Diese Arbeit wurde von der Natural Sciences and Engineering Research Council of Canada Ausrüstung, Entdeckung und Discovery Accelerator Grants zu JMBNRB ausgezeichnet unterstützt erkennt Unterstützung von der Carnegie Institution of Washington Post-Doc-Fellowship-Programm. Stephen Elardo auch vor dankte für seine Hilfe, um die Dreharbeiten mit der Kolben-Zylinder-Presse am Geophysical Lab.

Die Autoren haben nichts zu offenbaren.

Die Ergebnisse der Einbeziehung freie Experimente durchgeführt unter Verwendung der hier beschriebenen Protokolle wurden bereits mit Literaturdaten in Artikeln 29 (Os, Ir, Au), 30 (Re, Au) und 31 (Pt) verglichen. Pt ist sehr lehrreich in Den Nutzen des Einschlusses freien Lauf-Produkte. Für Experimente bei niedrigen f O 2 ausgeführt, Ertel et al. 48 zu einer stabilen Ursprung zugeordnet Einschlüsse und damit eingeschränkten Datenreduktion auf ...

Terrestrial Akkretion wird gedacht, um als eine Reihe von Kollisionen zwischen planetesimals mit chondritischen Massenzusammensetzung stattgefunden haben, endet in einem riesigen Schlagphase dachte Mond 1,2 Bildung verantwortlich. Erwärmung des Proto-Erde durch Stöße und dem Zerfall von kurzlebigen Isotopen war ausreichend, um umfangreiche Schmelzen und die Bildung einer Magmaozean oder Teichen, durch die dichten Fe-reichen metallischen Schmelzen steigen könnte verursachen. Bei Erreichen der Basis des Magmaozean, metallische Schmelzen Begegnung eine rheologische Grenze, stall, und final Metallsilikat Gleichgewicht, bevor er schließlich durch den Festmantel absteigend auf die wachsende Kern 2 zu unterziehen. Weitere chemische Kommunikation zwischen Metall und Silikatphasen als metallische Schmelze durchläuft der feste Teil des Mantels wird angenommen, dass ausgeschlossen werden kann aufgrund der großen Größe und rasante Abfahrt von Metall diapirs 3. Diese primäre Differenzierung der Erde in einen metallischen Kern und Silikat mant6 - le wird heute sowohl von geophysikalischen und geochemischen Beobachtungen 4 offenbart. Interpretation dieser Beobachtungen auf plausible Bedingungen für Metallsilikat-Gleichgewicht an der Basis eines Magmaozean zu erhalten, erfordert jedoch eine entsprechende Datenbank von Versuchsergebnissen. Die primitive oberen Mantels (PUM) ist eine hypothetische Reservoir, das die Silikatrest Kernbildung und seine Zusammensetzung spiegelt daher das Verhalten von Spurenelementen während der Metallsilikat Gleichgewicht. Spurenelemente werden zwischen Metall und Silikat schmilzt während der Kerntrennung auf der Basis ihrer Affinität geochemischen verteilt. Der Betrag eines Elemente Bevorzugung der Metallphase kann durch das Metallsilikat-Verteilungskoeffizienten beschrieben <img alt="Gleichung 1" src="/files/ftp_upload/52725/52725eq1.jpg" /><img alt="Gleichung 2" src="/files/ftp_upload/52725/52725eq2.jpg" /> (1) Wo <img alt="Gleichung 3" src="/files/ftp_upload/52725/52725eq3.jpg" /> und <img alt="Gleichung 4" src="/files/ftp_upload/52725/52725eq4.jpg" /> bezeichnen die Konzentration des Elementes i in Metall und Silikatschmelze auf. Werte <img alt="Gleichung 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> &gt; 1 zeigen siderophile (Eisen-liebenden) Verhalten und jene &lt;1 lithophile (rock-liebenden) Verhalten. Schätzungen der PUM Zusammensetzung zeigen, dass Elemente siderophile relativ Chondriten 7, in der Regel als Vertreter der Groß Zusammensetzung der Erde 6,8 als erschöpft. Dieser Abbau ist auf Sequestrierung von siderophile Elemente durch den Kern, und für feuerfeste Elemente seiner Größe sollte direkt Werte spiegeln <img