Conformational Mechanics of Polymer Adsorption Transitions at Attractive Substrates

Conformational phases of a semiflexible off-lattice homopolymer model near an attractive substrate are investigated by means of multicanonical computer simulations. In our polymer-substrate model, nonbonded pairs of monomers as well as monomers and the substrate interact via attractive van der Waals forces. To characterize conformational phases of this hybrid system, we analyze thermal fluctuations of energetic and structural quantities, as well as adequate docking parameters. Introducing a solvent parameter related to the strength of the surface attraction, we construct and discuss the solubility-temperature phase diagram. Apart from the main phases of adsorbed and desorbed conformations, we identify several other phase transitions such as the freezing transition between energy-dominated crystalline low-temperature structures and globular entropy-dominated conformations.Comment: 13 pages, 15 figure

Insights into shallow magmatic processes in large silicic magma bodies: the trace element record in the Fish Canyon magma body, Colorado

Highly evolved rhyolite glass plus near-solidus mineral assemblages in voluminous, dacitic, crystal-rich ignimbrites provide an opportunity to evaluate the late magmatic evolution of granodiorite batholiths. This study reports laser-ablation ICP-MS analyses of trace element concentrations in feldspars, hornblende, biotite, titanite, zircon, magnetite, and interstitial glass of the crystal-rich Fish Canyon Tuff. The high-silica rhyolite glass is characterized by relatively high concentrations of feldspar-compatible elements (e.g., 100ppm Sr and 500ppm Ba) and low concentrations of Y (40) compared to many well-studied high-silica rhyolite glasses and whole-rock compositions. Most minerals record some trace element heterogeneities, with, in particular, one large hornblende phenocryst showing four- to six-fold core-to-rim increases in Sr and Ba coupled with a decrease in Sc. The depletions of Y and HREE in the Fish Canyon glass relative to the whole-rock composition (concentrations in glass ~30% of those in whole rocks) reflect late crystallization of phases wherein these elements were compatible. As garnet is not stable at the low-P conditions at which the Fish Canyon magma crystallized, we show that a combination of modally abundant hornblende (~4%) + titanite (~0.5-1%) and the highly polymerized nature of the rhyolitic liquid led to Y and HREE depletions in melt. Relatively high Sr and Ba contents in glass and rimward Sr and Ba increases in euhedral, concentrically zoned hornblende suggest partial feldspar dissolution and a late release of these elements to the melt as hornblende was crystallizing, in agreement with textural evidence for feldspar (and quartz) resorption. Both observations are consistent with thermal rejuvenation of the magma body prior to eruption, during which the proportion of melt increased via feldspar and quartz dissolution, even as hydrous and accessory phases were crystallizing. Sr/Y in Fish Canyon glass (13-18) is lower than the typical "adakitic” value (>40), confirming that high Sr/Y is a reliable indicator of high-pressure magma generation and/or differentiation wherein garnet is implicate

Electronic in-plane symmetry breaking at field-tuned quantum criticality in CeRhIn5

Electronic nematics are exotic states of matter where electronic interactions break a rotational symmetry of the underlying lattice, in analogy to the directional alignment without translational order in nematic liquid crystals. Intriguingly such phases appear in the copper- and iron-based superconductors, and their role in establishing high-temperature superconductivity remains an open question. Nematicity may take an active part, cooperating or competing with superconductivity, or may appear accidentally in such systems. Here we present experimental evidence for a phase of nematic character in the heavy fermion superconductor CeRhIn5. We observe a field-induced breaking of the electronic tetragonal symmetry of in the vicinity of an antiferromagnetic (AFM) quantum phase transition at Hc~50T. This phase appears in out-of-plane fields of H*~28T and is characterized by substantial in-plane resistivity anisotropy. The anisotropy can be aligned by a small in-plane field component, with no apparent connection to the underlying crystal structure. Furthermore no anomalies are observed in the magnetic torque, suggesting the absence of metamagnetic transitions in this field range. These observations are indicative of an electronic nematic character of the high field state in CeRhIn5. The appearance of nematic behavior in a phenotypical heavy fermion superconductor highlights the interrelation of nematicity and unconventional superconductivity, suggesting nematicity to be a commonality in such materials

PREDICTIVE VALUE OF FRC AND RESPIRATORY COMPLIANCE ON PULMONARY GAS EXCHANGE INDUCED BY HIGH FREQUENCY JET VENTILATION IN HUMANS

