Determination of Pt,Pd and Rh in Brassica Napus using solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry

Conventional approaches for the analysis of platinum group elements (PGEs) in plant material suffer from sample digestion which results in sample dilution and therefore requires high sample intakes to maintain the sensitivity. The presented solid-sampling method avoids sample digestion while improving sensitivity when compared to digestion-based inductively coupled plasma optical emission spectrometry (ICP-OES) methods and allows the analysis of sample masses of 5 mg or less. Detection limits of 0.38 μg g^− 1, 0.14 μg g^− 1 and 0.13 μg g^− 1 were obtained for Pt, Pd and Rh, respectively using a sample intake of 5 mg. The reproducibility of the procedure ranged between 4.7% (Pd) relative standard deviation (RSD, n = 7) and 7.1% (Rh) RSD for 25 ng analytes. For quantification, aqueous standards were applied on paper filter strips and dried. Only the dried filters were introduced into the electrothermal vaporization unit. This approach successfully removed memory-effects observed during analysis of platinum which occurred only if liquid standards came into contact with the graphite material of the furnace. The presented method for overcoming the Pt-memory-effects may be of further interest for the analysis of other carbide-forming analytes as it does not require any technical modification of the graphite furnace (e.g., metal inlays, pyrolytic coating). Owing to lack of suitable certified reference materials, the proposed method was compared with conventional ICP-OES analysis of digested samples and a good agreement was obtained. As a result of the low sample consumption, it was possible to determine the spatial distribution of PGEs within a single plant. Significant differences in PGE concentrations were observed between the shoots (stem, leaves) and the roots. Pd was mainly found in the roots, whereas Pt and Rh were also found in higher concentrations in the shoots.     

Evaluation of four sample treatments for determination of platinum in automotive catalytic converters by graphite furnace atomic absorption spectrometry

Conventional and microwave assisted digestion, both using aqua regia, alkaline fusion with lithium metaborate and aqueous slurries were evaluated as sample treatments for determination of Pt in automotive catalytic converters by Graphite Furnace Atomic Absorption Spectrometry (GF-AAS). Determination of platinum by GF-AAS in samples of the catalytic converter's substrates, prepared by the four methods described, indicates that the highest platinum concentration i.e. maximum Pt extraction in the range of 748 ± 15–998 ± 10 μg mL^− 1, is obtained for samples dissolved by alkaline fusion, closely followed by analysis of aqueous plus Triton X-100 slurries 708 ± 14–958 ± 10 μg mL^− 1, while neither one of the acid digestion procedures achieved total dissolution of the samples. Slurry analysis is thus shown to be a viable alternative and is recommended, based on its speed and ease of implementation. Aqueous standards calibration curves and the standard addition methods were also compared. The results showed that no appreciable matrix effects are present, regardless of the sample preparation procedure used. Precision of the measurements, expressed as percentage relative standard deviation, ranged between 2.5 to 4.9%. Accuracy of the results was assessed by recovery tests which rendered values between 98.9 and 100.9%.     

Microwave plasma chemical vapor deposition of nano-composite C/Pt thin-films

Composite carbon–platinum thin-films of nano-crystalline graphitic carbon decorated with uniformly-dispersed 2–4 nm Pt nano-particles have been synthesized from a solid organic precursor by a one-step microwave plasma chemical vapor deposition (MPCVD). The fast Ar-plasma discharge and the presence of microwave radiation accelerate the formation of sites suitable for in situ heterogeneous nucleation, and consequently, the fine dispersion of metal in the carbonaceous matrix. The electrochemical response of the 2 μm C/Pt thin-film electrode displays electrochemical activity, which is attributed to the high ca. 18 m²/g effective surface area of Pt nano-particles.     

