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Magnetite (Fe3O4) is one of the most common accessory minerals in magmatic rocks, and it can accommodate a wide variety of major, minor and trace elements that can be measured by laser ablation ICP-MS. In this study, we investigate the chemical compositions of magnetite from four carbonatite complexes (Oka, Mushgai Khudag, Hongcheon and Bayan Obo). The minor elements (Mg, Ti, Al, Mn) in magnetite vary significantly both within and between different complexes. High field strength elements (Zr, Hf, Nb, Ta, U, Th) are generally depleted in magnetite from carbonatite complexes, whereas K, Rb, Cs, Ca and P are commonly below detection limits. V and Zn display significant variations from tens to thousands of ppm. Co, Ni and Ga are present in ppm or tens of ppm, whereas Cu, Sr, Y, Ba and Pb are characterized by sub-ppm levels. Mo and Ge are identified at the ppm level, whereas a consistent concentration of 2–5 ppm is observed for Ge. The determined chemical compositions of magnetite from carbonatite complexes are quite distinguishable compared to those formed in silicate and sulfide melts. This is clearly shown using multielement variation diagrams, and the distinct signatures of carbonatite-related magnetite include strong positive anomalies of Mn and Zn and negative anomalies of Cu, Co and Ga. The discriminant diagrams of Ti vs. Zr + Hf, Ti vs. Nb + Ta and Ni/Cr vs. Ti are applicable for distinguishing magmatic and hydrothermal magnetite in carbonatite-related environments. In addition, the discriminant diagram of Zn/Co vs. Cu/Mo and Cu vs. Zr + Hf can be used to distinguish carbonatite-related magnetite from magnetite that formed in other environments.

This study was carried out in order to find a possible use for waste produced during the processing of vegetables and maize. Anaerobic fermentation is a suitable way to handle this wet and easily biodegradable organic material. The aim of this study was to evaluate the impact of waste corn kernels, peas, crushed corn kernels, French beans, mixed vegetables (broccoli, cauliflower, peas and carrot), corn leaf and corn husk on anaerobic fermentation. Anaerobic fermentation tests was carried out in batch fermenters (5 dm3) for 21 days at 42 °C. During this period the quantity and quality of biogas produced were monitored. The following substrate parameters were determined: dry matter content, organic dry matter content, nutrients content (protein, fat, fibre, starch, acid detergent fibre, neutral detergent fibre) and elemental composition. The hypothesis predicting the inhibitory impact of substrates on the anaerobic process was not confirmed. Biogas production after 21 days of hydraulic retention time ranged from 0.6773 m3/kg of organic dry matter (peas) to 1.1108 m3/kg of organic dry matter (mixed vegetables). All substrates had the final concentration of methane in the biogas ranged from 59.43 to 65.97%vol. The hypothesis about the impact of pre-treatment of substrates (crushing) on the quantity of the biogas produced was confirmed. The biogas production from the crushed corn kernel was significantly higher than the biogas production from substrates with a similar composition of nutrients (corn kernel, peas). Vegetables and maize waste produced during processing is a suitable substrate for anaerobic fermentation.

The Mushgai Khudag complex consists of numerous silicate volcanic-plutonic rocks including melanephelinites, theralites, trachytes, shonkinites, and syenites and also hosts numerous dykes and stocks of magnetite-apatite-enriched rocks and carbonatites. It hosts the second largest REE–Fe–P–F–Sr–Ba deposit in Mongolia, with REE mineralization associated with magnetite-apatite-enriched rocks and carbonatites. The bulk rock REE content of these two rock types varies from 21,929 to 70,852 ppm, which is much higher than that of syenites (716 ± 241 ppm). Among these, the altered magnetite-apatite-enriched rocks are characterized by the greatest level of REE enrichment (58,036 ± 13,313 ppm). Magmatic apatite from magnetite-apatite-enriched rocks is commonly euhedral with purple luminescence, and altered apatite displays variable purple to blue luminescence and shows fissures and hollows with deposition of fine-grained monazite aggregates. Most magmatic apatite within syenite is prismatic and displays oscillatory zoning with variable purple to yellow luminescence. Both magmatic and altered apatite from magnetite-apatite-enriched rocks were dated using in situ U–Pb dating and found to have ages of 139.7 ± 2.6 and 138.0 ± 1.3 Ma, respectively, which supports the presence of late Mesozoic alkaline magmatism. In situ 87Sr/86Sr ratios obtained for all types of apatite and calcite within carbonatite show limited variation (0.70572–0.70648), which indicates derivation from a common mantle source. All apatite displays steeply fractionated chondrite-normalized REE trends with significant LREE enrichment (46,066 ± 71,391 ppm) and high (La/Yb)N ratios ranging from 72.7 to 256. REE contents and (La/Yb)N values are highly variable among different apatite groups, even within the same apatite grains. The variable REE contents and patterns recorded by magmatic apatite from the core to the rim can be explained by the occurrence of melt differentiation and accompanying fractional crystallization. The Y/Ho ratios of altered apatite deviate from the chondritic values, which reflects alteration by hydrothermal fluids. Altered apatite contains a high level of REE (63,912 ± 31,785 ppm), which are coupled with increased sulfur and/or silica contents, suggesting that sulfate contributes to the mobility and incorporation of REEs into apatite during alteration. Moreover, altered apatite is characterized by higher Zr/Hf, Nb/Ta, and (La/Yb)N ratios (179 ± 48, 19.4 ± 10.3, 241 ± 40, respectively) and a lack of negative Eu anomalies compared with magmatic apatite. The distinct chemical features combined with consistent Sr isotopes and ages for magmatic and altered apatite suggest that pervasive hydrothermal alterations at Mushgai Khudag are most probably being induced by carbonatite-evolved fluids almost simultaneously after the alkaline magmatism.

