Questo lavoro è stato sostenuto dai scienze naturali e ingegneria Research Council del Canada Attrezzatura, Scoperta e Discovery Accelerator Sovvenzioni concesse a JMBNRB riconosce il sostegno della Carnegie Institution di programma di borse post-dottorato Washington. Stephen Elardo è anche ringraziato per la sua assistenza prima di filmare con la stampa cilindro-pistone presso il Laboratorio di Geofisica.

Gli autori non hanno nulla da rivelare.

I risultati degli esperimenti senza inclusione effettuati utilizzando i protocolli descritti qui sono stati precedentemente confrontati con i dati di letteratura nei riferimenti 29 (Os, Ir, Au), 30 (Re, Au) e 31 (Pt). Pt è molto istruttiva per dimostrare l&#39;utilità di run-prodotti privi di inclusione. Per esperimenti condotti a bassa f O 2, Ertel et al. 48 assegnato inclusioni ad un&#39;origine stabile e quindi limitata riduzione dei dati alla...

Accrescimento terrestre si pensa che si sono verificati una serie di collisioni fra planetesimi con una composizione di massa chondritic, terminante con una fase di gigante impatto ritenuta responsabile per la formazione di luna 1,2. Riscaldamento del proto-Terra da impatti e il decadimento degli isotopi di breve durata era sufficiente a provocare gravi fusione e la formazione di un oceano magma o stagni attraverso cui denso fusi metallici Fe-ricchi potevano scendere. Dopo aver raggiunto la base del magma mare, fonde metalliche incontrano un confine reologico, stallo, e sottoposti equilibrio metallo-silicati finale prima infine scendere attraverso il mantello solido alla crescente nucleo 2. Ulteriori comunicazione chimica tra metallo e fasi silicati come metallo fuso attraversa la parte solida del mantello è pensato per essere preclusa a causa delle grandi dimensioni e rapida discesa del diapirs metallici 3. Questa differenziazione primario della Terra in un nucleo metallico e mant silicatole viene rivelato oggi da entrambe le osservazioni geofisiche e geochimiche 4-6. Interpretazione queste osservazioni per produrre condizioni plausibili di equilibrio metallo-silicati alla base di un magma mare, tuttavia, richiede un adeguato database di risultati sperimentali. Il mantello superiore primitiva (PUM) è un serbatoio ipotetico comprendente il residuo di silicato di formazione del nucleo e la sua composizione riflette quindi il comportamento di oligoelementi durante equilibrio metallo-silicati. Gli oligoelementi sono distribuiti tra il metallo e fusi silicatici durante nucleo segregazione sulla base della loro affinità geochimica. La grandezza di una preferenza elementi per la fase di metallo può essere descritta dal coefficiente di ripartizione metallo-silicati <img alt="Equazione 1" src="/files/ftp_upload/52725/52725eq1.jpg" /><img alt="Equazione 2" src="/files/ftp_upload/52725/52725eq2.jpg" /> (1) Dove <img alt="Equazione 3" src="/files/ftp_upload/52725/52725eq3.jpg" /> e <img alt="Equazione 4" src="/files/ftp_upload/52725/52725eq4.jpg" /> indicare la concentrazione dell&#39;elemento i in metallo e silicato sciogliere rispettivamente. Valori di <img alt="Equazione 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> &gt; 1 indicano siderophile comportamento (ferro amante) e quelle &lt;1 litofili (-rock amante) comportamento. Le stime della composizione mostrano PUM che siderophile elementi sono esauriti rispetto al condriti 7, tipicamente considerati come rappresentativi della composizione massa della Terra 6,8. Questo è dovuto alla deplezione sequestro di elementi siderophile dal nucleo, e per gli elementi refrattari sua magnitudine deve riflettere direttamente valori <img alt="Equazione 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> . Esperimenti di laboratorio quindi cercano di determinare i valori di <img alt="Equazione 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> nel corso di un raESN di pressione (P), la temperatura (T) e fugacità di ossigeno (O 2 f) condizioni che sono rilevanti per la segregazione metallica dalla base di un oceano di magma. I risultati di questi esperimenti possono quindi essere utilizzati per delimitare le regioni di P - T - f O 2 spazio che sono compatibili con l&#39;abbondanza PUM più elementi (es siderophile, 9 - 11). Le alte pressioni e temperature pertinenti ad uno scenario oceano di magma è possibile ricreare in laboratorio utilizzando un pistone-cilindro o stampa multi-incudine. L&#39;apparato pistone-cilindro fornisce accesso a pressione moderata (~ 2 GPa) e ad alta temperatura (~ 2.573 K) condizioni, ma consente grandi volumi di campione e una varietà di materiali capsula da utilizzare facilmente. Il tasso di raffreddamento rapido consente anche tempra di un campo di composizioni melt silicato ad un bicchiere, semplificando così l&#39;interpretazione strutturale dei run-prodotti.L&#39;apparato multi-incudine impiega tipicamente piccoli volumi di campione, ma con i disegni di montaggio adatti può raggiungere pressioni fino a ~ 27 GPa e temperature di circa 3000 K. L&#39;uso di questi metodi ha permesso dati partizionamento per molti dei moderatamente e leggermente siderophile elementi siano riuniti su una vasta gamma di P - condizioni T. Le previsioni di composizione PUM sulla base di questi dati suggeriscono equilibrio metallo-silicati avvenuto a condizioni medie di pressione e temperatura in eccesso di ~ 29 GPa e 3.000 K, rispettivamente, anche se i valori esatti dipendono dal modello. Per tenere conto per