Removal of Methylene Blue Dye from Aqueous Solutions Using Polymer Inclusion Membrane Containing Calix[4]pyrrole.

The effective purification of aqueous solutions of methylene blue dye was tested using polymer inclusion membranes (PIMs) that contained cellulose triacetate (CTA) as a polymer base, o-nitrophenyl octyl ether (o-NPOE) as a plasticizer, and meso-tetra methyl tetrakis-[methyl-2-(4-acetlphenoxy)] calix[4]pyrrole (KP) as a carrier. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy were used to define the microstructure and surface of PIMs. Experimental results showed that, with an increased concentration of methylene blue in an aqueous solution, the removal percentage also increased. Further observation showed that the flux increased with the rise in the source phase pH values from 3 to 10. The carrier and plasticizer content in the membrane significantly influenced the membrane's transport properties. The optimal composition of the membrane in percent by weight for KP was 74% plasticizer; 18% support, and 8% carrier. The maximum MB removal (93.10%) was achieved at 0.10 M HCl solution as the receiving phase. It was shown that the membrane with optimal composition showed good reusability and enabled the easy and spontaneous separation of methylene blue from aqueous solutions.

Efficient, fast, simple, and eco-friendly methods for separation of toxic chromium(VI) ions based on ion exchangers and polymer materials impregnated with Cyphos IL 101, Cyphos IL 104, or D2EHPA.

In this study, we present the results of the first comparison of the elimination of toxic Cr(VI) ions, which are hazardous contamination of the environment, from aqueous solutions using ion exchangers (IEs) and polymer materials (PMs) impregnated with D2EHPA or ionic liquids (Cyphos IL 101 and Cyphos IL 104). Sorption of Cr(VI) ions and desorption from the formulated sorption materials were carried out. In comparison, classical solvent extraction was accomplished. Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and atomic force microscopy (AFM) have been used for characterization of the structure of developed IEs and PMs. The highest efficiency of adsorption of Cr(VI) ions was obtained using PMs with ionic liquids (>82%). Desorption from these materials were also very efficient (>75%). On the contrary, the application of IEs allowed for obtaining the best results of both, sorption and desorption processes when using D2EHPA (75% and 72%, respectively). The application of PMs and IEs is part of the green chemistry, and the conducted elimination of chromium(VI) ions using developed materials allows for the conclusion that they can potentially be used on a larger scale, e.g., for the treatment of industrial wastewater rich in Cr(VI) ions.

The Application of Polymer Inclusion Membranes for the Removal of Emerging Contaminants and Synthetic Dyes from Aqueous Solutions-A Mini Review.

Pollution of the environment, including water resources, is currently one of the greatest challenges due to emerging new contaminants of anthropogenic origin. Of particular concern are emerging organic pollutants such as pharmaceuticals, endocrine disruptors, and pesticides, but also other industrial pollutants, for example, synthetic dyes. The growing demand for environmentally friendly and economical methods of removing emerging contaminants and synthetic dyes from wastewater resulted in increased interest in the possibility of using techniques based on the application of polymer inclusion membranes (PIMs) for this purpose. PIM-based techniques are promising methods for eliminating emerging contaminants and synthetic dyes from aqueous solutions, including wastewater, due to high efficiency, membranes versatility, ease/low cost of preparation, and high selectivity. This review describes the latest developments related to the removal of various emerging contaminants and synthetic dyes from aqueous solutions using PIMs over the past few years, with particular emphasis on research aimed at increasing the effectiveness and selectivity of PIMs, which may contribute to wider use of these methods in the future.

Possibility of New Active Substrates (ASs) to Be Used to Prevent the Migration of Heavy Metals to the Soil and Water Environments.

This paper aims to propose an alternative to the known permeable reactive barriers (PRBs). PRB is one of the methods, which is a reactive barrier placed below the ground, to clean up contaminated groundwater. New polymer active substrates (ASs) were used to prevent soil contamination by toxic heavy metals. The active substrates consisted of a mixture of poly(vinyl chloride), Aliquat 336, and bis(2-ethylhexyl)adipate, which was applied to the skeleton material (fiberglass or textile). Aliquat 336 was used as a binding agent for metal ions (Cr(VI), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II)). In contrast with the PRBs, the ASs (from AS-1 to AS-5) were obtained in a simple way using the pouring method. The obtained ASs could be recycled and reused. The active substrates were used for the binding of various metal ions from aqueous solutions and the examined soil. It was found that the active substrate AS-1 decreased the concentrations of nickel, cadmium, and lead by more than 50% and that of chromium by more than 90% in the aqueous solution. High sorption efficiency for chromium and zinc metals (81% and 66%) with the use of AS-2 was also found, owing to which the migration of metals from soil to water can be limited. In the soil environment, active substrate AS-5 with the addition of a plasticizer showed the greatest effectiveness. This solution resulted in a reduction in each tested metal ion of at least 50%, and reductions in cadmium, lead, and copper of over 70%.

