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.     

Ultrasound‐assisted extraction method for the simultaneous determination of emerging contaminants in freshwater sediments

Sediments are the fate of several emerging organic contaminants, such as pharmaceuticals, personal care products and hormones, and therefore an important subject in environmental monitoring studies. In the present work, a simple and sensitive method was developed, validated and applied for the simultaneous extraction of atenolol, caffeine, carbamazepine, diclofenac, ibuprofen, naproxen, propranolol, triclosan, estrone, 17‐β‐estradiol and 17‐α‐ethinylestradiol using ultrasound‐assisted extraction from freshwater sediment samples followed by solid‐phase extraction clean‐up and liquid chromatography with tandem mass spectrometry detection. The solvent type and extraction pH were evaluated to obtain the highest recoveries of the compounds. The best method shows absolute recoveries between 54.0 and 94.4% at 50 ng/g concentration. The method exhibits good precision with relative standard deviation ranging from 1.0–16%. The detection and quantification limits ranged from 0.006–0.067 and 0.016–0.336 ng/g, respectively. The developed method was successfully applied to freshwater sediment samples collected from different sites in Jundiaí River basin of São Paulo State, Brazil. The compounds atenolol, caffeine, propranolol and triclosan were detected in all the sampling sites with concentrations of 13.8, 41.0, 28.5 and 176 ng/g, respectively.     

Synthesis of voiced sounds using low-dimensional models of the vocal cords and time-varying subglottal pressure

The vocal cords play an important role on voice production. Air coming from the lungs is forced through the narrow space between the two vocal cords that are set in motion in a frequency that is governed by the tension of the attached muscles. The motion of the vocal cords changes the type of flow, that comes from the lungs, to pulses of air, and as the flow passes through the oral and nasal cavities, it is amplified and further modified until it is radiated from the mouth. This complex process can be modeled by a system of integral-differential equations. This paper considers two mechanical models previously used for explaining the dynamics of the vocal cords. It shows that the level of naturalness of the sound generated by these models is rather poor, and it proposes temporal variations of the parameters of the models to increase such level. Examples of synthetic vowels and diphthongs are given to assess the models. In general, the results show that, although the system of voice production is complex, we can achieve satisfactory results with relatively simple low-dimensional models, by suitable temporal variations of the aerodynamic parameters.     

Improved strategies for branching on general disjunctions

Within the context of solving Mixed-Integer Linear Programs by a Branch-and-Cut algorithm, we propose a new strategy for branching. Computational experiments show that, on the majority of our test instances, this approach enumerates fewer nodes than traditional branching. On average, on instances that contain both integer and continuous variables the number of nodes in the enumeration tree is reduced by more than a factor of two, and computing time is comparable. On a few instances, the improvements are of several orders of magnitude in both number of nodes and computing time.     

On the computation of protein backbones by using artificial backbones of hydrogens

NMR experiments provide information from which some of the distances between pairs of hydrogen atoms of a protein molecule can be estimated. Such distances can be exploited in order to identify the three-dimensional conformation of the molecule: this problem is known in the literature as the Molecular Distance Geometry Problem (MDGP). In this paper, we show how an artificial backbone of hydrogens can be defined which allows the reformulation of the MDGP as a combinatorial problem. This is done with the aim of solving the problem by the Branch and Prune (BP) algorithm, which is able to solve it efficiently. Moreover, we show how the real backbone of a protein conformation can be computed by using the coordinates of the hydrogens found by the BP algorithm. Formal proofs of the presented results are provided, as well as computational experiences on a set of instances whose size ranges from 60 to 6000 atoms.     

Dynamical properties of a particle in a wave packet: Scaling invariance and boundary crisis

Some dynamical properties present in a problem concerning the acceleration of particles in a wave packet are studied. The dynamics of the model is described in terms of a two-dimensional area preserving map. We show that the phase space is mixed in the sense that there are regular and chaotic regions coexisting. We use a connection with the standard map in order to find the position of the first invariant spanning curve which borders the chaotic sea. We find that the position of the first invariant spanning curve increases as a power of the control parameter with the exponent 2/3. The standard deviation of the kinetic energy of an ensemble of initial conditions obeys a power law as a function of time, and saturates after some crossover. Scaling formalism is used in order to characterise the chaotic region close to the transition from integrability to nonintegrability and a relationship between the power law exponents is derived. The formalism can be applied in many different systems with mixed phase space. Then, dissipation is introduced into the model and therefore the property of area preservation is broken, and consequently attractors are observed. We show that after a small change of the dissipation, the chaotic attractor as well as its basin of attraction are destroyed, thus leading the system to experience a boundary crisis. The transient after the crisis follows a power law with exponent −2.     

Casbane diterpene as a promising natural antimicrobial agent against biofilm-associated infections

Croton nepetaefolius is a native plant from northeastern Brazil that belongs to the Euphorbiaceae family. The biological action of this plant has been extensively explored, being the secondary metabolites responsible for its properties alkaloids, diterpenes, and triterpenes. This study aimed to evaluate the ability of casbane diterpene (CD), isolated from the ethanolic extract of C. nepetaefolius, to inhibit microbial growth and biofilm formation of several clinical relevant species (bacteria and yeasts). It was found that CD possessed biocidal and biostatic activity against the majority of the species screened, with minimal active concentrations ranging between 125 and 500 μg/mL. In addition, it was observed that biofilm formation was inhibited even when the planktonic growth was not significantly affected. In conclusion, CD showed potential to be a natural tool for the treatment of diseases caused by different infectious microorganisms.     

Invariant Measures for Cherry Flows

We investigate the invariant probability measures for Cherry flows, i.e. flows on the two-torus which have a saddle, a source, and no other fixed points, closed orbits or homoclinic orbits. In the case when the saddle is dissipative or conservative we show that the only invariant probability measures are the Dirac measures at the two fixed points, and the Dirac measure at the saddle is the physical measure. In the other case we prove that there exists also an invariant probability measure supported on the quasi-minimal set, we discuss some situations when this other invariant measure is the physical measure, and conjecture that this is always the case. The main techniques used are the study of the integrability of the return time with respect to the invariant measure of the return map to a closed transversal to the flow, and the study of the close returns near the saddle.     

Compact linearization for binary quadratic problems

We show that a well-known linearization technique initially proposed for quadratic assignment problems can be generalized to a broader class of quadratic 0–1 mixed-integer problems subject to assignment constraints. The resulting linearized formulation is more compact and tighter than that obtained with a more usual linearization technique. We discuss the application of the compact linearization to three classes of problems in the literature, among which the graph partitioning problem.