l&#39;abbondanza PUM di elementi sensibili certo redox (ad esempio, V, Cr) O f 2 è anche pensato di evolvere durante accrescimento da ~ 4-2 unità logaritmiche di sotto di tale imposta da co-esistente ferro e wüstite (FeO ) a condizioni equivalenti PT (il buffer di ferro-wüstite) 12. Nonostante l&#39;abbondanza PUM di mtutti gli elementi siderophile possono essere valutate con equilibrio metallo silicato alla base di un profondo oceano di magma, si è dimostrato difficile valutare se questa situazione vale anche per gli elementi più altamente siderophile (HSES). L&#39;affinità estremo dei HSES per ferro metallico indicato da bassa pressione (P ~ 0,1 MPa) e temperatura (T &lt;1.673 K) esperimenti suggerisce il silicato di terra deve essere fortemente impoverito in questi elementi. Le stime del contenuto HSE per PUM, tuttavia, indicano solo un moderato impoverimento relativo di condrite (Figura 1). Una soluzione comunemente ipotizzato per l&#39;eccesso HSE evidente è che la Terra ha subito un ritardo-accrescimento di materiale chondritic successive al core-formazione 13. Questo materiale tardo-maturato avrebbe mescolato con la PUM ed elevate concentrazioni di HSE, ma ha avuto un effetto trascurabile sugli elementi più abbondanti. In alternativa, è stato suggerito che la natura estremamente siderophile di HSES dimostrato dai bassi P </em&gt; - T esperimenti non persistono le elevate condizioni PT presenti durante nucleo formazione 14,15. Per testare queste ipotesi, esperimenti devono essere eseguite per determinare la solubilità e metallo-silicati compartimentazione HSES in condizioni appropriate. La contaminazione della porzione di silicato di run-prodotti bonificati in molti studi precedenti però, ha complicato l&#39;analisi di run-prodotto e oscurato i coefficienti di ripartizione veri per HSES tra metallo e fusi silicatici. In esperimenti di partizionamento dove sono presenti a concentrazioni appropriate per la natura delle HSES, l&#39;estrema preferenza di questi elementi per Fe-metallo impedisce loro misura nella massa fusa di silicato. Per aggirare questo problema, misurazioni di solubilità sono realizzati in cui la massa fusa di silicato è saturo nel HSE di interesse e valori <img alt="Equazione 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> sono calcolati utilizzando il formalismo di Borisov etal. 16. Silicato Temprato run-prodotti dagli esperimenti di solubilità HSE effettuati alle condizioni riducenti, tuttavia, spesso mostrano evidenza di contaminazione da disperso HSE ± Fe inclusioni 17. Nonostante il vicino onnipresenza di queste inclusioni in bassa f O 2 esperimenti contenenti Pt, Ir, Os, Re e Ru, (ad esempio, 18 - 27), non vi è notevole variabilità tra gli studi nella loro presentazione strutturale; confrontare per esempio si fa riferimento 22 e 26. Sebbene sia stato dimostrato che le inclusioni possono formare che sono una fase stabile nelle condizioni di esecuzione di un esperimento 28, ciò non preclude la formazione di inclusioni come campione si spegne. L&#39;incertezza che circonda l&#39;origine delle inclusioni rende il trattamento dei risultati analitici difficile, e ha portato ad ambiguità sulla vera solubilità in HSES ridotta fusi silicatici. Run-prodotti privi di inclusione sono tenuti a valutareche gli studi hanno adottato un approccio analitico che produce concentrazioni precise disciolti HSE. Notevoli progressi nel sopprimere la formazione di metallo-inclusioni a condizioni riducenti è stata ora dimostrata in esperimenti utilizzando un apparato cilindro-pistone, in cui il disegno campione è stato modificato da studi precedenti tramite l&#39;aggiunta di Au o Si alle materie prime 29 - 31. L&#39;aggiunta di Au o elementale Si ai materiali di partenza altera l&#39;evoluzione geometria campione o f O 2 dell&#39;esperimento rispettivamente. Questi metodi hanno lo scopo di sopprimere la formazione inclusione metallo modificando i tempi di HSE in-diffusione contro la riduzione del campione, e sono discussi in Bennett et al. 31. A differenza di alcuni precedenti tentativi di ripulire la fusione di silicato di inclusioni, come equilibrio assistito meccanicamente e la centrifugazione cilindro-pistone, il presente protocollo può essere attuata senza appar specializzatoatus ed è adatto per esperimenti di alta PT. Descritto in dettaglio qui è un approccio basato pistone-cilindro per determinare la solubilità di Re, Os, Ir, Ru, Pt e Au in silicato di massa fusa ad alta temperatura (&gt; 1.873 K), 2 GPa e una O f 2 simile a quella di il buffer di ferro-wüstite. L&#39;applicazione di un modello sperimentale simile può anche rivelarsi di successo in esperimenti HSE in altre pressioni, fornendo le relazioni di fase necessari, bagnando le proprietà e le relazioni cinetiche persistono le condizioni scelte. Dati comunque esistenti, sono sufficienti per prevedere se il nostro campione di progettazione avrà successo a pressioni corrispondenti ad un profondo oceano di magma. Anche delineato è un approccio generale utilizzato per determinare moderatamente e leggermente elemento siderophile (MSE e SSE rispettivamente) partizionamento utilizzando un dispositivo multi-incudine. Estensione del set di dati libera-inclusion per HSES ad alta pressione è in grado di utilizzare simili metodi multi-incudine. Togetere, queste procedure forniscono un mezzo per vincolare entrambe le condizioni di core-segregazione e dalle fasi di accrescimento terrestre.

