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Anti-cancer effect of Rumex obtusifolius in combination with arginase/nitric oxide synthase inhibitors via downregulation of oxidative stress, inflammation, and polyamine synthesis
PublikacjaCancer continues to be a leading cause of death worldwide, making the development of new treatment methods crucial in the fight against it. With cancer incidence rates increasing worldwide, ongoing research must focus on identifying new and effective ways to prevent and treat the disease. The combination of herbal extracts with chemotherapeutic agents has gained much interest as a novel strategy to combat cancer. Rumex obtusifolius...
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Novel decahedral TiO2 photocatalysts modified with Ru or Rh NPs: Insight into the mechanism
PublikacjaNovel decahedral TiO2 modified with Ru or Rh NPs were successfully synthesized by hydrothermal method. The effect of metal type as well as amount of noble metal precursor (0.05, 0.1, 0.2, 0.3 and 0.5 wt.%) on the photocatalytic activity were investigated. Decahedral TiO2 decorated by Ru and Rh nanoparticles was prepared by photodeposition method, whereas Rh doped TiO2 was obtained by onestep hydrothermal method with introduction...
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Quality of limes juices based on the aroma and antioxidant properties
PublikacjaKaffir (Citrus hystrix) and Key (Citrus aurantifolia) limes juices were investigated and compared. Two dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOF-MS) was applied to assess the botanical origin of Kaffir and Key limes juices, based on volatile substances. The biggest differences in the contents of selected terpenes in Kaffir and Key limes occur in chemical compounds such as Limonene,...
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Unlocking the Secrets of River Pollution: Analyzing Organic Pollutants in Sediments—Experimental Study
PublikacjaUntreated wastewater released into rivers can result in water pollution, the spread of waterborne diseases, harm to ecosystems, contamination of soil and groundwater, as well as air pollution and respiratory problems for nearby humans and animals due to the release of greenhouse gases. The current study aims to investigate the recent input of anthropogenic loads into the rivers using linear alkylbenzene (LAB), which is one of the...
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Electrochemical simulation of metabolic reduction and conjugation reactions of unsymmetrical bisacridine antitumor agents, C-2028 and C-2053
PublikacjaElectrochemistry (EC) coupled with analysis techniques such as liquid chromatography (LC) and mass spectrometry (MS) has been developed as a powerful tool for drug metabolism simulation. The application of EC in metabolic studies is particularly favourable due to the low matrix contribution compared to in vitro or in vivo biological models. In this paper, the EC(/LC)/MS system was applied to simulate phase I metabolism of the representative...
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Analityka surfaktantów w próbkach środowiskowych
PublikacjaSurfaktanty stanowią grupę związków charakteryzujących się specyficznymi właściwościami fizykochemicznymi (m.in. amfifilowa budowa, zdolność rozpuszczania się w cieczach o różnej polarności, zdolność do tworzenia micelli) i z tego względu są one wykorzystywane w wielu sferach działalności człowieka. Związki powierzchniowo-czynne ulegają różnorodnym przemianom fizykochemicznym, co umożliwia ich migrację między różnymi elementami...
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Chemical and biological stability of polyene macrolides
PublikacjaThe polyene macrolide antibiotics have been used in an-tifungal therapy since first o f them were discovered in 1950's. Up to now, four polyene macrolides are being used in medical practice, namely amphotericin B, nystatin, candi-cidin and pimaricin.The antifungal activity and mode of ac-tion of polyene macrolides is determined by their structure, chemical and physical properties.The main fragment of polyene...
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Prediction of Overall In Vitro Microsomal Stability of Drug Candidates Based on Molecular Modeling and Support Vector Machines. Case Study of Novel Arylpiperazines Derivatives
PublikacjaOther than efficacy of interaction with the molecular target, metabolic stability is the primary factor responsible for the failure or success of a compound in the drug development pipeline. The ideal drug candidate should be stable enough to reach its therapeutic site of action. Despite many recent excellent achievements in the field of computational methods supporting drug metabolism studies, a well-recognized procedure to model...
