Feasibility of gas chromatography-atmospheric pressure photoionization-high-resolution mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in environmental and feed samples.

In this work, the suitability of atmospheric pressure photoionization (APPI) has been assessed for the determination of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) by gas chromatography-high-resolution mass spectrometry (GC-HRMS). The APPI of target compounds has been tested in both positive and negative ion modes. Under positive ion mode, the analytes generated the molecular ion, which was favoured using dopants that promote charge exchange gas-phase reactions (i.e., benzene), while in negative ion mode, the ion [M-Cl+O]- for PCDFs and dl-PCBs were mainly formed, providing the best results using benzene and diethyl ether as dopants, respectively. Concerning PCDDs, highly chlorinated congeners were mainly ionized by means of the [M-Cl]- ion, whereas [M-Cl+O2]- was the base peak for tetraCDD and [M-Cl+O]- for penta- and hexaCDDs. Method quality parameters, in accordance with the current EU Regulation guidelines for food and feed analysis, showed the good performance of the two GC-APPI-HRMS (Orbitrap) methods since they provided high detection capability (low fg levels), good linearity, and satisfactory precision (RSD% < 9%). In addition, the GC-APPI-HRMS (Orbitrap) methods were validated by analysing selected environmental and feed samples and the results were compared to those obtained using conventional GC-EI-HRMS, demonstrating the good performance in the analysis of the target compounds. Hence, the GC-APPI-HRMS technique can be proposed as alternative to the conventional methods for the determination of PCDD/Fs and dl-PCBs in environmental and feed matrices.

Retention and transport of mecoprop on acid sandy-loam soils.

Interaction with soil components is one of the key processes governing the fate of agrochemicals in the environment. In this work, we studied the adsorption / desorption and transport of mecoprop (methylchlorophenoxypropionic acid or MCPP) in four acid sandy-loam soils with different organic matter contents. Kinetics of adsorption and adsorption/desorption at equilibrium were studied in batch experiments, whereas transport was studied in laboratory columns. Adsorption and desorption were found to be linear or nearly-linear. The kinetics of mecoprop adsorption were relatively fast in all cases (less than 24h). Adsorption and desorption were adequately described by the linear and Freundlich models, with KF values that ranged from 0.7 to 8.8Ln µmol1-nkg-1 and KD values from 0.3 to 3.6Lkg-1. The results of the transport experiments showed that the retention of mecoprop by soil was very low (less than 6.2%). The retention of mecoprop by the soils in all experiments increased with organic matter content. Overall, it was observed that mecoprop was weakly adsorbed by the soils, what would result in a high risk of leaching of this compound in the environment.

Theoretical study of carbon-based tips for scanning tunnelling microscopy.

Motivated by recent experiments, we present here a detailed theoretical analysis of the use of carbon-based conductive tips in scanning tunnelling microscopy. In particular, we employ ab initio methods based on density functional theory to explore a graphitic, an amorphous carbon and two diamond-like tips for imaging with a scanning tunnelling microscope (STM), and we compare them with standard metallic tips made of gold and tungsten. We investigate the performance of these tips in terms of the corrugation of the STM images acquired when scanning a single graphene sheet. Moreover, we analyse the impact of the tip-sample distance and show that it plays a fundamental role in the resolution and symmetry of the STM images. We also explore in depth how the adsorption of single atoms and molecules in the tip apexes modifies the STM images and demonstrate that, in general, it leads to an improved image resolution. The ensemble of our results provides strong evidence that carbon-based tips can significantly improve the resolution of STM images, as compared to more standard metallic tips, which may open a new line of research in scanning tunnelling microscopy.

Conformational ensemble of human α-synuclein physiological form predicted by molecular simulations.

We perform here enhanced sampling simulations of N-terminally acetylated human α-synuclein, an intrinsically disordered protein involved in Parkinson's disease. The calculations, consistent with experiments, suggest that the post-translational modification leads to the formation of a transient amphipathic α-helix. The latter, absent in the non-physiological form, alters protein dynamics at the N-terminal and intramolecular interactions.

