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Fast growing tree species such as Populus spp. in short rotation woody crop (SRWC) systems could be an environmentally friendly and cost-effective approach to ensure sustainable biomass production and mitigate the negative impacts on the environment caused by more intensive management aimed to promote additional biomass increment. Knowledge on variation of major biologically important elements’ and toxic heavy metals’ occurrence in fertilised hybrid aspen tree rings in marginal land may have important and relevant implications for the management practice and evaluation of element fluxes in SRWC ecosystems. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to determine the relative amount of major elements (K, Ca, Mg, P) and heavy metals (Cd, Hg, Pb) in stem wood plane on straight line trajectory starting from pith to bark with measurement step 0.1 mm. While inductively coupled plasma mass spectrometry (ICP-MS) was used to determine average content of the mentioned elements in mechanically separated tree rings to quantify data obtained using LA-ICP-MS method and expressed in relative units. Stem disc samples were collected from six year old hybrid aspen trees growing in marginal agricultural land in the central part of Latvia (hemi-boreal climate conditions) that were initially fertilised with biogas production residues, sewage sludge, and wood ash. We concluded that the content of analysed major elements and heavy metals in the hybrid aspen tree rings varied considerably not only within the analysed stem plane (across tree rings) of one sample tree, but also within one annual ring with significant differences between the content of major elements in earlywood and latewood. Nevertheless, the results of the content of major elements and heavy metals in hybrid aspen tree rings highlighted the significant impact of the initially used fertiliser (especially wood ash) on the average content of elements. Hybrid aspens can be considered bioindicators of both the management activities and general growing conditions even if soil pH is close to neutrality, suggesting a limited mobility of the heavy metals.

In the presented project the investigation on discrimination of geographic origin of wine in from border areas is carried out. Authentic wine samples from the border areas of Austria, Czech Republic, Slovakia (and from Serbia) are investigated and compared by applying different physico-chemical methods (e.g. IRMS, NMR, ICP-MS, ICP-OES, EPR, HPLC, UV-VIS, etc.). The comparison of the data sets from the participating countries and the different applied methods will show, to which extent a differentiation can still be achieved in the border areas of the respective countries, which methods prove most efficient and sensitive and if a combination of methods will lead to an increased sensitivity. Furthermore, we also investigate the causes for the potential differentiation, which might be environmentally determined, due to different agricultural and/or enological practices. Results from the first investigated vintage 2016 show a good separation of the respective geographic origins by isotope ratios and element concentrations as well as by other parameters. The relevant parameters for differentiation now have to be critically evaluated to exclude potential lab influences.

Investigation on discrimination of geographic origin in border areas is carried out by investigating and comparing authentic wine samples from the border areas of Austria, Czech Republic, Slovakia (and from Serbia) by applying different physico-chemical methods (e.g. IRMS, NMR, ICP-MS, ICP-OES, EPR, HPLC, UV-VIS, etc…). The comparison of the data sets from the participating countries and the different applied methods demonstrates, to which extent a differentiation can still be achieved in the border areas of the respective countries, which methods prove most efficient and sensitive and if a combination of methods leads to an increased sensitivity. Furthermore, we also investigate the potential causes for the differentiation, as the environment, different agricultural practices or enology. Analysis of two consecutive vintages shows significant variations between the two years, complicating direct comparison of regions beyond individual vintages. Still, several parameters are identified enabling correct and complete differentiation. However, some of them have been found to represent lab effects, whereas others are interpreted as resulting from different agricultural practices or environmentally driven. Only the latter two ones, if consistent, can be used for discrimination of geographic origin.

