Structural Properties, Order-Disorder Phenomena and Phase Stability of Orotic Acid Crystal Forms

Orotic acid (OTA) is reported to exist in the anhydrous (AH), monohydrate (Hy1) and dimethylsulfoxide monosolvate (SDMSO) forms. In this study we investigate the (de)hydration/desolvation behavior, aiming at an understanding of the elusive structural features of anhydrous OTA by a combination of experimental and computational techniques, namely, thermal analytical methods, gravimetric moisture (de)sorption studies, water activity measurements, X-ray powder diffraction, spectroscopy (vibrational, solid-state NMR), crystal energy landscape and chemical shift calculations. The Hy1 is a highly stable hydrate, which dissociates above 135°C and loses only a small part of the water when stored over desiccants (25°C) for more than one year. In Hy1, orotic acid and water molecules are linked by strong hydrogen bonds in nearly perfectly planar arranged stacked layers. The layers are spaced by 3.1 Å and not linked via hydrogen-bonds. Upon dehydration the X-ray powder diffraction and solid-state NMR peaks become broader indicating some disorder in the anhydrous form. The Hy1 stacking reflection (122) is maintained, suggesting that the OTA molecules are still arranged in stacked layers in the dehydration product. Desolvation of SDMSO, a non-layer structure, results in the same AH phase as observed upon dehydrating Hy1. Depending on the desolvation conditions different levels of order-disorder of layers present in anhydrous OTA are observed, which is also suggested by the computed low energy crystal structures. These structures provide models for stacking faults as intergrowth of different layers is possible. The variability in anhydrate crystals is of practical concern as it affects the moisture dependent stability of AH with respect to hydration

Multidecadal Signal of Solar Variability in the Upper Troposphere During the 20th Century

Studies based on data from the past 25-45 years show that irradiance changes related to the 11-yr solar cycle affect the circulation of the upper troposphere in the subtropics and midlatitudes. The signal has been interpreted as a northward displacement of the subtropical jet and the Ferrel cell with increasing solar irradiance. In model studies on the 11-yr solar signal this could be related to a weakening and at the same time broadening of the Hadley circulation initiated by stratospheric ozone anomalies. Other studies, focusing on the direct thermal effect at the Earth's surface on multidecadal scales, suggest a strengthening of the Hadley circulation induced by an increased equator-to-pole temperature gradient. In this paper we analyse the solar signal in the upper troposphere since 1922, using statistical reconstructions based on historical upper-air data. This allows us to address the multidecadal variability of solar irradiance, which was supposedly large in the first part of the 20th century. Using a simple regression model we find a consistent signal on the 11-yr time scale which fits well with studies based on later data. We also find a significant multidecadal signal that is similar to the 11-yr signal, but somewhat stronger. We interpret this signal as a poleward shift of the subtropical jet and the Ferrel cell. Comparing the magnitude of the two signals could provide important information on the feedback mechanisms involved in the solar climate relationship with respect to the Hadley and Ferrel circulations. However, in view of the uncertainty in the solar irradiance reconstructions, such interpretations are not currently possibl

Psychophysical investigation of facial expressions using computer animated faces

The human face is capable of producing a large variety of facial expressions that supply important information for communication. As was shown in previous studies using unmanipulated video sequences, movements of single regions like mouth, eyes, and eyebrows as well as rigid head motion play a decisive role in the recognition of conversational facial expressions. Here, flexible but at the same time realistic computer animated faces were used to investigate the spatiotemporal coaction of facial movements systematically. For three psychophysical experiments, spatiotemporal properties were manipulated in a highly controlled manner. First, single regions (mouth, eyes, and eyebrows) of a computer animated face performing seven basic facial expressions were selected. These single regions, as well as combinations of these regions, were animated for each of the seven chosen facial expressions. Participants were then asked to recognize these animated expressions in the experiments. The findings show that the animated avatar in general is a useful tool for the investigation of facial expressions, although improvements have to be made to reach a higher recognition accuracy of certain expressions. Furthermore, the results shed light on the importance and interplay of individual facial regions for recognition. With this knowledge the perceptual quality of computer animations can be improved in order to reach a higher level of realism and effectiveness

Plasma polymerization for biomedical applications: A review

Plasma polymers have long been of interest as thin film coatings on biomedical devices and products, to generate desirable surface properties for favorable bio-interfacial interactions. Plasma polymers have also been used as platforms for the covalent immobilization of bioactive molecules. More recently, additional aspects have been investigated, such as selective prevention of adhesion of microbial pathogens, either via plasma polymers per se or including antimicrobial drugs. Plasma polymers have also been investigated for the release of silver ions and small organic molecules. Complementing low-pressure plasma approaches, processes at atmospheric pressure have attracted interest recently, including for nano/biocomposite coatings. This contribution reviews the use of plasma polymers for intended biomedical applications, with a focus on more recent topic areas