Increased levels of dioxin-like substances in adipose tissue in patients with deep infiltrating endometriosis.

STUDY QUESTION: Are the levels of biologically active and the most toxic dioxin-like substances in adipose tissue of patients with deep infiltrating endometriosis (DIE) higher than in a control group without endometriosis? SUMMARY ANSWER: DIE patients have higher levels of dioxins and polychlorinated biphenyls (PCBs) in adipose tissue compared with controls without endometriosis. WHAT IS KNOWN ALREADY: Some studies have investigated the levels of dioxin-like substances, in serum samples, in patients with endometriosis, with inconsistent results. STUDY DESIGN, SIZE, DURATION: Case-control study including two groups of patients. The study group (DIE group) consisted of 30 patients undergoing laparoscopic surgery because of DIE. In all patients, an extensive preoperative work-up was performed including clinical exploration, magnetic resonance imaging (MRI) and transvaginal sonography. All patients with DIE underwent a confirmatory histological study for DIE after surgery. The non-endometriosis control group (control group), included the next consecutive patient undergoing laparoscopic surgery in our center due to adnexal benign gynecological disease (ovarian or tubal procedures other than endometriosis) after each DIE patient, and who did not present any type of endometriosis. PARTICIPANTS/MATERIALS, SETTING, METHODS: During the surgical procedure 1-2 g of adipose tissue from the omentum were obtained. Dioxin-like substances were analyzed in adipose tissue in DIE patients and controls without endometriosis. MAIN RESULTS AND THE ROLE OF CHANCE: The total toxic equivalence and concentrations of both dioxins and PCBs were significantly higher in patients with DIE in comparison with the control group (P < 0.05), mainly due to the significantly higher values of the two most toxic dioxins (2,3,7,8-tetrachlorodibenzo-p-dioxin [2,3,7,8-TCDD] and 1,2,3,7,8-pentachlorodibenzo-p-dioxin [1,2,3,7,8-PeCDD]) (P < 0.01 for each compound). The levels of furan 2,3,4,7,8-PeCDF were statistically higher in the DIE group compared with controls. Only four congeners of PCBs had toxic equivalence values and concentrations that were statistically higher in patients with DIE, but these included the most toxic and carcinogenic PCB-126 (PCB-114 P < 0.05; PCB-156 P < 0.05; PCB-189 P = 0.04; PCB-126 P < 0.01). LIMITATIONS, REASONS FOR CAUTION: Since few patients were recruited, the study is only exploratory. Our results need to be confirmed in larger and more heterogeneous population studies since environmental and even genetic factors involved in determining dioxins and PCBs widely vary in different countries. Furthermore, the strict eligibility criteria used may preclude generalization of the results to other populations and the surgery-based sampling frame may induce a selection bias. Finally, adipose tissue was obtained only from the omentum, and not from other adipose tissue of the body. WIDER IMPLICATIONS OF THE FINDINGS: Our results suggest a potential role of dioxin-like substances in the pathogenesis of DIE. Further studies are warranted to confirm our findings. STUDY FUNDING/COMPETING INTERESTS: None. TRIAL REGISTRATION NUMBER: Not applicable.

Exploration and trapping of mortal random walkers.

Exploration and trapping properties of random walkers that may evanesce at any time as they walk have seen very little treatment in the literature, and yet a finite lifetime is a frequent occurrence, and its effects on a number of random walk properties may be profound. For instance, whereas the average number of distinct sites visited by an immortal walker grows with time without bound, that of a mortal walker may, depending on dimensionality and rate of evanescence, remain finite or keep growing with the passage of time. This number can in turn be used to calculate other classic quantities such as the survival probability of a target surrounded by diffusing traps. If the traps are immortal, the survival probability will vanish with increasing time. However, if the traps are evanescent, the target may be spared a certain death. We analytically calculate a number of basic and broadly used quantities for evanescent random walkers.

Tailoring structural and electronic properties of RuO2 nanotubes: a many-body approach and electronic transport.