Titanite belongs to the common accessory minerals in Variscan (~360–350 Ma) metaluminous to slightly peraluminous tonalites to granodiorites of I-type affinity in the Tatric and Veporic Units, the Western Carpathians, Slovakia. It forms brown tabular prismatic-dipyramidal crystals (~0.5 to 10 mm in size) in association with quartz, plagioclase, and biotite. Titanite crystals commonly shows oscillatory, sector and convolute irregular zonal textures, reflecting mainly variations in Ca and Ti versus Al (1–2 wt. % Al2O3, 0.04–0.08 Al apfu), Fe (0.6–1.6 wt. % Fe2O3, 0.02–0.04 Fe apfu), REE (La to Lu + Y; ≤4.8 wt. % REE2O3, ≤ 0.06 REE apfu), and Nb (up to 0.5 wt. % Nb2O5, ≤0.01 Nb apfu). Fluorine content is up to 0.5 wt. % (0.06 F apfu). The compositional variations indicate the following principal substitutions in titanite: REE3+ + Fe3+ = Ca2+ + Ti4+, 2REE3+ + Fe2+ = 2Ca2+ + Ti4+, and (Al, Fe)3+ + (OH, F)− = Ti4+ + O2−. The U–Pb SHRIMP dating of titanite reveal their Variscan ages in an interval of 351.0 ± 6.5 to 337.9 ± 6.1 Ma (Tournaisian to Visean); titanite U–Pb ages are thus ~5 to 19 Ma younger than the primary magmatic zircon of the host rocks. The Zr-in-titanite thermometry indicates a relatively high temperature range of titanite precipitation (~650–750 °C), calculated for assumed pressures of 0.2 to 0.4 GPa and a(TiO2) = 0.6–1.0. Consequently, the textural, geochronological and compositional data indicate relatively high-temperature, most probably early post-magmatic (subsolidus) precipitation of titanite. Such titanite origin could be connected with a subsequent Variscan tectono-thermal event (~340 ± 10 Ma), probably related with younger small granite intrusions and/or increased fluid activity. Moreover, some titanite crystals show partial alteration and formation of secondary titanite (depleted in Fe and REE) + allanite-(Ce) veinlets (Sihla tonalite, Veporic Unit), which probably reflects younger Alpine (Cretaceous) tectono-thermal overprint of the Variscan basement of the Western Carpathians.

Perovskite (Prv) was discovered in an abyssal harzburgite from a “mélange” type blueschist-bearing accretionary wedge of the Western Carpathians (Meliata Unit, Slovakia). Perovskite-1 formation in serpentinized orthopyroxene may be simplified by the mass-balance reaction: Ca2Si2O6 (Ca-pyroxene-member)+2Fe2TiO4 (ulvöspinel molecule in spinel)+2H2O+O2=2CaTiO3 (Prv)+2SiO2+4FeOOH (goethite). Perovskite-2 occurs in a chlorite-rich blackwall zone separating serpentinite and rodingite veins, and in rodingite veins alone. The bulk-rock trace-element patterns suggest negligible differences from visually and microscopically less (“core”) to strongly serpentinized harzburgite due to serpentinization and rodingitization: an enrichment in LREE(La,Ce), Cs, ±Ba, U, Nb, Pb, As, Sb, ±Nd and Li in comparison with HREE, Rb and Sr. The U/Pb perovskite ages at ~135 Ma are interpreted to record the interaction of metamorphic fluids with harzburgite blocks in the Neotethyan Meliatic accretionary wedge. Our LA-ICP-MS mineral study provides a complex view on trace element behaviour during the two stages of rodingitization connected with Prv genesis. The positive anomalies of Cs, U, Ta, Pb, As, Sb, Pr and Nd in Cpx, Opx and Ol are combined with the negative anomalies of Rb, Ba, Th, Nb and Sr in these minerals. The similar positive anomalies of Cs, U, Ta, ±Be, As, Sb found in typical serpentinization and rodingitization minerals, with variable contents of La, Ce and Nd, and negative anomalies of Rb, Ba, Th, Nb and Sr suggest involvement of crustal fluids during MP-LP/LT accretionary wedge metamorphism. LA-ICP-MS study revealed strong depletion in LREE from Prv-1 to Prv-2, and a typically negative Eu (and Ti) anomaly for Prv-1, while a positive Eu (and Ti) anomaly for Prv-2. Our multi-element diagram depicts enrichment in U, Nb, La, Ce, As, Sb, Pr, Nd and decreased Rb, Ba, Th, Ta, Pb, Sr, Zr in both Prv generations. In general, both Prv generations are very close to the end-member composition. In spite of low concentrations of isomorphic constituents, Prv-1 and Prv-2 display the A(La,Ce)3++B(Fe,Cr)3+=ACa2++BTi4+ heterovalent couple substitution. A decrease of ferric iron in Prv-2 indicates increasing reduction conditions during rodingitization.