alt="Gleichung 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> . Laborexperimente daher versuchen, Werte zu bestimmen <img alt="Gleichung 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> über einen range des Drucks (P), der Temperatur (T) und Sauerstofffugazität (f O 2) Bedingungen, die für die Trennung von Metall mit der Basis eines Magmas Ozean sind. Die Ergebnisse dieser Experimente können dann verwendet werden, um Regionen des P beschreiben - T - f O 2 Raum, der mit der PUM Fluss mehrerer siderophile Elemente kompatibel sind (beispielsweise 9-11). Die hohen Drücke und relevant für ein Magma Ozean Szenario Temperaturen können im Labor unter Verwendung entweder eines Kolben-Zylinder-oder mehrAmbossPresse neu erstellt werden. Die Kolben-Zylinder-Vorrichtung Zugriff auf mittlerem Druck (ca. 2 GPa) und hoher Temperatur (~ 2.573 K) Bedingungen, jedoch können große Probenvolumina und eine Vielzahl von Kapselmaterialien problemlos verwendet werden. Die rasche Abkühlgeschwindigkeit erlaubt auch Abschrecken einer Reihe von Silikatschmelzmassen zu einem Glas, damit strukturelle Auslegung der Einlauf Produkte vereinfacht.Die Mehr Amboßvorrichtung verwendet typischerweise kleiner Probenvolumina, aber mit geeigneten Montage Motive können Drücke bis zu ~ 27 GPa und Temperaturen von ca. 3.000 K. Die Verwendung dieser Verfahren zur Partitionierung für viele der mäßig erlaubt und leicht siderophile Elemente sein erreichen T Bedingungen - über einen großen Bereich von P gesammelt. Vorhersagen der PUM-Zusammensetzung auf der Basis dieser Daten lassen vermuten, Metallsilikat Gleichgewicht trat bei mittleren Druck und Temperaturbedingungen von über ~ 29 GPa und 3000 K sind, obwohl die genauen Werte sind modellabhängig. Um für die PUM Fülle von bestimmten Redox-sensitive Elemente berücksichtigen (zB V, Cr) der f O 2 wird auch angenommen, während Akkretion von ~ 4-2 log-Einheiten unter dem durch Koexistenz Eisen und Wüstit auferlegt entwickeln (FeO ) bei äquivalenten PT Bedingungen (die Eisen Wüstit Puffer) 12. Obwohl die PUM Fülle von mirgendwelche siderophile Elemente können durch Metall-Silikat Gleichgewicht an der Basis eines tiefen Ozean Magma berücksichtigt werden, hat es sich als schwierig erwiesen, zu beurteilen, ob diese Situation gilt auch für den am höchsten siderophile Elemente (HSES). Die extreme Affinität der HSES für Eisen-Metall, das durch Niederdruck (P ~ 0,1 MPa) und der Temperatur (T &lt;1.673 K) Experimente zeigten, schlägt die Silikaterde sollte stark in diesen Elementen erschöpft. Schätzungen der HSE Inhalte für PUM zeigen jedoch, nur eine mäßige Erschöpfung relativ zu Chondriten (Abbildung 1). Eine häufig postulierte Lösung des scheinbaren HSE Überschuss ist, dass die Erde erlebte eine spät Akkretion von chondritischen Material im Anschluss an Kernbildung 13. Dieses spätgetretenen Materie würde mit der PUM vermischt haben und erhöht HSE Konzentrationen, hatte aber einen vernachlässigbaren Effekt auf reichlicher Elemente. Alternativ wurde vorgeschlagen, dass die extrem siderophile Natur HSES durch niedrige P angedeutet </em&gt; - T Experimente nicht den hohen PT während der Kernbildung 14,15 gegenwärtigen Bedingungen fortbestehen. Um diese Hypothese zu testen, müssen Experimente durchgeführt, um die Löslichkeit und Metallsilikat Partitionierung HSES bei geeigneten Bedingungen zu bestimmen. Verunreinigung des Silikat Teil abgeschreckt Laufprodukte in vielen früheren Studien hat jedoch Vorfeld Produktanalyse kompliziert und verdeckt die wahren Verteilungskoeffizienten für HSES zwischen Metall und Silikatschmelzen. In Experimenten, bei denen die Teilungs HSES in Konzentrationen angemessen Natur vorhanden sind, die extreme Vorzug dieser Elemente von Fe-Metall verhindert ihre Messung in der Silikatschmelze. Um dieses Problem zu umgehen, werden die Löslichkeit Messungen vorgenommen, in dem die silikatische Schmelze in gesättigter HSE von Interesse und Werte <img alt="Gleichung 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> werden mit dem Formalismus der Borisov et berechnetal. 