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The interpretation of Rydberg spectra of gaseous dimethylpiperidine (DMP) as showing the co-existence of a localized and delocalized mixed-valent DMP+ radical cation has generated a controversial discussion about the performance of various electronic-structure methods. We revisit this discussion by high-level computations. An apparent barrier separating localized and delocalized DMP+ minima at MRCI+Q and a few other levels reflects unphysical curve crossings of the reference wave functions. These discontinuities on the surface are removed in state-averaged MRCI+Q calculations, as well as at IP-EOM-CCSD or CCSD(T) levels. This has prompted a high-level computational study of the actually observed Rydberg state of neutral DMP. Indeed, the 3s-type Rydberg electron binds more strongly to a localized rather than to a delocalized positive charge distribution. This stabilizes the localized structure to the extent where it becomes a local minimum for the DMP∗ Rydberg state, in contrast to DMP+, explaining the experimental observations. This appears to be the first case where interactions of a Rydberg electron with the underlying cationic core alter molecular structure in such a fundamental way.

Erworben im Rahmen der Schweizer Nationallizenzen (http://www.nationallizenzen.ch) The quantitative assessment of lymphatic dermal clearance using NIR fluorescent tracers is particularly important for the early diagnosis of several potential disabling diseases. Currently, half-life values are computed using a mono-exponential mathematical model, neglecting diffusion of the tracer within the dermis after injection. The size and position of the region of interest are subjectively manually selected around the point of injection on the skin surface where the fluorescence signal intensity is averaged, neglecting any spatial information contained in the image. In this study we present and test a novel mathematical model allowing the objective quantification of dermal clearance, taking into consideration potential dermal diffusion. With only two parameters, this “clearance-diffusion” model is simple enough to be applied in a variety of settings and requires almost no prior information about the system. We demonstrate that if dermal diffusion is low, the mono-exponential approach is suitable but still lacking objectivity. However, if dermal diffusion is substantial, the clearance-diffusion model is superior and allows the accurate calculation of half-life values.

This manuscript presents an extendable set of complex auditory-visual scenes for hearing research that allow for ecologically valid testing in realistic scenes while also supporting reproducibility and comparability of scientific results., This work was supported by the DFG Collaborative Research Centre SFB 1330 Hearing Acoustics (HAPPAA), projects B1, C2, C4, and C5

For 6-DOF (degrees of freedom) interactive virtual acoustic environments (VAEs), the spatial rendering of diffuse late reverberation in addition to early (specular) reflections is important. In the interest of computational efficiency, the acoustic simulation of the late reverberation can be simplified by using a limited number of spatially distributed virtual reverb sources (VRS) each radiating incoherent signals. A sufficient number of VRS is needed to approximate spatially anisotropic late reverberation, e.g., in a room with inhomogeneous distribution of absorption at the boundaries. Here, a highly efficient and perceptually plausible method to generate and spatially render late reverberation is suggested, extending the room acoustics simulator RAZR [Wendt et al., J. Audio Eng. Soc., 62, 11 (2014)]. The room dimensions and frequency-dependent absorption coefficients at the wall boundaries are used to determine the parameters of a physically-based feedback delay network (FDN) to generate the incoherent VRS signals. The VRS are spatially distributed around the listener with weighting factors representing the spatially subsampled distribution of absorption coefficients on the wall boundaries. The minimum number of VRS required to be perceptually distinguishable from the maximum (reference) number of 96 VRS was assessed in a listening test conducted with a spherical loudspeaker array within an anechoic room. For the resulting low numbers of VRS suited for spatial rendering, optimal physically-based parameter choices for the FDN are discussed., submitted to the I3DA 2021 International Conference(IEEE Xplore Digital Library). arXiv admin note: text overlap with arXiv:2106.15888