A comparative study was carried out using magnetic nanoparticles (MNPs) for the fabrication of non-enzymatic sensors for the continuous and rapid detection and monitoring of H2O2. Various MNPs, differing in terms of their synthesis procedure and modification, were synthesized and characterized by different techniques. The electrochemical catalytic activity of the synthesized MNPs toward the reduction in H2O2 was investigated by cyclic voltammetry. The naked MNPs showed the highest catalytic activity among all the synthesized MNPs. The biosensor based on the naked MNPs was then applied in the determination of H2O2 using chronoamperometry. The parameters such as the applied cathodic potential and the amount of MNPs on the developed biosensor were optimized. Moreover, the analytical figures of merit, including reproducibility (RSD = 6.14%), sensitivity (m = 0.0676 &micro, A &micro, M&minus, 1), limit of detection (LOD) = 27.02 &micro, mol L&minus, 1, and limit of quantification (LOQ) = 89.26 &micro, 1 of the developed biosensor indicate satisfactory analysis. Finally, MNPs were successfully utilized for the determination of H2O2 in milk.

The service tree (Sorbus domestica) is a wild fruit tree with immense medicinal and industrial value. This study aimed at determining the four major groups of antioxidants (flavonoids, phenolic acids and aldehydes, catechin and procyanidin) in rootstocks of Crataegus laevigata (genotypes O-LE-14 and O-LE-21), Aronia melanocarpa (genotypes O-LE-14 and O-LE-21), Chaenomeles japonica (genotype O-LE-9) and Cydonia oblonga (BA 29) (genotypes O-LE-14 and O-LE-21). Hyperoside (Quercetin 3-D-galactoside) was the most abundant flavonoid compound, since its average content in the rootstocks of Crataegus laevigata (O-LE-21) was 180.68 &plusmn, 0.04 &mu, g&middot, g&minus, 1. Dihydrokaempherol was the least frequently found flavonoid compound, with an average concentration of 0.43 &plusmn, 0.01 &mu, 1 in all the rootstocks of plants considered in this study. Among the phenolic compounds, the most represented one was protocatechuic acid, with 955.92 &plusmn, 10.25 &mu, 1 in the rootstocks of Aronia melanocarpa (O-LE-14). On the other hand, the least represented p-Coumaric acid exhibited the average concentration of 0.34 &plusmn, 1 in the plant rootstocks. Epicatechin was the most abundant catechin compound, with a content of 3196.37 &plusmn, 50.10 &mu, 1 in the rootstocks of Aronia melanocarpa (O-LE-14). The lowest represented catechin compound was epigallocatechin, with the average concentration of 0.95 &plusmn, 0.08 &mu, 1 in the screened plant rootstocks. From the procyanidin compounds, the most abundant one was procyanidin b2 in the rootstocks of Crataegus laevigata (O-LE-14), with a concentration of 5550.40 &plusmn, 99.56 &mu, 1. On the contrary, procyanidin a2, with an average concentration of 40.35 &plusmn, 1.61 &mu, 1, represented the least frequent procyanidin compound in all the plant rootstocks screened herein.

The presented study deals with the observation of properties of methicillin-susceptible Staphylococcus aureus (MSSA) and methicillin-resistant S. aureus (MRSA) in the toxic arsenic environment and influence of arsenic on antioxidant capacity. Two forms of arsenic (As(III), As(V)) with different concentrations were used for induction of the oxidative stress in tested strains. Microbiological methods showed that the growth inhibition of MSSA was higher than that of MRSA in presence of both arsenic ions. As(III) showed 24% and 33% higher anti-microbial effects than As(V) against MSSA and MRSA respectively. A similar result was found also in the experiment of reduction of biofilm-formation. By using spectrophotometry, it was revealed that As(III) induced higher antioxidant production in both bacterial cultures. Methicillin-susceptible S. aureus produced an app. 50 mg equivalent of gallic acid (GAE/1 mg of protein) and MRSA produced an app. 15 mg of GAE/1 mg of protein. The productions of metallothionein in MSSA and MRSA were decreased up to 62.41% and 55.84% respectively in presence of As ions. Reduction of As(III) and As(V) concentrations leads to a decrease in antioxidant production and increased the formation of metallothionein. All of these changes in the results were found to be significant statistically. Taken together, these experiments proved that in comparison with MSSA, MRSA is less susceptible not only to the antimicrobial effects of antibiotics but also against effects caused by metalloids, as arsenic. Thus, it can be stated that MRSA abounds with complex defensive mechanisms, which may in the future constitute significant problem in the efficiency of antibiotics alternatives as metal ions or nanoparticles.

Glucose is a typical diagnostic marker of diabetes mellitus but it may be also helpful during diagnosis of some types of poisoning, immunological disorder or long-term stress at hospitalized patients. Diagnosis of diabetes mellitus in time is indispensable for prevention of life-threatening complication and so, accurate and easy device for non-invasive and accurate self-diagnosis is necessary. Simple assay based on filter paper with chitosan layer and with immobilized enzymes glucose oxidase and peroxidase and phone camera detection has been proposed for home-care glucose detection in urine. Data were processed in RGB (red–green–blue) color model when blue color channel showed the best sensitivity to changing glucose concentrations. Assay exerted linear regression from 0 to 4 mmol/l and limit of detection was set to be 166 µmol/l. Assay was not influenced by any interfering substances including maltose, sucrose, sorbitol or fructose or by urine matrix substance such as bovine serum albumin, ascorbic acid, uric acid or urea. Measurement of glucose from spiked urine samples reveals also no influence of the matrix on the assay. Long-term stability was measured and filter papers coated by enzymes showed excellent stability for at least 9 weeks without any special treatment or package. In comparison with differently modified filter paper, filter paper with both chitosan and enzymes showed the best sensitivity to changing glucose concentration. In a conclusion, simple (phone camera detection) and fast (3-min reaction) assay for quantitative detection of glucose from urine was optimized.