A one-step,clean, capping-agent-free electrochemical approach to prepare Pt nanoparticles with preferential (100) orientation and their high electrocatalytic activities

A clean and simple electrodeposition method without the use of any organic additives has been reported to prepare platinum nanoparticles with preferential (100) orientation directly on the conductive substrate. The formation of platinum nanoparticles exposing (100) facets was confirmed by electrochemical methods and high-resolution transmission electron microscopy. The fraction of Pt (100) sites increases as the electrodeposition current density increases from 0.2 to 10 mA cm^− 2. Furthermore, as the Pt (100) fraction increases, the specific activity of the Pt particles for ammonia oxidation increases obviously.     

Performance of plasma sputtered fuel cell electrodes with ultra-low Pt loadings

Ultra-low Pt content PEMFC electrodes have been manufactured using magnetron co-sputtering of carbon and platinum on a commercial E-Tek^® uncatalyzed gas diffusion layer in plasma fuel cell deposition devices. Pt loadings of 0.16 and 0.01 mg cm^?2 have been realized. The Pt catalyst is dispersed as small clusters with size less than 2 nm over a depth of 500 nm. PEMFC test with symmetric electrodes loaded with 10 μg cm^?2 led to maximum reproducible power densities as high as 0.4 and 0.17 W cm^?2 with Nafion^®212 and Nafion^®115 membranes, respectively.     

Flow injection analysis system with electrochemical detection for the simultaneous determination of nanomolar levels of acetaminophen and codeine

A simple, rapid and low-cost electroanalytical method is proposed for the determination of acetaminophen (ACP) and codeine (COD) at nanomolar levels in pharmaceutical and biological samples. The analytical procedure is based on a flow injection analysis system coupled to electrochemical detection, which was multiple pulse amperometry (FIA-MPA). Boron-doped diamond was used as the working electrode for electrochemical detection. The electrode was subjected to a cathodic pretreatment and was selected in this work due its good electrochemical performance. By applying the FIA-MPA method, after a number of optimization assays, the analgesics were simultaneously determined at excellent linear concentration ranges. The analytical curves ranged from 80 nmol L⁻¹ to 100 µmol L⁻¹ for ACP and from 50 nmol L⁻¹ to 10 µmol L⁻¹ for COD, and the obtained limits of detection were 30 nmol L⁻¹ and 35 nmol L⁻¹ for ACP and COD, respectively. The practical applicability of the electroanalytical method was evaluated from the ACP and COD determination in two sample matrices: commercial pharmaceutical samples and biological fluids. In the case of pharmaceutical formulation samples, the obtained results were statistically similar to those obtained using a reference chromatographic method. In addition, these drugs were simultaneously quantified in biological fluid samples of urine and human serum with excellent recovery percentages.     

Fabrication of the catalytic electrodes for methanol oxidation on electrospinning-derived carbon fibrous mats

The carbon fibrous mats with high conductivity (50 S cm⁻¹) formed by carbon nanofibers with an average diameter of ∼150 nm have been fabricated by thermally treating the electrospun polyacrylonitrile fibers. The platinum clusters are electrodeposited on the carbon nanofibrous mats (CFMs) by multi-cycle CV method. In contrast to the catalytic peak current of methanol oxidation on commercial catalyst (185 mA mg⁻¹ Pt), the catalytic peak current on optimum Pt/CFM electrode reaches to ∼420 mA mg⁻¹ Pt despite of the large size (50–200 nm) of the Pt clusters, revealing that the special structure of carbon fibrous mats is favorable to improve the performance of catalyst.     

