaboratorial comparisons are important as part of a system to guaranty the quality of analysis. To estimate the sources of uncertainty associated with the determination of toxic trace element concentrations in rice and to perform an interlaboratorial comparison, a sample containing cadmium, copper, lead and zinc was distributed to four Brazilian laboratories. The laboratories used atomic emission spectroscopy, graphite furnace atomic absorption spectroscopy and flame atomic absorption spectroscopy. The evaluation of the results provided by the laboratories was made by statistical and graphical methods comparing the results of each laboratory to the certified value.     

Carbon nanotube β-cyclodextrin-modified electrode for quantification of cocaine in seized street samples

Ionics - Detection and quantification of cocaine is a key tool in fields such as police apprehensions and the fight against drug trafficking. Thus, a simple, fast and inexpensive electroanalytical...     

Ligand and Metal Effects on the Stability and Adsorption Properties of an Isoreticular Series of MOFs Based on T‐Shaped Ligands and Paddle‐Wheel Secondary Building Units

The synthesis of stable porous materials with appropriate pore size and shape for desired applications remains challenging. In this work a combined experimental/computational approach has been undertaken to tune the stability under various conditions and the adsorption behavior of a series of MOFs by subtle control of both the nature of the metal center (Co²⁺, Cu²⁺, and Zn²⁺) and the pore surface by the functionalization of the organic linkers with amido and N‐oxide groups. In this context, six isoreticular MOFs based on T‐shaped ligands and paddle‐wheel units with ScD_0.33 topology have been synthesized. Their stabilities have been systematically investigated along with their ability to adsorb a wide range of gases (N₂, CO₂, CH₄, CO, H_2, light hydrocarbons (C₁–C₄)) and vapors (alcohols and water). This study has revealed that the MOF frameworks based on Cu²⁺ are more stable than their Co²⁺ and Zn²⁺ analogues, and that the N‐oxide ligand endows the MOFs with a higher affinity for CO₂ leading to excellent selectivity for this gas over other species.     

Delay equation formulation of a cyclin-structured cell population model

The aim of this paper is to derive a system of two renewal equations from individual-level assumptions concerning a cyclin-structured cell population. Nonlinearity arises from the assumption that the rate at which quiescent cells become proliferating is determined by feedback. In fact, we assume that this rate is a nonlinear function of a weighted population size. We characterize steady states and establish the validity of the principle of linearized stability.     

Preparation and liquid-crystalline properties of toluene-4-sulphonyl urethane of hydroxypropylcellulose

Abstract

A novel liquid-crystalline polymer, the toluene-4-sulphonyl urethane of hydroxypropylcellulose (TSUHPC), was prepared through chemical modification of hydroxypropylcellulose (HPC) of M_w = 60000 g mol^?1. The resulting polymer was characterized by infrared spectroscopy, differential scanning calorimetry (DSC) and polarizing microscopy. It was found that thermotropic liquid crystal phases are formed between about 60°C and 110°C. Concentrated solutions of TSUHPC in acetone and N,N-dimethylacetamide exhibit cholesteric behaviour, at room temperature. When approaching the lyotropic mesophase to solid transition, either by cooling or by solvent evaporation, very interesting arborescent structures of a seemingly fractal nature may be observed, depending on the kinetics of the transition. A banded texture can be observed when the polymer is sheared near the transition to the isotropic phase.     

Atom-Economic Synthesis of Functionalized Octahydroacridines from Citronellal or 3-(Phenylthio)-citronellal

Here we present a simple, solvent-free, one-pot, hetero-Diels–Alder reaction of (R)-citronellal or 3-(phenylthio)-citronellal with arylamines using solid-supported catalyst (SiO₂/ZnCl₂). This general, efficient, and improved method is selective, affording preferentially new trans-fused 3-(phenylthio)-octahydroacridines (S-OHAs) in good yields. The use of microwave irradiation facilitates the procedure and accelerates the reaction.