16. Abgeschreckt Silikat Laufprodukte aus HSE Löslichkeitsversuche bei reduzierenden Bedingungen durchgeführt wird, jedoch zeigen oft Beweise für Kontamination durch dispergiert HSE ± Fe Einschlüsse 17. Trotz der in der Nähe von Allgegenwart dieser Einschlüsse in niedrigen f O 2 Versuche, die Pt, Ir, Os, Re und Ru, (zB 18 - 27), gibt es bemerkenswerte Variabilität zwischen den Studien in ihrer strukturellen Darstellung; vergleiche beispielsweise verweist auf 22 und 26. Obwohl gezeigt wurde, dass Einschlüsse bilden, die eine stabile Phase bei den Ausführungsbedingungen des Experiments 28 sind, schließt dies nicht die Bildung von Einschlüssen auszuschließen, wenn die Probe gequencht. Unsicherheit bezüglich der Herkunft von Einschlüssen macht die Behandlung von Analysenergebnissen schwierig und hat zu Unklarheiten über den wahren Löslichkeit HSES führte zu einer verringerten Silikat schmilzt. Inclusion-Freilauf-Produkte erforderlich sind, um zu bewertenwelche Studien haben einen analytischen Ansatz, die präzise gelöst HSE Konzentrationen ergibt angenommen. 31 - erhebliche Fortschritte bei der Unterdrückung der Bildung von Metall-Einschlüsse reduzierenden Bedingungen hat sich nun in Versuchen unter Verwendung einer Kolben-Zylinder-Vorrichtung, in der die Probe wurde gemacht von früheren Studien entweder durch Zugabe von Au oder Si auf die Ausgangsstoffe 29 geändert nachgewiesen. Die Zugabe von Au oder elementarem Si auf die Ausgangsmaterialien verändert die Probengeometrie oder f O 2 -Entwicklung des Experiments auf. Diese Verfahren sollen die Metalleinschlussbildung durch Änderung der Zeitsteuerung des HSE-Lichtstreuung gegenüber Probe Reduktion zu unterdrücken, und sind in Bennett et al. 31 diskutiert. Im Gegensatz zu einigen früheren Versuchen, die Silikatschmelze Einschlüsse wie mechanisch unterstützten Äquilibrierung und dem Zentrifugieren Kolben-Zylinder zu reinigen, kann das vorliegende Protokoll ohne spezialisierte appar umgesetzt werdenatus und ist für hohe PT Experimenten. Hier im einzelnen beschrieben ist, ist ein Kolben-Zylinder-basierten Ansatz, um die Löslichkeit von Re, Os, Ir, Ru, Pt und Au in Silikatschmelze bei hoher Temperatur (&gt; 1.873 K), 2 GPa und einem f O 2 ähnlich der zu bestimmen, das Eisen-Wüstit Puffer. Anwendung einer ähnlichen Versuchsaufbau kann auch erfolgreich sein in HSE Versuche bei anderen Drücken, die Bereitstellung der erforderlichen Phasenbeziehungen, Benetzungseigenschaften und kinetischen Beziehungen bestehen zu den gewählten Bedingungen. Vorhandene Daten jedoch nicht ausreichen, um vorherzusagen, ob unsere Stichprobenplan wird bei Drücken, die einer tiefen Magmaozean erfolgreich. Auch umrissen ist ein allgemeiner Ansatz zur mäßig und leicht siderophile Element (MSE und SSE respectively) Partitionierung unter Verwendung eines Mehr Amboss Gerät. Erweiterung der Integration freien Datensatz für HSES Hochdruck wird wahrscheinlich ähnliche Mehr Amboss Verfahren verwenden. TogEther, diese Verfahren ein Mittel, um sowohl die Bedingungen der Kern-Segregation und die Phasen der terrestrischen Akkretion einzuschränken.