Efficient Recovery of Noble Metal Ions (Pd2+, Ag+, Pt2+, and Au3+) from Aqueous Solutions Using N,N'-Bis(salicylidene)ethylenediamine (Salen) as an Extractant (Classic Solvent Extraction) and Carrier (Polymer Membranes).

This paper presents the results of the first application of N,N'-bis(salicylidene)ethylenediamine (salen) as an extractant in classical liquid-liquid extraction and as a carrier in membrane processes designed for the recovery of noble metal ions (Pd2+, Ag+, Pt2+, and Au3+) from aqueous solutions. In the case of the utilization of membranes, both sorption and desorption were investigated. Salen has not been used so far in the sorption processes of precious metal ions. Recovery experiments were performed on single-component solutions (containing only one type of metal ions) and polymetallic solutions (containing ions of all four metals). The stability constants of the obtained complexes were determined spectrophotometrically. In contrast, electrospray ionization high-resolution mass spectrometry (ESI-HRMS) was applied to examine the elemental composition and charge of the generated complexes of chosen noble metal ions and salen molecules. The results show the great potential of N,N'-bis(salicylidene)ethylenediamine as both an extractant and a carrier. In the case of single-component solutions, the extraction percentage was over 99% for all noble metal ions (molar ratio M:L of 1:1), and in the case of a polymetallic solution, it was the lowest, but over 94% for platinum ions and the highest value (over 99%) for gold ions. The percentages of sorption (%Rs) of metal ions from single-component solutions using polymer membranes containing N,N'-bis(salicylidene)ethylenediamine as a carrier were highest after 24 h of the process (93.23% for silver(I) ions, 74.99% for gold(III) ions, 69.11% and 66.13% for palladium(II) and platinum(II) ions, respectively), similar to the values obtained for the membrane process conducted in multi-metal solutions (92.96%, 84.26%, 80.94%, and 48.36% for Pd(II), Au(III), Ag(I), and Pt(II) ions, respectively). The percentage of desorption (%Rdes) was very high for single-component solutions (the highest, i.e., 99%, for palladium solution and the lowest, i.e., 88%, for silver solution), while for polymetallic solutions, these values were slightly lower (for Pt(II), it was the lowest at 63.25%).

The Application of 2,6-Bis(4-Methoxybenzoyl)-Diaminopyridine in Solvent Extraction and Polymer Membrane Separation for the Recovery of Au(III), Ag(I), Pd(II) and Pt(II) Ions from Aqueous Solutions.

The work describes the results of the first application of 2,6-bis(4-methoxybenzoyl)-diaminopyridine (L) for the recovery of noble metal ions (Au(III), Ag(I), Pd(II), Pt(II)) from aqueous solutions using two different separation processes: dynamic (classic solvent extraction) and static (polymer membranes). The stability constants of the complexes formed by the L with noble metal ions were determined using the spectrophotometry method. The results of the performed experiments clearly show that 2,6-bis(4-methoxybenzoyl)-diaminopyridine is an excellent extractant, as the recovery was over 99% for all studied noble metal ions. The efficiency of 2,6-bis(4-methoxybenzoyl)-diaminopyridine as a carrier in polymer membranes after 24 h of sorption was lower; the percentage of metal ions removal from the solutions (%Rs) decreased in following order: Ag(I) (94.89%) > Au(III) (63.46%) > Pt(II) (38.99%) > Pd(II) (23.82%). The results of the desorption processes carried out showed that the highest percentage of recovery was observed for gold and silver ions (over 96%) after 48 h. The results presented in this study indicate the potential practical applicability of 2,6-bis(4-methoxybenzoyl)-diaminopyridine in the solvent extraction and polymer membrane separation of noble metal ions from aqueous solutions (e.g., obtained as a result of WEEE leaching or industrial wastewater).

Simultaneous Recovery of Precious and Heavy Metal Ions from Waste Electrical and Electronic Equipment (WEEE) Using Polymer Films Containing Cyphos IL 101.