The electrical conduction properties of ruthenium oxide nanocables are of high interest. These cables can be built as thin shells of RuO2 surrounding an inner solid nanowire of a dielectric insulating silica material. With this motivation we have investigated the structural, electronic and transport properties of RuO2 nanotubes using the density functional formalism, and applying many-body corrections to the electronic band structure. The structures obtained for the thinnest nanotubes are of the rutile type. The structures of nanotubes with larger diameters deviate from the rutile structure and have in common the formation of dimerized Ru-Ru rows along the axial direction. The cohesive energy shows an oscillating behavior as a function of the tube diameter. With the exception of the thinnest nanotubes, there is a correlation such that the electronic band structures of tubes with high cohesive energies show small gaps at the Fermi energy, whereas the less stable nanotubes exhibit metallic behavior, with bands crossing the Fermi surface. The electronic conductance of nanotubes of finite length connected to gold electrodes has been calculated using a Green-function formalism, and correlations have been established between the electronic band structure and the conductance at zero bias.

Improvement of scanning tunneling microscopy resolution with H-sensitized tips.

Recent scanning tunneling hydrogen microscopy (STHM) experiments on PTCDA (perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride)/Au(111) have shown unprecedented intramolecular and intermolecular spatial resolution. The origin of this resolution is studied using an accurate STHM theoretical simulation technique that includes a detailed description of the electronic structure of both the tip and sample. Our results show that H2 molecules are dissociated on the Au tip; the adsorbed H atoms change the density of states at the Fermi level (E(F)) of the tip, increasing its p-orbital character and reducing the s-orbital contribution. Also, due to the interaction with the H-decorated tip, E(F) is shifted to the middle of the PTCDA lowest unoccupied molecular orbital peak, increasing dramatically the density of states of the sample at E(F). These effects give rise to the enhanced STHM resolution.

Current use of high-resolution mass spectrometry in the environmental sciences.

During the last two decades, mass spectrometry (MS) has been increasingly used in the environmental sciences with the objective of investigating the presence of organic pollutants. MS has been widely coupled with chromatographic techniques, both gas chromatography (GC) and liquid chromatography (LC), because of their complementary nature when facing a broad range of organic pollutants of different polarity and volatility. A clear trend has been observed, from the very popular GC-MS with a single quadrupole mass analyser, to tandem mass spectrometry (MS-MS) and, more recently, high-resolution mass spectrometry (HRMS). For years GC has been coupled to HR magnetic sector instruments, mostly for dioxin analysis, although in the last ten years there has been growing interest in HRMS with time-of-flight (TOF) and Orbitrap mass analyzers, especially in LC-MS analysis. The increasing interest in the use of HRMS in the environmental sciences is because of its suitability for both targeted and untargeted analysis, owing to its sensitivity in full-scan acquisition mode and high mass accuracy. With the same instrument one can perform a variety of tasks: pre- and post-target analysis, retrospective analysis, discovery of metabolite and transformation products, and non-target analysis. All these functions are relevant to the environmental sciences, in which the analyst encounters thousands of different organic contaminants. Thus, wide-scope screening of environmental samples is one of the main applications of HRMS. This paper is a critical review of current use of HRMS in the environmental sciences. Needless to say, it is not the intention of the authors to summarise all contributions of HRMS in this field, as in classic descriptive reviews, but to give an overview of the main characteristics of HRMS, its strong potential in environmental mass spectrometry and the trends observed over the last few years. Most of the literature has been acquired since 2005, coinciding with the growth and popularity of HRMS in this field, with a few exceptions that deserve to be mentioned because of their relevance.

First-encounter time of two diffusing particles in two- and three-dimensional confinement.