© 2021 IEEE. Personal use of this material is permitted. Permission from IEEE must be obtained for all other uses, in any current or future media, including reprinting/republishing this material for advertising or promotional purposes, creating new collective works, for resale or redistribution to servers or lists, or reuse of any copyrighted component of this work in other works., The evaluation of the skin thermal properties is relevant for many applications ranging from clinical dermatology to cosmetology. We introduce a simple passive device, capable of rapidly measuring skin thermal parameters using transient surface temperature measurements. Thanks to the development of an analytic thermodynamic skin model, tissue thermal diffusivity can be extracted from experimental data. For validation purposes, the thermal response of the apparatus has been modelled using a layered finite-element 3D model of the skin in thermal contact with a metallic measuring tip. Simplified 1D analytical and semi-analytical models have also been developed with the intent of modelling the thermal properties of the skin surface. The simplified models can be used to fit the thermal response measured by the device and to extract the thermal diffusivity in real time.

Poly(ethylene oxide) (PEO) based electrolytes are of great importance for applications in electrochemical devices. Since their ion conductivity is severely hampered by crystallization, several approaches are carried out to enhance the low temperature ion conductivity of PEO such as the addition of polar solvents or the synthesis of more complex polymer architectures. In this study, solvent-like defects are introduced in the center of the PEO chain to reduce its crystallinity with the aim to enhance ion conductivity. The ion conductivities of four polymer electrolytes, containing either a 1,4-disubstituted 1,2,3-triazole (TR) or ortho-, meta- or para-disubstituted benzene defects are measured by impedance spectroscopy after addition of lithium perchlorate (LiClO4, EO:Li = 50:1) to the polymer. The TR containing sample shows a 15 to 700 times higher ion conductivity at T = − 10 °C as compared to the benzene containing PEOs with different substitution pattern. This can be explained by the lower glass transition temperature of the TR containing electrolytes compared to the benzene containing electrolytes. Furthermore, the dependence of the ion conductivity on the LiClO4 concentration in the melt at T = 70 °C is studied for TR containing electrolytes and compared to the respective defect free PEO22 electrolytes. The electrolytes with the TR defect have higher conductivities in the concentration range (50:1 ≥ EO:Li ≥ 8:1) compared to the uninterrupted PEO22 revealing that the incorporation of a solvent-like defect with high dielectric constant into a PEO chain is an effective strategy to enhance the ion conductivity of PEO electrolytes. This is also supported by 7Li NMR spectroscopy showing that LiClO4 is soluble 1,2,3-triazole but insoluble in benzene. Additionally, 1,2,3-triazoles can also coordinate Li+-ions and, thus, actively contribute to the transport of the Li+-ions.

The partly halogenated and N-alkylated closo-dodecaborates [B12Cl6H5N(propyl)3]− and [B12Br6H5NR3]− (R = ethyl–pentyl) were prepared by alkylation of [B12H11NH3]− and subsequent halogenation with elemental chlorine or N-bromosuccinimide. Simple metathesis reactions yielded the [HNMe3]+, [C6mim]+, [NBu4]+, and Na+ salts, which were characterized by heteronuclear NMR and IR spectroscopy as well as electrospray ionization mass spectrometry. The crystal structures of the salts [HNMe3][B12Br6H5N(ethyl)3]·CH3CN, [HNMe3][B12Br6H5N(propyl)3], Na[B12Br6H5N(butyl)3], and [HNMe3][B12Cl7H4N(propyl)3]·CH3CN were determined by single-crystal X-ray diffraction. The [C6mim]+ salts are thermally stable to temperatures higher than 300 °C. The melting points are between 57 and 80 °C, which classify the [C6mim]+ salts of [B12Cl6H5N(propyl)3]− and [B12Br6H5NR3]− (R = propyl–pentyl) as ionic liquids. The anions are oxidized only at potentials higher than 2 V versus Fc0/+ as determined by cyclic voltammetry. The solubility of t...