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Determination of benzodiazepines and Z-hypnotic drugs in whole blood samples by GC–MS/MS: Method development, validation and application
PublikacjaBenzodiazepines (BZDs) and Z-drugs are widely used as anxiolytics, sedative hypnotics, anticonvulsants and muscle relaxants. “Designer benzodiazepines” (DBZDs) are a new psychoactive substance class consisting of benzodiazepine derivatives that are not allowed for medical use and are known for being used recreationally. From a toxicologist standpoint, the huge number of such substances implicate a necessity for developing fast...
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Interspecific and intraspecific variation in organochlorine pesticides and polychlorinated biphenyls using non-destructive samples from Pygoscelis penguins
PublikacjaAs humans are present in Antarctica only for scientific and tourism-related purposes, it is often described as a pristine region. However, studies have identified measurable levels of Persistent Organic Pollutants (POPs), such as organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), in the Antarctic region. These are highly toxic anthropogenic compounds with tendency to travel long distances and reach remote environments, where...
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SimLE Stardust: How an experiment evolved from student tinkering to a stratospheric research platform
PublikacjaStratospheric balloons are one of the most accessible methods of near space exploration. Their applications include capturing of extreme living organisms whose existence in the stratosphere has been suggested in the literature. These potential microorganisms would have evolved to survive the unique environment of low temperature, low pressure and high solar radiation. This makes the development of...
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Molecular transformation of dissolved organic matter in manganese ore-mediated constructed wetlands for fresh leachate treatment
PublikacjaThe organic matter (OM) and nitrogen in Fresh leachate (FL) from waste compression sites pose environmental and health risks. Even though the constructed wetland (CW) can efficiently remove these pollutants, the molecular-level transformations of dissolved OM (DOM) in FL remain uncertain. This study reports the molecular dynamics of DOM and nitrogen removal during FL treatment in CWs. Two lab-scale vertical-flow CW systems were...
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DETERMINATION OF SURFACTANTS IN ENVIRONMENTAL SAMPLES. PART II. ANIONIC COMPOUNDS
PublikacjaSurfactants (SAA) with negative charge of polar group are named as anionic compounds. They are main constituent of most products containing synthetic surfactants. The linear alkylbenzene sulfonates (LAS), alkyl ethoxysulfates (AES) and alkyl sulfates (AS) are typically applied from this class of compounds. Those surfactants are ingredients of household detergents and cleaners, laundry detergents, cosmetic. Moreover they can be...
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Differences between selected volatile aromatic compound concentrations in sludge samples in various steps of wastewater treatment plant operations
PublikacjaSewage sludge, one of the main wastes generated during wastewater treatment, constitutes an important source of emissions of volatile chemical compounds such as volatile aromatic compounds These substances may undergo various changes as a result of operations and unit processes, which affects their concentrations in sewage sludge. An important factor determining the potential hazardousness of volatile organic compounds is the quality...
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A multi‑criteria approach to investigate spatial distribution,sources, and the potential toxicological effect of polycyclic aromatic hydrocarbons (PAHs) in sediments of urban retention tanks
PublikacjaBottom sediments deposited in retention tanks (RTs) located on two urban streams (Oliwski and Strzyza) in the central part of Gdansk (Poland) were analysed for polycyclic aromatic hydrocarbons’ (PAHs) content. PAHs were extracted from samples with methylene chloride, then the extracts were subjected to clean-up applying the solid phase extraction (SPE) method. Quantitative and qualitative determination of 16 PAHs was performed...
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Rapid and simple multi-analyte LC–MS/MS method for the determination of benzodiazepines and Z-hypnotic drugs in blood samples: Development, validation and application based on three years of toxicological analyses
PublikacjaBenzodiazepines (BZDs) and Z-drugs have been particularly important treatments for sleeping and anxiety disorders for many years. However, recently, a number of new benzodiazepines (named designer benzodiazepines, DBZDs) were synthesised, but some of them have never been used in the clinic; they reached the black drug market as new psychoactive substances and are used for recreational purposes. The abuse of these substances has...
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Keratinocyte-derived small extracellular vesicles supply antigens for CD1a-resticted T cells and promote their type 2 bias in the context of filaggrin insufficiency
PublikacjaIntroduction: Exosome-enriched small extracellular vesicles (sEVs) are nanosized organelles known to participate in long distance communication between cells, including in the skin. Atopic dermatitis (AD) is a chronic inflammatory skin disease for which filaggrin (FLG) gene mutations are the strongest genetic risk factor. Filaggrin insufficiency affects multiple cellular function, but it is unclear if sEV-mediated cellular communication...