The statistics of the first-encounter time of diffusing particles changes drastically when they are placed under confinement. In the present work, we make use of Monte Carlo simulations to study the behavior of a two-particle system in two- and three-dimensional domains with reflecting boundaries. Based on the outcome of the simulations, we give a comprehensive overview of the behavior of the survival probability S(t) and the associated first-encounter time probability density H(t) over a broad time range spanning several decades. In addition, we provide numerical estimates and empirical formulas for the mean first-encounter time 〈T〉, as well as for the decay time T characterizing the monoexponential long-time decay of the survival probability. Based on the distance between the boundary and the center of mass of two particles, we obtain an empirical lower bound t_{B} for the time at which S(t) starts to significantly deviate from its counterpart for the no boundary case. Surprisingly, for small-sized particles, the dominant contribution to T depends only on the total diffusivity D=D_{1}+D_{2}, in sharp contrast to the one-dimensional case. This contribution can be related to the Wiener sausage generated by a fictitious Brownian particle with diffusivity D. In two dimensions, the first subleading contribution to T is found to depend weakly on the ratio D_{1}/D_{2}. We also investigate the slow-diffusion limit when D_{2}≪D_{1}, and we discuss the transition to the limit when one particle is a fixed target. Finally, we give some indications to anticipate when T can be expected to be a good approximation for 〈T〉.

The role of central CB2 cannabinoid receptors on food intake in neonatal chicks.

The endocannabinoids (ECBs) have diverse physiological functions including the regulation of food intake and metabolism. In mammals, ECBs regulate feeding primarily through the CB1 receptors within the brain whereas the CB2 receptors are primarily involved in the regulation of immune function by direct action on peripheral immune cells and central glia. The central effect of ECBs on feeding behavior has not been studied in non-mammalian species. Therefore, the present study investigated the effect of CB65, a selective CB2 receptors agonist, on food intake in the neonatal chicks. In addition, the effect of astressin, a CRF receptor antagonist, on CB65-induced food intake was also investigated. Intracerebroventricular injection of the CB65 (1.25 µg) increased the food intake at 30- and 60-min post-injection significantly as compared to the control group. Pretreatment with a selective CB2 receptor antagonist, AM630, but not astressin, significantly attenuated the CB65-induced food intake. These results suggested that CB2 receptor agonists act on the brain to induce food intake.

Charging energy and barrier height of pentacene on Au(111): a local-orbital hybrid-functional density functional theory approach.

We analyze the pentacene/Au(111) interface by means of density functional theory (DFT) calculations using a new hybrid functional; in our approach we introduce, in a local-orbital formulation of DFT, a hybrid exchange potential, and combine it with a calculation of the molecule charging energy to properly describe the transport energy gap of pentacene on Au(111). Van der Waals forces are taken into account to obtain the adsorption geometry. Interface dipole potentials are also calculated; it is shown that the metal/pentacene energy level alignment is determined by the potential induced by the charge transfer between the metal surface and the organic material, as described by the induced density of interface states model. Our results compare well with the experimental data.

C6H6/Au(111): interface dipoles, band alignment, charging energy, and van der Waals interaction.

We analyze the benzene/Au(111) interface taking into account charging energy effects to properly describe the electronic structure of the interface and van der Waals interactions to obtain the adsorption energy and geometry. We also analyze the interface dipoles and discuss the barrier formation as a function of the metal work-function. We interpret our DFT calculations within the induced density of interface states (IDIS) model. Our results compare well with experimental and other theoretical results, showing that the dipole formation of these interfaces is due to the charge transfer between the metal and benzene, as described in the IDIS model.

Pseudo-two-dimensional dynamics in a system of macroscopic rolling spheres.

We study in this work the dynamics of a collection of identical hollow spheres (ping-pong balls) that rest on a horizontal metallic grid. Fluidization is achieved by means of a turbulent air current coming from below. The upflow is adjusted so that the particles do not levitate over the grid, resulting in quasi-two-dimensional dynamics. We show that the behavior of diffusion and correlations in this system is particularly rich. Noticeably as well (and related to the complex dynamical behavior), a variety of phases appear, with important peculiarities with respect to analogous setups. We observe gas, liquid, glass, and hexagonal crystal phases. Most notably, we show that the melting of the hexagonal crystal occurs in coexistence with a liquid phase. This strikingly differs from the corresponding transition in a purely two-dimensional systems of air-fluidized disks, for which no phase coexistence has been reported in the literature.

