NMR-spektroskopische Untersuchung der Reaktion von 3-Aminopropyltriethoxysilan mit Kieselsäurelösungen

29Si- und 14N-NMR-Untersuchungen der Reaktion von Aminopropyltriethoxysilan (APTS) und Kieselsäure (KS) in sauren wäßrigen Lösungen (Molverhältnis APTS/KS = 1:1, CSiO2 = 0,45 M; pH = 2,3) zeigen, daß durch APTS die Kondensationsreaktionen der KS stark verlangsamt werden. Als Ursachen werden partielle Kondensationsreaktionen des APTS mit der KS und das Vorliegen von NH3+-OSi Bindungen diskutiert. Durch die Dominanz von NH3+ gegenüber NH2-Gruppen bis pH 10,1 liegen auch in neutralen und schwach basischen APTS/KS-Lösungen kondensationsbeständige Kieselsäuren bzw. Silicatanionen vor. Durch Konzentrieren der APTS/KS-Lösungen sind kieselsäurereiche, wasserlösliche Feststoffe darstellbar

Numerical framework for transcritical real-fluid reacting flow simulations using the flamelet progress variable approach

An extension to the classical FPV model is developed for transcritical real-fluid combustion simulations in the context of finite volume, fully compressible, explicit solvers. A double-flux model is developed for transcritical flows to eliminate the spurious pressure oscillations. A hybrid scheme with entropy-stable flux correction is formulated to robustly represent large density ratios. The thermodynamics for ideal-gas values is modeled by a linearized specific heat ratio model. Parameters needed for the cubic EoS are pre-tabulated for the evaluation of departure functions and a quadratic expression is used to recover the attraction parameter. The novelty of the proposed approach lies in the ability to account for pressure and temperature variations from the baseline table. Cryogenic LOX/GH2 mixing and reacting cases are performed to demonstrate the capability of the proposed approach in multidimensional simulations. The proposed combustion model and numerical schemes are directly applicable for LES simulations of real applications under transcritical conditions.Comment: 55th AIAA Aerospace Sciences Meeting, Dallas, T

Synchronization of organ pipes: experimental observations and modeling

We report measurements on the synchronization properties of organ pipes. First, we investigate influence of an external acoustical signal from a loudspeaker on the sound of an organ pipe. Second, the mutual influence of two pipes with different pitch is analyzed. In analogy to the externally driven, or mutually coupled self-sustained oscillators, one observes a frequency locking, which can be explained by synchronization theory. Further, we measure the dependence of the frequency of the signals emitted by two mutually detuned pipes with varying distance between the pipes. The spectrum shows a broad ``hump'' structure, not found for coupled oscillators. This indicates a complex coupling of the two organ pipes leading to nonlinear beat phenomena.Comment: 24 pages, 10 Figures, fully revised, 4 big figures separate in jpeg format. accepted for Journal of the Acoustical Society of Americ

Unconventional carrier-mediated ferromagnetism above room temperature in ion-implanted (Ga, Mn)P:C

Ion implantation of Mn ions into hole-doped GaP has been used to induce ferromagnetic behavior above room temperature for optimized Mn concentrations near 3 at.%. The magnetism is suppressed when the Mn dose is increased or decreased away from the 3 at.% value, or when n-type GaP substrates are used. At low temperatures the saturated moment is on the order of one Bohr magneton, and the spin wave stiffness inferred from the Bloch-law T^3/2 dependence of the magnetization provides an estimate Tc = 385K of the Curie temperature that exceeds the experimental value, Tc = 270K. The presence of ferromagnetic clusters and hysteresis to temperatures of at least 330K is attributed to disorder and proximity to a metal-insulating transition.Comment: 4 pages, 4 figures (RevTex4

