Dissipation enhanced vibrational sensing in an olfactory molecular switch

Motivated by a proposed olfactory mechanism based on a vibrationally-activated molecular switch, we study electron transport within a donor-acceptor pair that is coupled to a vibrational mode and embedded in a surrounding environment. We derive a polaron master equation with which we study the dynamics of both the electronic and vibrational degrees of freedom beyond previously employed semiclassical (Marcus-Jortner) rate analyses. We show: (i) that in the absence of explicit dissipation of the vibrational mode, the semiclassical approach is generally unable to capture the dynamics predicted by our master equation due to both its assumption of one-way (exponential) electron transfer from donor to acceptor and its neglect of the spectral details of the environment; (ii) that by additionally allowing strong dissipation to act on the odorant vibrational mode we can recover exponential electron transfer, though typically at a rate that differs from that given by the Marcus-Jortner expression; (iii) that the ability of the molecular switch to discriminate between the presence and absence of the odorant, and its sensitivity to the odorant vibrational frequency, are enhanced significantly in this strong dissipation regime, when compared to the case without mode dissipation; and (iv) that details of the environment absent from previous Marcus-Jortner analyses can also dramatically alter the sensitivity of the molecular switch, in particular allowing its frequency resolution to be improved. Our results thus demonstrate the constructive role dissipation can play in facilitating sensitive and selective operation in molecular switch devices, as well as the inadequacy of semiclassical rate equations in analysing such behaviour over a wide range of parameters.Comment: 12 pages, 6 figures, close to published version, comments welcom

Sugar additives for MALDI matrices improve signal allowing the smallest nucleotide change (A:T) in a DNA sequence to be resolved

Sample preparation for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) of DNA is critical for obtaining high quality mass spectra. Sample impurity, solvent content, substrate surface and environmental conditions (temperature and humidity) all affect the rate of matrix–analyte co-crystallization. As a result, laser fluence threshold for desorption/ionization varies from spot to spot. When using 3-hydroxypicolinic acid (3-HPA) as the matrix, laser fluence higher than the threshold value reduces mass resolution in time-of-flight (TOF) MS as the excess energy transferred to DNA causes metastable decay. This can be overcome by either searching for ‘hot’ spots or adjusting the laser fluence. However, both solutions may require a significant amount of operator manipulation and are not ideal for automatic measurements. We have added various sugars for crystallization with the matrix to minimize the transfer of excess laser energy to DNA molecules. Fructose and fucose were found to be the most effective matrix additives. Using these additives, mass resolution for DNA molecules does not show noticeable deterioration as laser energy increases. Improved sample preparation is important for the detection of single nucleotide polymorphisms (SNPs) using primer extension with a single nucleotide. During automatic data acquisition it is difficult to routinely detect heterozygous A/T mutations, which requires resolving a mass difference of 9 Da, unless a sugar is added during crystallization

Residual Tumor Confers a 10-Fold Increased Risk of Regrowth in Clinically Nonfunctioning Pituitary Tumors.

ObjectiveWe evaluated tumor recurrence and regrowth rates following endoscopic transnasal transsphenoidal (TNTS) surgical removal in a consecutive series of clinically nonfunctioning pituitary adenomas (CNFTs).DesignRetrospective chart review of clinical, biochemical, and sellar MRI findings in all TNTS surgeries in patients with CNFT, performed by a single surgeon, between 2008 and 2015 (n = 280).PatientsNinety-three patients met eligibility criteria, with complete clinical, biochemical, and imaging follow-up for a 3-year minimum.ResultsOf 85 patients who were not irradiated, 3-month postsurgical MRI demonstrated no residual tumor in 58 of 85 (68.2%), equivocal findings in 12 of 85 (14.1%), and definite residual tumor in 15 of 85 (17.6%) patients. Six of 85 (7.1%) demonstrated tumor regrowth by 3 years, and 2 further patients demonstrated true tumor recurrence at 3 and 6 years after surgery, respectively, for a total recurrence rate of 9.4% (8 of 85). Eight of the 93 patients were irradiated between 3 months and 4 years after pituitary surgery. In 3 patients with tumor regrowth, 2 exhibited residual tumor and 1 had no residual findings at the 3-month postoperative imaging. Overall, Ki-67 labeling index or Knosp grading did not predict recurrence.ConclusionTumor recurrence at 3 years was low (1 of 58; 1.7%) if the 3-month postoperative MRI showed no residual tumor. The findings support a less frequent imaging schedule for this group. Patients with definite residual tumor visible at 3 months harbor the greatest risk for tumor growth, but regrowth does not occur in all patients (6 of 15; 40%)