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Composition and antimicrobial activity of fatty acids detected in the hygroscopic secretion collected from the secretory setae of larvae of the biting midge Forcipomyia nigra (Diptera: Ceratopogonidae)
PublikacjaThe hygroscopic secretion produced by the secretory setae of terrestrial larvae of the biting midge Forcipomyia nigra (Winnertz) was analysed using gas chromatography coupled with mass spectrometry (GC-MS). The viscous secretion is stored at the top of each seta and absorbs water from moist air. GC-MS analyses (four independent tests) showed that the secretion contained 12 free fatty acids, the most abundant of which were oleic...
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Simultaneous determination of ibuprofen and its metabolites in complex equine urine matrices by GC-EI-MS in excretion study in view of doping control
PublikacjaA novel assay for the simultaneous determination of ibuprofen (IBU) and its four probable metabolites, 1-hydroxyibuprofen (1-OH IBU), 2-hydroxyibuprofen (2-OH IBU), 3-hydroxyibuprofen (3-OH IBU) and carboxyibuprofen (CBX IBU) in equine urine samples with the application of Gas Chromatography-Electron Ionization-Mass Spectrometry (GC-EI-MS) has been developed and elaborated. The new approach for sample preparation including minimizing...
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Rapana venosa consumption improves the lipid profiles and antioxidant capacities in serum of rats fed an atherogenic diet
PublikacjaIn the recent years, the consumption of seafood has increased. There are no results on the studies of Rapana venosa (Rv) as a supplementation to the diets. We hypothesized that Rv would increase antioxidant capacity and reduce blood lipids, based on the composition of bioactive compounds and fatty acids. Therefore, the aim of this investigation was to evaluate in vitro and in vivo actions of Rv from contaminated (C) and non-C (NC)...
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Electrochemistry meets enzymes: Investigation of the biotransformation pathway of C-1311 based on electrochemical simulation in comparison to in vitro methods.
PublikacjaThe knowledge of the metabolic pathways and the biotransformation of new drugs is one of the major challenges in pharmaceutical research. It is crucial for elucidation of degradation routes of the new biologically active compounds, especially in the area of possible toxicity. Conventional in vitro drug metabolism studies are based on incubating drug candidate with e.g. hepatocytes or, most importantly, liver cell microsomes and...
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The Action Mechanisms, Anti-Cancer and Antibiotic-Modulation Potential of Vaccinium myrtillus L. Extract
PublikacjaHerbal medicinal products containing Vaccinium myrtillus L. (bilberry) fruits and fruit extracts are widely available in the market. Although bilberry leaves and stems are considered as bio-waste, they contain much higher levels of phenolic compounds than fruits. The study aimed to investigate the antimicrobial and anticancer potential of aerial part extracts from Vaccinium myrtillus L. (V. myrtillus, VM) plants harvested at high...
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Authentication of whisky due to its botanical origin and way of production by instrumental analysis and multivariate classification methods
PublikacjaHeadspacemass-spectrometry (HS-MS), mid infrared (MIR) and UV–vis spectroscopywere used to authenticate whisky samples from different origins and ways of production ((Irish, Spanish, Bourbon, TennesseeWhisky and Scotch). The collected spectra were processed with partial least-squares discriminant analysis (PLS-DA) to build the classification models. In all cases the five groups ofwhiskieswere distinguished, but the best resultswere...
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Określenie zawartości lotnych kwasów tłuszczowych (LKT) w odciekach pochodzących z mikrobiologicznej degradacji monosacharydów
PublikacjaOkreślenie zawartości lotnych kwasów tłuszczowych (LKT) w odciekach pochodzących z mikrobiologicznej degradacji monosacharydów. Milena Jabłońska, Maria Rybarczyk, Marta Wisielewska, Marek Lieder Politechnika Gdańska, Wydział Chemiczny, Katedra Technologii Chemicznej Zawartość lotnych kwasów tłuszczowych (LKT) w metabolitach pochodzących z mikrobiologicznego ogniwa paliwowego (MFC – Microbial Fuel Cell) świadczy o rozkładzie...