On the interaction of vortices with mixing layers

We describe the perturbations introduced by two counter-rotating vortices - in a two-dimensional configuration - or by a vortex ring - in an axisymmetric configuration - to the mixing layer between two counterflowing gaseous fuel and air streams of the same density. The analysis is confined to the near stagnation point region, where the strain rate of the unperturbed velocity field, A0, is uniform. We restrict our attention to cases where the typical distance 2r0 between the vortices - or the characteristic vortex ring radius r0 - is large compared to both the thickness, δv, of the vorticity core and the thickness, δm∼(ν/A0)1/2, of the mixing layer. In addition, we consider that the ratio, Γ/ν, of the vortex circulation, Γ, to the kinematic viscosity, ν, is large compared to unity. Then, during the interaction time, A0,-1, the viscous and diffusion effects are confined to the thin vorticity core and the thin mixing layer, which, when seen with the scale r0, appears as a passive interface between the two counterflowing streams when they have the same density. In this case, the analysis provides a simple procedure to describe the displacement and distortion of the interface, as well as the time evolution of the strain rate imposed on the mixing layer, which are needed to calculate the inner structure of the reacting mixing layer as well as the conditions for diffusion flame extinction and edge-flame propagation along the mixing layer. Although in the reacting case variable density effects due to heat release play an important role inside the mixing layer, in this paper the analysis of the inner structure is carried out using the constant density model, which provides good qualitative understanding of the mixing layer response

A CRISPR-Cas9-engineered mouse model for GPI-anchor deficiency mirrors human phenotypes and exhibits hippocampal synaptic dysfunctions

Pathogenic germline mutations in PIGV lead to glycosylphosphatidylinositol biosynthesis deficiency (GPIBD). Individuals with pathogenic biallelic mutations in genes of the glycosylphosphatidylinositol (GPI)-anchor pathway exhibit cognitive impairments, motor delay, and often epilepsy. Thus far, the pathophysiology underlying the disease remains unclear, and suitable rodent models that mirror all symptoms observed in human patients have not been available. Therefore, we used CRISPR-Cas9 to introduce the most prevalent hypomorphic missense mutation in European patients, Pigv:c.1022C > A (p.A341E), at a site that is conserved in mice. Mirroring the human pathology, mutant Pigv(341E) mice exhibited deficits in motor coordination, cognitive impairments, and alterations in sociability and sleep patterns, as well as increased seizure susceptibility. Furthermore, immunohistochemistry revealed reduced synaptophysin immunoreactivity in Pigv(341E) mice, and electrophysiology recordings showed decreased hippocampal synaptic transmission that could underlie impaired memory formation. In single-cell RNA sequencing, Pigv(341E)-hippocampal cells exhibited changes in gene expression, most prominently in a subtype of microglia and subicular neurons. A significant reduction in Abl1 transcript levels in several cell clusters suggested a link to the signaling pathway of GPI-anchored ephrins. We also observed elevated levels of Hdc transcripts, which might affect histamine metabolism with consequences for circadian rhythm. This mouse model will not only open the doors to further investigation into the pathophysiology of GPIBD, but will also deepen our understanding of the role of GPI-anchor–related pathways in brain development

The Leucine Zipper Domains of the Transcription Factors GCN4 and c-Jun Have Ribonuclease Activity

Basic-region leucine zipper (bZIP) proteins are one of the largest transcription factor families that regulate a wide range of cellular functions. Owing to the stability of their coiled coil structure leucine zipper (LZ) domains of bZIP factors are widely employed as dimerization motifs in protein engineering studies. In the course of one such study, the X-ray structure of the retro-version of the LZ moiety of yeast transcriptional activator GCN4 suggested that this retro-LZ may have ribonuclease activity. Here we show that not only the retro-LZ but also the authentic LZ of GCN4 has weak but distinct ribonuclease activity. The observed cleavage of RNA is unspecific, it is not suppressed by the ribonuclease A inhibitor RNasin and involves the breakage of 3′,5′-phosphodiester bonds with formation of 2′,3′-cyclic phosphates as the final products as demonstrated by HPLC/electrospray ionization mass spectrometry. Several mutants of the GCN4 leucine zipper are catalytically inactive, providing important negative controls and unequivocally associating the enzymatic activity with the peptide under study. The leucine zipper moiety of the human factor c-Jun as well as the entire c-Jun protein are also shown to catalyze degradation of RNA. The presented data, which was obtained in the test-tube experiments, adds GCN4 and c-Jun to the pool of proteins with multiple functions (also known as moonlighting proteins). If expressed in vivo, the endoribonuclease activity of these bZIP-containing factors may represent a direct coupling between transcription activation and controlled RNA turnover. As an additional result of this work, the retro-leucine zipper of GCN4 can be added to the list of functional retro-peptides