<table border="0" cellpadding="0" cellspacing="0">
	<tbody>
		<tr>
			<td>G10 Epoxy/Fiberglass Sheet</td>
			<td>Accurate plastics, Inc.</td>
			<td>GEES.020N.3648</td>
			<td></td>
		</tr>
		<tr>
			<td>Powdered starting materials- -Oxides, metals, carbonates</td>
			<td>Alfa Aesar</td>
			<td>Specific to desired experiment</td>
			<td></td>
		</tr>
		<tr>
			<td>Castable 2-part MgO ceramic</td>
			<td>Aremco</td>
			<td>Ceramcast - 584</td>
			<td></td>
		</tr>
		<tr>
			<td>PTFE Dry Lubricant</td>
			<td>Camie-Campbell</td>
			<td>2000 TFE-Coat</td>
			<td></td>
		</tr>
		<tr>
			<td>Graphite resistance heaters</td>
			<td>Carbone of America (Now owned by Mersen USA)</td>
			<td>Custom Order</td>
			<td></td>
		</tr>
		<tr>
			<td>Barium Carbonate</td>
			<td>Chemical Products Corporation</td>
			<td>Custom Order</td>
			<td>Calcined free-flowing (CFF) grade</td>
		</tr>
		<tr>
			<td>C-Type Thermocouple Wire (W26%Re, W5%Re)</td>
			<td>Concept Alloys</td>
			<td>N/A</td>
			<td>~0.25 mm diameter is suitable for most experiments</td>
		</tr>
		<tr>
			<td>Zirconia Cement</td>
			<td>Cotronics; Resbond 940 2-part cement</td>
			<td>N/A</td>
			<td>Use 100 parts powder for every 25 to 28 parts activator</td>
		</tr>
		<tr>
			<td>Polyvinyl Acetate (PVA) Glue</td>
			<td>e.g Bostik</td>
			<td>N/A</td>
			<td>Often sold as &#39;white glue&#39;</td>
		</tr>
		<tr>
			<td>Cyanoacrylate Glue</td>
			<td>e.g Krazy Glue/Loctite</td>
			<td>N/A</td>
			<td></td>
		</tr>
		<tr>
			<td>Piston cylinder pressure vessel and WC piston</td>
			<td>Hi-Quality Carbide Tooling Inc.</td>
			<td>Custom Order</td>
			<td></td>
		</tr>
		<tr>
			<td>Silica Glass Tubing</td>
			<td>Quartz Plus</td>
			<td>Custom Order</td>
			<td></td>
		</tr>
		<tr>
			<td>Crushable ZrO2 tubes</td>
			<td>Saint-Gobain</td>
			<td>Custom Order</td>
			<td></td>
		</tr>
		<tr>
			<td>Crushable MgO rods and tubes</td>
			<td>Saint-Gobain</td>
			<td>Custom Order</td>
			<td></td>
		</tr>
		<tr>
			<td>WC cubes for multi-anvil experiments</td>
			<td>Tungaloy</td>
			<td>Custom Order</td>
			<td>Cubes are grade-F WC alloy</td>
		</tr>
		<tr>
			<td>Single hole alumina tube for multi-anvil thermocouple</td>
			<td>Vesuvius McDanel</td>
			<td>AXS071730-04-06</td>
			<td></td>
		</tr>
		<tr>
			<td>4-hole alumina tube for piston cylinder thermocouple</td>
			<td>Vesuvius McDanel</td>
			<td>AXF1159--07-12&#160;</td>
			<td></td>
		</tr>
		<tr>
			<td>4-hole alumina tube for multi-anvil thermocouple</td>
			<td>Vesuvius McDanel</td>
			<td>AXF1159-04-06</td>
			<td></td>
		</tr>
	</tbody>
</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.

