Characterization of low molecular weight sulfur species in seaweed from the Antarctic continent.

Antarctic seaweeds are vital components of polar marine ecosystems, playing a crucial role in nutrient cycling and supporting diverse life forms. The sulfur content in these organisms is particularly interesting due to its implication in biogeochemical processes and potential impacts on local and global environmental systems. In this study, we present a comprehensive characterization of seaweed collected in the Antarctic in terms of their total sulfur content and its distribution among different classes of species, including thiols, using various methods and high-sensitivity techniques. The data presented in this paper are unprecedented in the scientific literature. These methods allowed for the determination of total sulfur content and the distribution of sulfur compounds in different fractions, such as water-soluble and proteins, as well as the speciation of sulfur compounds in these fractions, providing valuable insights into the chemical composition of these unique marine organisms. Our results revealed that the total sulfur concentration in Antarctic seaweeds varied widely across different species, ranging from 5.5 to 56 g kg-1 dry weight. Furthermore, our investigation into the sulfur speciation revealed the presence of various sulfur compounds, including sulfate, and some thiols, which were quantified in all ten seaweed species evaluated. The concentration of these individual sulfur species also displayed considerable variability among the studied seaweeds. This study provides the first in-depth examination of total sulfur content and sulfur speciation in brown and red Antarctic seaweeds.

Flow field-flow fractionation and single particle inductively coupled plasma mass spectrometry as a powerful tool for tracking and understanding the sensing mechanism of Ag-Au bimetallic nanoparticles toward cobalt ions.

BACKGROUND: Ag-Au bimetallic nanoparticles (BNPs), synthesized by using citrate reduction of Ag and Au ions, were used as sensor for detection of Co2+. In order to optimize sensing performance, it is necessary to control the particle size and size distribution of the original Ag-Au BNPs. Therefore, analytical methods based on the use of single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) and flow-field flow fractionation (FlFFF)-ICP-MS were developed to track the signal of Ag and Au in bimetallic nanoparticles at each step of the procedure: BNP synthesis, aggregation and sensing in order to understand the sensing mechanism. To better understand colorimetric sensing of Co2+ using Ag-Au BNPs, various solution mixtures were analyzed by using SP-ICP-MS and FlFFF-ICP-MS. RESULTS: SP-ICP-MS provided the information on the core size, size distribution and particle number concentration, as well as the heterogeneity of the particles synthesized by using various citrate concentrations and metal ratios. FlFFF-ICP-MS offered the information on hydrodynamic size as well as the signal intensity ratio of Ag and Au in BNPs and for the understanding of the aggregation of BNPs arising from the [Co(II)(en)3]2+ complex surrounding the surface of the BNPs. Under optimum sensing condition, the use of SP-ICP-MS for BNPs assisted detection of Co2+ improved the sensitivity of Co2+ determination by 20-fold in comparison with the conventional spectrophotometric analysis. SIGNIFICANCE: The information obtained from SP-ICP-MS and FlFFF-ICP-MS can be combinedly used to understand sensing mechanism and to select the best condition for synthesis of BNPs used as sensor. This study illustrates the usefulness of SP-ICP-MS and FlFFF-ICP-MS in the nanoparticle-based sensor development research area.

Characterization of halogen species in seaweeds from the Antarctic using a multi-technique approach.

BACKGROUND: Despite the recognized importance, the determination of halogens in Antarctic seaweeds remains understudied. Limited research exists due to challenges associated with sample preparation, and reliable analytical techniques for this type of analysis. Therefore, further investigations are necessary to bridge this knowledge gap and gain a comprehensive understanding of halogen metabolism in Antarctic seaweeds. METHODS: In this study, seaweeds from the coast of the Antarctic continent were characterized concerning the total content of halogens and their species. For this purpose, different sample preparation methods, based on extraction and combustion, combining highly selective and sensitive chromatographic and spectrometric multi-technique approaches were used. RESULTS: By using optimized methods, it was possible to determine total halogens content, the distribution of bromine and iodine in different classes of species (lipids, water-soluble, proteins, carbohydrates, and residue), as well as the identification of iodinated amino acids (MIT and DIT) in ten brown and red seaweeds. Bromate and iodate were not detected in the samples, which presented only bromide and iodide species in their composition. Additionally, unknown bromine and iodine species were observed in different extracts evaluated. Furthermore, 25 halogenated polyphenols were identified in seaweeds, of which only four were already reported in the literature. CONCLUSION: The results obtained in this study comprise unprecedented data in the literature on species of halogens present in seaweeds from the Antarctic environment.