Free energy and configurational entropy of liquid silica: fragile-to-strong crossover and polyamorphism

Recent molecular dynamics (MD) simulations of liquid silica, using the ``BKS'' model [Van Beest, Kramer and van Santen, Phys. Rev. Lett. {\bf 64}, 1955 (1990)], have demonstrated that the liquid undergoes a dynamical crossover from super-Arrhenius, or ``fragile'' behavior, to Arrhenius, or ``strong'' behavior, as temperature $T$ is decreased. From extensive MD simulations, we show that this fragile-to-strong crossover (FSC) can be connected to changes in the properties of the potential energy landscape, or surface (PES), of the liquid. To achieve this, we use thermodynamic integration to evaluate the absolute free energy of the liquid over a wide range of density and $T$. We use this free energy data, along with the concept of ``inherent structures'' of the PES, to evaluate the absolute configurational entropy $S_c$ of the liquid. We find that the temperature dependence of the diffusion coefficient and of $S_c$ are consistent with the prediction of Adam and Gibbs, including in the region where we observe the FSC to occur. We find that the FSC is related to a change in the properties of the PES explored by the liquid, specifically an inflection in the $T$ dependence of the average inherent structure energy. In addition, we find that the high $T$ behavior of $S_c$ suggests that the liquid entropy might approach zero at finite $T$, behavior associated with the so-called Kauzmann paradox. However, we find that the change in the PES that underlies the FSC is associated with a change in the $T$ dependence of $S_c$ that elucidates how the Kauzmann paradox is avoided in this system. Finally, we also explore the relation of the observed PES changes to the recently discussed possibility that BKS silica exhibits a liquid-liquid phase transition, a behavior that has been proposed to underlie the observed polyamorphism of amorphous solid silica.Comment: 14 pages, 18 figure

Derek Mahon's Seascapes Mediated through Greece: Antiquity in Modernity, Nature in Abstraction.

The article investigates various approaches to seascape in selected poems of the contemporary Irish poet, Derek Mahon, set against the background of references to Michael Longley, Seamus Heaney or Odysseus Elytis. The sea provides a perspective that cannot be overestimated in trying to get an insight into the communication and the clash between the culture of the South and the North. The two nations have often glimpsed at their reflection in the mirror of the surrounding seas, their history and mentality determined by their geographical position and largely insular experience. Elements such as the isolation from the mainland; the perception of the sea as a personification of the force ruling over life and death, as a threat and a promise; or the focus on some characteristic natural phenomena such as light or surface dominate the seascape imagery both in Greek and Irish literature. The sea often constitutes a border of antagonistic and complementary worlds: dream and reality, light and darkness, male and female, the real world and the underworld – and the vantage point of the poet changes accordingly. Some poems under discussion also explore a series of myths linked with the sea, the best known of which, the Odyssey, has remained a frame of reference for numerous contemporary Greek and Irish poets. Elytis's Cyclades or Longley's Mayo provide us with examples of 'private homelands'. As Longley once observed, “his part of Mayo” reminds him of Ithaca (sandy and remote) and of Greece in general: “I’ve often thought that that part of Ireland . . . looks like Greece. Or Greece looks like a dust-bowl version of Ireland,” which triggers further deliberations on seascape as the common ground for the two countries. Just as Elytis's Cyclades or Longley's Mayo, Mahon’s Cyclades provide us with examples of 'private homelands'. The focus of this article is Derek Mahon’s seascapes: purely Greek (‘Aphrodite’s Pool’), Irish seen through the prism of the Greek ones (‘Achill’) and purely Irish (‘Recalling Aran’). The level of abstraction in the last category is compared with Odysseus Elytis’s imagery of the Cyclades, while the first poem demystifies a practice which I termed as ‘myth trading’, one of consumerist tourism techniques