Effectively parallelizing SAT solving is an open andimportant issue. The current state-of-the-art isbased on parallel portfolios. This technique relieson running multiple solvers on the same instance inparallel. As soon one instance finishes the entirerun stops. Several succesful systems even use plainparallel portfolio (PPP), where the individual solversdo not exchange any information. This paper containsa thorough experimental evaluation which shows that PPPcan improve wall-clock running time because memory accessis still local, respectively the memory system can hidethe latency of memory access. In particular, there doesnot seem as much cache congestion as one might imagine.We also present some limits on the scalibility of PPP.Thus this paper gives one argument why PPP solvers are agood fit for todays multi-core architectures.

Halogenated and alkoxylated closo-dodecaborates [B12X11OR](2-) (X = Cl, Br; R = propyl, octyl, dodecyl) have been synthesized by halogenation of the known [B12H11OH](2-) anion followed by alkylation in the superbasic medium DMSO/KOH. The obtained sodium salts were transformed by simple metathesis reactions in aqueous solution to the tetrabutylammonium ([NBu4](+)) and 1-hexyl-3-methylimidazolium ([C6mim](+)) salts. All compounds were fully characterized by heteronuclear NMR, IR and Raman spectroscopy, ESI mass spectrometry, and thermal analytical measurements. Selected anions were also structurally characterized as their [Ph4P](+) salts by single crystal X-ray diffraction. The [C6mim](+) salts are thermally stable up to more than 300 °C and show clear melting points. Surprisingly, the compound [C6mim]2[B12Cl11O-propyl] having the short propyl group bound to the boron cluster shows the lowest melting point (96 °C) of all the investigated compounds. Thus this compound is a rare member of the class of ionic liquids consisting of dianions.

In models of ischemic stroke, TTC (2,3,5-triphenyltetrazolium chloride) staining is commonly applied for the fast and reliable visualization of hypoxic brain tissue and for defining the size of cerebral infarction and penumbra. Deciphering molecular processes of pathogenesis within the penumbra is of particular interest for the development of therapeutic strategies. The aim of this study was to assess whether TTC-stained tissues can easily and in a reliable quantitative manner be processed for further molecular and biochemical analyses. We applied phenol-based RNA isolation, protein lysis by conventional RIPA buffer, and combined RNA/protein isolation with NucleoSpinRNA/Protein-Kit. Gene and protein expression analyses were performed by RT-rtPCR and Western-blotting. Middle cerebral arteria occlusion (MCAO) in rats was performed following a standardized experimental procedure. After MCAO, TTC staining revealed massive cell death in cortical and sub-cortical areas. TTC processing did not affect the quality of tissue RNA and protein. The expression of housekeeping and regulatory genes and proteins revealed no difference between control and TTC-stained groups. The expression of known stroke-regulated genes such as TNFalpha and IL1beta revealed similar induction profiles after TTC staining as described in the literature. TTC staining allows the precise delineation of lesioned and primarily non-lesioned brain areas for subsequent dissection of selected tissue pieces for molecular analysis. Our study demonstrates that TTC-stained tissues in stroke animal models can be used for quantitative gene and protein expression analyses without constriction. Pathomechanisms of ongoing tissue damage within the penumbra region can now be investigated in detail.

Within the complex signalling network from pathogen-derived elicitor perception to defense-related gene activation, some immediate-early responding genes may have pivotal roles in downstream transcriptional regulation. We have identified the parsley (Petroselinum crispum) ELI17 gene as a particularly fast-responding gene possessing a new type of W box-containing, elicitor-responsive promoter element, E17. Highly selective E17-mediated reporter gene expression at pathogen infection sites in transgenic Arabidopsis thaliana plants demonstrated the potential of this promoter element for designing new strategies in resistance breeding as well as for further analysis of the early components of defense-related gene activation mechanisms. The protein encoded by the ELI17 gene exhibits various structural characteristics of established transcription factors and is designated as a CMPG protein according to the first four strictly conserved amino acids defining a newly emerging class of plant-specific proteins.