Study of metalation of thioredoxin by gold(I) therapeutic compounds using combined liquid chromatography/capillary electrophoresis with inductively coupled plasma/electrospray MS/MS detection.

The reactivity of thioredoxin (Trx1) with the Au(I) drug auranofin (AF) and two therapeutic N-heterocyclic carbene (NHC)2-Au(I) complexes (bis [1-methyl-3-acridineimidazolin-2-ylidene]gold(I) tetrafluoroborate (Au3BC) and [1,3-diethyl-4,5-bis(4methoxyphenyl)imidazol-2-ylidene]gold(I) (Au4BC)) was investigated. Direct infusion (DI) electrospray ionization (ESI) mass spectrometry (MS) allowed information on the structure, stoichiometry, and kinetics of formation of Trx-Au adducts. The fragmentation of the formed adducts in the gas phase gave insights into the exact Au binding site within the protein, demonstrating the preference for Trx1 Cys32 or Cys35 of AF or the (NHC)2-Au(I) complex Au3BC, respectively. Reversed-phase HPLC suffered from the difficulty of elution of gold compounds, did not preserve the formed metal-protein adducts, and favored the loss of ligands (phosphine or NHC) from Au(I). These limitations were eliminated by capillary electrophoresis (CE) which enabled the separation of the gold compounds, Trx1, and the formed adducts. The ICP-MS/MS detection allowed the simultaneous quantitative monitoring of the gold and sulfur isotopes and the determination of the metallation extent of the protein. The hyphenation of the mentioned techniques was used for the analysis of Trx1-Au adducts for the first time.

Effect of graded levels of selenium supplementation as selenite on expression of selenosugars, selenocysteine, and other selenometabolites in rat liver.

Using high pressure liquid chromatography (HPLC) coupled with selenium-specific inductively coupled plasma mass spectrometry (ICP-MS) and molecule specific (Orbitrap MS/MS) detection, we previously found that far more selenium (Se) is present as selenosugar (seleno-N-acetyl galactosamine) in Se-adequate turkey liver than is present as selenocysteine (Sec) in true selenoproteins, and that selenosugars account for half of the Se in high-Se turkey liver. To expand these observations to mammals, we studied Se metabolism in rats fed graded levels of selenite from 0 to 5 µg Se/g for 4 wk. In Se-adequate (0.24 µg Se/g) rats, 43% of liver Se was present as Sec, 32% was present as selenosugars, and 22% as inorganic Se bound to protein. In liver of rats fed 5 µg Se/g as selenite, the quantity of Sec remained at the Se-adequate plateau (11% of total Se), 22% was present as low molecular weight (LMW) selenosugars with substantial additional selenosugars linked to protein, but 64% was present as inorganic Se bound to protein. No selenomethionine was found at any level of selenite supplementation. Below the Se requirement, Se is preferentially incorporated into Sec-selenoproteins. Above the dietary Se requirement, selenosugars become by far the major LMW water soluble Se species in liver, and levels of selenosugar-decorated proteins are far higher than Sec-selenoproteins, making these selenosugar-decorated proteins the major Se-containing protein species in liver with high Se supplementation. This accumulation of selenosugars linked to cysteines on proteins or the build-up of inorganic Se bound to protein may underlie Se toxicity at the molecular level.

Selenomethionine supplementation and expression of selenosugars, selenocysteine, and other selenometabolites in rat liver.

Selenomethionine (SeMet) as a methionine analog can be incorporated into protein. In turkeys, we recently found that selenium (Se) as selenite is not metabolized to SeMet but rather to selenosugars (seleno-N-acetyl galactosamine) bound to protein as well as to selenocysteine (Sec) in selenoproteins. To characterize the metabolism of SeMet, we fed rats graded levels of SeMet from 0 to 5 µg Se/g in a Se-deficient diet for 4 wk, and investigated the fate and accumulation of liver Se using high pressure liquid chromatography (HPLC) coupled with Se-specific inductively coupled plasma mass spectrometry (ICP-MS) and molecule specific (Orbitrap MS/MS) detection. Up to 0.24 µg Se/g (Se requirement for maximal glutathione peroxidase activity), Sec accounted for ∼40% of total liver Se whereas SeMet only accounted for 3-11%. Analysis of water-soluble extracts found negligible low molecular weight (LMW) Se species in rats fed 0 and 0.08 µg Se/g, including no SeMet. At 0.24 µg Se/g and above, SeMet accounted for only 10% of LMW Se species, whereas methyl- and glutathionyl-selenosugars accounted for 70% of LMW Se species. Above the Se requirement, SeMet was ∼30% of the proteinaceous amino acids, whereas Sec levels fell to 5% in rats fed 5 µg Se/g as SeMet. Last, considerably less inorganic Se was bound to liver protein with high SeMet as compared to selenite in a parallel study. SeMet is efficiently metabolized and mixes with the common Se metabolite pool, where Se is preferentially incorporated into Sec and Sec-selenoproteins until selenoproteins plateau; with high SeMet intake, Se is increasingly accumulated as LMW selenosugars and as selenosugar-decorated proteins.

