A CD Study of a Structure-Based Selection of -Heterocyclic Bis-Carbene Gold(I) Complexes as Potential Ligands of the G-Quadruplex-Forming Human Telomeric hTel23 Sequence.

Herein, we report the structure-based selection via molecular docking of four -heterocyclic bis-carbene gold(I) complexes, whose potential as ligands for the hTel23 G-quadruplex structure has been investigated using circular dichroism (CD) spectroscopy, CD melting, and polyacrylamide gel electrophoresis (PAGE). The complex containing a bis(1,2,3,4,6,7,8,9-octahydro-11-11-pyridazino[1,2-a]indazol-11-yl) scaffold induces a transition from the hybrid (3 + 1) topology to a prevalent parallel G-quadruplex conformation, whereas the complex featuring a bis(2-(2-acetamidoethyl)-3-imidazo[1,5-a]pyridin-3(2)-yl) moiety disrupted the original G-quadruplex structure. These results deserve particular attention in light of the recent findings on the pathological involvements of G-quadruplexes in neurodegenerative diseases.

Extraction recovery and speciation of selenium in Se-enriched yeast.

The complete characterization of selenium-enriched yeast in terms of selenium species has been the goal of extensive research for the last three decades. This contribution addresses the two outstanding questions: the mass balance of the identified and reported selenium species and the possible presence of inorganic selenium. For this purpose, four procedures have been designed combining, in diverse order, the principal steps of selenium speciation analysis in Se-rich yeast: extraction of the Se-metabolome, derivatization of cysteine and Se-cysteine (SeCys) residues, proteolysis, and definitive Se recovery using SDS extraction, followed by mineralization.

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.

Oxaliplatin(IV) Prodrugs Functionalized with Gemcitabine and Capecitabine Induce Blockage of Colorectal Cancer Cell Growth-An Investigation of the Activation Mechanism and Their Nanoformulation.

The use of platinum-based anticancer drugs, such as cisplatin, oxaliplatin, and carboplatin, is a common frontline option in cancer management, but they have debilitating side effects and can lead to drug resistance. Combination therapy with other chemotherapeutic agents, such as capecitabine and gemcitabine, has been explored. One approach to overcome these limitations is the modification of traditional Pt(II) drugs to obtain new molecules with an improved pharmacological profile, such as Pt(IV) prodrugs.

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)-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)-Au(I) complex Au3BC, respectively.

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.

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.

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 MS on the basis of the exact molecular mass (±1 ppm) and MS or MS fragmentation.

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.

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.

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.

Identification of γ-Glutamyl-Selenomethionine as the Principal Selenium Metabolite in a Selenium-Enriched Probiotic, 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, 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.

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.

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.

A Novel Strategy for the Detection and Quantification of Nanoplastics by Single Particle Inductively Coupled Plasma Mass Spectrometry (ICP-MS).

A method for the detection and quantification of nanoplastics (NPTs) at environmentally relevant concentrations was developed. It is based on conjugating nanoplastics with functionalized metal (Au)-containing nanoparticles (NPs), thus making them detectable by highly sensitive inductively coupled plasma mass spectrometry (ICP-MS) operated in single particle (SP) mode. The selectivity of the method was achieved by the coupling of negatively charged carboxylate groups present at the surface of nanoplastics with a positively charged gelatin attached to the custom-synthesized AuNPs.

To-Do and Not-To-Do in Model Studies of the Uptake, Fate and Metabolism of Metal-Containing Nanoparticles in Plants.

Due to the increasing release of metal-containing nanoparticles into the environment, the investigation of their interactions with plants has become a hot topic for many research fields. However, the obtention of reliable data requires a careful design of experimental model studies. The behavior of nanoparticles has to be comprehensively investigated; their stability in growth media, bioaccumulation and characterization of their physicochemical forms taken-up by plants, identification of the species created following their dissolution/oxidation, and finally, their localization within plant tissues.

Long-Term Evaluation of Gadolinium Retention in Rat Brain After Single Injection of a Clinically Relevant Dose of Gadolinium-Based Contrast Agents.

Purpose: The aim of this study was to investigate the presence and chemical forms of residual gadolinium (Gd) in rat brain after a single dose of Gd-based contrast agent.

Methods: Four groups of healthy rats (2 sacrifice time-points, n = 10/group, 80 rats in total) were randomized to receive a single intravenous injection of 1 of the 3 Gd-based contrast agents (GBCAs) (gadoterate meglumine, gadobenate dimeglumine, or gadodiamide) or the same volume of 0.9% saline solution.