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			<td>Powdered starting materials- -Oxides, metals, carbonates</td>
			<td>Alfa Aesar</td>
			<td>Specific to desired experiment</td>
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			<td>Castable 2-part MgO ceramic</td>
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			<td>Concept Alloys</td>
			<td>N/A</td>
			<td>~0.25 mm diameter is suitable for most experiments</td>
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			<td>Zirconia Cement</td>
			<td>Cotronics; Resbond 940 2-part cement</td>
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			<td>e.g Krazy Glue/Loctite</td>
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			<td>Single hole alumina tube for multi-anvil thermocouple</td>
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			<td>4-hole alumina tube for piston cylinder thermocouple</td>
			<td>Vesuvius McDanel</td>
			<td>AXF1159--07-12&#160;</td>
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			<td>4-hole alumina tube for multi-anvil thermocouple</td>
			<td>Vesuvius McDanel</td>
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</table>

metal-silicate partitioning at high pressure and temperature: experimental methods and a protocol to suppress highly siderophile element inclusions

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.

Die folgenden Beispiele und Diskussionen konzentrieren sich auf Experimente, um festzustellen, HSE Löslichkeit in Silikat bei niedrigen f O 2 schmilzt. Für umfangreiche Beispiele, wie MSE und SSE Partitionierung von Daten aus Multi-Amboss-Experimente verwendet werden, um den P beschränken werden - T - f O 2 Bedingungen der Kernmetall Segregation, wird der Leser auf Referenzen 9 bezeichnet -. 11 7B-D zeigt zurück gestreut...

Watch this Scientific Journal Video about Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions at JoVE.co

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

We present a procedure to determine the metal-silicate partitioning of siderophile elements, emphasizing techniques that suppress the formation of metal inclusions in experiments for the noble metals. The results of these experiments are used to demonstrate the effect of core-formation on the highly siderophile element composition of the mantle.

Metall-Silikat-Partitionierung unter hohem Druck und Temperatur: Experimentelle Verfahren und ein Protokoll zum Unterdrücken von Hoch siderophile Element Einschlüsse

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from ...

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12.4K Aufrufe.  University of Toronto. We present a procedure to determine the metal-silicate partitioning of siderophile elements, emphasizing techniques that suppress the formation of metal inclusions in experiments for the noble metals. The results of these experiments are used to demonstrate the effect of core-formation on the highly siderophile element composition of the mantle.

Serie: Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. Specifically, the sapphire cell enables visual data collection from multiple loadings to solve a set of material balances to precisely determine phase composition. Ternary phase diagrams can then be established to determine the proportion of each component in each phase at a given condition. In principle, any ternary system can be studied although ternary systems (gas-liquid-liquid) are the specific examples discussed herein. For instance, the ternary THF-Water-CO2 system was studied at 25 and 40&#160;&#176;C and is described herein. Of key importance, this technique does not require sampling. Circumventing the possible disturbance of the system equilibrium upon sampling, inherent measurement errors, and technical difficulties of physically sampling under pressure is a significant benefit of this technique. Perhaps as important, the sapphire cell also enables the direct visual observation of the phase behavior. In fact, as the CO2 pressure is increased, the homogeneous THF-Water solution phase splits at about 2 MPa. With this technique, it was possible to easily and clearly observe the cloud point and determine the composition of the newly formed phases as a function of pressure.
The data acquired with the sapphire cell technique can be used for many applications. In our case, we measured swelling and composition for tunable solvents, like gas-expanded liquids, gas-expanded ionic liquids and Organic Aqueous Tunable Systems (OATS)1-4. For the latest system, OATS, the high-pressure sapphire cell enabled the study of (1) phase behavior as a function of pressure and temperature, (2) composition of each phase (gas-liquid-liquid) as a function of pressure and temperature and (3) catalyst partitioning in the two liquid phases as a function of pressure and composition. Finally, the sapphire cell is an especially effective tool to gather accurate and reproducible measurements in a timely fashion.