Determination of lead,cadmium and mercury in blood for assessment of environmental exposure: A comparison between inductively coupled plasma–mass spectrometry and atomic absorption spectrometry

A biomonitoring method for the determination of Pb, Cd, and Hg at background levels in whole blood by inductively coupled plasma-mass spectrometry is described. While this method was optimized for assessing Pb, Cd and Hg at environmental levels, it also proved suitable for assessing concentrations associated with occupational exposure. The method requires as little as 200 μl of blood that is diluted 1 + 49 for direct analysis in the inductively coupled plasma-mass spectrometer. Method performance is compared to well-established AAS methods. Initial method validation was accomplished using National Institute of Standards and Technology (NIST) Standard Reference Material 966, Toxic Metals in Bovine Blood. Method detection limits (3s) are 0.05 μg dl^− 1 for Pb, 0.09 μg l^− 1 for Cd; and 0.17 μg l^− 1 for Hg. Repeatability ranged from 1.4% to 2.8% for Pb; 3% to 10% for Cd; and 2.6% to 8.8% for Hg. In contrast, AAS method detection limits were 1 μg dl^− 1, 0.54 μg l^− 1, and 0.6 μg l^− 1, for Pb, Cd, and Hg, respectively. Further performance assessments were conducted over a 2-year period via participation in four international External Quality Assessment Schemes (EQAS) operated specifically for toxic metals in blood. This includes schemes operated by (a) the New York State Department of Health's Wadsworth Center, Albany, NY, USA (b) L′Institut National de Santé Publique du Québec, Centre de Toxicologie du Québec, Canada, (c) Friedrich-Alexander University, Erlangen, Germany, and (d) the University of Surrey, Guildford, UK Trace Elements scheme. The EQAS data reflect analytical performance for blind samples analyzed independently by both inductively coupled plasma-mass spectrometry and AAS methods.     

Comparison of performances of bioanodes modified with graphene oxide and graphene–platinum hybrid nanoparticles

The performances of graphene oxide (GO) and graphene–platinum hybrid nanoparticles (Gr-Pt hybrid NPs) were compared for biofuel cell (BFC) systems. This is the first study that constitutes these nanomaterials in BFC systems. For this purpose, fabricated bioanodes were combined with laccase modified biocathode in a single cell membraneless BFC. Power and current densities of these systems were calculated as 2.40 μW cm^− 2 and 211.90 μA cm^− 2 for GO based BFC and 4.88 μW cm^− 2 and 246.82 μA cm^− 2, for Gr-Pt hybrid NPs based BFC. As a result, a pioneer study which demonstrates the effective performances of combination of graphene with Pt was conducted.     

Development of a headspace-gas chromatography (HS-GC-PID-FID) method for the determination of VOCs in environmental aqueous matrices: Optimization,verification and elimination of matrix effect and VOC distribution on the Fortaleza Coast,Brazil

An analytical protocol combining a headspace technique with gas chromatography and detection by photoionization detector and flame ionization detector (HS-GC-PID-FID) was developed. This procedure was used to measure volatile organic compounds (VOCs) in environmental aqueous matrices and was applied in determination of VOCs on the coast of Fortaleza, Brazil. At optimum operating conditions, analytical figures of merit such as linearity (R ranged from 0.9983 to 0.9993), repeatability (5.62 to 9.63% and 0.02 to 0.19% for the quantitative and qualitative analyses, respectively), detection limits (0.22 to 7.48 μg L⁻¹) and sensibility were estimated. This protocol favors a fast sampling/sample preparation (in situ), minimizes the use of laboratory material, eliminates the matrix effect from environmental samples, and can be applied to river, estuarine and oceanic waters. The advantage of detectors in series is that a low sensitivity in detection in one is compensated by the other. Toluene was the most abundant VOC in the studied area, with an average concentration of 1.63 μg L⁻¹. It was followed by o-xylene (1.15 μg L⁻¹), trichloroethene (1.08 μg L⁻¹), benzene (0.86 μg L⁻¹), ethylbenzene (0.74 μg L⁻¹), carbon tetrachloride (0.55 μg L⁻¹), m/p-xylene (0.48 μg L⁻¹) and tetrachloroethene (0.46 μg L⁻¹), compounds which are very commonly detected in urban runoff from most cities. The results of the VOC distribution showed that port activity was not the main source of VOCs along the Fortaleza Coast, but that the contribution from urban runoff seemed more significant.     