Effects of softwood biochar on the status of nitrogen species and elements of potential toxicity in soils

The effects of softwood-derived biochar materials on the chemical behaviour of environmental contaminants in soils were examined in two microcosm scenarios. Addition of the biochar materials into an alkaline sandy soil significantly reduced NH3 volatilization and made it available for conversion into NO3- via nitrification. This process could be enhanced by an increased application rate of biochar produced at a higher pyrolysis temperature. Under the alkaline conditions encountered in the experiment, the biochar surfaces tended to be negatively charged which disfavours the adsorption of NO3-. Therefore, in a fully open system, the addition of biochar materials was likely to contribute to nitrate leaching from the fertilized alkaline sandy soil. The effects of the biochar materials on the immobilization of Fe2+ generated via anaerobic iron reduction in the inundated contaminated soil were not observed, except for the treatment with a higher dose of biochar material produced under pyrolysis temperature at 700°C after the 240th h of incubation. Arsenic showed similar behaviour to Fe. Zn tended to have a higher affinity to the biochar, as compared to Mn. Immobilization of Pb occurred regardless of whether or not the biochar is present

Teleportation of a quantum state of a spatial mode with a single massive particle

Mode entanglement exists naturally between regions of space in ultra-cold atomic gases. It has, however, been debated whether this type of entanglement is useful for quantum protocols. This is due to a particle number superselection rule that restricts the operations that can be performed on the modes. In this paper, we show how to exploit the mode entanglement of just a single particle for the teleportation of an unknown quantum state of a spatial mode. We detail how to overcome the superselection rule to create any initial quantum state and how to perform Bell state analysis on two of the modes. We show that two of the four Bell states can always be reliably distinguished, while the other two have to be grouped together due to an unsatisfied phase matching condition. The teleportation of an unknown state of a quantum mode thus only succeeds half of the time.Comment: 12 pages, 1 figure, this paper was presented at TQC 2010 and extends the work of Phys. Rev. Lett. 103, 200502 (2009

Comparison of potential growth rates of Ceratium hirundinella with observed population density changes

Ceratium hirundinella cells in Lake Constance divided during the second half of the night. Growth rates are calculated from the fraction of cells undergoing cell division. Potential growth rates are compared with observed changes in population density. The discrepancy between both is discussed as a possible function of fungal parasitism

Anomalous spectral weight in photoemission spectra of the hole doped Haldane chain Y2-xSrxBaNiO5

In this paper, we present photoemission experiments on the hole doped Haldane chain compound $Y_{2-x}Sr_xBaNiO_5$. By using the photon energy dependence of the photoemission cross section, we identified the symmetry of the first ionisation states (d type). Hole doping in this system leads to a significant increase in the spectral weight at the top of the valence band without any change in the vicinity of the Fermi energy. This behavior, not observed in other charge transfer oxides at low doping level, could result from the inhomogeneous character of the doped system and from a Ni 3d-O 2p hybridization enhancement due to the shortening of the relevant Ni-O distance in the localized hole-doped regions.Comment: 5 pages, 4 figure

Causality in Political Networks

As the study of political networks becomes more common in political science, greater attention to questions of causality is warranted. This essay explores competing visions of causality in political networks. Independent essays address issues of statistical model specification, identification of multi-step personal influence, measurement error, causality in historical perspective, and the insights of field experiments. These essays do not agree entirely on the nature of causality in political networks, though they commonly take seriously concerns regarding homophily, time- consistency, and the uniqueness of political network data. Serious consideration of these methodological issues promises to enhance the value-added of network analysis in the study of politics