Antimicrobial silver targets glyceraldehyde-3-phosphate dehydrogenase in glycolysis of .

Silver has long been used as an antibacterial agent, yet its molecular targets remain largely unknown. Using a custom-designed coupling of gel electrophoresis with inductively coupled plasma mass spectrometry (GE-ICP-MS), we identified six silver-binding proteins in . The majority of the identified proteins are associated with the central carbon metabolism of .

A chemical speciation insight into the palladium(ii) uptake and metabolism by Sinapis alba. Exposure to Pd induces the synthesis of a Pd-histidine complex.

Palladium is recognized as a technologically critical element (TCE) because of its massive use in automobile exhaust gas catalytic converters. The release of Pd into the environment in the form of nanoparticles of various size and chemical composition requires an understanding of their metabolism by leaving organisms. We provide here for the first time a chemical speciation insight into the identity of the ligands produced or used by a plant Sinapis alba L.

The Role of Iron and Copper on the Oligomerization Dynamics of DR_2577, the Main S-Layer Protein of .

Surface (S)-layers are cryptic structures that coat the external surface of the bacterial cell in many species. The paracrystalline regularity of the S-layer is due to the self-assembling of one or more protein units. The property of self-assembling seems to be mediated by specific topologies of the S-layer proteins as well as the presence of specific ions that provide support in building and stabilizing the bi-dimensional S-layer organization.

Selenized Plant Oil Is an Efficient Source of Selenium for Selenoprotein Biosynthesis in Human Cell Lines.

Selenium is an essential trace element which is incorporated in the form of a rare amino acid, the selenocysteine, into an important group of proteins, the selenoproteins. Among the twenty-five selenoprotein genes identified to date, several have important cellular functions in antioxidant defense, cell signaling and redox homeostasis. Many selenoproteins are regulated by the availability of selenium which mostly occurs in the form of water-soluble molecules, either organic (selenomethionine, selenocysteine, and selenoproteins) or inorganic (selenate or selenite).

Potential of Liquid Extraction Surface Analysis Mass Spectrometry (LESA-MS) for the Characterization of Polymer-Based Materials.

Liquid extraction surface analysis mass spectrometry (LESA -MS) is a direct analysis method suitable for the analysis of polymers. It is based on a fast and efficient extraction of polymer components, such as non-intentionally added species (NIAS), post-polymerization residues, or additives, and residues resulting from specific uses followed by their MS detection. In comparison with batch methods, it is a "green" method, using negligible volumes of organic solvents, and it is cost-effective, avoiding lengthy sample preparation procedures.

Lanthanide polymer labels for multiplexed determination of biomarkers in human serum samples by means of size exclusion chromatography-inductively coupled plasma mass spectrometry.

Lanthanide polymer-labelled antibodies were investigated to improve the analytical figures of merit of homogeneous immunoassays with inductively coupled plasma mass spectrometry (ICP-MS) detection for multiplexed biomarker analysis in human serum samples. Specific monoclonal antibodies against four cancer biomarkers (CEA, sErbB2, CA 15.3 and CA 125) were labelled with different polymer-based lanthanide group to increase the number of metal labels per binding site.

Comparison of analytical methods using enzymatic activity, immunoaffinity and selenium-specific mass spectrometric detection for the quantitation of glutathione peroxidase 1.

Glutathione peroxidase 1 (Gpx1), one of the most responsive selenoproteins to the variation of selenium concentration, is often used to evaluate "selenium status" at a cellular or organismal level. The four major types of analytical methodologies to quantify Gpx1 were revisited. They include (i) an enzymatic assay, (ii, iii) polyacrylamide gel electrophoresis (PAGE) with (ii) western blot detection of protein or (iii) inductively coupled plasma mass spectrometry (ICP MS) detection of selenium, and (iv) size-exclusion chromatography with ICP MS detection.

Prediction of biodegradability of aromatics in water using QSAR modeling.

The study was aimed at developing models for predicting the biodegradability of aromatic water pollutants. For that purpose, 36 single-benzene ring compounds, with different type, number and position of substituents, were used. The biodegradability was estimated according to the ratio of the biochemical (BOD) and chemical (COD) oxygen demand values determined for parent compounds ((BOD/COD)), as well as for their reaction mixtures in half-life achieved by UV-C/HO process ((BOD/COD)).