[High percentage of adrenergic symptoms in extraadrenal chromaffin tumors]. / Manifestaciones adrenérgicas de los tumores del tejido cromafín extraadrenal.

UNLABELLED: Descriptive retrospective study of 14 patients with paragangliomas (PGL) attended in the University Hospital of Vigo (Pontevedra) during the last 25 years to evaluating their characteristics and neuroendocrine potential. RESULTS: 71.4% were diagnosed due to mass tumoral effect, 21.4% due to adrenergic symptoms and 7.1% incidentally. Regarding to symptoms and signs 66.7% of PGL Simpatic (PGLS) and 40% of PGL Parasimpatic (PGLPS) presented adrenergic symptoms. Urine catecholamine analysis was carried out to 4 PGLS and high levels were found in all patients. The tumoral size reached a mean value of 37.8+/-18.9 mm, there were not differences found between both types of tumors. Inmunohistoquimia showed positive Chromogranine A stain in all patients. Two PGLS were maligns. Eleven patients had positive outcome, 2 PGLS died, and 1 PGLPS remains not cured. CONCLUSIONS: High percentage of patients had clinical manifestations related to catecholamine hyperproduction. We believe that due to the risk related to surgical treatment, malignance, multiple location and family associations, it would be advisable to carry out a complete examination prior to surgery.

First-encounter time of two diffusing particles in confinement.

We investigate how confinement may drastically change both the probability density of the first-encounter time and the associated survival probability in the case of two diffusing particles. To obtain analytical insights into this problem, we focus on two one-dimensional settings: a half-line and an interval. We first consider the case with equal particle diffusivities, for which exact results can be obtained for the survival probability and the associated first-encounter time density valid over the full time domain. We also evaluate the moments of the first-encounter time when they exist. We then turn to the case with unequal diffusivities and focus on the long-time behavior of the survival probability. Our results highlight the great impact of boundary effects in diffusion-controlled kinetics even for simple one-dimensional settings, as well as the difficulty of obtaining analytic results as soon as the translational invariance of such systems is broken.

Reaction-diffusion and reaction-subdiffusion equations on arbitrarily evolving domains.

Reaction-diffusion equations are widely used as the governing evolution equations for modeling many physical, chemical, and biological processes. Here we derive reaction-diffusion equations to model transport with reactions on a one-dimensional domain that is evolving. The model equations, which have been derived from generalized continuous time random walks, can incorporate complexities such as subdiffusive transport and inhomogeneous domain stretching and shrinking. Inhomogeneously growing domains are frequently encountered in biological phenomena involving stochastic transport, such as tumor growth and morphogen gradient formation. A method for constructing analytic expressions for short-time moments of the position of the particles is developed and moments calculated from this approach are shown to compare favorably with results from random walk simulations and numerical integration of the reaction transport equation. The results show the important role played by the initial condition. In particular, it strongly affects the time dependence of the moments in the short-time regime by introducing additional drift and diffusion terms. We also discuss how our reaction transport equation could be applied to study the spreading of a population on an evolving interface. From a more general perspective, our findings help to mitigate the scarcity of analytic results for reaction-diffusion problems in geometries displaying nonuniform growth. They are also expected to pave the way for further results, including the treatment of first-passage problems associated with encounter-controlled reactions in such domains.

On a novel rate theory for transport in narrow ion channels and its application to the study of flux optimization via geometric effects.