In this article, the application of a polymer film containing the ionic liquid Cyphos IL 101 for the simultaneous recovery of precious and heavy metal ions ((Ni(II), Zn(II), Co(II), Cu(II), Sn(II), Pb(II), Ag(I), Pd(II), and Au(III)) from waste electrical and electronic equipment (WEEE) is described. The experiments were performed for solutions containing metal ions released from computer e-waste due to leaching carried out with concentrated nitric(V) acid and aqua regia. It was found that the applied polymer film allows for the efficient recovery of precious metals (98.9% of gold, 79.3% of silver, and 63.6% of palladium). The recovery of non-ferrous metals (Co, Ni, Cu, Zn, Sn, and Pb) was less efficient (25-40%). Moreover, the results of the performed sorption/desorption processes show that the polymer film with Cyphos IL 101 can be successfully used after regeneration to recover metals ions several times.

2,6-Bis((benzoyl-R)amino)pyridine (R = H, 4-Me, and 4-NMe2) Derivatives for the Removal of Cu(II), Ni(II), Co(II), and Zn(II) Ions from Aqueous Solutions in Classic Solvent Extraction and a Membrane Extraction.

In this paper, the application of new substituted 2,6-bis((benzoyl-R)amino)pyridine (R = H, 4-Me, and 4-NMe2) derivatives for the recovery of copper(II), nickel(II), cobalt(II), and zinc(II) ions from aqueous solutions was described. The structures of the synthesized compounds were confirmed by nuclear magnetic resonance spectroscopy (NMR), electrospray ionization high-resolution mass spectrometry (ESI HRMS), and tandem mass spectrometry methods (HCD MS/MS). Three different derivatives of 2,6-bis((benzoyl-R)amino)pyridine were used as carriers in membrane processes and as extractants in classic solvent extraction. In each case, the single derivative recovery was carried out on a model solution that contained only one type of metal ions. Spectrophotometry studies were performed to determine the stability constants of the complexes formed by the synthesized species with analyzed metals ions. The results obtained indicate that the synthesized compounds form stable complexes with Cu(II), Ni(II), Co(II), and Zn(II) ions and can be used in both types of studied recovery processes. However, the effectiveness of the synthesized compounds in the recovery of metal ions depends both on the structure of compounds and properties of metals as well as on their concentration.

N,N'-Bis(salicylidene)ethylenediamine (Salen) as an Active Compound for the Recovery of Ni(II), Cu(II), and Zn(II) Ions from Aqueous Solutions.

In this paper, three main methods of metal ion separation, i.e., liquid-liquid extraction, transport across polymer inclusion membranes (PIMs), and sorption/desorption, are described. In all of them, N,N'-bis(salicylidene)ethylenediamine (salen) was used as an active compound, i.e., as an extractant or as a carrier for the recovery of Ni(II), Cu(II), or Zn(II) ions from aqueous solutions. In each case, the recovery was performed on a model solution, which contained only a single metal ion. The obtained results were compared with the author's previous results for the separation of metal ions using ß-diketones, since both ß-diketones and salen form the so-called Werner-type complexes. Electrospray ionization high-resolution mass spectrometry (ESI-HRMS) was also applied to confirm the ability of the carrier to form complexes with metal ions in a solution. Moreover, spectrophotometry was used to determine the stability constant of the obtained complexes.

Sorption of Cu(II), Zn(II) and Pb(II) Ions in an Aqueous Solution on the PVC-Acetylacetone Composites.

The possibility of removing Cu(II), Zn(II) and Pb(II) ions by sorption on new PVC-based composite materials with different contents of acetylacetone (acac) and porophor was investigated. Composites were characterized using a scanning electron microscope and by infrared spectral analysis (FTIR). Sorption tests were conducted at 20 °C. It has been shown that the equilibrium is established in about 4 h. The reduction in ion concentration in the solution depended on the content of both acac and porophor in the composite. The maximal reduction in ion concentration ranged from 8% to 91%, 10⁻85% and 6⁻50% for Cu(II), Zn(II) and Pb(II) ions, respectively, depending on the composite composition. The best results were obtained for the composite containing 30% w/w of acac and 10% of porophor. For this composite, the sorption capacity after 4 h sorption for Zn(II), Cu(II) and Pb(II) ions was 26.65, 25.40, and 49.68 mg/g, respectively. Kinetic data were best fitted with a pseudo⁻second-order equation.

The Influence of the Morphology and Mechanical Properties of Polymer Inclusion Membranes (PIMs) on Zinc Ion Separation from Aqueous Solutions.

