Nitrate Pathways, Processes, and Timing in an Agricultural Karst System: Development and Application of a Numerical Model

An edited version of this paper was published by AGU. Copyright 2019 American Geophysical Union.Nitrogen (N) contamination within agricultural‐karst landscapes and aquifers is widely reported; however, the complex hydrological pathways of karst make N fate difficult to ascertain. We developed a hydrologic and N numerical model for agricultural‐karst, including simulation of soil, epikarst, phreatic, and quick flow pathways as well as biochemical processes such as nitrification, mineralization, and denitrification. We tested the model on four years of nitrate (NO3−) data collected from a phreatic conduit and an overlying surface channel in the Cane Run watershed, Kentucky, USA. Model results indicate that slow to moderate flow pathways (phreatic and epikarst) dominate the N load and account for nearly 90% of downstream NO3− delivery. Further, quick flow pathways dilute NO3− concentrations relative to background aquifer levels. Net denitrification distributed across soil, epikarst, and phreatic water removes approximately 36% of the N inputs to the system at rates comparable to nonkarst systems. Evidence is provided by numerical modeling that NO3− accumulation via evapotranspiration in the soil followed by leaching through the epikarst acts as a control on spring NO3− concentration and loading. Compared to a fluvial‐dominated immature karst system, mature‐karst systems behave as natural detention basins for NO3−, temporarily delaying NO3− delivery to downstream waters and maintaining elevated NO3− concentrations for days to weeks after hydrologic activity ends. This study shows the efficacy of numerical modeling to elucidate complex pathways, processes, and timing of N in karst systems

Tailor-made nanostructures bridging chaos and order for highly efficient white organic light-emitting diodes

Organic light-emitting diodes (OLEDs) suffer from notorious light trapping, resulting in only moderate external quantum efficiencies. Here, we report a facile, scalable, lithography-free method to generate controllable nanostructures with directional randomness and dimensional order, significantly boosting the efficiency of white OLEDs. Mechanical deformations form on the surface of poly(dimethylsiloxane) in response to compressive stress release, initialized by reactive ions etching with periodicity and depth distribution ranging from dozens of nanometers to micrometers. We demonstrate the possibility of independently tuning the average depth and the dominant periodicity. Integrating these nanostructures into a two-unit tandem white organic light-emitting diode, a maximum external quantum efficiency of 76.3% and a luminous efficacy of 95.7 lm W−1 are achieved with extracted substrate modes. The enhancement factor of 1.53 ± 0.12 at 10,000 cd m−2 is obtained. An optical model is built by considering the dipole orientation, emitting wavelength, and the dipole position on the sinusoidal nanotexture

The influence of reaction conditions on the oxidation of cyclohexane via the in-situ production of H2O2

The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), both key materials in the production of Nylon. Herein we demonstrate that through the in-situ production of H2O2 supported AuPd nanoparticles catalyse the formation of KA oil under conditions where activity is limited when using molecular O2, with no loss in catalytic activity observed upon re-use. The effect of key reaction parameters, including reaction temperature, catalyst mass and H2:O2 ratio are evaluated

Stochastic Pulse Switching in a Degenerate Resonant Optical Medium

Using the idealized integrable Maxwell-Bloch model, we describe random optical-pulse polarization switching along an active optical medium in the Lambda-configuration with disordered occupation numbers of its lower energy sub-level pair. The description combines complete integrability and stochastic dynamics. For the single-soliton pulse, we derive the statistics of the electric-field polarization ellipse at a given point along the medium in closed form. If the average initial population difference of the two lower sub-levels vanishes, we show that the pulse polarization will switch intermittently between the two circular polarizations as it travels along the medium. If this difference does not vanish, the pulse will eventually forever remain in the circular polarization determined by which sub-level is more occupied on average. We also derive the exact expressions for the statistics of the polarization-switching dynamics, such as the probability distribution of the distance between two consecutive switches and the percentage of the distance along the medium the pulse spends in the elliptical polarization of a given orientation in the case of vanishing average initial population difference. We find that the latter distribution is given in terms of the well-known arcsine law

Foliations of Isonergy Surfaces and Singularities of Curves

It is well known that changes in the Liouville foliations of the isoenergy surfaces of an integrable system imply that the bifurcation set has singularities at the corresponding energy level. We formulate certain genericity assumptions for two degrees of freedom integrable systems and we prove the opposite statement: the essential critical points of the bifurcation set appear only if the Liouville foliations of the isoenergy surfaces change at the corresponding energy levels. Along the proof, we give full classification of the structure of the isoenergy surfaces near the critical set under our genericity assumptions and we give their complete list using Fomenko graphs. This may be viewed as a step towards completing the Smale program for relating the energy surfaces foliation structure to singularities of the momentum mappings for non-degenerate integrable two degrees of freedom systems.Comment: 30 pages, 19 figure