Copper-zinc/chitosan complex hydrogels: Rheological, degradation and biological properties.

Polymer hydrogels crosslinked by therapeutic metal ions have attracted increased interest in recent years due to their unique and versatile properties. Chitosan hydrogels are widely investigated for various biomedical applications such as tissue engineering and drug delivery. Copper and zinc ions are considered as therapeutic metal ions, that have important roles in bone regeneration. The aim of this study was to investigate the physicochemical and biological properties of bimetallic-chitosan complex hydrogels with different cupric and zinc ions content. Scanning electron microscopy (SEM) revealed changes in the morphology from the microstructure with larger, tubular pores for aerogels with higher Zn content, to the sheets-like structure with long pores for samples with higher Cu content. FTIR analysis indicated the formation of bimetallic-chitosan aerogels. The obtained X-ray diffraction patterns showed a broadening of chitosan's characteristic diffraction maximum, while characterization of physical properties showed decreased swelling ability and increased shear modulus with higher Cu content. ICP-MS results showed a negligible amount of copper and zinc ions released under physiological conditions during 24 h indicating a strong physical crosslink between metal ions and chitosan chains. Furthermore, accelerated in vitro degradation showed that hydrogels maintained good stability during four weeks of lysozyme activity. The MTT assay indicated that the cytotoxicity of Cu2+-Zn2+/chitosan complexes could be adjusted by the amount of cupric ions. All results imply that Cu2+ and Zn2+ ions act as physical crosslinkers of the polymer network. Also, results are in agreement with the prediction of density functional theory (DFT) which indicated stronger chitosan-Cu tetrahedral aqua complex interactions in comparison to the chitosan-[Zn(H2O)4]2+ interactions.

Quantitative Determination of Iron-Siderophore Complexes in Peat by Isotope-Exchange Size-Exclusion UPLC-Electrospray Ionization High-Resolution Accurate Mass (HRAM) Mass Spectrometry.

A method was developed for the quantification of iron-siderophore complexes by electrospray high-resolution accurate mass (HRAM) mass spectrometry (MS) without the need for authentic standards. The bulk of iron-siderophore complexes was purified by solid-phase extraction (SPE) and concentrated by evaporation. The individual complexes were identified by fast size-exclusion chromatography (FastSEC)-Orbitrap MSn on the basis of the exact molecular mass (±1 ppm) and MS2 or MS3 fragmentation. Their capability to readily exchange the natural 56Fe for the added 58Fe was demonstrated by SEC with ICP MS and ESI MS detection. The method was applied to the analysis of peat sampled in the eastern part of the French Pyrenean mountains. Nineteen siderophores belonging to four different classes were identified and quantified. The results were validated using ICP MS detection of iron by matching the sum of iron complexes determined by isotope exchange-ESI MS within each peak observed by FastSEC-ICP MS.

Detection of secondary cyanobacterial metabolites using LC-HRMS in Lake Karaoun.