Nickel(Ni)-containing materials have been widely used in a wide range of medical applications, including orthopaedics. Despite their excellent properties, there is still a problem with the release of nickel ions into the patient's body, which can cause changes in the behaviour of surrounding cells and tissues. This study aims to evaluate the effects of Ni on bone cells with an emphasis on the determination of Ni localization in cellular compartments in time. For these purposes, one of the most suitable models for studying the effects induced by metal implants was used-the patient's osteoarthritic cells. Thanks to this it was possible to simulate the pathophysiological conditions in the patient's body, as well as to evaluate the response of the cells which come into direct contact with the material after the implantation of the joint replacement. The largest differences in cell viability, proliferation and cell cycle changes occurred between Ni 0.5 mM and 1 mM concentrations. Time-dependent localization of Ni in cells showed that there is a continuous transport of Ni ions between the nucleus and the cytoplasm, as well as between the cell and the environment. Moreover, osteoarthritic osteoblasts showed faster changes in concentration and ability to accumulate more Ni, especially in the nucleus, than physiological osteoblasts. The differences in Ni accumulation process explains the higher sensitivity of patient osteoblasts to Ni and may be crucial in further studies of implant-derived cytotoxic effects., (© 2024. The Author(s).)

Herby, the interaction of metallothioneins with commonly used Pt-based anticancer drugs - cisplatin, carboplatin, and oxaliplatin - was investigated using the combined power of elemental (i.e. LA-ICP-MS, CE-ICP-MS) and molecular (i.e. MALDI-TOF-MS) analytical techniques providing not only required information about the interaction, but also the benefit of low sample consumption. The amount of Cd and Pt incorporated within the protein was determined for protein monomers and dimer/oligomers formed by non-oxidative dimerization. Moreover, fluorescence spectrometry using Zn 2+ -selective fluorescent indicator - FluoZin3 - was employed to monitor the ability of Pt drugs to release natively occurring Zn from the protein molecule. The investigation was carried out using two protein isoforms (i.e. MT2, MT3), and significant differences in behaviour of these two isoforms were observed. The main attention was paid to elucidating whether the protein dimerization/oligomerization may be the reason for the potential failure of the anticancer therapy based on these drugs. Based on the results, it was demonstrated that the interaction of MT2 (both monomers and dimers) interacted with Pt drugs significantly less compared to MT3 (both monomers and dimers). Also, a significant difference between monomeric and dimeric forms (both MT2 and MT3) was not observed. This may suggest that dimer formation is not the key factor leading to the inactivation of Pt drugs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Metal recycling is essential for strengthening a circular economy. Microbial leaching (bioleaching) is an economical and environmentally friendly technology widely used to extract metals from insoluble ores or secondary resources such as dust, ashes, and slags. On the other hand, microbial electrolysis cells (MECs) would offer an energy-efficient application for recovering valuable metals from an aqueous solution. In this study, we investigated a MEC for Zn recovery from metal-laden bioleachate for the first time by applying a constant potential of -100 mV vs. Ag/AgCl (3 M NaCl) on a synthetic wastewater-treating bioanode. Zn was deposited onto the cathode surface with a recovery efficiency of 41 ± 13% and an energy consumption of 2.55 kWh kg -1 . For comparison, Zn recovery from zinc sulfate solution resulted in a Zn recovery efficiency of 100 ± 0% and an energy consumption of 0.70 kWh kg -1 . Furthermore, selective metal precipitation of the bioleachate was performed. Individual metals were almost completely precipitated from the bioleachate at pH 5 (Al), pH 7 (Zn and Fe), and pH 9 (Mg and Mn)., Competing Interests: SS, CH, ASC, and MH were employed by K1-MET GmbH. LB was employed by Voestalpine Stahl GmbH. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Spiess, Kucera, Vaculovic, Birklbauer, Habermaier, Sasiain Conde, Mandl and Haberbauer.)