Column solid phase extraction and determination of ultra-trace Au,Pd and Pt in environmental and geological samples

A new sorbent based on cysteine modified silica gel (SiG-cys) was prepared and studied for preconcentration and separation of noble metals Au(III), Pd(II), Pt(II), Pt(IV). Its extraction efficiency was examined by batch and column solid phase extraction procedures. Laboratory experiments performed showed that sorbent is characterized with high selectivity, permiting quantitative sorption (93–97%) of noble metals Au, Pd and Pt from acidic media 0.1–2 mol L^? 1 HCl and unsignificant sorption (less than 2%) for common base metals like Cu, Fe, Mn and Zn. The analytes retained on the sorbent are effectively eluted with 0.1 mol L^? 1 thiourea in 0.1 mol L^? 1 HCl and measured by ETAAS or ICP OES under optimal instrumental parameters. The sorbent showed high mechanical and chemical stability and extraction efficiency was not changed after 500 cycles of sorption/desorption. The sorbent was successfully applied in analyticals procedures for preconcentration and determination of Au, Pd and Pt in geological and soil samples. Detection limits (3σ criteria) achieved, depending on the instrumental methods used are: ETAAS (0.005 μg L^? 1 for Au in river and sea water, 0.002 μg g^? 1 for Au in copper ore and copper concentrate); ICP OES (0.03 μg L^? 1 for Pd and 0.06 μg L^? 1 for Pt in river and sea water, 0.006 μg g^? 1 for Pd in copper ore and copper concentrate and 0.002 μg g^? 1 for soluble Pt in soil). The accuracy of the procedures developed was confirmed by added/found method for sea and river water; by the analysis of national certified materials (copper ore and copper concentrate for Au and Pd) and by determination of the sum of soluble Pt(II) + Pt(IV) in spiked soil samples.     

Studying the oxygen reduction and hydrogen oxidation reactions under realistic fuel cell conditions

A new approach to test fuel cell catalysts under conditions of high mass transport and variable temperature is described. This approach relies upon utilising a 5 μm thick gold grid to act as a catalyst support in contact with a perfluorsulfonic acid (PFSA) membrane in a true three electrode electrochemical configuration. The gold grid has 20 μm × 20 μm sized holes in it which allow the reactant gas to reach the catalyst layer. The high electrical conductivity and low profile of the grid ensure that electrical and mass transport losses are minimal. We have used this configuration to look at the oxygen reduction reaction (orr) and the hydrogen oxidation reaction (hor) on a platinum-black and platinum on carbon catalyst at a loading of about 10 μg cm⁻². We find that for the orr we can measure kinetic currents over the entire range of relevant fuel cell operating potentials (0.55–1 V). Although platinum-black shows higher specific catalytic activity towards the orr than platinum on carbon at high potentials, this performance benefit is reduced at lower potentials. For the hor we measure exchange current densities of 0.022 A cm⁻² and 0.026 A cm⁻² respectively on the Pt-Black and Pt/C. These values indicate that there does not appear to be a size effect for the hor, unlike the orr.     

Photometric determination of thioglycolic acid in cosmetics by using a stopped-flow reverse flow-injection system and the formation of gold nanoparticles

The positive effect of thiol compounds as reducing agents in the synthesis of gold nanoparticles in the presence of a micellar medium of Triton X-100 has been photometrically studied using a reverse flow-injection system which operates in the stopped-flow mode (SF-rFIA). The analytical usefulness of this new system has been assessed by its application to the determination of thioglycolic acid (TGA), which was chosen as the analyte model. The dynamic range of the calibration graph was 5.97–80 μmol L^?1, and the detection limit was 1.73 μmol L^?1. The behaviour of other thiol compounds on the system has been also studied. The precision of the method, expressed as relative standard deviation, ranged between 1.5 and 2.3%. The method was applied to the determination of TGA in several cosmetic samples with acceptable recoveries in all instances, which ranged between 90.32 and 101.46%.     