Eu(III) and Tb(III) Schiff base complexes are applicable in various fields such as sensing, assays, screening protocols in vitro, and imaging studies in vitro or in vivo. Fluorescent europium and terbium complexes and their interaction with cell penetrating peptide (KKKRKC) can represent an excellent key for understanding pathway of peptide transportation though cell membrane and the application of Schiff base complexes as potential antibacterial drugs. The Schiff base–metal complexes and its conjugates with peptide were tested for their antibacterial activity against Pseudomonas aeruginosa and Salmonella typhimurium. Schiff base–metal complexes conjugated with peptide show minor toxicity in normal human PNT1A cells and high antibacterial activity against P. aeruginosa and S. typhimurium, where IC50 down to 125.9 and/or 36.1 µM were found for P. aeruginosa and S. typhimurium, respectively. Our results strongly suggest that Schiff base–metal complexes conjugated with peptide have great potential to be developed into highly effective antibacterial drug.

Nanobiosynthesis belongs to the most recent methods for synthesis of nanoparticles. This type of synthesis provides many advantages including the uniformity in particle shape and size. The biosynthesis has also a significant advantage regarding chemical properties of the obtained particles. In this study, we characterized the basic properties and composition of quantum dots (QDs), obtained by the extracellular biosynthesis by Escherichia coli. Furthermore, the toxicity of the biosynthesized QDs was compared to QDs prepared by microwave synthesis. The obtained results revealed the presence of cyan CdTe QDs after removal of substantial amounts of organic compounds, which stabilized the nanoparticle surface. QDs toxicity was evaluated using three cell lines Human Foreskin Fibroblast (HFF), Human Prostate Cancer cells (PC-3) and Breast Cancer cells (MCF-7) and the MTT assay. The test revealed differences in the toxicity between variants of QDs, varying about 10% in the HFF and 30% in the MCF-7 cell lines. The toxicity of the biosynthesized QDs to the PC-3 cell lines was about 35% lower in comparison with the QDs prepared by microwave synthesis.

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements (REE). Both carbonatites and nepheline syenite-fluorite-calcite veinlets are host to a previously unreported macroscale texture involving pseudo-graphic intergrowths of fluorite and calcite. The inclusions within calcite occur as either pure fluorite, with associated REE minerals within the surrounding calcite, or as mixed calcite-fluorite inclusions, with associated zirconosilicate minerals. Consideration of the nature of the texture, and the proportions of fluorite and calcite present (∼29 and 71 mol%, respectively), indicates that these textures most likely formed either through the immiscible separation of carbonate and fluoride melts, or from cotectic crystallization of a carbonate-fluoride melt. Laser ablation ICP-MS analyses show the pure fluorite inclusions to be depleted in REE relative to the calcite. A model is proposed, in which a carbonate-fluoride melt phase enriched in Zr and the REE, separated from a phonolitic melt, and then either unmixed or underwent cotectic crystallization to generate an REE-rich carbonate melt and an REE-poor fluoride phase. The separation of the fluoride phase (either solid or melt) may have contributed to the enrichment of the carbonate melt in REE, and ultimately its saturation with REE minerals. Previous data have suggested that carbonate melts separated from silicate melts are relatively depleted in the REE, and thus melt immiscibility cannot result in the formation of REE-enriched carbonatites. The observations presented here provide a mechanism by which this could occur, as under either model the textures imply initial separation of a mixed carbonate-fluoride melt from a silicate magma. The separation of an REE-enriched carbonate-fluoride melt from phonolitic magma is a hitherto unrecognized mechanism for REE-enrichment in carbonatites, and may play an important role in the formation of shallow magmatic REE deposits. Keywords: Silicate-carbonate-fluoride melt immiscibility, Carbonatite, Alkaline syenite, Shallow REE deposit, Lugiin Gol, Mongolia

MS, AF and FW acknowledge the support of the NERC SoS:RARE consortium grant (NE/M011267/1). D. Kavecsanszki acknowledges the support of a postgraduate fellowship from the College of Engineering, Mathematics and Physical Sciences at the University of Exeter. The rare earth elements are unusual when defining giant-sized ore deposits, as resources are often quoted as total rare earth oxide, but the importance of a deposit may be related to the grade for individual, or a limited group of, the elements. Taking the total REE resource, only one currently known deposit (Bayan Obo) would class as giant (>1.7×107 tonnes contained metal), but a range of others classify as large (>1.7×106 tonnes). With the exception of unclassified resource estimates from the Olympic Dam IOCG deposit, all of these deposits are related to alkaline igneous activity – either carbonatites or agpaitic nepheline syenites. The total resource in these deposits must relate to the scale of the primary igneous source, but the grade is a complex function of igneous source, magmatic crystallisation, hydrothermal modification and supergene enrichment during weathering. Isotopic data suggest that the sources conducive to the formation of large REE deposits are developed in subcontinental lithospheric mantle, enriched in trace elements either by plume activity, or by previous subduction. The reactivation of such enriched mantle domains in relatively restricted geographical areas may have played a role in the formation of some of the largest deposits (e.g. Bayan Obo). Hydrothermal activity involving fluids from magmatic to meteoric sources may result in the redistribution of the REE and increases in grade, depending on primary mineralogy and the availability of ligands. Weathering and supergene enrichment of carbonatite has played a role in the formation of the highest grade deposits at Mount Weld (Australia) and Tomtor (Russia). For the individual REE with the current highest economic value (Nd and the HREE), the boundaries for the large and giant size classes are 2 orders of magnitude lower, and deposits enriched in these metals (agpaitic systems, ion absorption deposits) may have significant economic impact in the near future. Publisher PDF