High-pressure Sapphire Cell for Phase Equilibria Measurements of CO2/Organic/Water Systems

The high pressure sapphire cell apparatus is a unique tool to study, without sampling, phase behavior under a wide range of pressures. Using a cathetometer, very precise volume measurements can be recorded to measure liquid expansion and phase composition. Thus, this synthetic method enables the study of (1) phase equilibria of multi-component mixtures and (2) the partition behavior of catalyst or model compounds as a function of pressure.

Hochdruck-Sapphire-Zelle für Phasengleichgewichte Messungen der CO<sub&gt; 2</sub&gt; / Bio-/ Wasser-Systeme

The high pressure sapphire cell apparatus was constructed to visually determine the composition of multiphase systems without physical sampling. ...

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Chemie

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel &#945;-diimine ethylene polymerization catalyst. Initial polymerizations with the catalyst lead to optimized reaction conditions, including catalyst concentration, ethylene pressure and reaction time. Using gas-uptake data for these reactions, a procedure to calculate the initial rate of propagation (kp) is presented. Using the optimized conditions, the ability of the nickel &#945;-diimine polymerization catalyst to undergo chain transfer with diethylzinc (ZnEt2) during ethylene polymerization was investigated. A procedure to assess the ability of the catalyst to undergo chain transfer (from molecular weight and 13C NMR data), calculate the degree of chain transfer, and calculate chain transfer rates (ke) is presented.

A protocol for the high-throughput analysis of polymerization catalyst, chain transfer polymerizations, polyethylene characterization, and reaction kinetic analysis is presented.

Ethylenpolymerisationen Mit Parallel Druckreaktoren und eine kinetische Analyse chain transfer polymerization

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel ...

Preparation of Carbon Nanosheets at Room Temperature

Amphiphilic molecules equipped with a reactive, carbon-rich "oligoyne" segment consisting of conjugated carbon-carbon triple bonds self-assemble into defined aggregates in aqueous media and at the air-water interface. In the aggregated state, the oligoynes can then be carbonized under mild conditions while preserving the morphology and the embedded chemical functionalization. This novel approach provides direct access to functionalized carbon nanomaterials. In this article, we present a synthetic approach that allows us to prepare hexayne carboxylate amphiphiles as carbon-rich siblings of typical fatty acid esters through a series of repeated bromination and Negishi-type cross-coupling reactions. The obtained compounds are designed to self-assemble into monolayers at the air-water interface, and we show how this can be achieved in a Langmuir trough. Thus, compression of the molecules at the air-water interface triggers the film formation and leads to a densely packed layer of the molecules. The complete carbonization of the films at the air-water interface is then accomplished by cross-linking of the hexayne layer at room temperature, using UV irradiation as a mild external stimulus. The changes in the layer during this process can be monitored with the help of infrared reflection-absorption spectroscopy and Brewster angle microscopy. Moreover, a transfer of the carbonized films onto solid substrates by the Langmuir-Blodgett technique has enabled us to prove that they were carbon nanosheets with lateral dimensions on the order of centimeters.

We present the synthesis of an amphiphilic hexayne and its use in the preparation of carbon nanosheets at the air-water interface from a self-assembled monolayer of these reactive, carbon-rich molecular precursors.

Herstellung von Kohlenstoff-Nanoschichten bei Raumtemperatur

Amphiphilic molecules equipped with a reactive, carbon-rich "oligoyne" segment consisting of conjugated carbon-carbon triple bonds self-assemble into ...