Although the general concept of nanotechnology relies on exploitation of size-dependent properties of nanoscaled materials, the relation between the size/morphology of nanoparticles with their biological activity remains not well understood. Therefore, we aimed at investigating the biological activity of Se nanoparticles, one of the most promising candidates of nanomaterials for biomedicine, possessing the same crystal structure, but differing in morphology (nanorods vs. spherical particles) and aspect ratios (AR, 11.5 vs. 22.3 vs. 1.0) in human cells and BALB/c mice. Herein, we report that in case of nanorod-shaped Se nanomaterials, AR is a critical factor describing their cytotoxicity and biocompatibility. However, spherical nanoparticles (AR 1.0) do not fit this statement and exhibit markedly higher cytotoxicity than lower-AR Se nanorods. Beside of cytotoxicity, we also show that morphology and size substantially affect the uptake and intracellular fate of Se nanomaterials. In line with in vitro data, in vivo i.v. administration of Se nanomaterials revealed the highest toxicity for higher-AR nanorods followed by spherical nanoparticles and lower-AR nanorods. Moreover, we revealed that Se nanomaterials are able to alter intracellular redox homeostasis, and affect the acidic intracellular vesicles and cytoskeletal architecture in a size- and morphology-dependent manner. Although the tested nanoparticles were produced from the similar sources, their behavior differs markedly, since each type is promising for several various application scenarios, and the presented testing protocol could serve as a concept standardizing the biological relevance of the size and morphology of the various types of nanomaterials and nanoparticles., (© 2022 The Authors.)

The biological leaching of metals from different waste streams by bacteria is intensively investigated to address metal recycling and circular economy goals. However, usually external addition of sulfuric acid is required to maintain the low pH optimum of the bacteria to ensure efficient leaching. Extremely acidophilic Acidithiobacillus spp. producing sulfuric acid and ferric iron have been investigated for several decades in the bioleaching of metal-containing ores. Their application has now been extended to the extraction of metals from artificial ores and other secondary sources. In this study, an optimized process for producing biogenic sulfuric acid from elemental sulfur by two sulfur-oxidizing species, A. thiooxidans and A. caldus and their combinations, was investigated in batch and stirred tank experiments. Using a combined culture of both species, 1.05 M and 1.4 M biogenic sulfuric acid was produced at 30 °C and 6% elemental sulfur in batch and semi continuous modes, respectively. The acid produced was then used to control the pH in a heap bioleaching system in which iron- and sulfur-oxidizing A. ferrooxidans was applied to biologically leach metals from waste incineration residuals. Metals like Cu, Ni, Al, Mn, and Zn were successfully recovered by 99, 93, 84, 77 and 68%, respectively within three weeks of heap bioleaching. Overall, a potential value recovery of incorporated metals >70% could be achieved. This highlights the potential and novelty of applying extremely acidophilic sulfur-oxidizing bacteria for cheap and efficient production of biogenic sulfuric acid and its use in pH control., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Here, we present the potential analytical applications of photochemistry in combination with fluorescence fingerprinting. Our approach analyzes the fluorescence of samples after ultraviolet light (UV) treatment. Especially in presence of metal ions and thiol-containing compounds, the fluorescence behavior changes considerably. The UV-induced reactions (changes) are unique to a given sample composition, resulting in distinct patterns or fingerprints (typically in the 230-600 nm spectral region). This method works without the need for additional chemicals or fluorescent probes, only suitable diluent must be used. The proposed method (UV fingerprinting) suggests the option of recognizing various types of pharmaceuticals, beverages (juices and wines), and other samples within only a few minutes. In some studied samples (e.g. pharmaceuticals), significant changes in fluorescence characteristics (mainly fluorescence intensity) were observed. We believe that the fingerprinting technique can provide an innovative solution for analytical detection., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The main dose-limiting side effect of cisplatin is nephrotoxicity. The utilization of cisplatin is an issue of balancing tumour toxicity versus platinum-induced nephrotoxicity. In this study, we focused on intraorgan distribution of common essential trace elements zinc, copper, and iron in healthy mouse kidneys and distribution of platinum after cisplatin treatment. Renal distribution in 12 nontreated Nu-Nu mice (males) was assessed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Furthermore, 9 Nu-Nu mice were treated with cisplatin. The order of elements concentration in kidneys was as follows: Fe > Zn > Cu. All three metals showed the higher concentrations at the cortex and medulla (28.60, 3.35, and 93.83  μ g/g for Zn, Cu, and Fe, respectively) and lower concentration at the pelvis and the urinary tract (20.20, 1.93, and 62.48  μ g/g for Zn, Cu, and Fe, respectively). No statistically significant difference between cortex and medulla was observed for these elements. After platinum treatment, the concentration of platinum in kidneys was enhanced more than 60-times, p < 0.001. Platinum significantly showed the highest accumulation in cortex (2.11  μ g/g) with a gradient distribution. Platinum was less accumulated in medulla and pelvis than in cortex, and the lowest accumulation occurred in the urinary tract (1.13  μ g/g). Image processing has been successfully utilized to colocalize metal distribution using LA-ICP-MS and histological samples images., Competing Interests: The authors declare that there is no conflict of interest regarding the publication of this paper., (Copyright © 2021 Petr Stepka et al.)

