Plasma Photocathodes

Plasma wakefield accelerators offer accelerating and focusing electric fields three to four orders of magnitude larger than state-of-the-art radiofrequency cavity-based accelerators. Plasma photocathodes can release ultracold electron populations within such plasma waves and thus open a path toward tunable production of well-defined, compact electron beams with normalized emittance and brightness many orders of magnitude better than state-of-the-art. Such beams will have far-reaching impact for applications such as light sources, but also open up new vistas on high energy and high field physics. This paper reviews the innovation of plasma photocathodes, and reports on the experimental progress, challenges, and future prospects of the approach. Details of the proof-of-concept demonstration of a plasma photocathode in 90° geometry at SLAC FACET within the E-210: Trojan Horse program are described. Using this experience, alongside theoretical and simulation-supported advances, an outlook is given on future realizations of plasma photocathodes such as the upcoming E-310: Trojan Horse-II program at FACET-II with prospects toward excellent witness beam parameter quality, tunability, and stability. Future installations of plasma photocathodes also at compact, hybrid plasma wakefield accelerators, will then boost capacities and open up novel capabilities for experiments at the forefront of interaction of high brightness electron and photon beams.     

Rheological characterization of coatings with regard to application and film formation

Summary The rheological properties and their functional dependencies, involved in the flow behavior of coatings during application and drying, are discussed. From the available rheometrical techniques a characterization of coatings is proposed, which reflects the most important rheological parameters with respect to the application process. This characterization includes measurement of (i) the change of viscosity during the drying period, (ii) the viscosity of the coating, ready for application, in the shear range from below 1 s^–1 to more than 10000 s^–1, (iii) the thixotropic recovery of viscosity at a shear rate below 1 s^–1 following shearing at a shear rate, where all structures are broken, or being at least 3 decades higher than the measuring rate, (iv) the stress relaxation from a low shear rate where relaxation times are largest or from a realistically high shear rate, and (v) the change in the composition of the material during drying in terms of evaporation.This characterization is found to be closely related to many of the different flow problems occurring in the application process. It may be extended more fully to elucidate specific problems, since the present characterization has been limited in order to make it a useful tool in routine work. For the same reason versatile rotational viscometers, normally used in coatings laboratories, are the most advanced instruments required for the characterization. This characterization, furthermore, is consistent with theoretical approaches to rheology, thereby giving access to an extension of the validity of the measurements on theoretical grounds and to use of extensive knowledge of how well-defined materials behave and interact in the design of coatings with a certain flow behavior. The framework of the characterization is found to be crucial in relating application process and rheology, whereas the specific measurements can be made in various ways.

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Zusammenfassung Die rheologischen Eigenschaften und ihre funktionellen Abhängigkeiten, welche das Fließverhalten von Anstrichstoffen während deren Applikation und Trocknung beeinflussen, werden besprochen. Mit Hilfe von gebräuchlichen rheometrischen Verfahren wird eine Charakterisierung von Anstrichstoffen vorgeschlagen, welche die wichtigsten rheologischen Parameter in Verbindung mit dem Applikationsprozeß berücksichtigt. Diese Charakterisierung umfaßt folgende Messungen: 1. Die scheinbare Viskosität während der Trocknung, 2. die Viskosität des Anstrichstoffes unmittelbar vor dessen Applikation, im Bereich von Schergeschwindigkeiten von unter 1 s^–1 bis über 10000 s^–1, 3. die thixotrope Rückbildung der Viskosität bei einer Schergeschwindigkeit unter 1 s^–1, gemessen nach Beendigung einer Scherbeanspruchung mit einer Geschwindigkeit, welche die gesamte Struktur aufzubrechen imstande war oder mindestens 3 Zehnerpotenzen höher liegt als die Meßgeschwindigkeit, 4. die Spannungsrelaxation, ausgehend von einer niedrigen Schergeschwindigkeit, wo die Relaxationszeiten am größten sind, oder von einer realistisch hohen Schergeschwindigkeit, und 5. die Veränderung des Materials während seiner Trocknung infolge Verdampfung seiner flüchtigen Anteile.Diese Charakterisierung wurde zu vielen verschiedenen Fließproblemen, wie sie während des Applikationsprozesses vorkommen, in enger Beziehung stehend gefunden. Sie könnte erweitert werden, um noch speziellere Probleme deuten zu können, doch ist die Charakterisierung als nützliches Hilfsmittel für Routinearbeiten begrenzt. Aus dem gleichen Grunde wurden für die Charakterisierung keine Instrumente vorgeschlagen, die komplizierter als Rotationsviskosimeter sind.Die vorliegende Charakterisierung ist in Übereinstimmung mit den theoretischen Grundlagen der Rheologie, so daß die Meßergebnisse auf theoretischer Basis verallgemeinert werden können. Für die Formulierung von Anstrichstoffen mit gemessenem Fließverhalten endlich können die Kenntnisse über Verhalten und Wechselwirkung theoretisch definierter Stoffe mit Nutzen angewandt werden.Der oben gegebene Charakterisierungsrahmen erwies sich als entscheidend für die Anwendbarkeit der Rheologie auf den Applikationsprozeß, die spezifischen Messungen hingegen können auf verschiedene Weise ausgeführt werden.

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Paper, presented at the Annual Conference of the Deutsche Rheologische Gesellschaft in Berlin, May 8–10, 1978.

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With 3 figures     

Single-camera Doppler global velocimetry based on frequency modulation techniques

The main advantage of the described Doppler global velocimeter (DGV) systems based on frequency modulation (FM) or frequency shift keying (FSK) is that no reference detector is required. The frequency variation of the laser light during one modulation period additionally allows an on-line calibration of the complete DGV system. Thus, the new method has the potential to reduce the uncertainty of conventional DGV velocity measurements since time resolved velocity field measurements on a spinning disc have shown standard deviations down to 0.02 m/s. On investigating flow fields, velocity components notably less than 0.5 m/s were resolved.     