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of trifluoromethoxylated aromatic compounds remains a formidable challenge in organic synthesis. Conventional approaches often suffer from poor substrate scope, or require use of highly toxic, difficult-to-handle, and/or thermally labile reagents. Herein, we report a user-friendly protocol for the synthesis of methyl 4-acetamido-3-(trifluoromethoxy)benzoate using 1-trifluoromethyl-1,2-benziodoxol-3(1H)-one (Togni reagent II). Treating methyl 4-(N-hydroxyacetamido)benzoate (1a) with Togni reagent II in the presence of a catalytic amount of cesium carbonate (Cs2CO3) in chloroform at RT afforded methyl 4-(N-(trifluoromethoxy)acetamido)benzoate (2a). This intermediate was then converted to the final product methyl 4-acetamido-3-(trifluoromethoxy)benzoate (3a) in nitromethane at 120 &#176;C. This procedure is general and can be applied to the synthesis of a broad spectrum of ortho-trifluoromethoxylated aniline derivatives, which could serve as useful synthetic building blocks for the discovery and development of new pharmaceuticals, agrochemicals, and functional materials.

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

An operationally simple procedure for the synthesis of ortho-trifluoromethoxylated aniline derivatives via a two-step sequence of O-trifluoromethylation of N-aryl-N-hydroxyacetamide followed by thermally induced intramolecular OCF3-migration is reported.

Protokoll für die Synthese von<em&gt; Ortho</em&gt; -trifluoromethoxylated Anilin-Derivate

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

Rapid High-throughput Species Identification of Botanical Material Using Direct Analysis in Real Time High Resolution Mass Spectrometry

We demonstrate that direct analysis in real time-high resolution mass spectrometry can be used to produce mass spectral profiles of botanical material, and that these chemical fingerprints can be used for plant species identification. The mass spectral data can be acquired rapidly and in a high throughput manner without the need for sample extraction, derivatization or pH adjustment steps. The use of this technique bypasses challenges presented by more conventional techniques including lengthy chromatography analysis times and resource intensive methods. The high throughput capabilities of the direct analysis in real time-high resolution mass spectrometry protocol, coupled with multivariate statistical analysis processing of the data, provide not only class characterization of plants, but also yield species and varietal information. Here, the technique is demonstrated with two psychoactive plant products, Mitragyna speciosa (Kratom) and Datura (Jimsonweed), which were subjected to direct analysis in real time-high resolution mass spectrometry followed by statistical analysis processing of the mass spectral data. The application of these tools in tandem enabled the plant materials to be rapidly identified at the level of variety and species.

A method for species identification of botanical material by direct analysis in real time-high resolution mass spectrometry and multivariate statistical analysis is presented.

Schnelle Hochdurchsatz-Spezies Identifizierung von Pflanzen von Material mit Direktanalyse in Echtzeit hochauflösender Massenspektrometrie

We demonstrate that direct analysis in real time-high resolution mass spectrometry can be used to produce mass spectral profiles of botanical material, ...

High Pressure Single Crystal Diffraction at PX^2

In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the GSECARS 13-BM-C beamline at the Advanced Photon Source. The DAC program at 13-BM-C is part of the Partnership for Extreme Xtallography (PX^2) project. BX-90 type DACs with conical-type diamond anvils and backing plates are recommended for these experiments. The sample chamber should be loaded with noble gas to maintain a hydrostatic pressure environment. The sample is aligned to the rotation center of the diffraction goniometer. The MARCCD area detector is calibrated with a powder diffraction pattern from LaB6. The sample diffraction peaks are analyzed with the ATREX software program, and are then indexed with the RSV software program. RSV is used to refine the UB matrix of the single crystal, and with this information and the peak prediction function, more diffraction peaks can be located. Representative single crystal diffraction data from an omphacite (Ca0.51Na0.48)(Mg0.44Al0.44Fe2+0.14Fe3+0.02)Si2O6 sample were collected. Analysis of the data gave a monoclinic lattice with P2/n space group at 0.35 GPa, and the lattice parameters were found to be: a = 9.496 &#177;0.006 &#197;, b = 8.761 &#177;0.004 &#197;, c = 5.248 &#177;0.001 &#197;, &#946; = 105.06 &#177;0.03&#186;, &#945; = &#947; = 90&#186;.

In this report, we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell at the GSECARS 13-BM-C beamline at the Advanced Photon Source. ATREX and RSV programs are used to analyze the data.

High Pressure Einkristalldiffraktometrie bei PX ^ 2

In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the ...