RF switch positioner for communications satellite network

The RF switch positioner is a simple, lightweight, redundant positioning mechanism used to reconfigure the antenna beam on the INTELSAT VI satellite. It simultaneously rotates approximately 100 squareax waveguide switches through a full 360 deg. The RF switch positioner has been space qualified and has performed to expectations in conjunction with the feed networks in range testing

High performance p-type organic thin film transistors with an intrinsically photopatternable, ultrathin polymer dielectric layer

AbstractA high-performing bottom-gate top-contact pentacene-based oTFT technology with an ultrathin (25–48nm) and electrically dense photopatternable polymeric gate dielectric layer is reported. The photosensitive polymer poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) is patterned directly by UV-exposure (λ=254nm) at a dose typical for conventionally used negative photoresists without the need for any additional photoinitiator. The polymer itself undergoes a photo-Fries rearrangement reaction under UV illumination, which is accompanied by a selective cross-linking of the macromolecules, leading to a change in solubility in organic solvents. This crosslinking reaction and the negative photoresist behavior are investigated by means of sol–gel analysis. The resulting transistors show a field-effect mobility up to 0.8cm2V−1s−1 at an operation voltage as low as −4.5V. The ultra-low subthreshold swing in the order of 0.1Vdec−1 as well as the completely hysteresis-free transistor characteristics are indicating a very low interface trap density. It can be shown that the device performance is completely stable upon UV-irradiation and development according to a very robust chemical rearrangement. The excellent interface properties, the high stability and the small thickness make the PNDPE gate dielectric a promising candidate for fast organic electronic circuits

Promiscuous hydrogen in polymerising plasmas

Historically, there have been two opposing views regarding deposition mechanisms in plasma polymerisation, radical growth and direct ion deposition, with neither being able to fully explain the chemistry of the resultant coating. Deposition rate and film chemistry are dependent on the chemistry of the plasma phase and thus the activation mechanisms of species in the plasma are critical to understanding the relative contributions of various chemical and physical routes to plasma polymer formation. In this study, we investigate the roles that hydrogen plays in activating and deactivating reactive plasma species. Ethyl trimethylacetate (ETMA) is used as a representative organic precursor, and additional hydrogen is added to the plasma in the form of water and deuterium oxide. Optical emission spectroscopy confirms that atomic hydrogen is abundant in the plasma. Comparison of the plasma phase mass spectra of ETMA/H2O and ETMA/D2O reveals that (1) proton transfer from hydronium is a common route to charging precursors in plasma, and (2) hydrogen abstraction (activation) and recombination (deactivation) processes are much more dynamic in the plasma than previously thought. Consideration of the roles of hydrogen in plasma chemistry may then provide a more comprehensive view of deposition processes and bridge the divide between the two disparate schools of thought.Solmaz Saboohi, Hans J. Griesser, Bryan R. Coad, Robert D. Short and Andrew Michelmor

Antifungal coatings by caspofungin immobilization onto biomaterials surfaces via a plasma polymer interlayer

Published Online: 14 October 2015Not only bacteria but also fungal pathogens, particularly Candida species, can lead to biofilm infections on biomedical devices. By covalent grafting of the antifungal drug caspofungin, which targets the fungal cell wall, onto solid biomaterials, a surface layer can be created that might be able to provide long-term protection against fungal biofilm formation. Plasma polymerization of propionaldehyde (propanal) was used to deposit a thin (∼20 nm) interfacial bonding layer bearing aldehyde surface groups that can react with amine groups of caspofungin to form covalent interfacial bonds for immobilization. Surface analyses by x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry confirmed the intended grafting and uniformity of the coatings, and durability upon extended washing. Testing for fungal cell attachment and ensuing biofilm formation showed that caspofungin retained activity when covalently bound onto surfaces, disrupting colonizing Candida cells. Mammalian cytotoxicity studies using human primary fibroblasts indicated that the caspofungin-grafted surfaces were selective in eliminating fungal cells while allowing attachment and spreading of mammalian cells. These in vitro data suggest promise for use as antifungal coatings, for example, on catheters, and the use of a plasma polymer interlayer enables facile transfer of the coating method onto a wide variety of biomaterials and biomedical devices.Stefani S. Griesser, Marek Jasieniak, Bryan R. Coad, and Hans J. Griesse