Amperometric biosensors based on deposition of gold and platinum nanoparticles on polyvinylferrocene modified electrode for xanthine detection

In this study, new xanthine biosensors, XO/Au/PVF/Pt and XO/Pt/PVF/Pt, based on electroless deposition of gold(Au) and platinum(Pt) nanoparticles on polyvinylferrocene(PVF) coated Pt electrode for detection of xanthine were presented. The amperometric responses of the enzyme electrodes were measured at the constant potential, which was due to the electrooxidation of enzymatically produced H₂O₂. Compared with XO/PVF/Pt electrode, XO/Au/PVF/Pt and XO/Pt/PVF/Pt exhibited excellent electrocatalytic activity towards the oxidation of the analyte. Effect of Au and Pt nanoparticles was investigated by monitoring the response currents at the different deposition times and the different concentrations of KAuCl₄ and PtBr₂. Under the optimal conditions, the calibration curves of XO/Au/PVF/Pt and XO/Pt/PVF/Pt were obtained over the range of 2.5 × 10^?3 to 0.56 mM and 2.0 × 10^?3 to 0.66 mM, respectively. The detection limits were 7.5 × 10^?4 mM for XO/Au/PVF/Pt and 6.0 × 10^?4 mM for XO/Pt/PVF/Pt. The effects of interferents, the operational and the storage stabilities of the biosensors and the applicabilities of the proposed biosensors to the drug samples analysis were also evaluated.     

Highly ordered platinum-nanotube arrays for oxidative determination of trace arsenic(III)

A novel method for the oxidative determination of trace arsenic(III) was investigated on highly ordered platinum-nanotube array electrodes (PtNTAEs). The PtNTAEs with a highly organized structure were fabricated by electrochemical deposition of platinum in a 3-aminopropyltrimethoxysilane-modified porous anodic alumina template (PAA). The morphologies and structures of PtNTAEs were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Electrochemical experiments proved that the PtNTAEs exhibited better performance for As(III) analysis in comparison with platinum nanoparticles-coated GCE (Pt_nano/GCE) or Pt foil electrode. The PtNTAEs showed to provide higher reproducibility and lower detection limit. The relative standard deviation (RSD) was 3.5% for 50 repeated measurements of 20 μM As(III), and the limit of detection (LOD) was 0.1 ppb, which was typically 1–2 orders of magnitude lower than that of Pt_nano/GCE or Pt foil electrode.     

Unique CO-tolerance of Pt–WOx materials

Well-defined tungsten-oxide-supported platinum nanoparticles (Pt/WO_x) were elaborated by impregnation-reduction of a platinum salt onto commercial monoclinic WO₃. Field-emission gun scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) revealed that the Pt particles are well-distributed on the oxide support, present a narrow particle size distribution centered on ca. 2–3 nm and a low degree of agglomeration. Carbon black was added to ensure electronic percolation in the electrodes during the electrochemical measurements. CO_ads electrooxidation currents were monitored at potentials as low as 0.1 V vs. RHE on Pt/WO_x, demonstrating high CO-tolerance compared to carbon-supported Pt or PtRu catalysts.     

Determination of Mo and V in multiphase gasoline emulsions by electrothermal atomic absorption spectrometry

This paper proposes an alternative analytical method using electrothermal atomic absorption spectrometry to determine Mo and V in multiphase gasoline emulsions. Samples were prepared by mixing gasoline with a nitric acid solution (0.1% v/v) and two cationic surfactants. The mixture was sonicated, resulting in an emulsive system. Calibration was done by using the aforementioned solutions with added analyte. The detection limits (3σ) of Mo and V were 0.9 μg l^− 1 and 4.7 μg l^− 1, respectively. The accuracy and precision of the proposed method were evaluated by the analysis of samples spiked with metallo-organic standard and the relative standard deviation obtained ranged from 1.2% to 4.4% in samples spiked with 2 μg l^− 1 of each metal. The recovery rates varied from 91.2% to 101.6%. The proposed method was applied to determine Mo and V in samples of gasoline from different gas stations.     