Non-equilibrium Microwave Plasma for Efficient High Temperature Chemistry

A flowing microwave plasma based methodology for converting electric energy into internal and/or translational modes of stable molecules with the purpose of efficiently driving non-equilibrium chemistry is discussed. The advantage of a flowing plasma reactor is that continuous chemical processes can be driven with the flexibility of startup times in the seconds timescale. The plasma approach is generically suitable for conversion/activation of stable molecules such as CO2, N2 and CH4. Here the reduction of CO2 to CO is used as a model system: the complementary diagnostics illustrate how a baseline thermodynamic equilibrium conversion can be exceeded by the intrinsic non-equilibrium from high vibrational excitation. Laser (Rayleigh) scattering is used to measure the reactor temperature and Fourier Transform Infrared Spectroscopy (FTIR) to characterize in situ internal (vibrational) excitation as well as the effluent composition to monitor conversion and selectivity.

This article describes a flowing microwave reactor that is used to drive efficient non-equilibrium chemistry for the application of conversion/activation of stable molecules such as CO2, N2 and CH4. The goal of the procedure described here is to measure the in situ gas temperature and gas conversion.

Nicht-Gleichgewicht Microwave Plasma für effiziente Hochtemperatur-Chemie

A flowing microwave plasma based methodology for converting electric energy into internal and/or translational modes of stable molecules with the purpose ...

A Straightforward Method for Glucosinolate Extraction and Analysis with High-pressure Liquid Chromatography (HPLC)

Glucosinolates are a well-studied and highly diverse class of natural plant compounds. They play important roles in plant resistance, rapeseed oil quality, food flavoring, and human health. The biological activity of glucosinolates is released upon tissue damage, when they are mixed with the enzyme myrosinase. This results in the formation of pungent and toxic breakdown products, such as isothiocyanates and nitriles. Currently, more than 130 structurally different glucosinolates have been identified. The chemical structure of the glucosinolate is an important determinant of the product that is formed, which in turn determines its biological activity. The latter may range from detrimental (e.g., progoitrin) to beneficial (e.g., glucoraphanin). Each glucosinolate-containing plant species has its own specific glucosinolate profile. For this reason, it is important to correctly identify and reliably quantify the different glucosinolates present in brassicaceous leaf, seed, and root crops or, for ecological studies, in their wild relatives. Here, we present a well-validated, targeted, and robust method to analyze glucosinolate profiles in a wide range of plant species and plant organs. Intact glucosinolates are extracted from ground plant materials with a methanol-water mixture at high temperatures to disable myrosinase activity. Thereafter, the resulting extract is brought onto an ion-exchange column for purification. After sulfatase treatment, the desulfoglucosinolates are eluted with water and the eluate is freeze-dried. The residue is taken up in an exact volume of water, which is analyzed by high-pressure liquid chromatography (HPLC) with a photodiode array (PDA) or ultraviolet (UV) detector. Detection and quantification are achieved by conducting comparisons of the retention times and UV spectra of commercial reference standards. The concentrations are calculated based on a sinigrin reference curve and well-established response factors. The advantages and disadvantages of this straightforward method, when compared to faster and more technologically advanced methods, are discussed here.

A Straightforward Method for Glucosinolate Extraction and Analysis with High-pressure Liquid Chromatography HPLC

Here, we describe in great detail an established and robust protocol for the extraction of glucosinolates from ground plant materials. After an on-column sulfatase treatment of the extracts, the desulfoglucosinolates are eluted and analyzed by high-pressure liquid chromatography.

Eine einfache Methode zur Glucosinolate Extraktion und Analyse mit Hochdruck-Flüssigkeitschromatographie (HPLC)

Glucosinolates are a well-studied and highly diverse class of natural plant compounds. They play important roles in plant resistance, rapeseed oil ...