The transport of Zn(II) ions across polymer inclusion membranes (PIMs) with acetylacetone (ACAC) or di(2-ethylhexyl)phosphoric acid (D2EHPA) as carriers was studied. Polymeric membranes consisting of polyvinylchloride (PVC) as the support, bis(2-ethylhexyl)adipate (DAO) as plasticizer, and ACAC or D2EHPA as ion carriers were investigated. The highest recovery factors for Zn(II) ions were observed in the case of a membrane containing 20% acac (99.6%) and 60% D2EHPA (56.3%). The prepared PIMs were examined using atomic force microscopy (AFM) techniques. Their mechanical properties were also determined. The influence of membrane morphology and mechanical properties on the zinc transport process was discussed.

MicroRNA expression patterns in canine mammary cancer show significant differences between metastatic and non-metastatic tumours.

BACKGROUND: MicroRNAs may act as oncogenes or tumour suppressor genes, which make these small molecules potential diagnostic/prognostic factors and targets for anticancer therapies. Several common oncogenic microRNAs have been found for canine mammary cancer and human breast cancer. On account of this, large-scale profiling of microRNA expression in canine mammary cancer seems to be important for both dogs and humans. METHODS: Expression profiles of 317 microRNAs in 146 canine mammary tumours of different histological type, malignancy grade and clinical history (presence/absence of metastases) and in 25 control samples were evaluated. The profiling was performed using microarrays. Significance Analysis of Microarrays test was applied in the analysis of microarray data (both unsupervised and supervised data analyses were performed). Validation of the obtained results was performed using real-time qPCR. Subsequently, predicted targets for the microRNAs were searched for in miRBase. RESULTS: Results of the unsupervised analysis indicate that the primary factor separating the samples is the metastasis status. Predicted targets for microRNAs differentially expressed in the metastatic vs. non-metastatic group are mostly engaged in cell cycle regulation, cell differentiation and DNA-damage repair. On the other hand, the supervised analysis reveals clusters of differentially expressed microRNAs unique for the tumour type, malignancy grade and metastasis factor. CONCLUSIONS: The most significant difference in microRNA expression was observed between the metastatic and non-metastatic group, which suggests a more important role of microRNAs in the metastasis process than in the malignant transformation. Moreover, the differentially expressed microRNAs constitute potential metastasis markers. However, validation of cfa-miR-144, cfa-miR-32 and cfa-miR-374a levels in blood samples did not follow changes observed in the non-metastatic and metastatic tumours.

Immune Cells in Cancer Therapy and Drug Delivery.

Recent studies indicate the critical role of tumour associated macrophages, tumour associated neutrophils, dendritic cells, T lymphocytes, and natural killer cells in tumourigenesis. These cells can have a significant impact on the tumour microenvironment via their production of cytokines and chemokines. Additionally, products secreted from all these cells have defined specific roles in regulating tumour cell proliferation, angiogenesis, and metastasis. They act in a protumour capacity in vivo as evidenced by the recent studies indicating that macrophages, T cells, and neutrophils may be manipulated to exhibit cytotoxic activity against tumours. Therefore therapy targeting these cells may be promising, or they may constitute drug or anticancer particles delivery systems to the tumours. Herein, we discussed all these possibilities that may be used in cancer treatment.

The application of capillary electrophoresis techniques in toxicological analysis.

Capillary electrophoresis (CE) comprises a group of techniques used to separate chemical mixtures. Analytical separation is based on different electrophoretic mobilities, thereby allowing qualitative and quantitative evaluations to be made. The application of CE in medical science, especially in toxicological studies, is developing rapidly because of the short time required for analysis and its high sensitivity, selectivity and ability to determine substances of an acidic, alkaline and neutral character. This review focuses on the possibility of applying CE in toxicological analysis. Advances in different CE analyses and detection techniques connected with this method are described.

[Effect of tobacco smoking on albumin concentration and ß-glucuronidase activity in urine of smelters]. / Wplyw palenia papierosów na stezenie albumin i aktywnosc ß-glukuronidazy w moczu hutników.

The aim of present study was to estimate the nephrotoxicity of occupational exposure to heavy metals on albumin concentration and ß-glucuronidase activity in the urine of smoking and non-smoking smelters. The study was performed in urine of 101 smoking and non-smoking smelters as well as 65 smoking and non-smoking male subjects unexposed to heavy metals. Section into smoking and non-smoking groups was made on basis on direct personal interview and by determination of serum cotinine concentration. The concentration of albumin in urine was measured with commercial test (Micro-Albumin ELISA Cat. No 5MA 74212, ORGENTEC Diagnostika Gmbh, Germany). The activity of ß-glucuronidase in urine were determined in urine using 4-nitrophenyl ß D-glucuronide (Cat. No 73677, Sigma Aldrich, Germany) as a substrate. We have observed higher albumin concentration and ß-glucuronidase activity in urine of smoking and non-smoking smelters when compared to control groups. We have also found the influence of tobacco smoke as well as amount of cigarettes smoked on albumin concentration in urine of smoking smelters. A statistically significant difference was detected between activity of ß-glucuronidase in urine of smoking and non-smoking smelters, which suggest as additional negative factor of exposure to tobacco smoke. Analyzing the impact of smoking intensity we have found higher albumin concentration and ß-glucuronidase activity in urine of smelters smoking ≥20 cigarettes per day when compared to smelters smoking <20 cigarettes per day. The elevation of albumin concentration and ß-glucuronidase activity in urine of workers occupational exposure to heavy metals and tobacco smoke indicated, that environmental exposure on these factors can disorders kidney functions.

Effective endogenous gene silencing mediated by pH responsive peptides proceeds via multiple pathways.

Cationic amphipathic histidine rich peptides possess high plasmid DNA and siRNA delivery capabilities. To further understand the pH responsive siRNA delivery process and evaluate the capabilities of such peptides we have investigated their ability to mediate specific silencing of endogenous GAPDH gene activity in MCF-7 and A549 cells and compared this with plasmid DNA delivery. A substantial and selective reduction of both GAPDH activity and expression was achieved using pH responsive peptide vectors, which compared favourably with that mediated by commercially available non-viral vectors in terms of efficacy and toxicity. Furthermore, by comparing the efficacy of both gene delivery and silencing mediated by a series of such peptides, their sensitivities to known inhibitors of endocytotic processes, and their route of uptake via confocal live cell imaging, we show that both plasmid DNA and siRNA are internalised via endocytosis. However siRNA entry facilitated by LAH4-L1, proceeds via a cholesterol dependent mechanism, in contrast to DNA transfer which is associated with clathrin dependent endocytosis. Furthermore, using peptides that respond at increasingly acidic pH, we demonstrate that the route of entry for the siRNA that ultimately mediates silencing is peptide specific and whilst some pH responsive peptides promote the escape of labelled siRNA from endosomes, others may promote entry via alternative mechanisms.

[Urinary N-acetyl-beta-D-glucosaminidase and its isoenzymes in smoking and non-smoking workers at copper foundry occupational co-exposed to arsenic cadmium and lead]. / Aktywnosc N-acetylo-beta-D-glukozaminidazy i jej izoform w moczu palacych i niepalacych pracowników huty narazonych zawodowo na arsen, kadm i olów.

The kidneys are the critical organs in the case of a long-term occupational or environmental exposure to heavy metals and tobacco smoke. In diagnostics of renal damage useful are the methods which determine the activity of renal enzymes, quantify in urine (e.g. beta-glucuronidase, N-acetyl-beta-D-glucosaminidase). N-acetyl-beta-D-glucosaminidase (NAG) is one of the most often determined factors of tubular damage, since its activity increases in early stages of renal injury, ahead of appearance of excretory dysfunction. The aim of this research was to assess the influence of occupational exposure of copper-foundry workers to heavy metals (arsenic, cadmium, lead) on total activity of N-acetyl-beta-D-glucosaminidase and its molecular forms in urine. The investigated group was made up of 95 founders (smokers n = 51, non-smokers n = 44) and 43 people in control group (smokers n = 16, non-smokers n = 27). The concentrations of arsenic (As) and cadmium (Cd) were determined in urine, whilst the level of lead (Pb) was determined in whole blood. The activities of NAG and its isoforms were determined in urine. Smoking and non-smoking founders' urine demonstrated 14 times higher concentrations of arsenic levels in comparison with smoking and nonsmoking control group. Cadmium concentrations were 3.5 times higher in urine of smoking founders in comparison with smoking control group and about 3 times higher in case of nonsmoking founders in comparison with non-smoking control group. 7 times increase of lead concentration was observed in the whole blood within the smoking founders group in comparison with the smoking control group. In the blood of non-smoking founders was demonstrated about 10 times increase of lead concentration in comparison with the non-smoking control group. About 3-times increase of total NAG's activity was observed in urine of smoking founders and 4-times increase of non-smoking founders in comparison with smoking and non-smoking control group. The highest activity of NAG-B was observed in urine of smoking founders (11.35 +/- 7.85 U/g creatinine), then non-smoking founders (9.7 +/- 8.75 U/ g creatinine). It was confirmed, that the activity of N-acetyl-beta-D-glucosaminidase is a good factor in the assessment of occupational exposure to heavy metals like arsenic, cadmium and lead.