Gli esempi che seguono e concentrare la discussione su esperimenti per determinare HSE solubilità in silicato fonde a basse f O 2. Per esempi completi di come MSE e dati partizionamento SSE da esperimenti multi-incudine possono essere utilizzati per vincolare la P - T - f O 2 condizioni d&#39;anima in metallo segregazione, si rimanda ai riferimenti. 9 - 11 Figura 7B-D visualizza indietro immagini elettroni sparse da tipici run-prodott...

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.

Partizionamento metallo-silicato ad alta pressione e temperatura: metodi sperimentali e un protocollo per sopprimere altamente Siderophile Element Inclusioni

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

metal-silicate-partitioning-at-high-pressure-temperature-experimental

Research

Education

JoVE Journal

JoVE Core

Chemistry

Chemical Equilibrium

SCIENTISTS IN ACTION

12.4K Views.  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.

Video: 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.

Ad alta pressione Sapphire cellulare per la fase Equilibri misurazioni di CO<sub&gt; 2</sub&gt; / biologici / Water Systems

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

Ricerca

Chimica

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.

Polimerizzazione a etilene in reattori a pressione parallele e una analisi cinetica di polimerizzazione a catena Transfer

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.

Preparazione di carbonio nanosheets a temperatura ambiente

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.

Protocollo per la sintesi di<em&gt; Ortho</em&gt; Derivati ​​all&#39;anilina -trifluoromethoxylated

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.

Rapid high-throughput Specie Identificazione del materiale botanico Utilizzando l&#39;analisi diretta in tempo reale ad alta risoluzione Spettrometria di Massa

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.

Alta pressione singolo cristallo di diffrazione a 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.

Plasma microonde non equilibrato per una chimica ad alta temperatura efficiente

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.

Un metodo semplice per glucosinolati estrazione e l&#39;analisi con alta pressione cromatografia liquida (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.

Un metodo pratico per estrazione ed analisi con cromatografia liquida dei neurotrasmettitori della catecolamina e loro metaboliti

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.

Metodi sperimentali per una produzione efficiente di idrogeno solare nell'ambiente di microgravità

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