SUMMARY To determine if functional residual capacity (FRC), compliance of the respiratory system (C), or underlying pulmonary disease are predictive for the efficacy of high frequency jet ventilation (HFJV) on pulmonary gas exchange, we investigated six adult patients within 4 h of abdominal surgery and six patients with severe adult respiratory distress syndrome. Gas exchange during intermittent positive pressure ventilation (IPPV) was compared with that during HFJV at frequencies of 100 b.p.m. (HFJV100) and 200 b.p.m. (HFJV200), resulting in a minute ventilation of about 400 ml kg−1 with both ventilatory frequencies, and in both groups of patients. Baseline FRC and C were measured during IPPV with the multiple-breath nitrogen washout method and from expiratory pressure-volume curves, respectively. Changes in the alveolar-arterial oxygen difference (PAO2−PaO2): FlO2 ratio induced by HFJV correlated negatively with C (HFJV100: r = −0.78, P <0.005; HFJV200: r = −0.84, P < 0.005); that is, greater oxygenation was obtained in patients with a better compliance. Similarly, changes in arterial partial pressure of carbon dioxide (Paco2) induced by HFJV correlated negatively with C (HFJV100: r = −0.77, P < 0.001; HFJV200: r = —0.61, P < 0.05). In contrast, there was no significant correlation between FRC measured during IPPV and changes in (PAO2−PaO2): FlO2 ratio or Paco2 induced by HFJV, as these changes were influenced more by the patient's pulmonary disease than by baseline FRC. These results should be interpreted in the context of different underlying pathophysiological mechanisms reducing FRC in both groups of patient

Employing bacteria machinery for antibiotic detection: using DNA gyrase for ciprofloxacin detection

This work describes a new successful approach for designing biosensors that detect antibiotics. It makes use of a biomimetic strategy, by employing the biochemical target of a given antibiotic as its biorecognition element. This principle was tested herein for quinolones, which target DNA gyrase in bacteria. Ciprofloxacin (CIPRO) was tested as a representative antibiotic from the quinolone group; the sensitivity of biosensor to this group was confirmed by checking the response to another quinolone antibiotic (norfloxacin, NOR) and to a non-quinolone antibiotic (ampicillin, AMP). The biorecognition element used was DNA gyrase attached by ionic interactions to a carbon support, on a working electrode on common screen-printed electrodes (SPEs). The response against antibiotics was tested for increasing concentrations of CIPRO, NOR or AMP, and following the subsequent electrical changes by electrochemical impedance spectroscopy. The DNAgyrase biosensor showed sensitive responses for CIPRO and NOR, for concentrations down to 3.02nM and 30.2nM, respectively, with a very wide response range for CRIPRO, up to 30.2µM. Its response was also confirmed selective for quinolones, when compared to its response against AMP. Further comparison to an immunosensor of similar design (adding antibodies instead of DNA gyrase) was made, revealing favourable features for the new biomimetic biosensor with 1.52nM of limit of detection (LOD). Overall, the new approach presented herein is simple and effective for antibiotic detection, displaying a selective response against a given antibiotic group. The use of bacterial machinery as biorecognition element in biosensors may also provide a valuable tool to study the mechanism of action in bacterial cells of new drugs. This is especially important in the development of new drugs to fight bacterial resistance.The authors acknowledge funding from project PTDC/AAG-TEC/5400/2014 funded by European funds, through FEDER (European Funding or Regional Development) via COMPETE2020 – POCI (operational program for internationalization and competitively) and by national funding through the National Foundation for Science and Technology, I.P. (FCT). ARC also acknowledge funding to National Foundation for Science and Technology, I.P., through the PhD Grant, SFRH/BD/130107/2017.info:eu-repo/semantics/publishedVersio

Contact angles mediate equilibrium fractionation between soil water and water vapor