Carbonatites are abundant in the rare earth elements (REE), and they host the most important REE resources in the world. However, the mechanisms that concentrate these elements during carbonatitic magmatic processes are still poorly constrained. Here, we report the occurrence of apatite-hosted melt inclusions from the Ulgii Khiid carbonatites, Mongolia, and use these to reconstruct the evolution of REE concentrations and patterns in early, primary carbonatite magma. The melt inclusions consist of a varied polycrystalline assemblage of daughter minerals, including calcite, diopside, phlogopite, magnetite, pyrite, monazite, parisite, and a phosphate glass which is remarkably enriched in REE. Heating-quenching experiments show that the homogenization temperatures of the inclusions are above 1200 °C and produce three immiscible liquid phases (i.e., phosphate-, silicate-, and Fe-silicate-melt). The phosphate melt has much higher REE content than the silicate melts. We, therefore, suggest that the melt inclusions trapped a REE-, P- and silicate-enriched carbonate melt produced via carbonate-silicate liquid immiscibility. During this process, both REE and P preferentially incorporated into the carbonate melt. With subsequent crystal fractionation of REE- and P-poor carbonate and silicate minerals, the separated carbonatitic melt becomes P-REE-saturated, forming REE minerals and an immiscible REE-rich phosphate melt. The phosphate melt is highly efficient at concentrating REE during the immiscibility process and plays a crucial role in controlling the REE budget in the P-rich carbonatite magmas.

Modification of carbon materials, especially graphene-based materials, has wide applications in electrochemical detection such as electrochemical lab-on-chip devices. A glassy carbon electrode (GCE) modified with chemically alternated graphene oxide was used as a working electrode (glassy carbon modified by graphene oxide with sulphur containing compounds and Nafion) for detection of nucleobases in hydrolysed samples (HCl pH = 2.9, 100 °C, 1 h, neutralization by NaOH). It was found out that modification, especially with trithiocyanuric acid, increased the sensitivity of detection in comparison with pure GCE. All processes were finally implemented in a microfluidic chip formed with a 3D printer by fused deposition modelling technology. As a material for chip fabrication, acrylonitrile butadiene styrene was chosen because of its mechanical and chemical stability. The chip contained the one chamber for the hydrolysis of the nucleic acid and another for the electrochemical detection by the modified GCE. This chamber was fabricated to allow for replacement of the GCE.

The Huanglongpu carbonatite-related Mo ore field is located in the Lesser Qinling Orogenic belt in the southern margin of the North China block. The ore field is composed of six deposits, Yuantou, Wengongling, Dashigou, Shijiawan, Taoyuan and Erdaohe, all of which are genetically related to carbonatite dykes except for the Shijiawan deposit which is associated with a granitic porphyry. The Yuantou carbonatite dykes intruded into Archean gneiss and other carbonatites emplaced into Mesoproterozoic volcanic and sediment rocks. The carbonatites are mainly composed of calcite and variable amounts of quartz and K-feldspar and minor molybdenite. Re–Os dating of molybdenite from the Yuantou carbonatite yields a weighted average age of 225.0 ± 7.6 Ma, consistent with the molybdenite age (221 Ma) from the Dashigou deposit. The rocks are characterized by high heavy REE (HREE) contents and consistent flat REE distribution patterns with La/Ybcn ~ 1. Quartz in the carbonatites from Yuantou and Dashigou deposits shows consistent O isotopes (8.1–10.2‰) similar to the associated calcite (7.2–9.5‰). The quartz and associated K-feldspar contain lower Zr, Hf and higher HREE abundances and negligible Eu anomaly relative to those from the granite porphyry in Shijiawan. Both minerals are primary products in the carbonatitic liquid, and not captured from the wall-rocks or crustal-derived silicate magmas, or a hydrothermal origin. Thus, the Huanglongpu carbonatitic liquids were enriched in Si and Mo, which may be produced by intensely fractional crystallization of non-silicate minerals.

This study shows the effects of spices, and their phenolic and flavonoid compounds, on prostate cell lines (PNT1A, 22RV1 and PC3). The results of an MTT assay on extracts from eight spices revealed the strongest inhibitory effects were from black pepper and caraway seed extracts. The strongest inhibitory effect on prostatic cells was observed after the application of extracts of spices in concentration of 12.5 mg.mL- 1. An LC/MS analysis identified that the most abundant phenolic and flavonoid compounds in black pepper are 3,4-dihydroxybenzaldehyde and naringenin chalcone, while the most abundant phenolic and flavonoid compounds in caraway seeds are neochlorogenic acid and apigenin. Using an MTT assay for the phenolic and flavonoid compounds from spices, we identified the IC50 value of ~1 mmol.L- 1 PNT1A. The scratch test demonstrated that the most potent inhibitory effect on PNT1A, 22RV1 and PC3 cells is from the naringenin chalcone contained in black pepper. From the spectrum of compounds assessed, the naringenin chalcone contained in black pepper was identified as the most potent inhibitor of the growth of prostate cells. info:eu-repo/semantics/openAccess

Toxic metal contamination of the environment is a global issue. In this paper, we present a low-cost and rapid production of amalgam electrodes used for determination of Cd(II) and Pb(II) in environmental samples (soils and wastewaters) by on-site analysis using difference pulse voltammetry. Changes in the electrochemical signals were recorded with a miniaturized potentiostat (width: 80 mm, depth: 54 mm, height: 23 mm) and a portable computer. The limit of detection (LOD) was calculated for the geometric surface of the working electrode 15 mm(2) that can be varied as required for analysis. The LODs were 80 ng.mL(-1) for Cd(II) and 50 ng.mL(-1) for Pb(II), relative standard deviation, RSD

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.

Sulfur mustard, in a chemical name bis(2-chloroethyl) sulfide, is a chemical warfare agent. It is cytotoxic and blister forming once spread over the skin. Though exact molecular mechanism of sulfur mustard toxic action remains unknown, inflammation and oxidative stress development are considered as the most relevant pathological consequences. Applications of either low-molecular weight antioxidants or cofactors for enzymatic antioxidants are considered as suitable ways how to ameliorate the poisoning. In this article, survey of literature on countermeasures against sulfur mustard poisoning are given and evidence of oxidative stress role during sulfur mustard poisoning and availability of antioxidants for the therapy are discussed.