Herein, we report a new simple and easy-to-use approach for the characterization of protein oligomerization based on fluorescence resonance energy transfer (FRET) and capillary electrophoresis with LED-induced detection. The FRET pair consisted of quantum dots (QDs) used as an emission tunable donor (emission wavelength of 450 nm) and a cyanine dye (Cy3), providing optimal optical properties as an acceptor. Nonoxidative dimerization of mammalian metallothionein (MT) was investigated using the donor and acceptor covalently conjugated to MT. The main functions of MTs within an organism include the transport and storage of essential metal ions and detoxification of toxic ions. Upon storage under aerobic conditions, MTs form dimers (as well as higher oligomers), which may play an essential role as mediators in oxidoreduction signaling pathways. Due to metal bridging by Cd 2+ ions between molecules of metallothionein, the QDs and Cy3 were close enough, enabling a FRET signal. The FRET efficiency was calculated to be in the range of 11-77%. The formation of MT dimers in the presence of Cd 2+ ions was confirmed by MALDI-MS analyses. Finally, the process of oligomerization resulting in FRET was monitored by CE, and oligomerization of MT was confirmed., Competing Interests: Declaration of competing interest Authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Hazardous waste disposal via incineration generates a substantial amount of ashes and slags which pose an environmental risk due to their toxicity. Currently, these residues are deposited in landfills with loss of potentially recyclable raw material. In this study, the use of acidophilic bioleaching bacteria (Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, and Leptospirillum ferrooxidans) as an environmentally friendly, efficient strategy for the recovery of valuable metals from incineration residues was investigated. Zinc, Cobalt, Copper, and Manganese from three different incineration residues were bio-extracted up to 100% using A. ferrooxidans under ferrous iron oxidation. The other metals showed lower leaching efficiencies based on the type of culture used. Sulfur-oxidizing cultures A. ferrooxidans and A. thiooxidans, containing sulfur as the sole substrate, expressed a significantly lower leaching efficiency (up to 50%). According to ICP-MS, ashes and slags contained Fe, Zn, Cu, Mn, Cr, Cd, and Ni in economically attractive concentrations between 0.2 and 75 mg g -1 . Compared to conventional hydrometallurgical and pyrometallurgical processes, our biological approach provides many advantages such as: the use of a limited amount of used strong acids (H 2 SO 4 or HCl), recycling operations at lower temperatures (~30 °C) and no emission of toxic gases during combustion (i.e., dioxins and furans)., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Cancer-associated fibroblasts (CAFs) are one of the most abundant and critical components of the tumor stroma. CAFs can impact many important steps of cancerogenesis and may also influence treatment resistance. Some of these effects need the direct contact of CAFs and cancer cells, while some involve paracrine signals. In this study, we investigated the ability of head and neck squamous cell carcinomas (HNSCC) patient-derived CAFs to promote or inhibit the colony-forming ability of HNSCC cells. The effect of cisplatin on this promoting or inhibiting influence was also studied. The subsequent analysis focused on changes in the expression of genes associated with cancer progression. We found that cisplatin response in model HNSCC cancer cells was modified by coculture with CAFs, was CAF-specific, and different patient-derived CAFs had a different "sensitizing ratio". Increased expression of VEGFA , PGE2S , COX2 , EGFR , and NANOG in cancer cells was characteristic for the increase of resistance. On the other hand, CCL2 expression was associated with sensitizing effect. Significantly higher amounts of cisplatin were found in CAFs derived from patients who subsequently experienced a recurrence. In conclusion, our results showed that CAFs could promote and/or inhibit colony-forming capability and cisplatin resistance in HNSCC cells via paracrine effects and subsequent changes in gene expression of cancer-associated genes in cancer cells.