Harmful algal blooms events have been reported worldwide and during the last decades are occurred with increasing frequency and intensity due to the climate change and the high inputs of nutrients in freshwaters from anthropogenic activities. During blooms cyanobacteria release in water their toxic secondary metabolites, known as cyanotoxins, along with other bioactive metabolites. Due to the negative impacts of these compounds on aquatic ecosystems and public health, there is an urgent need to detect and identify known and unknown cyanobacterial metabolites in surface waters. In the frame of the present study, a method based on liquid chromatography - high resolution mass spectrometry (LC-HRMS) was developed to investigate the presence of cyanometabolites in bloom samples from Lake Karaoun, Lebanon. Data analysis was performed using Compound Discoverer software with related tools and databases in combination to the CyanoMetDB mass list for detection, identification and structural elucidation of the cyanobacterial metabolites. In the course of this study, 92 cyanometabolites were annotated including 51 cyanotoxins belonging to microcystins, 15 microginins, 10 aeruginosins, 6 cyclamides, 5 anabaenopeptins, a cyanopeptolin, the dipeptides radiosumin B and dehydroradiosumin, the planktoncyclin and a mycosporine-like amino acid. Out of them, 7 new cyanobacterial metabolites, the chlorinated MC-ClYR, [epoxyAdda5]MC-YR, MC-LI, aeruginosin 638, aeruginosin 588, microginin 755C and microginin 727 were discovered. Moreover, the presence of anthropogenic contaminants was recorded indicating the pollution of the lake and emphasizing the need for assessment of the co-occurrence of cyanotoxins, other cyanobacterial metabolites and other compounds hazardous to the environment. Overall, results prove the suitability of the proposed approach for the detection of cyanobacterial metabolites in environmental samples but also highlight the necessity of spectral libraries for these compounds, considering the absence of their reference standards.

Study of metal and organic contaminants transported by microplastics in the Lebanese coastal environment using ICP MS, GC-MS, and LC-MS.

An untargeted study of multiclass contaminants associated with microplastics (MPs) in the East Mediterranean was carried out. Samples were collected in 2020-2021 from the shoreline at 14 different locations, along the Lebanese coast. Attenuated Total Reflectance (ATR) FTIR spectroscopy showed the predominant presence of polyethylene and polypropylene among plastic debris. The non-polar and polar organic compounds sorbed on the MPs were identified and quantified by GC - TOF MS and LC - electrospray MS/MS, respectively. Deconvolution of accurate GC-MS scan data allowed the identification of >130 organic pollutants, 64 of which could be confirmed by matching with the authentic standards, among which a number of previously unreported in targeted GC-MS(MS) methods. In addition to highly toxic, legacy chlorinated pollutants, high levels (average values from 0.8 to 4.0 µg g-1) of some musks, UV filters and UV absorbers were detected. Untargeted LC-MS demonstrated the persistence of several pesticides (i.e., chlorpyrifos) and pharmaceuticals, such as phenacetin and minoxidil, which were quantified. In addition, a study of metals associated with microplastics using ICP-MS confirmed the high potential of microplastics to act as a vector of, among others, toxic metals, such as Cd, Pb, Bi or Hg.

A green and fast microwave-assisted synthesis of selenium nanoparticles and their characterization under gastrointestinal conditions using mass spectrometry.

We present a novel microwave-assisted green synthesis of selenium nanoparticles (SeNPs) using yeast extract as source of a non-toxic reducing and capping agents. Effects of synthesis and gastrointestinal digestion conditions on the biogenic Se particle size distribution and number concentration using SP ICP MS were evaluated. The median equivalent diameter of SeNPs varied depending on the synthesis conditions. Upon incubation in simulated gastric juice, the increase of SeNPs size was observed, whereas after simulated intestinal juice addition, their size came back close to the initial value. The biomolecules contained in yeast extract, which play predominant role in the synthesis of SeNPs, were identified by non-targeted qualitative analysis using LC Orbitrap ESI MS. The use of the state-of-the-art MS techniques allowed both the comprehensive assessment of the processes leading to the SeNPs formation and the evaluation of their behavior under gastrointestinal conditions which is of utmost importance for their use as a novel selenium source.

Relationships between Molecular Characteristics of Novel Organic Selenium Compounds and the Formation of Sulfur Compounds in Selenium Biofortified Kale Sprouts.

Due to problems with selenium deficiency in humans, the search for new organic molecules containing this element in plant biofortification process is highly required. Selenium organic esters evaluated in this study (E-NS-4, E-NS-17, E-NS-71, EDA-11, and EDA-117) are based mostly on benzoselenoate scaffolds, with some additional halogen atoms and various functional groups in the aliphatic side chain of different length, while one compound contains a phenylpiperazine moiety (WA-4b). In our previous study, the biofortification of kale sprouts with organoselenium compounds (at the concentrations of 15 mg/L in the culture fluid) strongly enhanced the synthesis of glucosinolates and isothiocyanates. Thus, the study aimed to discover the relationships between molecular characteristics of the organoselenium compounds used and the amount of sulfur phytochemicals in kale sprouts. The statistical partial least square model with eigenvalues equaled 3.98 and 1.03 for the first and second latent components, respectively, which explained 83.5% of variance in the predictive parameters, and 78.6% of response parameter variance was applied to reveal the existence of the correlation structure between molecular descriptors of selenium compounds as predictive parameters and biochemical features of studied sprouts as response parameters (correlation coefficients for parameters in PLS model in the range-0.521 ÷ 1.000). This study supported the conclusion that future biofortifiers composed of organic compounds should simultaneously contain nitryl groups, which may facilitate the production of plant-based sulfur compounds, as well as organoselenium moieties, which may influence the production of low molecular weight selenium metabolites. In the case of the new chemical compounds, environmental aspects should also be evaluated.

Effects of the fermentation process on the selenite metabolism and selenium incorporation and speciation in a probiotic Bifidobacterium longum.

The influence of the fermentation process on selenite metabolism by a probiotic Bifidobacterium longum DD98 and its consequent enrichment in selenium (Se) were studied. The effects of sodium selenite (Na2SeO3) concentration (18-400 µg/ml), feeding time (12, 16, and 24 h), and fermentation stage (secondary and tertiary fermentation) were evaluated by measuring (i) the total Se content and its distribution between the water-soluble metabolome fraction and the water-insoluble fraction; (ii) the total concentrations of the two principal Se compounds produced: selenomethionine (SeMet) and γ-glutamyl-selenomethionine (γ-Glu-SeMet), and (iii) the speciation of Se in the metabolite fraction. The results revealed that the fermentation process notably changed the Se incorporation into metabolites (γ-Glu-SeMet and free SeMet) and proteins (bound-SeMet) in B. longum DD98. In particular, the production of SeMet was negatively correlated to that of γ-Glu-SeMet when no red precipitate was seen in the bacteria. The study offers a tool for the control of the optimization of the fermentation process towards the desired molecular speciation of the incorporated Se and hence contributes to the production of Se-enriched probiotics with good qualities and bioactivities.

Isotopologue pattern based data mining for selenium species from HILIC-ESI-Orbitrap-MS-derived spectra.

Automated and specific picking of selenium-containing molecular entities has not been an obvious option for software tools associated with electrospray high-resolution mass spectrometry (MS). In our study, a comprehensive pattern matching approach based on intra-isotopologue distance and isotopologue ratio data was critically evaluated in terms of reproducibility and selenium isotope selection on three samples, including selenized Torula yeast and the selenium hyperaccumulator plant Cardamine violifolia. Hydrophilic interaction liquid chromatography was applied to provide a one-step separation for water soluble metabolites to put an end to the need for either orthogonal setups or poor retention on reversed phase chromatography. Assistance from inductively coupled plasma-MS was taken only for chromatographic verification purposes, and the involvement of absolute mass defect (MD) data in selenometabolite-specific screening was assessed by multivariate statistical tools. High focus was placed on screening efficiency and on the validation of discovered selenized molecules to avoid reporting of artefacts. From the >1000 molecular entries detected, selenium-containing molecules were picked up with a recovery rate of >88% and a false positive rate of <10%. Isotop(ologu)e pairs of 78Se-80Se and 80Se-82Se proved to be the most performant in the detection. On the basis of accurate mass information and hypothetical deamination processes, elemental composition could be proposed for 72 species out of the 75 selenium species encountered without taking into account selenocompound databases. Absolute MD data were used to significantly differentiate a potentially sample-specific subgroup of false positive molecular entities from non-selenized and selenized entities.

Chitosan-Boric Acid Scaffolds for Doxorubicin Delivery in the Osteosarcoma Treatment.

Biologically compatible chitosan-based scaffolds have been considered a promising platform for tissue regeneration, tumor treatment, and targeted drug delivery. Chitosan-based scaffolds can be utilized as pH-sensitive drug carriers with targeted drug delivery resulting in less invasive tumor treatments. Further improvement with bioactive ions, such as borate ions, can result in the dual functionality of chitosan carriers provided by simultaneous antitumor efficacy and tissue regeneration. Here, boric acid-containing crosslinked chitosan scaffolds were prepared as delivery systems of doxorubicin, a chemotherapy drug used in the treatment of osteosarcoma. The encapsulation of boric acid was indicated by FTIR spectroscopy, while the ICP-MS analysis indicated the rapid release of boron in phosphate buffer (pH 6.0) and phosphate-buffered saline solution (pH 7.4). The obtained chitosan-boric acid scaffolds exhibit a highly porous and interconnected structure responsible for high swelling capacity, while enzymatic degradation indicated good scaffolds stability during four weeks of incubation at pH 6.0 and 7.4. Furthermore, the release of doxorubicin investigated in phosphate buffers indicated lower doxorubicin concentrations at pH 7.4 with respect to pH 6.0. Finally, the cytotoxicity of prepared doxorubicin-encapsulated scaffolds was evaluated on human sarcoma cells indicating the scaffolds' potential as cytostatic agents.

Identification of γ-Glutamyl-Selenomethionine as the Principal Selenium Metabolite in a Selenium-Enriched Probiotic, Bifidobacterium longum, by Two-Dimensional HPLC-ICP MS and HPLC-ESI Orbitrap MS.

Selenium (Se)-enriched probiotics are potential sources of organic Se in the human diet, but their application in food is debated because most selenized probiotics and their metabolites are not well-characterized. We analyzed a Se-enriched probiotic, Bifidobacterium longum DD98, to unveil its Se metabolite profiles by two-dimensional high-performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP MS) and HPLC-electrospray ionization Orbitrap MS. A major Se metabolite was identified as gamma-glutamyl-selenomethionine (γ-Glu-SeMet), which accounted for 42.5 ± 3.4% of water-soluble Se. Most of the remaining Se was present as SeMet (35.2 ± 0.6%) in a free or protein-bound form. In addition, 11 minor Se metabolites were identified, eight of which had not been reported before in probiotics. Six of the identified compounds contained γ-Glu-SeMet as the core structure, constituting a γ-Glu-SeMet family. This study demonstrates the presence of γ-Glu-SeMet in a probiotic, showing a different selenite metabolite pathway from that of Se-enriched yeast, and it offers an alternative and potentially attractive source of organic Se for food and feed supplementation.

Comprehensive Speciation Analysis of Residual Gadolinium in Deep Cerebellar Nuclei in Rats Repeatedly Administered With Gadoterate Meglumine or Gadodiamide.

PURPOSE: Several preclinical studies have reported the presence of gadolinium (Gd) in different chemical forms in the brain, depending on the class (macrocyclic versus linear) of Gd-based contrast agent (GBCA) administered. The aim of this study was to identify, with a special focus on insoluble species, the speciation of Gd retained in the deep cerebellar nuclei (DCN) of rats administered repeatedly with gadoterate or gadodiamide 4 months after the last injection. METHODS: Three groups (N = 6/group) of healthy female Sprague-Dawley rats (SPF/OFA rats; Charles River, L'Arbresle, France) received a cumulated dose of 50 mmol/kg (4 daily intravenous administrations of 2.5 mmol/kg, for 5 weeks, corresponding to 80-fold the usual clinical dose if adjusted for man) of gadoterate meglumine (macrocyclic) or gadodiamide (linear) or isotonic saline for the control group (4 daily intravenous administrations of 5 mL/kg, for 5 weeks). The animals were sacrificed 4 months after the last injection. Deep cerebellar nuclei were dissected and stored at -80°C before sample preparation. To provide enough tissue for sample preparation and further analysis using multiple techniques, DCN from each group of 6 rats were pooled. Gadolinium species were extracted in 2 consecutive steps with water and urea solution. The total Gd concentrations were determined by inductively coupled plasma mass spectrometry (ICP-MS). Soluble Gd species were analyzed by size-exclusion chromatography coupled to ICP-MS. The insoluble Gd species were analyzed by single-particle (SP) ICP-MS, nanoscale secondary ion mass spectroscopy (NanoSIMS), and scanning transmission electron microscopy with energy-dispersive X-ray spectroscopy (STEM-EDX) for elemental detection. RESULTS: The Gd concentrations in pooled DCN from animals treated with gadoterate or gadodiamide were 0.25 and 24.3 nmol/g, respectively. For gadoterate, the highest amount of Gd was found in the water-soluble fractions. It was present exclusively as low-molecular-weight compounds, most likely as the intact GBCA form. In the case of gadodiamide, the water-soluble fraction of DCN was composed of high-molecular-weight Gd species of approximately 440 kDa and contained only a tiny amount (less than 1%) of intact gadodiamide. Furthermore, the column recovery calculated for this fraction was incomplete, which suggested presence of labile complexes of dissociated Gd3+ with endogenous molecules. The highest amount of Gd was detected in the insoluble residue, which was demonstrated, by SP-ICP-MS, to be a particulate form of Gd. Two imaging techniques (NanoSIMS and STEM-EDX) allowed further characterization of these insoluble Gd species. Amorphous, spheroid structures of approximately 100-200 nm of sea urchin-like shape were detected. Furthermore, Gd was consistently colocalized with calcium, oxygen, and phosphorous, strongly suggesting the presence of structures composed of mixed Gd/Ca phosphates. No or occasional colocalization with iron and sulfur was observed. CONCLUSION: A dedicated analytical workflow produced original data on the speciation of Gd in DCN of rats repeatedly injected with GBCAs. The addition, in comparison with previous studies of Gd speciation in brain, of SP element detection and imaging techniques allowed a comprehensive speciation analysis approach. Whereas for gadoterate the main fraction of retained Gd was present as intact GBCA form in the soluble fractions, for linear gadodiamide, less than 10% of Gd could be solubilized and characterized using size-exclusion chromatography coupled to ICP-MS. The main Gd species detected in the soluble fractions were macromolecules of 440 kDa. One of them was speculated to be a Gd complex with iron-binding protein (ferritin). However, the major fraction of residual Gd was present as insoluble particulate species, very likely composed of mixed Gd/Ca phosphates. This comprehensive Gd speciation study provided important evidence for the dechelation of linear GBCAs and offered a deeper insight into the mechanisms of Gd deposition in the brain.

Speciation of metals in indigenous plants growing in post-mining areas: Dihydroxynicotianamine identified as the most abundant Cu and Zn ligand in Hypericum laricifolium.

Ag, As, Cu, Pb and Zn were found to be the principal metallic contaminants of a post-mining area of Peru (Hualgayoc, Cajamarca). Study of metal distribution amongst roots, stems, and leaves of four indigenous hypertolerant plant species, Arenaria digyna, Puya sp., Hypericum laricifolium, Nicotiana thyrsiflora indicated significant translocation of Zn (0.6 < TF ≤ 10.0) and Cu (0.4 < TF ≤ 6.5) into aerial plant organs and substantial water-extractable fraction (20-60%) of these metals, except for A. digyna (root and stems). A study of the metal speciation by ultrahigh-performance size-exclusion (fast-SEC) and hydrophilic ion interaction (HILIC) liquid chromatography with dual ICP (inductively coupled plasma) and electrospray (ESI) Orbitrap MS detection revealed the presence of nicotianamine and deoxymugineic acid copper and zinc complexes in roots, stem and leaves of N. thyrsiflora and Puya sp., and nicotianamine alone in A. digyna. A previously unreported compound, dihydroxy-nicotianamine was identified as the most abundant Cu and Zn ligand in H. laricifolium. The presence of arsenobetaine and an arsenosugar was confirmed by ESI MS. Ag and Pb were hardly translocated to leaves and were found as high molecular species; one of the Pb-containing species co-eluted in fast-SEC-ICP MS with rhamnogalacturonan-II-Pb complex commonly found in in the walls of plants.

Nanoplastic Labelling with Metal Probes: Analytical Strategies for Their Sensitive Detection and Quantification by ICP Mass Spectrometry.

The detection and quantification of nanoplastics in aquatic environments is one of the major challenges in environmental and analytical research nowadays. The use of common analytical techniques for this purpose is not only hampered by the size of nanoplastics, but also because they are mainly made of carbon. In addition, the expected concentrations in environmental samples are below the detection limit of the majority of analytical techniques. In this context, the great detection capabilities of Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in its Single Particle mode (SP-ICP-MS) have made of this technique a good candidate for the analysis of nanoplastics. Since the monitoring of carbon by ICP-MS faces several difficulties, the use of metal tags, taking advantage of the great potential of nanoplastics to adsorb chemical compounds, has been proposed as an alternative. In this perspectives paper, three different strategies for the analysis of polystyrene (PS) nanoplastics by SP-ICP-MS based on the use of metals species (ions, hydrophobic organometallic compound, and nanoparticles) as tags are presented and discussed. Advantages and disadvantages of each strategy, which rely on the labelling process, are highlighted. The metal nanoparticles labelling strategy is shown as a promising tool for the detection and quantification of nanoplastics in aqueous matrices by SP-ICP-MS.