This work was supported by the Natural Sciences and Engineering Research Council of Canada Equipment, Discovery and Discovery Accelerator Grants awarded to J.M.B. N.R.B acknowledges support from the Carnegie Institution of Washington post-doctoral fellowship program. Stephen Elardo is also thanked for his assistance prior to filming with the piston-cylinder press at the Geophysical Lab.

The Authors have nothing to disclose.

The results of inclusion-free experiments performed using the protocols outlined here have previously been compared with literature data in references29 (Os, Ir, Au), 30 (Re, Au) and 31 (Pt). Pt is most instructive in demonstrating the usefulness of inclusion-free run-products. For experiments run at low fO2, Ertel et al.48 assigned inclusions to a stable origin and therefore restricted data reduction to the lowest counts-per-second region of time-r...

Terrestrial accretion is thought to have occurred as a series of collisions between planetesimals with a chondritic bulk composition, terminating in a giant-impact phase thought responsible for moon formation1,2. Heating of the proto-earth by impacts and the decay of short-lived isotopes was sufficient to cause extensive melting and the formation of a magma ocean or ponds through which dense Fe-rich metallic melts could descend. Upon reaching the base of the magma ocean, metallic melts encounter a rheological boundary, stall, and undergo final metal-silicate equilibrium before eventually descending through the solid mantle to the growing core2. Further chemical communication between metal and silicate phases as metallic melt traverses the solid portion of the mantle is thought to be precluded due to the large size and rapid descent of metal diapirs3. This primary differentiation of the Earth into a metallic core and silicate mantle is revealed today by both geophysical and geochemical observations4&#8211;6. Interpreting these observations to yield plausible conditions for metal-silicate equilibrium at the base of a magma ocean, however, requires an appropriate database of experimental results.
The primitive upper mantle (PUM) is a hypothetical reservoir comprising the silicate residue of core formation and its composition therefore reflects the behaviour of trace elements during metal-silicate equilibrium. Trace elements are distributed between metal and silicate melts during core segregation on the basis of their geochemical affinity. The magnitude of an elements preference for the metal phase can be described by the metal-silicate partition coefficient <img alt="Equation 1" src="/files/ftp_upload/52725/52725eq1.jpg" />
<img alt="Equation 2" src="/files/ftp_upload/52725/52725eq2.jpg" />&#160; &#160; &#160; &#160; &#160;(1)
Where <img alt="Equation 3" src="/files/ftp_upload/52725/52725eq3.jpg" /> and <img alt="Equation 4" src="/files/ftp_upload/52725/52725eq4.jpg" /> denote the concentration of element i in metal and silicate melt respectively. Values of <img alt="Equation 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> &#62;1 indicate siderophile (iron-loving) behaviour and those &#60;1 lithophile (rock-loving) behavior. Estimates of the PUM composition show that siderophile elements are depleted relative to chondrites7, typically considered as representative of Earth&#8217;s bulk composition6,8. This depletion is due to sequestration of siderophile elements by the core, and for refractory elements its magnitude should directly reflect values of <img alt="Equation 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> . Lab experiments therefore seek to determine values of <img alt="Equation 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> over a range of pressure (P), temperature (T) and oxygen fugacity (fO2) conditions that are relevant to metal segregation from the base of a magma ocean. The results of these experiments may then be used to delineate regions of P-T-fO2 space that are compatible with the PUM abundance of multiple siderophile elements (e.g.,9&#8211;11).
The high pressures and temperatures relevant to a magma ocean scenario can be recreated in the laboratory using either a piston-cylinder or multi-anvil press. The piston-cylinder apparatus provides access to moderate pressure (~2 GPa) and high temperature (~2,573 K) conditions, but enables large sample volumes and a variety of capsule materials to be easily used. The rapid cooling rate also permits quenching of a range of silicate melt compositions to a glass, thus simplifying textural interpretation of the run-products. The multi-anvil apparatus typically employs smaller sample volumes but with suitable assembly designs can achieve pressures up to ~27 GPa and temperatures of ~3,000 K. The use of these methods has allowed partitioning data for many of the moderately and slightly siderophile elements to be gathered over a large range of P-T conditions. Predictions of the PUM composition based on these data suggest metal-silicate equilibrium occurred at average pressure and temperature conditions in excess of ~29 GPa and 3,000 K respectively, although the exact values are model dependent. In order to account for the PUM abundance of certain redox sensitive elements (e.g.,&#160;V, Cr) the fO2 is also thought to evolve during accretion from ~4 to 2 log units below that imposed by co-existing iron and w&#252;stite (FeO) at equivalent P-T conditions (the iron-w&#252;stite buffer)12.