Immunochemical methods are used not only in clinical practice for the diagnosis of a wide range of diseases but also in basic and advanced research. Based on the unique reaction between the antibody and its respective antigens, it serves to specifically recognize target molecules in biological complex samples. Current methods of labelling antibodies with elemental labels followed by detection by inductively coupled plasma mass spectrometry (ICP-MS) allow detection of multiple antigens in parallel in a single analysis. Using the laser ablation (LA) modality (LA-ICP-MS), it is also possible to monitor the spatial distribution of biogenic elements. Moreover, the employment of metal nanoparticle-labeled antibodies expands the applicability also to molecular imaging by LA-ICP-MS. In this work, conjugates of model monoclonal antibody (DO-1, recognizing p53 protein) with various metal nanoparticles-based labels were created and utilized in dot-blot analysis in order to compare their benefits and disadvantages. Based on experiments with the p53 protein standard, commercial kits of gold nanoparticles proved to be the most suitable for the preparation of conjugates. The LA-ICP-MS demonstrated very good repeatability, wide linear dynamic range (0.1-14 ng), and limit of detection was calculated as a 1.3 pg of p53 protein.

Chemotherapy plays an essential role in the management of cancer worldwide. However, it is a non-specific treatment limited by major drawbacks, thus identification and testing of new promising molecular structures representing potential drug candidates are urgently needed. In this work, ferrocene complexes as potential antitumor drugs that display cytotoxicity in low micromolar concentrations against ovarian cancer cells A2780 and SK-OV-3 were investigated to identify their mode of action. Their mechanism of cellular accumulation was studied using differential pulse voltammetry and inductively coupled plasma - mass spectrometry. Their mode of cell death induction was determined by changes in the mitochondrial membrane potential, production of reactive oxygen species and by Annexin V staining. Transferrin receptors were identified as key mediators of intracellular accumulation of ferrocenes and the extent of cellular uptake reflected the anticancer activity of individual compounds. Functional analysis revealed activation of intrinsic apoptosis as a dominant mechanism leading to regulated cell death induced in ovarian cancer cells by ferrocenes. Ferrocenes represent a group of promising sandwich organometallic complexes exerting cytotoxic activity. We suggest their application not only as standalone chemotherapeutics but also as modifying substituents of known drugs to improve their antitumor effects., (Copyright © 2019 Elsevier B.V. All rights reserved.)

For the first time, the combination of molecularly imprinted polymer (MIP) technology with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is presented with focus on an optimization of the LA-ICP-MS parameters such as laser beam diameter, laser beam fluence, and scan speed using CdS quantum dots (QDs) as a template and dopamine as a functional monomer. A non-covalent imprinting approach was employed in this study due to the simplicity of preparation. Simple oxidative polymerization of the dopamine that creates the self-assembly monolayer seems to be an ideal choice. The QDs prepared by UV light irradiation synthesis were stabilized by using mercaptosuccinic acid. Formation of a complex of QD-antibody and QD-antibody-antigen was verified by using capillary electrophoresis with laser-induced fluorescence detection. QDs and antibody were connected together via an affinity peptide linker. LA-ICP-MS was employed as a proof-of-concept for detection method of two types of immunoassay: 1) antigen extracted from the sample by MIP and subsequently overlaid/immunoreacted by QD-labelled antibodies, 2) complex of antigen, antibody, and QD formed in the sample and subsequently extracted by MIP. The first approach provided higher sensitivity (MIP/NIP), however, the second demonstrated higher selectivity. A mixture of proteins with size in range 10-250 kDa was used as a model sample to demonstrate the capability of both approaches for detection of IgG in a complex sample.