The selective oxidation of cyclohexane via In-situ H2O2 production over supported Pd-based catalysts

The oxidation of cyclohexane via the in-situ production of H2O2 from molecular H2 and O2 offers an attractive route to the current industrial means of producing cyclohexanone and cyclohexanol (KA oil), key materials in the production of Nylon. The in-situ route has the potential to overcome the significant economic and environmental concerns associated with the use of commercial H2O2, while also allowing for the use of far lower reaction temperatures than those typical of the purely aerobic route to KA oil. Herein we demonstrate the efficacy of a series of bi-functional Pd-based catalysts, which offer appreciable concentrations of KA oil, under conditions where limited activity is observed using O2 alone. In particular the introduction of V into a supported Pd catalyst is seen to improve KA oil concentration by an order of magnitude, compared to the Pd-only analogue. In particular we ascribe this improvement in catalytic performance to the development of Pd domains of mixed oxidation state upon V incorporation as evidenced through X-ray photoelectron spectroscopy

Cys-Ph-TAHA: a lanthanide binding tag for RDC and PCS enhanced protein NMR

Here we present Cys-Ph-TAHA, a new nonadentate lanthanide tag for the paramagnetic labelling of proteins. The tag can be easily synthesized and is stereochemically homogenous over a wide range of temperatures, yielding NMR spectra with a single set of peaks. Bound to ubiquitin, it induced large residual dipolar couplings and pseudocontact shifts that could be measured easily and agreed very well with the protein structure. We show that Cys-Ph-TAHA can be used to label large proteins that are biochemically challenging such as the Lac repressor in a 90 kDa ternary complex with DNA and inducer

A comparative study of palladium-gold and palladium-tin catalysts in the direct synthesis of H2O2

Herein we evaluate the promotive effect of Au and Sn incorporation into supported Pd nanoparticles for the direct synthesis of H2O2 from molecular H2 and O2. The introduction of both secondary metal modifiers was found to result in a significant enhancement in catalytic performance, although, in the case of the PdSn system, it was identified that relatively large quantities of the secondary metal were required to rival the activity observed over optimal Au-containing formulations, with the 0.25%Pd–2.25%Sn/TiO2 catalyst offering comparable H2O2 synthesis rates to the optimised 0.25%Pd–0.25%Au/TiO2 formulation. The introduction of Sn was found to considerably improve Pd dispersion, correlating with an improvement in selective H2 utilisation. Notably, the optimal PdSn catalyst identified in this work achieves superior H2O2 selectivities compared to the PdAu analogue and is able to rival the performance of state-of-the-art materials

Sferična kristalizacija zdravilnih učinkovin

Spherical crystallization of drugs is the process of obtaining larger particles by agglomeration during crystallization. The most common techniques used to obtain such particles are spherical agglomeration and quasi-emulsion solvent diffusion. Ammonia diffusion systems and crystallo-co-agglomeration are extensions of these techniques. By controlling process parameters during crystallization, such as temperature, stirring rate, type and amount of solvents, or excipient selection, it is possible to control the formation of agglomerates and obtain spherical particles of the desired size, porosity, or hardness. Researchers have reported that the particles produced have improved micromeritic, physical, and mechanical properties, which make them suitable for direct compression. In some cases, when additional excipients are incorporated during spherical crystallization, biopharmaceutical parameters including the bioavailability of drugs can also be tailored.Sferična kristalizacija je postopek izdelave večjih delcev z aglomeracijo manjših med samo kristalizacijo. Najpogosteje uporabljeni tehniki za izdelavo takšnih delcev sta sferična aglomeracija in kvaziemulzija z difuzijo topila. Sistem z difuzijo amoniaka in kristalo-ko-aglomeracija sta razširitvi teh dveh metod. Z nadzorovanjem procesnih parametrov med kristalizacijo, kot sta temperatura in hitrost mešanja, z izbiro lastnosti in množine topil ter z izbiro pomožnih snovi, lahko vplivamo na nastanek aglomeratov in izdelamo sferične delce želenih velikosti, primerne poroznosti ali trdote. Raziskovalci poročajo, da imajo izdelani delci izboljšane pretočne lastnosti, izboljšane druge fizikalne in mehanske lastnosti zaradi česar so primerni za direktno tabletiranje. V nekaterih primerih lahko ob vgradnji ustreznih pomožnih snovi, ki jih dodamo med procesom sferične kristalizacije, izboljšamo tudi biofarmacevtske lastnosti zdravilnih učinkovin vključno s povečanjem biološke uporabnosti