Soil water potential is a function of grain size, adhesion and cohesion energy. The mechanical equilibrium between the interfacial free energies between water-gas, water-solid and solid-gas, leads to a particular contact angle at the three phase boundary water-solid-gas. The contact angle of the solid-soil affects the water retention in soils. Contact angles &gt;0 lead to a shift of the water retention curve to simulating a coarser soil texture. Thus, a certain amount of water is stronger bound in a soil with a low contact angle compared to the same soil with a high contact angle. The relationship between the contact angle and the fractionation of water stable isotopes between soil water and water vapor has yet not been studied. We present a simple laboratory experiment with soil samples ranging from sand to silt to clay. Two subsamples were hydrophobized (or treated with) using dichlorodimethylsilane to produce different contact angles. Subsamples were transferred into Ziploc bags spiked with water of known isotopic composition and the headspace filled with dry air. After equilibration (at least 24h) the headspace was measured for its isotopic signature with a Laserspectrometer. Soil water potential was measured with a soil water potential meter and the contact angle determined with the Wilhelmy-plate-method (WPM). The working hypothesis is that the equilibrium between water and water vapor depends on the matric potential. Having the same pore and the same water content water repellency affects the soil water potential. Therefore the hydrophobized soil will change the equilibrium fractionation between water and water vapor. Hence, the contact angle between adsorbed water and water vapor is related to isotope effects

Construction and Performance of a Micro-Pattern Stereo Detector with Two Gas Electron Multipliers

The construction of a micro-pattern gas detector of dimensions 40x10 cm**2 is described. Two gas electron multiplier foils (GEM) provide the internal amplification stages. A two-layer readout structure was used, manufactured in the same technology as the GEM foils. The strips of each layer cross at an effective crossing angle of 6.7 degrees and have a 406 um pitch. The performance of the detector has been evaluated in a muon beam at CERN using a silicon telescope as reference system. The position resolutions of two orthogonal coordinates are measured to be 50 um and 1 mm, respectively. The muon detection efficiency for two-dimensional space points reaches 96%.Comment: 21 pages, 17 figure

Recursive Graphical Construction for Feynman Diagrams of Quantum Electrodynamics

We present a method for a recursive graphical construction of Feynman diagrams with their correct multiplicities in quantum electrodynamics. The method is first applied to find all diagrams contributing to the vacuum energy from which all n-point functions are derived by functional differentiation with respect to electron and photon propagators, and to the interaction. Basis for our construction is a functional differential equation obeyed by the vacuum energy when considered as a functional of the free propagators and the interaction. Our method does not employ external sources in contrast to traditional approaches.Comment: Author Information under http://www.physik.fu-berlin.de/~kleinert/institution.html Latest update of paper also at http://www.physik.fu-berlin.de/~kleinert/29

Controls on lithium concentration and diffusion in zircon

This study was supported by ETH Research Grants ETH-34 15-2 (JS), ETH-14 16-1 (FM) and by Swiss National Science Foundation research grant 200020-153112/1 (NK).Thermal annealing of zircons prior to uranium-lead dating by laser ablation inductively coupled plasma mass spectrometry is a commonly-implemented procedure which improves data accuracy and precision by partially repairing radiation damage from the decay of uranium and thorium. However, it also leads to significantly higher concentrations of lithium in the zircon lattice, which become positively correlated with trivalent yttrium and rare earth elements. Prior to such treatments, zircons typically contain lithium below detection limits (typically <0.55 μg g−1), unless correlated with lanthanum and aluminum (i.e., melt/mineral inclusion tracer elements). This suggests that lithium in zircon is primarily sequestered within inclusions, and is able to permeate the crystal lattice to couple with yttrium and rare earth elements during the thermal annealing procedure. This process occurs 2–3 orders of magnitude faster than diffusion experiments have previously determined, indicating that another diffusion mechanism may apply. A model is proposed, whereby: (i) charge compensation of stoichiometrically over-abundant trivalent cations under water-rich magmatic conditions is likely accomplished by hydrogen, given the incompatibility of lithium in zircon and the abundance of hydrogen. However, (ii) conditions that are high temperature and low pressure (characteristic of both thermal annealing and the syn-eruptive environment), drive silicate melt inclusions to exsolve water, generating a motive force for both hydrogen and lithium from inclusions to permeate the lattice in order to reestablish electrochemical equilibrium between the interior and exterior of the zircon. To test the pressure dependency of lithium migration in the zircon lattice, thermal annealing experiments were performed at 850 °C and 1 bar, 2 kbar and 6 kbar using zircons from the Fish Canyon Tuff. The experiments demonstrate that thermal annealing at 2 and 6 kbar inhibits lithium mobility, with zircons registering lithium concentrations below detection limits similar to controls. The experimental results suggest that lithium concentrations in zircon are vulnerable to rapid perturbation by decompression (concurrent with high temperatures), which further indicate that lithium-in-zircon diffusion data should be interpreted with caution.Publisher PDFPeer reviewe