SUMMARY In parsley ( Petroselinum crispum ), members of the ELI7 gene family were rapidly transcriptionally activated following treatment with an elicitor derived from the phytopathogen Phytophthora sojae . Several cDNA and genomic ELI7 clones were isolated. The deduced amino acid sequences revealed close similarity to fatty acid desaturases/hydroxylases, however, the precise functions are still unknown. Analysis of the promoters of two strongly elicitor-induced family members, ELI7.1 and ELI7.2 , allowed us to functionally pinpoint a novel, independently acting regulatory region (S box), the only major sequence similarity between the two gene promoters. In situ RNA / RNA hybridization using an ELI7.1 gene-specific probe demonstrated that expression of this gene is rapidly and locally induced around infection sites in planta as well.

Treatment of cultured parsley cells (Petroselinum crispum) with fungal elicitor caused large increases in the activities of chitinase and 1,3-beta-glucanase. Chitinase activity accumulated predominantly in the culture medium, whereas 1,3-beta-glucanase activity was located almost exclusively intracellularly. Extracellular chitinase activity was resolved into six different isoenzymes, all of which were purified and characterized. All six isoforms were acidic proteins (pI 3.8-5.3), with molecular mass 30-38 kDa. Four were exochitinases and two were endochitinases. The most abundant isoform also showed lysozyme activity. Three of the exochitinases were glycoproteins and two of these were reactive with an antiserum specific for xylose in complex glycosidic structures. The exochitinases constituted relatively small proportions of the total chitinase activity and may serve a different function in cellular metabolism compared to the more abundant endochitinases.

Cell-free DNA is of increasing interest in different fields, such as cancer research, prenatal diagnosis, and the diagnosis of nonmalignant diseases. The quantity of free-circulating DNA in plasma, serum, and other body fluids is usually low and its isolation is still a challenge. Here we evaluate the application of the new commercially available NucleoSpin Plasma XS Kit for the isolation of cell-free DNA from plasma, serum, and cell-free bronchial lavage samples. The NucleoSpin columns proved superior to the QIAamp system in terms of DNA yield, purity, and retrieval of small DNA fragments. The procedure is fast and easy to standardize and might be valuable for laboratories working in the field of CNAPS.

Treatment of cultured parsley (Petroselinum crispum L.) cells with a structurally defined peptide elicitor (Pep25) of fungal origin has previously been shown to cause rapid and large changes in the levels of various desaturated fatty acids. We isolated two distinct parsley cDNAs sharing high sequence similarity with microsomal [omega]-6 fatty acid desaturases (FADs). One of them was functionally identified as a [delta]12 FAD by expression in the yeast Saccharomyces cerevisiae. Two dienoic fatty acids, hexadecadienoic and linoleic, which were not detectable in control cells, together constituted up to 12% of the total fatty acids in the transformed yeast cells. [delta]12 FAD mRNA accumulated rapidly and transiently in elicitor-treated parsley cells, protoplasts, and leaves. These and previous results indicate that fatty acid desaturation is an important early component of the complex defense response of parsley to attempted fungal infection.

The UML Profile for Modeling and Analysis of Real-Time and Embedded (MARTE) systems has recently been adopted by the OMG. Its Time Model extends the informal and simplistic Simple Time package proposed by UML2 and offers a broad range of capabilities required to model real-time systems including discrete/dense and chronometric/logical time. MARTE OMG specification introduces a Time Structure inspired by Time models of the concurrency theory and proposes a new clock constraint specification language (CCSL) to specify, within the context of UML, logical and chronometric time constraints. This paper introduces the formal semantics of a fundamental subset of CCSL clock constraints and proposes a process to use CCSL both as a high-level specification language for UML models and as a golden model to verify the conformance of implementations with the specification. A digital filtering video application is used as a running example to support the discussion. The application is first formally specified with CCSL and the specification is refined based on feedback from our CCSL-dedicated simulator. In a second phase, an Esterel program of the application is considered. This program is instrumented with observers derived from the CCSL specification. Esterel Studio formal verification facilities are then used to check the conformity of the Esterel implementation with the CCSL specification. A specific library of Esterel observers has been built for this purpose.