Nowadays increasing attention has been focused on polyphenolic compounds as the main representants of antioxidants in horticultural crops including fruits. The edible honeysuckle has an unique position among lesser known fruits due to its high level of antioxidants. In the present study we determined polyphenolic profile and antioxidant capacity of four Russian cultivars of edible honeysuckle including ‘Gerda 25’, ‘Amfora’, ‘Morena’, ‘Lipnicka’, which found together in a single location in Mendel University in Brno, The Czech Republic. Polyphenolic compounds were detected by high performance liquid chromatography coupled with electrochemical detector (HPLC-ED). The antioxidant capacity was measured by DPPH test. According to the results there were differences among cultivars in terms of polyphenolic content and antioxidant activity and Lonicera kamtschatica ‘Gerda 25’ were found to be possessed the highest content of phenolic compounds corresponding to the highest value of antioxidant activity.

The nanotechnological concept is based on size-dependent properties of particles in the 1–100 nm range. Nevertheless, the connection between their size and effect is still not clear. Thus, we focused on reductive colloidal synthesis, characterization and biological testing of Pt nanoparticles (PtNPs) capped with biocompatible polymer polyvinylpyrrolidone (PVP). Synthesized PtNPs were of 3 different primary sizes (approx. ∼10; ∼14 and > 20 nm) and demonstrated exceptional haemocompatibility. In vitro treatment of three different types of malignant cells (prostate – LNCaP, breast – MDA-MB-231 and neuroblastoma – GI-ME-N) revealed that even marginal differences in PtNPs diameter resulted in changes in their cytotoxicity. The highest cytotoxicity was observed using the smallest PtNPs-10, where 24IC 50 was lower (3.1–6.2 μg/mL) than for cisplatin (8.1–19.8 μg/mL). In contrast to MDA-MB-231 and LNCaP cells, in GI-ME-N cells PtNPs caused noticeable changes in their cellular structure without influencing their viability. Post-exposure analyses revealed that PtNPs-29 and PtNPs-40 were capable of forming considerably higher amount of reactive oxygen species with consequent stimulation of expression of metallothionein (MT1/2 and MT3), at both mRNA and protein level. Overall, our pilot study demonstrates that in the nanoscaled world even the smallest differences can have crucial biological effect.

Interactions of silver phosphate nanoparticles (SPNPs) and selenium nanoparticles (SeNPs) with Staphylococcus aureus cultures have been studied at the cellular, molecular and protein level. Significant antibacterial effects of both SPNPs and SeNPs on S. aureus were observed. At a concentration of 300 μM, SPNPs caused 37.5% inhibition of bacterial growth and SeNPs totally inhibited bacterial growth. As these effects might have been performed due to the interactions of nanoparticles with DNA and proteins, the interaction of SPNPs or SeNPs with the amplified zntR gene was studied. The presence of nanoparticles decreased the melting temperatures of the nanoparticle complexes with the zntR gene by 23% for SeNPs and by 12% for SPNPs in comparison with the control value. The concentration of bacterial metallothionein was 87% lower in bacteria after application of SPNPs (6.3 μg mg(-1) protein) but was increased by 29% after addition of SeNPs (63 μg mg(-1) protein) compared with the S. aureus control (49 μg mg(-1) protein). Significant antimicrobial effects of the nanoparticles on bacterial growth and DNA integrity provide a promising approach to reducing the risk of bacterial infections that cannot be controlled by the usual antibiotic treatments.

Nucleic acids belong to the most important molecules and therefore the understanding of their properties, function and behavior is crucial. Even though a range of analytical and biochemical methods have been developed for this purpose, one common step is essential for all of them – isolation of the nucleic acid from the from complex sample matrix. The use of magnetic particles for the separation of nucleic acids has many advantages over other isolation methods. In this study, an isolation procedure for extraction of DNA was optimized. Each step of the isolation process including washing, immobilization and elution was optimized and therefore the efficiency was increased from 1.7% to 28.7% and the total time was shortened from 75 to 30 min comparing to the previously described method. Quantification of the particular parameter influence was performed by square-wave voltammetry using hanging drop mercury electrode. Further, we compared the optimized method with standard chloroform extraction and applied on isolation of DNA from Staphylococcus aureus and Escherichia coli.

Carcinoma of prostate (CaP) is the second most frequent malignant tumor occurring in men in Europe. Currently there is discussion on a wide range of potential CaP markers. One of them-nonprotein amino acid sarcosine, also known as N-methylglycine was chosen as a challenge for the development of microfluidic system with isolation by modified paramagnetic microparticles. Therefore, the aim of this study was to design a low-cost, simple, and rapid microfluidic system based on sarcosine isolation with modified paramagnetic microparticles and subsequent analysis on the ion exchange LC. We modified Dowex microparticles with Fe2O3 nanoparticles. Our paramagnetic microparticles were able to establish the binding with sarcosine. Moreover, we designed microfluidic device for sarcosine determination. Analysis of samples was carried out with LOD of 1 uM of a sarcosine that is sufficient because it is similar to concentrations of a sarcosine observed in the CaP patients.

Polymers are currently widely used to replace a variety of natural materials with respect to their favourable physical and chemical properties, and due to their economic advantage. One of the most important branches of application of polymers is the production of different products for medical use. In this case, it is necessary to face a significant disadvantage of polymer products due to possible and very common colonization of the surface by various microorganisms that can pose a potential danger to the patient. One of the possible solutions is to prepare polymer with antibacterial/antimicrobial properties that is resistant to bacterial colonization. The aim of this study was to contribute to the development of antimicrobial polymeric material ideal for covering vascular implants with subsequent use in transplant surgery. Therefore, the complexes of polymeric substances (hyaluronic acid and chitosan) with silver nitrate or silver phosphate nanoparticles were created, and their effects on gram-positive bacterial culture of Staphylococcus aureus were monitored. Stages of formation of complexes of silver nitrate and silver phosphate nanoparticles with polymeric compounds were characterized using electrochemical and spectrophotometric methods. Furthermore, the antimicrobial activity of complexes was determined using the methods of determination of growth curves and zones of inhibition. The results of this study revealed that the complex of chitosan, with silver phosphate nanoparticles, was the most suitable in order to have an antibacterial effect on bacterial culture of Staphylococcus aureus. Formation of this complex was under way at low concentrations of chitosan. The results of electrochemical determination corresponded with the results of spectrophotometric methods and verified good interaction and formation of the complex. The complex has an outstanding antibacterial effect and this effect was of several orders higher compared to other investigated complexes.

Pathogenic bacteria have become a serious socio-economic concern. Immunomagnetic separation-based methods create new possibilities for rapidly recognizing many of these pathogens. The aim of this study was to use superparamagnetic particles-based fully automated instrumentation to isolate pathogen Staphylococcus aureus and its Zn(II) containing proteins (Zn-proteins). The isolated bacteria were immediately purified and disintegrated prior to immunoextraction of Zn-proteins by superparamagnetic beads modified with chicken anti-Zn(II) antibody. S. aureus culture was treated with ZnCl(2). Optimal pathogen isolation and subsequent disintegration assay steps were carried out with minimal handling. (i) Optimization of bacteria capturing: Superparamagnetic microparticles composed of human IgG were used as the binding surface for acquiring live S. aureus. The effect of antibodies concentration, ionic strength, and incubation time was concurrently investigated. (ii) Optimization of zinc proteins isolation: pure and intact bacteria isolated by the optimized method were sonicated. The extracts obtained were subsequently analyzed using superparamagnetic particles modified with chicken antibody against zinc(II) ions. (iii) Moreover, various types of bacterial zinc(II) proteins precipitations from particle-surface interactions were tested and associated protein profiles were identified using SDS-PAGE. Use of a robotic pipetting system sped up sample preparation to less than 4 h. Cell lysis and Zn-protein extractions were obtained from a minimum of 100 cells with sufficient yield for SDS-PAGE (tens ng of proteins). Zn(II) content and cell count in the extracts increased exponentially. Furthermore, Zn(II) and proteins balances were determined in cell lysate, extract, and retentate.

Panxi region in west Sichuan province is one of the most economically significant REE mineralization belts in China, and includes the large Maoniuping and Daluxiang deposits and the minor Lizhuang deposit. The REE mineralization in these deposits is spatially and temporally associated with carbonatite–syenite complexes. Large proportional fluorites and REE minerals occurring as veins intrude Cretaceous granite and Oligocene syenite in Maoniuping, and Oligocene syenite and carbonatite in Lizhuang, and Miocene syenite in Daluxiang. Fluorite is also one of main gangue minerals in the world-class Bayan Obo REE deposit. We present a comparison of the trace element and isotopic compositions of fluorites from four REE deposits in the Panxi region and Bayan Obo. The fluorites from Maoniuping and Daluxiang are characterized by variable REE patterns, with either LREE enrichment or LREE depletion relative to MREE. Typically they have a larger range in La/Ho compared to Y/Ho ratios, and pronounced positive Y anomaly relative to chondrite-normalized REE patterns. Their REE distribution patterns are controlled by fluoride-complexes and the loss of separate LREE-rich minerals. Different Y/Ho (ca. 73 vs. 108) and initial Sr isotopic (ca. 0.7061 vs. 0.7077) ratios are observed between the fluorites from Maoniuping and Daluxiang, reflecting their different source compositions. This contrasts with the fluorites from Maoniuping and Lizhuang, which have similar initial Sr isotopes, and appear to be cogenetic. However, the Lizhuang fluorite shows a consistent depletion of LREE relative to MREE, as well as lower Y/Ho ratios and higher HREE content than that in Maoniuping. In this respect the Lizhuang fluorite may have precipitated from a late-stage fluid following abundant fluorite and REE mineral deposition in Maoniuping. Carbonate, more than fluoride complexing, appears to have a stronger control on REE fractionation in the Lizhuang fluorites. The fluorites from three deposits in Panxi region show uniform initial Sr and Nd isotopic compositions similar to their associated carbonatites, but differ from ore-veins found intruding wall rocks, e.g. granite in Maoniuping and syenite in Daluxiang. This is not consistent with a model for fluorite formation involving interaction of F-rich, carbonatite-exsoloved fluid with wall rocks. Instead, the fluorite in Panxi region may precipitate from a residual carbonthermal fluid, which was dominated by Ca, CO2 but also contained F, H2O and REE, and derived from the fractioned carbonatitic magma. Fluorite deposition produced a sharp drop in the activity of F−, which destabilized the REE fluoride complexes and caused deposition of REE minerals. In Bayan Obo, the fluorite typically has higher La/Ho than that in Panxi region and is characterized by a consistent LREE enrichment relative to MREE and negligible to positive Y anomalies. This is consistent with the compositional change of the hydrothermal fluids, which were infiltrated by external F-, LREE-rich fluids. The 87Sr/86Sr of Bayan Obo fluorite is relatively low radiogenic, and has a large range (0.7038–0.7065): similar characteristics to the carbonatite dykes found near the ore bodies. This supports a model for fluorite and REE mineral genesis involving the interaction of a carbonatite-derived fluid and the ore-hosted dolomitic marble.

The western part of the Khan Bogd complex comprises (in order of emplacement): microcline-phyric granite, peralkaline aegirine-arfvedsonite granite (main intrusive phase) and aplite-pegmatite veins confined predominantly to the apical parts of the intrusion. These rocks are interpreted to represent products of extreme fractional crystallization what involved an increase in index of peralkalinity (from 1.0 in the porphyritic granite to 1.3 in the main phase to 2.5 in the pegmatite) and whole-rock Zr content (864 to 1130 to 16900 ppm). The hydrothermal stage involved replacement of the primary elpidite by late-stage Ca-rich elpidite or armstrongite, and then precipitation of minor gittinsite and abundant zircon. With the exception of zircon, all secondary zirconosilicates exhibit relative enrichment in light REE.

Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock-forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100–260 ppm) and relatively flat chondrite-normalized REE distribution patterns [average (La/Yb)CN = 1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and fluorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing fluorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb)CN ≈ 0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates ⇒ calcite ⇒ REE-fluorocarbonates) from an initially REE-rich carbonatitic liquid.

The Qinling molybdenum belt is a prominent metallogenic structure in central China hosting several significant porphyry- and porphyry–skarn-type deposits. The Huanglongpu Mo deposit in the north-western part of the belt is unique in that it is associated with carbonatite dykes, rather than felsic magmatism. The carbonatites are composed largely of Sr–Mn-rich calcite and characterized by high concentrations of Sr and rare-earth elements (REE), and stable-isotope values indicative of a mantle source (δ13CPDB = − 6.7 ± 0.2‰ and δ18OSMOW = 8.2 ± 1.0‰). Molybdenite is associated with galena and REE minerals (parisite, bastnasite and monazite). Both molybdenite and galena are characterized by high Re contents (up to 0.4 and 0.2 wt.%, respectively) and Re/(Mo, Pb) ratios approaching the primitive-mantle values. In contrast to the rock-forming calcite, the REE minerals are enriched in light REE, whose relative proportion increases from parisite-(Ce) [average (La/Nd)n = 2.1] to bastnasite-(Ce) and monazite-(Ce) [average (La/Nd)n = 3.1, 4.6, respectively]. The whole-rock compositions are characterized by some of the highest Mo and heavy REE abundances reported for carbonatites to date: up to 1010 ppm Mo, 1130 ppm Y + Gd…Lu and (La/Yb)n = 1.2–2.7. The unusual trace-element geochemistry of the Huanglongpu rocks may ultimately reflect the composition of their mantle source, but their enrichment in Mo + Re was undoubtedly enhanced through preferential partitioning of these elements into a light REE–Pb–S-rich fluid derived from the carbonatitic magma modified by calcite fractionation. The present work shows that Mo can be retained, transported and deposited by carbonatitic fluids capable of generating economic Mo deposits.

Although cancer is one of the most dangerous and the second most lethal disease in the world, current therapy including surgery, chemotherapy, radiotherapy, etc., is highly insufficient not in the view of therapy success rate or the amount of side effects. Accordingly, procedures with better outcomes are highly desirable. Iron oxide nanoparticles (IONPs) present an innovative tool-ideal for innovation and implementation into practice. This review is focused on summarizing some well-known facts about pharmacokinetics, toxicity, and the types of IONPs, and furthermore, provides a survey of their use in cancer diagnosis and therapy.

V této práci jsme se zaměřili na rozdíly mezi bakteriálních kultur E. coli, získaných ze stěrů infekčních ran pacientů ve srovnání s laboratorním E. coli. Navíc blokování proteinu odpovědné za syntézu glutathion (-glutamyl-cystein synthasy GCL) za použití 10 mM buthionin sulfoximin byla zkoumána. Každý E. coli ukázala výrazné rozdíly v rezistenci vůči antibiotikům. Podle odhodlaný odolné, E. coli byly rozděleny do experimentálních skupin na základě statistického vyhodnocení jejich vlastností jako odolnější a citlivější. Tyto skupiny byly také použity pro nalezení rozdíly mezi nimi v závislosti na glutathion dráhy o rezistenci na antibiotika. Citlivější E. coli vykazovaly stejné kinetiky glutathionu syntézy zatímco blokuje GCL (km 0,1 um), ve srovnání s non-blokování. Kromě toho, nejčastější mutace v genech glutathion syntetázy, glutathion peroxidázy a glutathionreduktasy byly pozorovány v této skupině ve srovnání s laboratorní E. coli. Skupina "odolnější" E. coli vykazovaly rozdíly v km mezi 0,3 a 0,8 uM. Počet mutací ve srovnání s E. coli laboratoře byla podstatně nižší v porovnání s jinou skupinou. In this work, we focused on the differences between bacterial cultures of E. coli obtained from swabs of infectious wounds of patients compared to laboratory E. coli. In addition, blocking of the protein responsible for the synthesis of glutathione (-glutamylcysteine synthase—GCL) using 10 mM buthionine sulfoximine was investigated. Each E. coli showed significant differences in resistance to antibiotics. According to the etermined resistance, E. coli were divided into experimental groups based on a statistical evaluation of their properties as more resistant and more sensitive. These groups were also used for finding the differences in a dependence of the glutathione pathway on resistance to antibiotics. More sensitive E. coli showed the same kinetics of glutathione synthesis while blocking GCL (Km 0.1 M), as compared to non-blocking. In addition, the most frequent mutations in genes of glutathione synthetase, glutathione peroxidase and glutathione reductase were observed in this group compared to laboratory E.coli. The group of “more resistant” E. coli exhibited differences in Km between 0.3 and 0.8 M. The number of mutations compared to the laboratory E. coli was substantially lower compared to the other group.