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Optical-Spectrometry-Based Method for Immunosuppressant Medicine Level Detection in Aqueous Solutions
PublikacjaIn this paper, an investigation into detecting immunosuppressive medicine in aqueous solutions using a spectrometry-based technique is described. Using optical transmissive spectrometry, absorbance measurements in the spectra range from 250 nm to 1000 nm were carried out for different cyclosporine A (CsA) concentrations in aqueous solutions. The experiment was conducted for samples both with and without interferent substances—glucose...
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Dopants and gas modifiers in ion mobility spectrometry
PublikacjaThe ion mobility techniques, including the most commonly used drift-tube ion mobility spectrometry (IMS) and differential mobility spectrometry (DMS), are used successfully for the detection of a wide range of organic compounds in the gas phase. In order to improve detection quality, admixtures are added to gas streams flowing through the detector. Dopants mostly prevent the ionization of interfering chemicals however, better detection...
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Determination of metals in water samples by atomic absorption spectrometry and flame emission spectrometry
PublikacjaMetal species in environmental waters are relevant to characterize the metal toxicity, the mobility between different environmental compartments, and for remediation purposes in case of contamination. The concentration of many trace metals in natural water samples are generally at µg/l level. The paper describes determination of metals in water samples based on flame atomic emission and flame atomic absorption spectrometry.
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MONTE CARLO MODELING OF OPTICAL SENSOR FOR POST-OPERATIVE FREE FLAP MONITORING
PublikacjaAfter a preliminary study of the currently employed methods in vitality monitoring of the tissue flaps (TRAM, DIEP, SIEA), a usefulness of optical techniques is discussed. It seems that one of the most promising in monitoring tissue flaps blood flow is a near infrared spectrometry (NIRS). However, a special design of a measurement sensor has to be developed. First, basing on the literature study an optical “window” is characterized....
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Inner-shell fragmentation of molecules into neutral fragments in high-Rydberg states induced by soft X-ray excitation with pulsed-field ionization
PublikacjaIn the present communication, we will show the results of measurements probing the production of neutral high-Rydberg fragments at the K edges of the molecules containing oxygen and nitrogen atoms. The experiments were performed at the Gas Phase beamline of the Elettra synchrotron radiation laboratory (Trieste, Italy), exploiting a combined soft X-ray excitation with pulsed-field ionization and ion time-of-flight (TOF) spectrometry...
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The effect of metal cluster deposition route on structure and photocatalytic activity of mono- and bimetallic nanoparticles supported on TiO2 by radiolytic method
PublikacjaTiO2 (P25) was modified with small and relatively monodisperse mono- and bimetallic clusters (Ag, Pd, Pt, Ag/Pd, Ag/Pt and Pd/Pt) induced by radiolysis to improve its photocatalytic activity. The as-prepared samples were characterized by X-ray fluorescence spectrometry (XRF), photoluminescence spectrometry (PL), diffuse reflectance spectroscopy (DRS), X-ray powder diffractometry (XRD), scanning transition electron microscopy (STEM)...
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Transparent thin films of Cu-TiO2 with visible light photocatalytic acitivity
PublikacjaThin films of Cu–TiO2 with a high level of transparency were prepared by a dip-coating procedure on the glass surface. CuCl2 was used as a copper precursor added during sol – gel synthesis of TiO2. The extension of optical absorption into the visible region of as-prepared thin films was indicated by UV/Vis spectroscopy. Only the anatase phase was detected by X-ray di ffraction analysis (XRD). The presence of copper in the structure...
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Application of deep eutectic solvents in atomic absorption spectrometry
PublikacjaAtomic absorption spectrometry (AAS) is a widely applied technique for metal quantification due to its practicality, easy use and low cost. However, to improve the metrological characteristics of AAS, in particular the sensitivity and the detection limit, sample pretreatment is commonly used before the detection step itself. In consideration of the principles of Green Analytical Chemistry, new solvents are being introduced into...
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Influence of Diosmin Treatment on the Level of Oxidative Stress Markers in Patients with Chronic Venous Insufficiency
PublikacjaOxidative stress plays an important role in the pathophysiology of many human disorders, while antioxidants prevent the development of various adverse symptoms. Diosmin is a natural flavonoid applied in vascular system disorders, especially in chronic venous insufficiency (CVI), and it plays a significant part in the alleviation of CVI symptoms. Due to antioxidant activity, it also has the ability to scavenge the oxygen free radicals...