Photoelectrochemical water splitting using a Cu(In,Ga)Se2 thin film

The effects of surface modification and reaction conditions on the photoelectrochemical properties of polycrystalline Cu(In,Ga)Se₂ (CIGS) thin films for water splitting were studied. CIGS modified with platinum particles (Pt/CIGS) generated a cathodic photocurrent at potentials up to + 0.4 V vs. RHE at pH = 9.5. The photocurrent was stable for 16 h, which resulted in a turnover number of over 500. A CdS-inserted film (Pt/CdS/CIGS) had significantly improved properties compared to Pt/CIGS: a 0.3 V higher onset potential of cathodic photocurrent and a three-fold increase in the quantum efficiency. Our results suggest the feasibility of CIGS as a photocathode for biphotoelectrochemical water splitting.     

Application of non-aggressive sample preparation and electrothermal atomic absorption spectrometry to quantify platinum in biological matrices after cisplatin nanoparticle administration

A reproducible, simple, rapid and sensitive electrothermal atomic absorption spectrometry (ETAAS) method using low volume of sample (< 50 μL) was described for the quantitative analysis of cis-diamminedichloroplatinum (II) (cisplatin) in several biological matrices after PLGA [Poly (d,l-lactic-co-glycolic acid)] cisplatin nanoparticles (NP) administration to tumor-bearing mice. The validation parameters such as specificity, linearity, accuracy and precision obtained in this method were according to FDA guidelines and are presented in the text, as well as the limit of detection and quantification. Two applications were carried out with this method. In-vitro application was used to measure the loading efficacy of cisplatin in the formulation, and to characterize the drug kinetic release in culture cell medium. For in-vivo application, three groups of nu/nu mice injected with tumor cells were treated with 5 mg kg^? 1 dose of free cisplatin by intravenous and intraperitoneal routes, respectively, and with NP by intraperitoneal route. Blood samples were collected at different times, to measure cisplatin plasma concentrations, and at the end of the study, different organs were removed from each animal to quantify drug distribution. Additionally, the relationship between cisplatin levels and its apoptotic activity in each tumor sample, could be also characterized. This simple and sensitive method without aggressive manipulation allowed the quantification of cisplatin in different biological matrices with independence of the formulation used. Therefore, these pre-clinical results show the possibility to include this method for clinical applications.     

Evaluation of a platinum electrode modified with hydroxyapatite in the lead(II) determination in a square wave voltammetric procedure

The behavior of a modified carbon platinum electrode (Pt) for lead(II) determination by square wave voltammetry (SWV) was studied. The modified electrode is obtained by electrodeposition of hydroxyapatite (HAP) on the surface of a bare platinum electrode. The new electrode (HAP/Pt) revealed interesting electroanalytical detection of lead(II) based on the adsorption of this metal onto hydroxyapatite under open circuit conditions. After optimization of the experimental and voltammetric conditions, the best voltammetric responses-current intensity and voltammetric profile were obtained in 0.2 mol L^?1 KNO₃ with: 30 min accumulation time, 5 mV pulse amplitude and 1 mV s^?1 scan rate. The observed detection (DL, 3σ) and quantification (DL, 10σ) limits in pure water were 2.01 × 10^?8 and 6.7 × 10^?7 mol L^?1, respectively. The reproducibility of the proposed method was determined from five different measurements in a solution containing 2.2 × 10^?6 mol L^?1 lead(II) with a coefficients of variation of 2.08%.The electrochemical of hydroxyapatite at platinum surfaces was characterized, after calcinations 900 °C, by X-ray diffraction, infrared spectroscopy, chemical and electrochemical analysis.