1,721,080 research outputs found
Fast iron speciation in seawater by catalytic Competitive Ligand Equilibration-Cathodic Stripping Voltammetry with tenfold sample size reduction
Iron speciation analysis in seawater is a fundamental step to understand the cycling of this element in oceanic waters, in view of its central role in regulating primary productivity and its connection to global planetary cycles. At present, analytical procedures are the bottleneck for speciation analysis, in term of both time and sample size requirement. Here we present a novel instrumental configuration for the speciation analysis of iron by the Competitive Ligand Equilibration - Cathodic Stripping Voltammetry (CLE-CSV) procedure. The new system features a 1 mL microcell and a silver wire pseudoreference enabling a tenfold reduction of the sample volume. 2,3-dihydroxynaphthalene was used as the complexing ligand and atmospheric oxygen as the catalytic enhancer because they ensured the best analytical performances in terms of detection capabilities. The side reaction coefficient for the FeDHN complex αFe'DHN was calibrated against EDTA and an average value of 9.25 for logK’Fe'DHN was calculated. The method was successfully validated in UV digested seawater using diethylenetriaminepentaacetic acid (DTPA), which has known stability constant for iron. The method was lastly applied to six samples from the Ross Sea water column (Antarctica), demonstrating its fit for purpose for the detection of trace amounts of iron ligands in seawater. Thanks to the employed instrumental configuration and the high sensitivity, the proposed method achieved a tenfold reduction in sample size, a tenfold increase in sensitivity compared with other methods employing DHN and halved the analysis time with respect to the fastest method reported in the literature. Half an hour is enough to measure a 12 point titration, making the analysis of at least three titrations per day feasible. It is expected that the application of this procedure will foster the sample throughput, thanks to the reduced analysis time, and make possible the analysis of limitedly available and challenging samples, like porewater and vent fluids via the tenfold reduction in sample size
Exploring bufferless iron speciation in seawater by Competitive Ligand Equilibration-Cathodic Stripping Voltammetry: Does pH control really matter?
Iron speciation in seawater is of the utmost importance as this element plays a central role in the regulation of primary productivity. Here we present the development of a CLE-CSV (Competitive Ligand Equilibration-Cathodic Stripping Voltammetry) procedure for iron speciation in seawater avoiding for the first time the use of the pH buffer (2,3-dihydroxynaphthalene is used as the added ligand, atmospheric oxygen as the catalytic enhancer and a 1 mL volume per sample aliquot). The unbuffered method was setup, validated by using known ligands and finally applied to the analysis of six seawater samples from the Ross Sea (Antarctica). The validation procedure demonstrated that ultratrace levels of ligands may be reliably determined and the application to seawater samples proved that the complex natural ligand pool can be detected with results undistinguishable from the ones obtained by the buffered procedure. The proposed method demonstrated a new principle in trace element speciation analysis by CLE-CSV, namely that the equilibration step may be performed at natural pH, whereas the pH may be set at its optimal value for sensitivity during analysis, thanks to the raise in pH at the electrode/solution interface caused by oxygen reduction. This change in paradigm paves the way to the investigation of iron speciation at natural pH in traditionally difficult samples that show circumneutral or slightly acidic pH values. The relevance of the here proposed approach to existing speciation procedures by CLE-CSV is also discussed
Strategies for the characterization and optimization of adsorptive stripping voltammetry with catalytic enhancement for ultratrace element determination: The case of iron 2,3-dihydroxynaphthalene complex with catalytic enhancement by atmospheric oxygen
A comprehensive approach to the characterization and setup of metal determination by adsorptive stripping voltammetry with catalytic enhancement (CAdSV) is presented. The focus is on the understanding of the chemical features of these procedures to demonstrate which parameters can influence the analytical performances: the CAdSV method for the determination of iron at trace level using 2,3-dihydroxynaphthalene (DHN) is taken as case study. First, the ligand degradation was investigated by 1H NMR spectroscopy highlighting a significant degradation at alkaline pH of around 33% in 12 h. The use of degraded DHN had a detrimental effect on the analytical sensitivity, highlighting the need to frequently prepare the ligand. The thermodynamics of ligand and complex adsorption onto the working electrode (hanging mercury drop electrode, HMDE) was subsequently studied: both showed a strong adsorption onto the mercury surface (βDHN = 2.5·103 ± 5·102 L mol−1; βFe-DHN = 5.5·105 ± 8·104 L mol−1), but no competition for the mercury surface between the ligand and the complex was evident as determined by the multicomponent Langmuir isotherm. The mechanism of the electrode reaction was also investigated with and without the catalytic enhancement of the signal caused by air oxygen. The reduction of the complex Fe-DHN in purged solution showed α = 0.57 and k0 = 79 cm s−1, highlighting a quasireversible mechanism. The apparent catalytic constant (k'cat) was 168 s−1 for 1 mL sample volume: the simultaneous study of the kinetic and catalytic constant showed that the current signal was mostly influenced by the kinetic of the reaction
Localization of p27 Beta4 Binding protein gene (ITGB4BP) to human chromosome region 20q11.2
Expression of a highly conserved protein, p27BBP, during the progression of human colorectal cancer
Urban mobility demand profiles: Time series for cars and bike-sharing use as a resource for transport and energy modeling
The transport sector is currently facing a significant transition, with strong drivers including decarbonization and digitalization trends, especially in urban passenger transport. The availability of monitoring data is at the basis of the development of optimization models supporting an enhanced urban mobility, with multiple benefits including lower pollutants and CO2 emissions, lower energy consumption, better transport management and land space use. This paper presents two datasets that represent time series with a high temporal resolution (five-minute time step) both for vehicles and bike sharing use in the city of Turin, located in Northern Italy. These high-resolution profiles have been obtained by the collection and elaboration of available online resources providing live information on traffic monitoring and bike sharing docking stations. The data are provided for the entire year 2018, and they represent an interesting basis for the evaluation of seasonal and daily variability patterns in urban mobility. These data may be used for different applications, ranging from the chronological distribution of mobility demand, to the estimation of passenger transport flows for the development of transport models in urban contexts. Moreover, traffic profiles are at the basis for the modeling of electric vehicles charging strategies and their interaction with the power grid
Going Beyond Counting First Authors in Author Co-citation Analysis
The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
p27BBP/eIF6 is constitutively expressed in vitro, but highly modulated in vivo. Genomic structure and expression studies
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