We present a novel rate theory based on the notions of splitting probability and mean first passage time to describe single-ion conduction in narrow, effectively one-dimensional membrane channels. In contrast to traditional approaches such as transition state theory or Kramers theory, transitions between different conduction states in our model are governed by rates which depend on the full geometry of the potential of mean force (PMF) resulting from the superposition of an equilibrium free energy profile and a transmembrane potential induced by a nonequilibrium constraint. If a detailed theoretical PMF is available (e.g., from atomistic molecular dynamics simulations), it can be used to compute characteristic conductance curves in the framework of our model, thereby bridging the gap between the atomistic and the mesoscopic level of description. Explicit analytic solutions for the rates, the ion flux, and the associated electric current can be obtained by approximating the actual PMF by a piecewise linear potential. As illustrative examples, we consider both a theoretical and an experimental application of the model. The theoretical example is based on a hypothetical channel with a fully symmetric sawtooth equilibrium PMF. For this system, we explore how changes in the spatial extent of the binding sites affect the rate of transport when a linear voltage ramp is applied. Already for the case of a single binding site, we find that there is an optimum size of the site which maximizes the current through the channel provided that the applied voltage exceeds a threshold value given by the binding energy of the site. The above optimization effect is shown to arise from the complex interplay between the channel structure and the applied electric field, expressed by a nonlinear dependence of the rates with respect to the linear size of the binding site. In studying the properties of current-voltage curves, we find a double crossover between sublinear and superlinear behaviors as the size of the binding site is varied. The ratio of unidirectional fluxes clearly deviates from the Ussing limit and can be characterized by a flux ratio exponent which decreases below unity as the binding site becomes wider. We also explore effects arising from changes in the ion bulk concentration under symmetric ionic conditions and the presence of additional binding sites in the hypothetical channel. As for the experimental application, we show that our rate theory is able to provide good fits to conductance data for sodium permeation through the gramicidin A channel. Possible extensions of the theory to treat the case of an asymmetric equilibrium PMF, fluctuations in the mean number of translocating ions, the case of fluctuating energy barriers, and multi-ion conductance are briefly discussed.

Standard and fractional Ornstein-Uhlenbeck process on a growing domain.

We study normal diffusive and subdiffusive processes in a harmonic potential (Ornstein-Uhlenbeck process) on a uniformly growing or contracting domain. Our starting point is a recently derived fractional Fokker-Planck equation, which covers both the case of Brownian diffusion and the case of a subdiffusive continuous-time random walk (CTRW). We find a high sensitivity of the random walk properties to the details of the domain growth rate, which gives rise to a variety of regimes with extremely different behaviors. At the origin of this rich phenomenology is the fact that the walkers still move while they wait to jump, since they are dragged by the deterministic drift arising from the domain growth. Thus, the increasingly long waiting times associated with the aging of the subdiffusive CTRW imply that, in the time interval between two consecutive jumps, the walkers might travel over much longer distances than in the normal diffusive case. This gives rise to seemingly counterintuitive effects. For example, on a static domain, both Brownian diffusion and subdiffusive CTRWs yield a stationary particle distribution with finite width when a harmonic potential is at play, thus indicating a confinement of the diffusing particle. However, for a sufficiently fast growing or contracting domain, this qualitative behavior breaks down, and differences between the Brownian case and the subdiffusive case are found. In the case of Brownian particles, a sufficiently fast exponential domain growth is needed to break the confinement induced by the harmonic force; in contrast, for subdiffusive particles such a breakdown may already take place for a sufficiently fast power-law domain growth. Our analytic and numerical results for both types of diffusion are fully confirmed by random walk simulations.

First-passage properties of mortal random walks: Ballistic behavior, effective reduction of dimensionality, and scaling functions for hierarchical graphs.

We consider a mortal random walker on a family of hierarchical graphs in the presence of some trap sites. The configuration comprising the graph, the starting point of the walk, and the locations of the trap sites is taken to be exactly self-similar as one goes from one generation of the family to the next. Under these circumstances, the total probability that the walker hits a trap is determined exactly as a function of the single-step survival probability q of the mortal walker. On the nth generation graph of the family, this probability is shown to be given by the nth iterate of a certain scaling function or map q→f(q). The properties of the map then determine, in each case, the behavior of the trapping probability, the mean time to trapping, the temporal scaling factor governing the random walk dimension on the graph, and other related properties. The formalism is illustrated for the cases of a linear hierarchical lattice and the Sierpinski graphs in two and three Euclidean dimensions. We find an effective reduction of the random walk dimensionality due to the ballistic behavior of the surviving particles induced by the mortality constraint. The relevance of this finding for experiments involving travel times of particles in diffusion-decay systems is discussed.