A Convenient Method for Extraction and Analysis with High-Pressure Liquid Chromatography of Catecholamine Neurotransmitters and Their Metabolites

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and related diseases, but their precise measurement is still a challenge. Many protocols have been described for neurotransmitter measurement by a variety of instruments, including high-pressure liquid chromatography (HPLC). However, there are shortcomings, such as complicated operation or hard-to-detect multiple targets, which cannot be avoided, and presently, the dominant analysis technique is still HPLC coupled with sensitive electrochemical or fluorimetric detection, due to its high sensitivity and good selectivity. Here, a detailed protocol is described for the pretreatment and detection of catecholamines with high pressure liquid chromatography with electrochemical detection (HPLC-ECD) in real urine samples of infants, using electrospun composite nanofibers composed of polymeric crown ether with polystyrene as adsorbent, also known as the packed-fiber solid phase extraction (PFSPE) method. We show how urine samples can be easily precleaned by a nanofiber-packed solid phase column, and how the analytes in the sample can be rapidly enriched, desorbed, and detected on an ECD system. PFSPE greatly simplifies the pretreatment procedures for biological samples, allowing for decreased time, expense, and reduction of the loss of targets. 
Overall, this work illustrates a simple and convenient protocol for solid-phase extraction coupled to an HPLC-ECD system for simultaneous determination of three monoamine neurotransmitters (norepinephrine (NE), epinephrine (E), dopamine (DA)) and two of their metabolites (3-methoxy-4-hydroxyphenylglycol (MHPG) and 3,4-dihydroxy-phenylacetic acid (DOPAC)) in infants' urine. The established protocol was applied to assess the differences of urinary catecholamines and their metabolites between high-risk infants with perinatal brain damage and healthy controls. Comparative analysis revealed a significant difference in urinary MHPG between the two groups, indicating that the catecholamine metabolites may be an important candidate marker for early diagnosis of cases at risk for brain damage in infants.

We present a convenient solid-phase extraction coupled to high-pressure liquid chromatography (HPLC) with electrochemical detection (ECD) for simultaneous determination of three monoamine neurotransmitters and two of their metabolites in infants' urine. We also identify the metabolite MHPG as a potential biomarker for the early diagnosis of brain damage for infants.

Eine bequeme Methode für die Extraktion und Analyse mit Hochdruck-Flüssigkeitschromatographie Katecholamin Neurotransmitter und deren Metabolite

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and ...

Experimental Methods for Efficient Solar Hydrogen Production in Microgravity Environment

Long-term space flights and cis-lunar research platforms require a sustainable and light life-support hardware which can be reliably employed outside the Earth's atmosphere. So-called 'solar fuel' devices, currently developed for terrestrial applications in the quest for realizing a sustainable energy economy on Earth, provide promising alternative systems to existing air-revitalization units employed on the International Space Station (ISS) through photoelectrochemical water-splitting and hydrogen production. One obstacle for water (photo-) electrolysis in reduced gravity environments is the absence of buoyancy and the consequential, hindered gas bubble release from the electrode surface. This causes the formation of gas bubble froth layers in proximity to the electrode surface, leading to an increase in ohmic resistance and cell-efficiency loss due to reduced mass transfer of substrates and products to and from the electrode. Recently, we have demonstrated efficient solar hydrogen production in microgravity environment, using an integrated semiconductor-electrocatalyst system with p-type indium phosphide as the light-absorber and a rhodium electrocatalyst. By nanostructuring the electrocatalyst using shadow nanosphere lithography and thereby creating catalytic 'hot spots' on the photoelectrode surface, we could overcome gas bubble coalescence and mass transfer limitations and demonstrated efficient hydrogen production at high current densities in reduced gravitation. Here, the experimental details are described for the preparations of these nanostructured devices and further on, the procedure for their testing in microgravity environment, realized at the Bremen Drop Tower during 9.3 s of free fall.

Efficient solar-hydrogen production has recently been realized on functionalized semiconductor-electrocatalyst systems in a photoelectrochemical half-cell in microgravity environment at the Bremen Drop Tower. Here, we report the experimental procedures for manufacturing the semiconductor-electrocatalyst device, details of the experimental set-up in the drop capsule and the experimental sequence during free fall.

Experimentelle Methoden zur effizienten Solarhydrogenproduktion in der Mikrogravitationsumgebung

Long-term space flights and cis-lunar research platforms require a sustainable and light life-support hardware which can be reliably employed outside the ...