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Seasonal changes of mercury speciation in the coastal sediments
PublikacjaPurpose Mercury speciation in sediments is linked to environmental conditions and processes. Domination of particular mercury species depends on its source, displays considerable seasonal behavior, and may be further modified due to oxygen levels, icing conditions, or the input of fresh organic matter. The purpose of this study was to examine the coastal area of the Gulf of Gdańsk in terms of mercury contamination and the influence...
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Determination of heavy metals in eyeshadows from China
PublikacjaPersonal care products and cosmetics are used daily by many people, causing local exposure to certain chemical substances through the application directly inside the oral cavity, on the skin, lips, eyes, and mucosa. Eyeshadows are among the most commonly used types of cosmetics. According to scientifc reports, they may contain heavy metals, especially in non-original products. The exposure to said heavy metals may cause local skin...
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Accumulation of radioisotopes and heavy metals in selected species of mushrooms
PublikacjaSeven species of forest mushrooms from different regions of Poland (edible: Imleria badia, Cantharellus cibarius, Xerocomus subtomentosus, Suillus luteus and inedible by humans but being food for animals: Paxillus involutus, Tylopilus felleus and Russula emetica) were analyzed for radioisotope activity (Cs-137, K-40, Bi-214 and Pb-210) as well as concentrations of heavy metals (aluminum, chromium, cadmium, manganese, iron, lead,...
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The influence of Be addition on the structure and thermal properties of alkali-silicate glasses
PublikacjaBe-Na-(Li)-Si oxide glasses containing up to 15 mol% of BeO were prepared. Their structure was characterized by X-ray powder diffraction and Raman as well as infrared spectroscopic techniques, while their chemical compositions were examined by Inductively Coupled Plasma Optical Emission Spectrometry. All materials were found to be amorphous and contain Al contaminations from minor dissolution of the alumina crucibles. The results...
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Phytoremediation of heavy metals by white cabbage
PublikacjaPhytoremediation is regarded as the cheapest and environmentally most friendly technology for cleaning up soil. The most widespread and most profitable technique is phytoextraction, used mainly for removing heavy metals and radioactive elements from thesoil. Over 400 plant species have been identified as natural metal hyperaccumulators representing about 0.2 % of all angiosperms. Unfortunately, most of these plants are characterised...
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The use of Kamienna głowa cabbage species for phytoextraction of zinc and cadmium from the soil
PublikacjaAlthough traditional technologies for cleaning contaminated soils have proven to be efficient, they are usually expensive, labor intensive, and in the case of soil, they produce severe disturbance. Most recently, the use of plants in metal extraction (phytoremediation) has appeared as a promising alternative in the removal of heavy metal excess from soil. Phytoremediation uses of plant for pollutant stabilization, extraction, degradation,...
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Impact of Cultivation Conditions, Ethylene Treatment, and Postharvest Storage on Selected Quality and Bioactivity Parameters of Kiwifruit “Hayward” Evaluated by Analytical and Chemometric Methods
PublikacjaOrganic, semiorganic, and conventional “Hayward” kiwifruits, treated with ethylene for 24 h and stored during 10 days, were assessed by UV spectrometry, fluorometry, and chemometrical analysis for changes in selected characteristics of quality (firmness, dry matter and soluble solid contents, pH, and acidity) and bioactivity (concentration of polyphenols via Folin-Ciocalteu and p-hydroxybenzoic acid assays). All of the monitored...
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Dissociative photo-double-ionization of isoxazole
PublikacjaIn the present communication, we present results on the photo-double-ionization and fragmentation of the isoxazole molecules. The experiments were carried out at the CiPo beamline at the Elettra-Sincrotrone radiation facility exploiting the VUV excitation and the ion time-of-flight spectrometry combined with the PEPICO technique. The dissociative processes where only one electron is emitted are quite well known [1]. However, double...
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The Chemical and Biological Properties of Nanohydroxyapatite Coatings with Antibacterial Nanometals, Obtained in the Electrophoretic Process on the Ti13Zr13Nb Alloy
PublikacjaThe risk of an early inflammation after implantation surgery of titanium implants has caused the development of different antimicrobial measures. The present research is aimed at characterizing the effects of nanosilver and nanocopper dispersed in the nanohydroxyapatite coatings, deposited on the Ti13Zr13Nb alloy, and on the chemical and biological properties of the coatings.The one-stage deposition process was performed by the...