Although the PUM abundance of many siderophile elements can be accounted for by metal-silicate equilibrium at the base of a deep magma ocean, it has proved difficult to assess if this situation also applies to the most highly siderophile elements (HSEs). The extreme affinity of the HSEs for iron-metal indicated by low pressure (P ~0.1 MPa) and temperature (T &#60;1,673 K) experiments suggests the silicate earth should be strongly depleted in these elements. Estimates of the HSE content for PUM, however, indicate only a moderate depletion relative to chondrite (Figure 1). A commonly posited solution to the apparent HSE excess is that Earth experienced a late-accretion of chondritic material subsequent to core-formation13. This late-accreted material would have mixed with the PUM and elevated HSE concentrations but had a negligible effect on more abundant elements. Alternatively, it has been suggested that the extremely siderophile nature of HSEs indicated by low P-T experiments does not persist to the high P-T conditions present during core-formation14,15. In order to test these hypotheses, experiments must be carried out to determine the solubility and metal-silicate partitioning of HSEs at appropriate conditions. Contamination of the silicate portion of quenched run-products in many previous studies however, has complicated run-product analysis and obscured the true partition coefficients for HSEs between metal and silicate melts.
In partitioning experiments where the HSEs are present at concentration levels appropriate to nature, the extreme preference of these elements for Fe-metal prevents their measurement in the silicate melt. To circumvent this problem, solubility measurements are made in which the silicate melt is saturated in the HSE of interest and values of <img alt="Equation 5" src="/files/ftp_upload/52725/52725eq5.jpg" /> are calculated using the formalism of Borisov et al.16. Quenched silicate run-products from HSE solubility experiments performed at reducing conditions, however, often display evidence for contamination by dispersed HSE&#177;Fe inclusions17. Despite the near ubiquity of these inclusions in low fO2 experiments containing Pt, Ir, Os, Re and Ru, (e.g., 18&#8211;27), there is notable variability between studies in their textural presentation; compare for example references 22 and 26. Although it has been demonstrated that inclusions can form which are a stable phase at the run conditions of an experiment28, this does not preclude the formation of inclusions as the sample is quenched. Uncertainty surrounding the origin of inclusions makes the treatment of analytical results difficult, and has led to ambiguity over the true solubility of HSEs in reduced silicate melts. Inclusion-free run-products are required to assess which studies have adopted an analytical approach that yields accurate dissolved HSE concentrations. Considerable progress in suppressing the formation of metal-inclusions at reducing conditions has now been demonstrated in experiments using a piston-cylinder apparatus, in which the sample design was amended from previous studies by adding either Au or Si to the starting materials29&#8211;31. The addition of Au or elemental Si to the starting materials alters the sample geometry or fO2 evolution of the experiment respectively. These methods are intended to suppress metal inclusion formation by altering the timing of HSE in-diffusion versus sample reduction, and are discussed in Bennett et al.31. Unlike some previous attempts to cleanse the silicate melt of inclusions, such as mechanically assisted equilibration and the centrifuging piston-cylinder, the present protocol can be implemented without specialized apparatus and is suitable for high P-T experiments.
Described in detail here is a piston-cylinder based approach to determine the solubility of Re, Os, Ir, Ru, Pt and Au in silicate melt at high temperature (&#62;1,873 K), 2 GPa and an fO2 similar to that of the iron-w&#252;stite buffer. Application of a similar experimental design may also prove successful in HSE experiments at other pressures, providing the required phase relations, wetting properties and kinetic relationships persist to the chosen conditions. Existing data however, are insufficient to predict whether our sample design will be successful at pressures corresponding to a deep magma ocean. Also outlined is a general approach used to determine moderately and slightly siderophile element (MSE and SSE respectively) partitioning using a multi-anvil device. Extension of the inclusion-free dataset for HSEs to high pressure is likely to employ similar multi-anvil methods. Together, these procedures provide a means to constrain both the conditions of core-segregation and the stages of terrestrial accretion.

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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.

The following examples and discussion focus on experiments to determine HSE solubility in silicate melts at low fO2. For comprehensive examples of how MSE and SSE partitioning data from multi-anvil experiments may be used to constrain the P-T-fO2 conditions of core metal segregation, the reader is referred to references9&#8211;11. Figure 7B-D&#160;displays back scattered electron images from typical experimental ru...

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.

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 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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...

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

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

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds