The environment as the first victim: The impacts of the war on the preservation areas in Ukraine.

The war in Ukraine has had a devastating impact on the environment. Military actions have caused the release of hazardous substances into the environment, such as pollutants and toxic chemicals, that have contaminated the water, soil, and air, posing a threat to both human health and the environment. This has resulted in widespread destruction and contamination of natural habitats and resources and has disrupted wildlife populations and ecosystems. The impacts of military activity on the soils of protected areas are particularly critical, as they are the basis of biotic and landscape diversity and require special management and scientifically based monitoring measures even in peaceful conditions. In this context, this communication paper aims to provide an overview of the impacts of the war on the soils in four Ukrainian protected areas, namely Chornobyl Radiation and Ecological Biosphere Reserve; Desniansko-Starohutskyi National Nature Park; Holosiivskyi National Nature Park, and Hetmanskyi National Nature Park. To address these aspects, this paper combined GIS analysis and secondary data including soil samples obtained during field expeditions, to provide evidence of how ground battles, occupation, terrestrial land mines, and explosions can severely impact the soils. Practical and theoretical implications of the military actions are also discussed.

Silver Complexes of Miconazole and Metronidazole: Potential Candidates for Melanoma Treatment.

Melanoma, arguably the deadliest form of skin cancer, is responsible for the majority of skin-cancer-related fatalities. Innovative strategies concentrate on new therapies that avoid the undesirable effects of pharmacological or medical treatment. This article discusses the chemical structures of [(MTZ)2AgNO3], [(MTZ)2Ag]2SO4, [Ag(MCZ)2NO3], [Ag(MCZ)2BF4], [Ag(MCZ)2SbF6] and [Ag(MCZ)2ClO4] (MTZ-metronidazole; MCZ-miconazole) silver(I) compounds and the possible relationship between the molecules and their cytostatic activity against melanoma cells. Molecular Hirshfeld surface analysis and computational methods were used to examine the possible association between the structure and anticancer activity of the silver(I) complexes and compare the cytotoxicity of the silver(I) complexes of metronidazole and miconazole with that of silver(I) nitrate, cisplatin, metronidazole and miconazole complexes against A375 and BJ cells. Additionally, these preliminary biological studies found the greatest IC50 values against the A375 line were demonstrated by [Ag(MCZ)2NO3] and [(MTZ)2AgNO3]. The compound [(MTZ)2AgNO3] was three-fold more toxic to the A375 cells than the reference (cisplatin) and 15 times more cytotoxic against the A375 cells than the normal BJ cells. Complexes of metronidazole with Ag(I) are considered biocompatible at a concentration below 50 µmol/L.

Biodiesel Production by Methanolysis of Rapeseed Oil-Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO).

Alkaline earth metal oxide (MgO, CaO, SrO) catalysts supported on BEA zeolite were prepared by a wet impregnation method and tested in the transesterification reaction of rapeseed oil with methanol towards the formation of biodiesel (FAMEs-fatty acid methyl esters). To assess the influence of the SiO2/Al2O3 ratio on the catalytic activity in the tested reaction, a BEA zeolite carrier material with different Si/Al ratios was used. The prepared catalysts were tested in the transesterification reaction at temperatures of 180 °C and 220 °C using a molar ratio of methanol/oil reagents of 9:1. The transesterification process was carried out for 2 h with the catalyst mass of 0.5 g. The oil conversion value and efficiency towards FAME formation were determined using the HPLC technique. The physicochemical properties of the catalysts were determined using the following research techniques: CO2-TPD, XRD, BET, FTIR, and SEM-EDS. The results of the catalytic activity showed that higher activity in the tested process was confirmed for the catalysts supported on the BEA zeolite characterized by the highest silica/alumina ratio for the reaction carried out at a temperature of 220 °C. The most active zeolite catalyst was the 10% CaO/BEA system (Si/Al = 300), which showed the highest triglyceride (TG) conversion of 90.5% and the second highest FAME yield of 94.6% in the transesterification reaction carried out at 220 °C. The high activity of this system is associated with its alkalinity, high value of the specific surface area, the size of the active phase crystallites, and its characteristic sorption properties in relation to methanol.

The New Elastomeric Compounds Made of Butyl Rubber Filled with Phyllosilicates, Characterized by Increased Barrier Properties and Hydrophobicity and Reduced Chemical Degradation.

The aim of the study was to produce new elastomeric materials containing butyl rubber (IIR) filled with silica and phyllosilicates (vermiculite, montmorillonite, perlite or halloysite tubes) with enhanced hydrophobicity and barrier properties and reduced chemical degradation. It was found that the filler type had a significant impact on the degree of cross-linking of butyl rubber and the properties of its vulcanizates. The highest degree of cross-linking and the highest mechanical strength were achieved for IIR composites filled with Arsil with perlite or halloysite tubes. The highest surface hydrophobicity (119°) was confirmed for the IIR vulcanizates with Arsil and montmorillonite. All tested samples showed high barrier properties because both the gas diffusion rate coefficient and the permeability coefficient reached low values. Both unfilled and filled IIR vulcanizates retained chemical resistance in contact with methanol for 480 min. Hour-long contact of a polar solvent (methanol) with each of the vulcanizates did not cause material degradation, while the presence of a non-polar solvent (n-heptane) worsened the mechanical parameters by up to 80%. However, the presence of fillers reduced the chemical degradation of vulcanizates (in the case of cured IIR filled with Arsil and halloysite tubes by 40% compared to the composite without fillers).

Silver, Its Salts and Application in Medicine and Pharmacy.

The healing properties of silver have been used since ancient times. The main aim of the study was to collect and review the literature on the clinical potential of silver, its salts and complex compounds. The second goal was to present an outline of the historical use of silver in medicine and pharmacy, taking into account the possibility of producing pharmaceutical drug forms on the premises of pharmacies. In the context of the growing resistance of microorganisms to available, widely used antibiotics, silver plays a key role. There is only one known case of bacterial resistance to silver-the Pseudomonas stutzeri strain, which naturally occurs in silver mines. The development of research in the field of coordination chemistry offers great opportunities in the design of new substances in which silver ions can be incorporated. These substances exhibit increased potency and often an extended antimicrobial spectrum. Silver-based compounds are, however, only limited to external applications, as opposed to their historic oral administration. Advanced studies of their physicochemical, microbiological, cytotoxic and genotoxic properties are ongoing and full of challenges. The improvement of the methods of synthesis gives the possibility of applying the newly synthesized compounds ex tempore, as was the case with the complex of metronidazole with silver (I) nitrate. Some of these experimental efforts performed in vitro are followed with clinical trials. The third and final goal of this study was to present the possibility of obtaining an ointment under the conditions of an actual pharmacy using silver (I) salts and a ligand, both of which are active substances with antimicrobial properties.

Use of copper-functionalized cotton waste in combined chemical and biological processes for production of valuable chemical compounds.

Cotton textiles modified with copper compounds have a documented mechanism of antimicrobial action against bacteria, fungi, and viruses. During the COVID-19 pandemic, there was pronounced interest in finding new solutions for textile engineering, using modifiers and bioactive methods of functionalization, including introducing copper nanoparticles and complexes into textile products (e.g. masks, special clothing, surface coverings, or tents). However, copper can be toxic, depending on its form and concentration. Functionalized waste may present a risk to the environment if not managed correctly. Here, we present a model for managing copper-modified cotton textile waste. The process includes pressure and temperature-assisted hydrolysis and use of the hydrolysates as a source of sugars for cultivating yeast and lactic acid bacteria biomass as valuable chemical compounds.

The Shear Bond Strength of Resin-Based Luting Cement to Zirconia Ceramics after Different Surface Treatments.

Due to its unique properties, zirconia is increasingly being used in dentistry, but surface preparation for bonding is difficult because of its polycrystalline structure. This study aimed to determine the effect of a new etching technique (Zircos-E) on Ceramill Zi (Amann Girrbach). The effect of etching and the use of primers (Monobond Plus and MKZ Primer) on the bond strength of zirconia with resin cement (NX3) was assessed. Shear bond strength was evaluated after storage in water for 24 h and after thermal aging (5000 thermocycling at 5 °C/55 °C). A scanning electron microscope (Hitachi S-4700) was used to evaluate the surface structure before and after the Zircos-E system. The roughness parameters were assessed using an SJ-410 profilometer. The etched zirconia surface is more homogeneous over the entire surface, but some localized forms of erosion exist. The etching of zirconia ceramics caused changes in the surface structure of zirconia and a significant increase in the shear bond strength between zirconia and resin cement. The use of primers positively affects the adhesion between resin cement and zirconia. Aging with thermocycler significantly reduced the shear bond strength, with one exception-sandblasted samples with MKZ Primer. Standard ceramic surface preparation, involving only alumina sandblasting, does not provide a satisfactory bond. The use of etching with the Zircos-E system and primers had a positive effect on the strength of the zirconium-resin cement connection.

Effect of CaO, Al2O3, and MgO Supports of Ni Catalysts on the Formation of Graphite-like Carbon Species during the Boudouard Reaction and Methane Cracking.

The investigation of the course of the Boudouard reaction and methane cracking was performed over nickel catalysts based on oxides of calcium, aluminum, and magnesium. The catalytic samples were synthesized by the impregnation method. The physicochemical characteristics of the catalysts were determined using atomic adsorption spectroscopy (AAS), Brunauer-Emmett-Teller method analysis (BET), temperature-programmed desorption of ammonia and carbon dioxide (NH3- and CO2-TPD), and temperature-programmed reduction (TPR). Qualitative and quantitative identification of formed carbon deposits after the processes were carried out using total organic carbon analysis (TOC), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The selected temperatures for the Boudouard reaction and methane cracking (450 and 700 °C, respectively) were found to be optimal for the successful formation of graphite-like carbon species over these catalysts. It was revealed that the activity of catalytic systems during each reaction is directly related to the number of weakly interacted nickel particles with catalyst support. Results of the given research provide insight into the mechanism of carbon deposit formation and the role of the catalyst support in this process, as well as the mechanism of the Boudouard reaction.

Evaluation of the Selected Mechanical and Aesthetic Properties of Experimental Resin Dental Composites Containing 1-phenyl-1,2 Propanedione or Phenylbis(2,4,6-trimethylbenzoyl)-phosphine Oxide as a Photoinitiator.

The goal of this study was to compare the mechanical properties of experimental resin dental composites containing a conventional photoinitiating system (camphorquinone CQ and 2-(dimethylami-no)ethyl methacrylate (DMAEMA)) to a photoinitiator system containing 1-phenyl-1,2 propanedione (PPD) with 2-(dimethylami-no)ethyl methacrylate) or acting alone phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (BAPO). The manually produced composites consisted of an organic matrix: bis-GMA (60 wt. %), TEGDMA (40 wt. %), and silanized silica filler (45 wt. %). The composites contained 0.4/0.8 wt. %, 0.8/1.6 wt. %, and 1/2 wt. % of PPD/DMAEMA and another group included 0.25, 0.5, or 1 wt. % of BAPO. Vickers hardness, microhardness (in the nanoindentation test), diametral tensile strength, and flexural strength were assessed, and CIE L* a* b* colorimetric analysis was conducted for each composite produced. The highest average Vickers hardness values were obtained for the composite containing 1 wt. % BAPO (43.73 ± 3.52 HV). There was no statistical difference in the results of diametral tensile strength for the experimental composites tested. The results of 3-point bending tests were the highest for composites containing CQ (77.3 ± 8.84 MPa). Despite the higher hardness of experimental composites including PPD or BAPO, compared with composites with CQ, the overall results indicate that the composite with CQ still represents a better solution when used as a photoinitiator system. Moreover, the composites containing PPD and DMAEMA are not promising in terms of color or mechanical properties, especially as they require significantly longer irradiation times.

Zn Modification of Pd/TiO2/Ti Catalyst for CO Oxidation.

The main goal of this study was to modify the activity of Pd/TiO2/Ti catalyst in the reaction of CO oxidation by the addition of Zn. Plasma electrolytic oxidation (PEO) of Ti wire was conducted to produce a uniform porous layer of TiO2. A mixture of Pd and Zn was then introduced by means of adsorption. After reduction treatment, the activity of the samples was examined by oxidation of 5% CO in a temperature range from 80-350 °C. Model catalysts with sufficient amounts of the metals for physico-chemical investigation were prepared to further investigate the reaction between Pd and Zn during CO oxidation. The structures and compositions of the samples were investigated using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), inductively coupled plasma mass spectrometry (ICP-MS), Fourier transform infrared (FTIR), and X-ray diffraction (XRD). Modification of Pd/TiO2/Ti catalyst by Zn with a Pd:Zn atomic ratio of 2:1 decreased the temperature of complete CO oxidation from 220 °C for Pd/TiO2/Ti to 180 °C for Pd-Zn/TiO2/Ti. The temperature of 50% CO conversion on Pd-Zn(2:1)/TiO2/Ti was around 55 °C lower than in the reaction on monometallic Pd catalyst. The addition of Zn to the Pd catalyst lowered the binding energy of CO on the surface and improved the dissociative adsorption of oxygen, facilitating the oxidation of CO. FTIR showed that the bridging form of adsorbed CO is preferred on bimetallic systems. Analysis of the surface compositions of the samples (SEM-EDS, TOF-SIMS) showed higher amounts of oxygen on the bimetallic systems.

Can TPO as Photoinitiator Replace "Golden Mean" Camphorquinone and Tertiary Amines in Dental Composites? Testing Experimental Composites Containing Different Concentration of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide.

The aim of this research was to compare the biomechanical properties of experimental composites containing a classic photoinitiating system (camphorquinone and 2-(dimethylami-no)ethyl methacrylate) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as a photoinitiator. The produced light-cured composites consisted of an organic matrix-Bis-GMA (60 wt.%), TEGDMA (40 wt.%) and silanized silica filler (45 wt.%). Composites contained 0.27; 0.5; 0.75 or 1 wt.% TPO. Vickers hardness, microhardness (in the nanoindentation test), diametral tensile strength, resistance to three-point bending and the CIE L* a* b* colorimetric analysis was performed with each composite produced. The highest average Vickers hardness values were obtained for the composite containing 1 wt.% TPO (43.18 ± 1.7HV). The diametral tensile strength remains on regardless of the type and amount of photoinitiator statistically the same level, except for the composite containing 0.5 wt.% TPO for which DTS = 22.70 ± 4.7 MPa and is the lowest recorded value. The highest average diametral tensile strength was obtained for the composite containing 0.75 wt.% TPO (29.73 ± 4.8 MPa). The highest modulus of elasticity characterized the composite containing 0.75 wt.% TPO (5383.33 ± 1067.1 MPa). Composite containing 0.75 wt.% TPO has optimal results in terms of Vickers hardness, diametral tensile strength, flexural strength and modulus of elasticity. Moreover, these results are better than the parameters characterizing the composite containing the CQ/DMAEMA system. In terms of an aesthetic composite containing 0.75 wt.%. TPO is less yellow in color than the composite containing CQ/DMAEMA. This conclusion was objectively confirmed by test CIE L* a* b*.

Assessment of the Authenticity of Whisky Samples Based on the Multi-Elemental and Multivariate Analysis.

Two hundred and five samples of whisky, including 170 authentic and 35 fake products, were analyzed in terms of their elemental profiles in order to distinguish them according to the parameter of their authenticity. The study of 31 elements (Ag, Al, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Te, Tl, U, V, Ca, Fe, K, Mg, P, S, Ti and Zn) was performed using the Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and Cold Vapor-Atomic Absorption (CVAAS) techniques. Additionally, the pH values of all samples were determined by pH-meter, and their isotopic ratios of 88Sr/86Sr, 84Sr/86Sr, 87Sr/86Sr and 63Cu/65Cu were assessed, based on the number of counts by ICP-MS. As a result of conducted research, elements, such as Mn, K, P and S, were identified as markers of whisky adulteration related to the age of alcohol. The concentrations of manganese, potassium and phosphorus were significantly lower in the fake samples (which were not aged, or the aging period was much shorter than legally required), compared to the original samples (in all cases subjected to the aging process). The observed differences were related to the migration of these elements from wooden barrels to the alcohol contained in them. On the other hand, the sulfur concentration in the processed samples was much higher in the counterfeit samples than in the authentic ones. The total sulfur content, such as that of alkyl sulfides, decreases in alcohol with aging in the barrels. Furthermore, counterfeit samples can be of variable origin and composition, so they cannot be characterized as one group with identical or comparable features. Repeatedly, the element of randomness dominates in the production of these kinds of alcohols. However, as indicated in this work, the extensive elemental analysis supported by statistical tools can be helpful, especially in the context of detecting age-related adulteration of whisky. The results presented in this paper are the final part of a comprehensive study on the influence of selected factors on the elemental composition of whisky.

Profiling and imaging of forensic evidence - A pan-European forensic round robin study part 1: Document forgery.

The forensic scenario, on which the round robin study was based, simulated a suspected intentional manipulation of a real estate rental agreement consisting of a total of three pages. The aims of this study were to (i) establish the amount and reliability of information extractable from a single type of evidence and to (ii) provide suggestions on the most suitable combination of compatible techniques for a multi-modal imaging approach to forgery detection. To address these aims, seventeen laboratories from sixteen countries were invited to answer the following tasks questions: (i) which printing technique was used? (ii) were the three pages printed with the same printer? (iii) were the three pages made from the same paper? (iv) were the three pages originally stapled? (v) were the headings and signatures written with the same ink? and (vi) were headings and signatures of the same age on all pages? The methods used were classified into the following categories: Optical spectroscopy, including multispectral imaging, smartphone mapping, UV-luminescence and LIBS; Infrared spectroscopy, including Raman and FTIR (micro-)spectroscopy; X-ray spectroscopy, including SEM-EDX, PIXE and XPS; Mass spectrometry, including ICPMS, SIMS, MALDI and LDIMS; Electrostatic imaging, as well as non-imaging methods, such as non-multimodal visual inspection, (micro-)spectroscopy, physical testing and thin layer chromatography. The performance of the techniques was evaluated as the proportion of discriminated sample pairs to all possible sample pairs. For the undiscriminated sample pairs, a distinction was made between undecidability and false positive claims. It was found that none of the methods used were able to solve all tasks completely and/or correctly and that certain methods were a priori judged unsuitable by the laboratories for some tasks. Correct results were generally achieved for the discrimination of printer toners, whereas incorrect results in the discrimination of inks. For the discrimination of paper, solid state analytical methods proved to be superior to mass spectrometric methods. None of the participating laboratories deemed addressing ink age feasible. It was concluded that correct forensic statements can only be achieved by the complementary application of different methods and that the classical approach of round robin studies to send standardised subsamples to the participants is not feasible for a true multimodal approach if the techniques are not available at one location.

An Evaluation of the Hydrolytic Stability of Selected Experimental Dental Matrices and Composites.

Materials with potential use as dental restoration should be evaluated in an aggressive environment. Such accelerated aging is widely used in other industries and allows the assessment of service life. In the presented study, three neat resins (UDMA/Bis-GMA/TEGDMA 70/10/20 wt.%, UDMA/Bis-GMA/TEGDMA 40/40/20 wt.% and UDMA/Bis-EMA/TEGDMA 40/40/20 wt.%) and three composites based on these matrices were tested before and after aging protocols (I-7500 cycles, 5 °C and 55 °C, water and 7 days, 60 °C, 0.1 M NaOH; II-5 days, 55 °C, water and 7 days, 60 °C, 0.1 M NaOH). Flexural strength (FS), diametral tensile strength (DTS) and hardness (HV) were determined. Applied aging protocols resulted in a decrease in the value of the FS, DTS and HV. Larger changes were noticed for the neat resins. Materials in which the content of bis-GMA was lower or substituted by bis-EMA showed better resistance to degradation. The choice of mixtures with monomers characterized by lower sorption values may favorably affect hydrolytic stability. It was shown that for composites there was a drastic decrease in hardness, which suggests a more superficial effect of the used protocols. However, degradation of the surface layer can result in a growing problem over time given that the mastication processes are an inherent element in the oral environment.

The Elemental Fingerprints of Different Types of Whisky as Determined by ICP-OES and ICP-MS Techniques in Relation to Their Type, Age, and Origin.

A total of 170 samples of whisky from 11 countries were analysed in terms of their elemental profiles. The levels of 31 elements were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS): Ag, Al, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Sb, Sn, Sr, Te, Tl, U, and V, Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) Ca, Fe, K, Mg, P, S, Ti, and Zn and Cold Vapor-Atomic Absorption (CV-AAS): Hg techniques in those alcoholic samples. A comparative analysis of elemental profiles was made on the basis of the content of chosen elements with regard to selected parameters: country of origin, type of whisky (single malt and blended) and age of products. One of the elements which clearly distinguishes single malt and blended types of whisky is copper. Single malt Scotch whisky had a uniform concentration of copper, which is significantly higher for all malt whisky samples when compared with the blended type. Analysis of samples from the USA (n = 26) and Ireland (n = 15) clearly revealed that the objects represented by the same product but originating from independent bottles (e.g., JB, JDG, BUS brands) show common elemental profiles. On the other hand, comparative analysis of Scotch whisky with respect to aging time revealed that the longer the alcohol was aged, (i.e., the longer it stayed in the barrel), the higher the content of Cu and Mn that was recorded.

CO Oxidation over Pd Catalyst Supported on Porous TiO2 Prepared by Plasma Electrolytic Oxidation (PEO) of a Ti Metallic Carrier.

A porous TiO2 layer was prepared with the plasma electrolytic oxidation (PEO) of Ti. In a further step, Pd was deposited on the TiO2 surface layer using the adsorption method. The activity of the Pd/TiO2/Ti catalyst was investigated during the oxidation of CO to CO2 in a mixture of air with 5% CO. The structure of the catalytic active layer was studied using a scanning electron microscope equipped with an energy dispersive spectrometer (SEM-EDS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), inductively coupled plasma mass spectrometry (ICP-MS), and X-ray diffraction (XRD). The PEO process provided a porous TiO2 layer with a uniform thickness in the range of 5-10 µm, which is desirable for the production of Pd-supported catalysts. A TOF-SIMS analysis showed the formation of Pd nanoparticles after the adsorption treatment. The conversion of CO to CO2 in all samples was achieved at 150-280 °C, depending on the concentration of Pd. The composition of Pd/ TiO2/Ti was determined using ICP-MS. The optimum concentration of Pd on the surface of the catalyst was approximately 0.14% wt. This concentration was obtained when a 0.4% PdCl2 solution was used in the adsorption process. Increasing the concentration of PdCl2 did not lead to a further improvement in the activity of Pd/ TiO2/Ti.

Zinc Coordination Compounds with Benzimidazole Derivatives: Synthesis, Structure, Antimicrobial Activity and Potential Anticancer Application.

Developing new, smart drugs with the anticancer activity is crucial, especially for cancers, which cause the highest mortality in humans. In this paper we describe a series of coordination compounds with the element of health, zinc, and bioactive ligands, benzimidazole derivatives. By way of synthesis we have obtained four compounds named C1, C2, C4 and C4. Analytical analyses (elemental analysis (EA), flame atomic absorption spectrometry (FAAS)), spectroscopic (Fourier transform infrared spectroscopy (FT-IR), mass spectrometry (MS)) and thermogravimetric (TG) methods and the definition of crystal structures were used to explore the nature of bonding and to elucidate the chemical structures. The collected analytical data allowed the determination of the stoichiometry in coordination compounds, thermal stability, crystal structure and way of bonding. The cytotoxicity effect of the new compounds as a potential antitumor agent on the glioblastoma (T98G), neuroblastoma (SK-N-AS) and lung adenocarcinoma (A549) cell lines and human normal skin fibroblasts (CCD-1059Sk) was also determined. Cell viability was determined by the MTT assay. The results obtained confirmed that conversion of ligands into the respective metal complexes significantly improved their anticancer properties. The complexes were screened for antibacterial and antifungal activities. The ADME technique was used to determine the physicochemical and biological properties.

Golden and Silver-Golden Chitosan Hydrogels and Fabrics Modified with Golden Chitosan Hydrogels.

Golden and silver-golden chitosan hydrogels and hydrogel-modified textiles of potential biomedical applications are investigated in this work. The hydrogels are formed by reactions of chitosan with HAuCl4·xH2O. For above the critical concentration of chitosan (c*), chitosan-Au hydrogels were prepared. For chitosan concentrations lower than c*, chitosan-Au nano- and microgels were formed. To characterise chitosan-Au structures, sol-gel analysis, UV-Vis spectrophotometry and dynamic light scattering were performed. Au concentration in the hydrogels was determined by the flame atomic absorption spectrophotometry. Colloidal chitosan-Au solutions were used for the modification of fabrics. The Au content in the modified fabrics was quantified by inductively coupled plasma mass spectrometry technique. Scanning electron microscopy with energy dispersion X-ray spectrometer was used to analyse the samples. Reflectance spectrophotometry was applied to examine the colour of the fabrics. The formation of chitosan-Au-Ag hydrogels by the competitive reaction of Au and Ag ions with the chitosan macromolecules is reported.

The Elemental Profile of Beer Available on Polish Market: Analysis of the Potential Impact of Type of Packaging Material and Risk Assessment of Consumption.

Twenty-five elements, including the most essential and toxic metals, were determined in fifty beer samples stored in cans and bottles by Inductively Coupled Plasma Mass Spectrometry (ICP-MS), Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Cold Vapor Atomic Absorption Spectroscopy (CVAAS) techniques. The packaging material was analyzed using the Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) technique. The control of the level of individual metals is necessary, not only to maintain the organoleptic properties of the product, but also to fulfill the standards regarding the permissible maximum concentrations. Metals can originate from different sources, including the brewing water, malt grains, hops, adjuncts, fruits, and spices. They may also come from contamination from the brewery equipment, i.e., vessels and tanks, including beer packing, storing and transporting (kegs, casks, cans). Discriminant analysis revealed that the differentiation of three types of beer (Lager, Ale, Craft) was possible, based on elemental concentrations, for the reduced data set after their selection using the Kruskal-Wallis test. The analysis of the impact of the packaging material (can or bottle) proved that when this parameter was used as a differentiating criterion, the difference in the content of Na, Al, Cu and Mn can be indicated. The risk assessment analysis showed that the consumption of beer in a moderate quantity did not have any adverse effect in terms of the selected element concentrations, besides Al. However, in the case of Al, the risk related to consumption can be considered, but only for the beer stored in cans produced from aluminum.

Determination of Metallic Impurities by ICP-MS Technique in Eyeshadows Purchased in Poland. Part I.

Eye shadows, which are products willingly and frequently used by women and even children, have been reported in literature to contain toxic metals. In this work, a total of 94 eye shadows samples available on the Polish market were collected. Eye shadow products have been selected in order to include several parameters important from the point of view of the typical consumer such as: product type (mat/pearl), consumer group (for adults and children), price range (very cheap, medium price, expensive and very expensive), color (twelve different colors were tested), manufacturer (eight brands were investigated) or country of production (four countries were included). The concentration of selected metals (Ag, Ba, Bi, Cd, Pb, Sr, Tl) was determined by ICP-MS technique after the sample extraction with a mixture of nitric acid and hydrogen peroxide in a microwave closed system. For Ag, Cd and Tl, some results were below the established limit of quantification for the employed technique. The presence of strontium, barium, lead and bismuth was confirmed in all studied samples. The obtained results for analyzed elements were, in general, quite comparable with the data reported by other authors. A small number of samples exceeding the permissible values (two samples were beyond the limit value for Cd of 0.5 mg/kg and one exceed the acceptable concentration for Pb of 10 mg/kg) also proves a relatively good condition of the Polish cosmetics market and suggests insubstantial risk for the potential consumers. The results gathered for some of the eye shadows intended for children turned out to be alarmingly high, in particular for elements such as Cd. The highest concentration of Cd reached almost 4 mg/kg, while of Pb amounted to 16 mg/kg. The presence of the statistically significant differences was confirmed for all included parameters with an exception of the color of the eye shadow. Considering the results acquired only for Cd and Pb with respect to the country of origin, the least contaminated cosmetics by metallic impurities seem to be the one produced in Canada, while the ones presenting the highest health risk among all studied eye shadows are make-up cosmetics originating from Poland and Italy. Multivariate analysis of a large data set using CA methods and PCA provided valuable information on dependencies between variables and objects.