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Investigation of vortex assisted magnetic deep eutectic solvent based dispersive liquid–liquid microextraction for separation and determination of vanadium from water and food matrices: Multivariate analysis
PublikacjaA new and simple vortex assisted magnetic deep eutectic solvent dispersive liquid–liquid microextraction procedure (VA-MDES-DLLME) was developed for the determination of vanadium (V) in food and water samples by flame atomic absorption spectrometry (FAAS). In the extraction medium, a bis(acetylpivalylmethane) ethylenediimine (H2APM2en) was used for the complexation of V(V) in sample solution at pH 6. The VA-MDES-DLLME was optimized...
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Soft X-ray Induced Production of Neutral Fragments in High-Rydberg States at the O 1s Ionization Threshold of the Water Molecule
PublikacjaDissociation of water molecules after soft X-ray absorption can yield neutral fragments in high-Rydberg (HR) states. We have studied the production of such fragments by field ionization and ion time-of-flight (TOF) spectrometry. Neutral HR fragments are created at all resonances below the O 1s ionization potential (IP) and particularly within 1 eV above the O 1s IP. The latter effect is due to the recapture of the O 1s photoelectrons...
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Do You Know What You Drink? Comparative Research on the Contents of Radioisotopes and Heavy Metals in Different Types of Tea from Various Parts of the World
PublikacjaThe aim of this study was to assess the potential health risks of radioactive elements and heavy metals ingested through the consumption of various types of tea imported to the Polish market (black, green, red, oolong and white). The concentrations [Bq/kg] of radionuclides (40K, 137Cs, 226Ra, 210Pb and 228Th) in tea leaves before and after brewing were measured using γ-ray spectrometry with high-purity germanium (HPGe). The concentrations...
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Mercury concentrations in marine biota with special focus on grey and ringed seals
PublikacjaMarine organisms are exposed and sensitive to effects of environmental contamination by heavy metals including different forms of mercury. Baltic seals as the top predators of the marine ecosystem are even more endangered due to (considerable) longevity as well as a long biological half-time of toxin elimination. The concentrations of mercury in seals from the Baltic is poorly known, thus the aim of this work is to determine and...
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Ultrasound assisted dispersive solid phase microextraction using polystyrene-polyoleic acid graft copolymer for determination of Sb(III) in various bottled beverages by HGAAS
PublikacjaA new polyoleic acid-polystyrene (PoleS) block/graft copolymer was synthesized and applied as adsorbent for ultrasound assisted dispersive solid phase microextraction (UA-DSPME) of Sb(III) in different bottled beverages and analysis using hydride generation atomic absorption spectrometry (HGAAS). Adsorption capacity of the PoleS was 150 mg g−1. Several sample preparation parameters such as sorbent amount, solvent type, pH, sample...
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NOx Photooxidation over Different Noble Metals Modified TiO2
PublikacjaWe compared the activity enhancement effect of noble metal deposited on TiO2 in photocatalytic nitrogen oxides oxidation. Titanium dioxide was decorated with Ag, Au, Pt or Pd in the sol-gel process. Synthesized catalysts were characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller measurement (BET), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX)....
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Analytical chemistry in technical approaches: immobilization of biosorbent waste containing heavy metals in cemented materials
PublikacjaAn ecologically safe and economically justified method of stabilization of the used biosorbents was developed. Sorbent contaminated with heavy metals has been successfully solidified/stabilized using a hydraulic binder. The test results indicated that up to 1% of the biosorbent residue used could be added without compromising the compressive strength of the mortar. The compressive strength of the modified mortars did not change...
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Preconcentration and Analytical Methods for Determination of Methyl Tert-Butyl Ether and Other Fuel Oxygenates and Their Degradation Products in Environment: A Review
PublikacjaFuel oxygenates (FOs) are mainly ethers or alcohols which are added to gasoline either to boost the octane number or to make the fuel burning process more "cleaner" with increasing the oxygen content, or to obtain a combination of both effects. FOs are water soluble with high mobility in the environment which presence even at very low concentrations lower the quality of water making it unsafe or unpleasant due to their objectionable...