We report a facile method for detection of metallothionein (MT), a promising clinically relevant biomarker, in spiked plasma samples. This method, for the first time, integrates molecularly imprinted polymers as purification/pretreatment step with matrix assisted laser desorption/ionization time-of-flight mass spectrometric detection and with laser ablation inductively coupled plasma mass spectrometry for analysis of MTs. The prepared MT-imprinted polydopamine layer showed high binding capacity and specific recognition properties toward the template. Optimal monomer (dopamine) concentration was found to be 16 mM of dopamine. This experimental setup allows to measure µM concentrations of MT that are present in blood as this can be used for clinical studies recognizing MT as marker of various diseases including tumour one. Presented approach not only provides fast sample throughput but also avoids the limitations of methods based on use of antibodies (e.g. high price, cross-reactivity, limited availability in some cases, etc.)., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this paper, we describe the labelling of antibodies by gold nanoparticles (AuNPs) with diameters of 10 and 60 nm with detection by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Additionally, the AuNPs labelling strategy is compared with commercially available labelling reagents based on MeCAT (metal coded affinity tagging). Proof of principle experiments based on dot blot experiments were performed. The two labelling methods investigated were compared by sensitivity and limit of detection (LOD). The absolute LODs achieved were in the range of tens of picograms for AuNP labelling compared to a few hundred picograms by the MeCAT labelling.

The main mechanism of action of platinum-based cytostatic drugs - cisplatin, oxaliplatin and carboplatin - is the formation of DNA cross-links, which restricts the transcription due to the disability of DNA to enter the active site of the polymerase. The polymerase chain reaction (PCR) was employed as a simplified model of the amplification process in the cell nucleus. PCR with fluorescently labelled dideoxynucleotides commonly employed for DNA sequencing was used to monitor the effect of platinum-based cytostatics on DNA in terms of decrease in labeling efficiency dependent on a presence of the DNA-drug cross-link. It was found that significantly different amounts of the drugs - cisplatin (0.21 μg/mL), oxaliplatin (5.23 μg/mL), and carboplatin (71.11 μg/mL) - were required to cause the same quenching effect (50%) on the fluorescent labelling of 50 μg/mL of DNA. Moreover, it was found that even though the amounts of the drugs was applied to the reaction mixture differing by several orders of magnitude, the amount of incorporated platinum, quantified by inductively coupled plasma mass spectrometry, was in all cases at the level of tenths of μg per 5 μg of DNA., (Copyright © 2017 Elsevier Inc. All rights reserved.)

We describe a new procedure for the parallel mapping of selected metals in histologically characterized tissue samples. Mapping is achieved via image registration of digital data obtained from two neighbouring cryosections by scanning the first as a histological sample and subjecting the second to laser ablation inductively coupled plasma mass spectrometry. This computer supported procedure enables determination of the distribution and content of metals of interest directly in the chosen histological zones and represents a substantial improvement over the standard approach, which determines these values in tissue homogenates or whole tissue sections. The potential of the described procedure was demonstrated in a pilot study that analysed Zn and Cu levels in successive development stages of pig melanoma tissue using MeLiM (Melanoma-bearing-Libechov-Minipig) model. We anticipate that the procedure could be useful for a complex understanding of the role that the spatial distribution of metals plays within tissues affected by pathological states including cancer.