A Gallium‐Substituted Distibene and an Antimony‐Analogue Bicyclo[1.1.0]butane: Synthesis and Solid‐State Structures

RGa {R=HC[C(Me)N(2,6‐iPr₂C₆H₃)]₂} reacts with Sb(NMe₂)₃ with insertion into the Sb? N bond and elimination of RGa(NMe₂)₂ ( 2 ), yielding the Ga‐substituted distibene R(Me₂N)GaSb?SbGa(NMe₂)R ( 1 ). Thermolysis of 1 proceeded with elimination of RGa and 2 and subsequent formation of the bicyclo[1.1.0]butane analogue [R(Me₂N)Ga]₂Sb₄ ( 3 ).     

CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation

Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained.     

Nickel‐Triad Complexes of a Side‐on Coordinating Distannene

NHC adducts of the stannylene Trip₂Sn (Trip=2,4,6‐triisopropylphenyl) were reacted with zero‐valent Ni, Pd, and Pt precursor complexes to cleanly yield the respective metal complexes featuring a three‐membered ring moiety Sn‐Sn‐M along with carbene transfer onto the metal and complete substitution of the starting ligands. Thus the easily accessible NHC adducts to stannylenes are shown to be valuable precursors for transition‐metal complexes with an unexpected Sn? Sn bond. The complexes have been studied by X‐ray diffraction and NMR spectroscopy as well as DFT calculations. The compounds featuring the structural motif of a distannametallacycle comprised of a [(NHC)₂M⁰] fragment and Sn₂Trip₄ represent rare higher congeners of the well‐known olefin complexes. DFT calculations indicate the presence of a π‐type Sn–Sn interaction in these first examples for acyclic distannenes symmetrically coordinating to a zero‐valent transition metal.     

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O2-tolerant NAD+-reducing [NiFe] hydrogenase

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD⁺-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H₂ conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by ⁵⁷Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD⁺-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective ¹³C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.     

In Situ FTIR Spectroscopy Study of the Photodegradation of Acetaldehyde and azo Dye Photobleaching on Bismuth‐Modified TiO2

The photocatalytic properties of bismuth‐modified titania were studied by photobleaching of two aqueous azo dyes solutions (Reactive Black 5 and Acid Orange 7), and by photoinduced decomposition (PID) of acetaldehyde using in situ FTIR spectroscopy. Low bismuth doping concentrations up to 3 at.% is shown to lead to an increased photobleaching rate of both azo dyes solutions. Too high Bi dopant concentrations lead to less developed crystallite nanoparticles and exhibit weaker adsorption capacity. Bismuth doping altered the adsorption kinetics of acetaldehyde resulting in different surface products, and a modified photocatalytic reaction pathway was inferred.     

Nitrogen uptake of nickel free austenitic stainless steel powder during heat treatment—an XPS study

In austenitic stainless steel nitrogen stabilizes the austenitic phase, improves the mechanical properties and increases the corrosion resistance. Nitrogen alloying enables to produce austenitic steels without the element nickel which is high priced and classified as allergy inducing. A novel production route is nitrogen alloying of CrMn‐prealloyed steel powder via the gas phase. This is beneficial as the nitrogen content can be adjusted above the amount that is reached during conventional casting. A problem which has to be overcome is the oxide layer present on the powder surface which impedes both the sintering process and the uptake of nitrogen. This study focuses on whether heat treatment under pure nitrogen is an appropriate procedure to enable sintering and nitrogen uptake by reduction of surface oxides. X‐ray photoelectron spectroscopy (XPS) in combination with scanning electron microscopy (SEM) and energy dispersive X‐ray spectrometry (EDS) are used to investigate the surface of powdered FeMn19Cr17C0.4N heat treated under nitrogen atmosphere. The analyses showed reduction of iron oxides already at 500 °C leading to oxide‐free metallic surface zones. Mn and Cr oxides are reduced at higher temperatures. Distinct nitrogen uptake was registered, and successful subsequent sintering was reached. Copyright © 2014 John Wiley & Sons, Ltd.     

Addressing a Common Misconception: Ammonium Acetate as Neutral pH “Buffer” for Native Electrospray Mass Spectrometry

Native ESI-MS involves the transfer of intact proteins and biomolecular complexes from solution into the gas phase. One potential pitfall is the occurrence of pH-induced changes that can affect the analyte while it is still surrounded by solvent. Most native ESI-MS studies employ neutral aqueous ammonium acetate solutions. It is a widely perpetuated misconception that ammonium acetate buffers the analyte solution at neutral pH. By definition, a buffer consists of a weak acid and its conjugate weak base. The buffering range covers the weak acid pK_a ± 1 pH unit. NH₄ ⁺ and CH₃-COO^? are not a conjugate acid/base pair, which means that they do not constitute a buffer at pH 7. Dissolution of ammonium acetate salt in water results in pH 7, but this pH is highly labile. Ammonium acetate does provide buffering around pH 4.75 (the pK_a of acetic acid) and around pH 9.25 (the pK_a of ammonium). This implies that neutral ammonium acetate solutions electrosprayed in positive ion mode will likely undergo acidification down to pH 4.75 ± 1 in the ESI plume. Ammonium acetate nonetheless remains a useful additive for native ESI-MS. It is a volatile electrolyte that can mimic the solvation properties experienced by proteins under physiological conditions. Also, a drop from pH 7 to around pH 4.75 is less dramatic than the acidification that would take place in pure water. It is hoped that the habit of referring to pH 7 solutions as ammonium acetate “buffer” will disappear from the literature. Ammonium acetate “solution” should be used instead.

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