In this study a device for automatic electrochemical analysis was designed. A three electrodes detection system was attached to a positioning device, which enabled us to move the electrode system from one well to another of a microtitre plate. Disposable carbon tip electrodes were used for Cd(II), Cu(II) and Pb(II) ion quantification, while Zn(II) did not give signal in this electrode configuration. In order to detect all mentioned heavy metals simultaneously, thin-film mercury electrodes (TFME) were fabricated by electrodeposition of mercury on the surface of carbon tips. In comparison with bare electrodes the TMFEs had lower detection limits and better sensitivity. In addition to pure aqueous heavy metal solutions, the assay was also performed on mineralized rock samples, artificial blood plasma samples and samples of chicken embryo organs treated with cadmium. An artificial neural network was created to evaluate the concentrations of the mentioned heavy metals correctly in mixture samples and an excellent fit was observed (R2 = 0.9933). V této studii byla navržena automatická elektrochemická analýza. Detekční systém složený ze tří elektrod byl připojen k polohovacímu zařízení, které nám umožnilo manipulaci s elektrodou z jedné jamky na druhou mikrotitrační destičky. Jednorázový uhlíkový tip elektrody byl použit pro kvantifikaci Cd (II), Cu (II) a Pb (II) iontů, zatímco Zn (II) neměl signál v této konfiguraci elektrody. Aby bylo možné odhalit všechny uvedené těžké kovy současně pomocí tenkovrstvé rtuťové elektrody (TFME), byly vyrobeny podle elektrodepozicí rtuti na povrchu hrotů uhlíku. Ve srovnání s holýma elektrodami se TMFEs měli nižší detekční limity a lepší citlivost. Kromě čistého vodného roztoku těžkých kovů ....

Clinoptilolite is a natural mineral with exceptional physical characteristics resulting from its special crystal structure, mainstreamed into a large zeolite group called heulandites. An overall view of the research related to the synthesis, modification and application of synthetic clinoptilolite is presented. A single phase of clinoptilolite can be hydrothermally synthesized for 1–10 days in an autoclave from various silica, alumina, and alkali sources with initial Si/Al ratio from 3.0 to 5.0 at a temperature range from 120 to 195 °C. Crystallization rate and crystallinity of clinoptilolite can be improved by seeding. The modification of clinoptilolite has received noticeable attention from the research community, since modified forms have specific properties and therefore their area of application has been broadening. This paper provides a review of the use of organic compounds such as quarter alkyl ammonium, polymer, amine and inorganic species used in the modification process, discusses the processes and mechanisms of clinoptilolite modification, and identifies research gaps and new perspectives.

Platinum-based cytostatics, such as cisplatin, carboplatin or oxaliplatin are widely used agents in the treatment of various types of tumors. Large amounts of these drugs are excreted through the urine of patients into wastewaters in unmetabolised forms. This phenomenon leads to increased amounts of platinum ions in the water environment. The impacts of these pollutants on the water ecosystem are not sufficiently investigated as well as their content in water sources. In order to facilitate the detection of various types of platinum, we have developed a new, rapid, screening flow injection analysis method with electrochemical detection (FIA-ED). Our method, based on monitoring of the changes in electrochemical behavior of analytes, maintained by various pH buffers (Britton-Robinson and phosphate buffer) and potential changes (1,000, 1,100 and 1,200 mV) offers rapid and cheap selective determination of platinum-based cytostatics and platinum chlorides, which can also be present as contaminants in water environments. Na bázi platiny cytostatika, jako je cisplatina, karboplatina a oxaliplatina jsou široce používané prostředky pro léčbu různých typů nádorů. Velké množství těchto léků jsou vylučovány močí pacientů do odpadních vod v nezměněné formě. Tento jev vede ke zvýšení množství platiny iontů ve vodním prostředí. Dopady těchto znečišťujících látek na vodní ekosystém, nejsou dostatečně zkoumány, jakož i jejich obsah ve vodních zdrojích. S cílem usnadnit detekci různých typů platiny, jsme vyvinuli novou, rychlou metodu analýzy vstřikování screening toku s elektrochemickou detekcí (FIA-ED). Naše metoda, založená na sledování změn v elektrochemickém chování analytů, které vedou různé pH pufry (Britton-Robinson a fosfátového pufru) a případné změny (1,000, 1,100 a 1,200 mV) nabízí rychlé a levné selektivní stanovení platinových cytostatik a platiny chloridů, které mohou být také přítomny jako nečistoty ve vodním prostředí.

In this study, we focused on microfluidic electrochemical analysis of zinc complexes (Zn(phen)(his)Cl-2, Zn(his)Cl-2) and ZnS quantum dots (QDs) using printed electrodes. This method was chosen due to the simple (easy to use) instrumentation and variable setting of flows. Reduction signals of zinc under the strictly defined and controlled conditions (pH, temperature, flow rate, accumulation time and applied potential) were studied. We showed that the increasing concentration of the complexes (Zn(phen)(his)Cl-2, Zn(his)Cl-2) led to a decrease in the electrochemical signal and a significant shift of the potential to more positive values. The most likely explanation of this result is that zinc is strongly bound in the complex and its distribution on the electrode is very limited. Changing the pH from 3.5 to 5.5 resulted in a significant intensification of the Zn(II) reduction signal. The complexes were also characterized by UV/VIS spectrophotometry, chromatography, and ESI-QTOF mass spectrometry. V této studii jsme se zaměřili na mikrofluidní elektrochemickou analýzu komplexů zinku (Zn (fenyl) (jeho) Cl-2, Zn (jeho) Cl-2) a ZnS kvantové tečky (QDS) za použití tištěných elektrod. Tato metoda byla zvolena z důvodu jednoduchému (snadné použití přístrojového vybavení) a variabilnímu nastavení toků. Byly studovány signály Redukční zinku v rámci přísně definovaných a kontrolovaných podmínek (pH, teplota, průtok, doba akumulace a aplikované potenciál). Ukázali jsme, že zvyšující se koncentrace komplexů (Zn (phen) (jeho) Cl-2, Zn (jeho) Cl-2) vede ke snížení elektrochemického signálu a významný posun potenciálu na více pozitivních hodnot. Nejpravděpodobnějším vysvětlením tohoto výsledku je, že zinek je silně vázána v komplexu a jeho rozložení na elektrodě je velmi omezený. Změna pH 3,5-5,5 vedlo k významnému zesílení Zn (II) signálu snížení. Komplexy byly také charakterizovány pomocí UV spektrofotometrie / VIS, chromatografie a ESI-QTOF hmotnostní spektrometrií. (Přeloženo strojově)