Herein, we describe a novel approach for targeting of ubiquitous protein apoferritin (APO)-encapsulating doxorubicin (DOX) to prostate cancer using antibodies against prostate-specific membrane antigen (PSMA). The conjugation of anti-PSMA antibodies and APO was carried out using HWRGWVC heptapeptide, providing their site-directed orientation. The prostate-cancer-targeted and nontargeted nanocarriers were tested using LNCaP and HUVEC cell lines. A total of 90% of LNCaP cells died after treatment with DOX (0.25 μM) or DOX in nontargeted and prostate-cancer-targeted APO, proving that the encapsulated DOX toxicity for LNCaP cells remained the same. Free DOX showed higher toxicity for nonmalignant cells, whereas the toxicity was lower after treatment with the same dosage of APO-encapsulated DOX (APODOX) and even more in prostate-cancer-targeted APODOX. Hemolytic assay revealed exceptional hemocompatibility of the entire nanocarrier. The APO encapsulation mechanism ensures applicability using a wide variety of chemotherapeutic drugs, and the presented surface modification enables targeting to various tumors.

Cisplatin belongs to the most widely used cytostatic drugs. The determination of the presence of the DNA-cisplatin adducts may not only signal the guanine-rich regions but also monitor the interaction reaction between DNA and the drug in terms of speed of interaction. In this work, the combined advantages of magnetic particles-based isolation/purification with fluorescent properties of quantum dots (QDs) and antibodies targeted on specific recognition of DNA-cisplatin adducts are demonstrated. The formation of a complex between magnetic particles with surface modified by anti-dsDNA antibody, cisplatin-modified DNA and QDs labelled anti-cisplatin-modified DNA antibody was suggested and optimized., Competing Interests: The authors declare no conflicts of interest.

Double-pulse laser-induced breakdown spectroscopy (DP-LIBS) was optimized for microspatial analyses of fossil and recent snake vertebrae. As complimentary techniques, solution analysis by inductively coupled plasma mass spectrometry and synchrotron radiation X-ray microtomography was utilized in order to determine the overall concentration of the selected elements in the samples and to visualize nondestructively the fossil sample microstructure, respectively. Elemental mapping of pathological bony tissue by DP-LIBS has been proven as a powerful tool for considering the osteitis deformans phases in fossil vertebrae.

The paper presents the results of heavy metals determination in samples of sedimentary rocks from the Mosina-Krajkowo water well field (Poland). The concentration of heavy metals was analysed by type of rock (sand, gravel, warp, silt, till, and clay). Variation of heavy metal concentrations with depth was studied taking into account the age series of the rocks (fluvial sediments of the modern Warta River valley, sediments of the Baltic Glaciation, tills of the Middle-Polish Glaciation, sediments of the Masovian Interglacial (Holstein), tills of the Poznań series) and granulometric fractions. The grain sizes considered included: >2.0, 2.0-1.0, 1.0-0.5, 0.5-0.25, 0.25-0.1, 0.1-0.063, and <0.063 mm. The concentrations of the heavy metals studied were found to change with the type of rock, age series, and granulometric fraction. The levels of the metals were determined by the technique of atomic absorption spectrometry with flame atomisation (F-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES).

A novel off-line coupling of capillary electrophoresis (CE) and inductively coupled plasma mass spectrometry (ICPMS) is reported here. The coupling interface is based on the connection of a separation capillary to a deposition capillary via a liquid junction maintaining high separation efficiency and sample utilization due to the self-focusing effect and lack of pressure-induced flow in comparison with nebulizer-like interfaces. The separation is recorded in the form of droplets of CE effluent on a suitable substrate--a poly(ethylene terephthalate) glycol (PETG) sample plate placed inside a partially evacuated chamber. Substrate-assisted laser desorption (SALD) is used to vaporize the sample fractions and to enable further transfer to the ICPMS. The mechanism of SALD is examined using model samples deposited on a variety of substrates. The highest response is obtained for a PETG substrate; sample desorption due to ablation of PETG is found to outweigh direct ablation of sample. Detection limits are given for several metal elements. Finally, a rapid (2.5-min), high-resolution separation of Cr(III)/Cr(VI) species injected in subpicomolar quantity is shown.