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Chronic kidney disease (CKD) is one of the major problems of modern medicine and a huge socioeconomic burden. Thorough knowledge of metabolic alterations associated with this condition is vital to prevent its progression. However, still little is known about metabolic disorders associated with CKD. In this study, we used 1 H NMR spectroscopy and multivariate analysis to identify alterations in serum metabolites of patients with various stages of CKD. 1 H NMR spectroscopy followed by multivariate analysis showed that CKD patients differed from the controls in terms of 15 endogenous metabolites, and MetPA analysis demonstrated significant intergroup differences in 5 potential target pathways and 14 metabolites. Owing a good performance of discriminant models, these findings suggest that CKD patients and healthy controls differ in terms of their metabolic fingerprints. In turn, the results of MetPA analysis imply that CKD and its progression exert an effect on selected metabolic pathways. This study provided a better insight into metabolic alterations associated with CKD, and identified some target pathways that can be potentially modified to slow down the progression of this serious and debilitating disease., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A constant problem in veterinary medicine, human healthcare, agriculture, forestry and horticulture is the large number of pests, and the lack of effective methods to combat them which cause no harm to the rest of the environment. It is recommended and desired to reduce the use of chemicals and increase the use of agents based on knowledge acquired in the fields of biology, chemistry and agrochemicals. To learn the defense mechanisms of insects we should consider not only the site of their physiological ability to protect against external factors (cuticle), but also the possibility of chemical protection, formed by all compounds on the surface and in the body of insects. In this study, a procedure was developed to determine the esters of carboxylic acids in insect lipids. Headspace solid-phase microextraction was followed by gas chromatography coupled with gas spectrometry. First, the best conditions were selected for the analysis to obtain the best chromatographic separation. An RTx-5 column was used for this purpose. Polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate fibers were used to isolate acid esters. PDMS/DVB fiber achieved the best conditions for the extraction; the extraction time was 50 min, the extraction temperature was 105°C and the desorption time was 10 min at 230°C. These solid-phase microextraction conditions were used to analyze volatile compounds extracted from insects belonging to the Dermestidae family., (Copyright © 2017 John Wiley & Sons, Ltd.)

The knowledge of the sorption mechanism of different chemicals onto third generation carbon sorbents such as carbon nanotubes (CNTs) is needed in order to project systems for the effective removal of pollutants from the environment. This paper reports evaluation of the sorption mechanism of selected ionic liquids (ILs), being considered as potential pollutant in environment, onto various CNTs. CNTs characterized by the smallest diameter and the biggest surface area showed the highest sorption capacity to isolate ILs from an aqueous solution. CNTs with a bigger diameter, a functionalized surface and particularly a helical shape showed a lower sorption capacity. The sorption mechanism has been defined as complex, including van der Waals, π-π and electrostatic interactions with dominating π-π interactions. Due to the relatively high sorption coefficient (355.98 ± 20.69-6397.10 ± 355.42 L kg -1 depending on the IL) the study showed that multi-walled carbon nanotubes can potentially be used to effectively isolate ILs from an aqueous solution. Moreover, proved in this study, the fast sorption kinetic, and uncomplicated regeneration process, leading to an even higher sorption capacity, means that CNTs are promising material which could find potential applications in the treatment of water contaminated by ILs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The brinjal eggplant (Solanum melongena L.) is an important vegetable species worldwide, while African eggplants (S. aethiopicum L., S. macrocarpon L.) are indigenous vegetable species of local significance. Taxonomy of eggplants and their wild relatives is complicated and still unclear. Hence, the objective of the study was to clarify taxonomic position of cultivars and landraces of brinjal, its wild relatives and African eggplant species and their wild ancestors using chemotaxonomic markers and multivariate analysis techniques for data processing, with special attention paid to the recognition of markers characteristic for each group of the plants. The total of 34 accessions belonging to 9 species from genus Solanum L. were used in the study. Chemotaxonomic analysis was based on the profiles of cuticular n-alkanes and methylalkanes, obtained using gas chromatography-mass spectrometry and gas chromatography with flame ionization detector. Standard hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used for the classification, while the latter and two-way HCA allowed to identify markers responsible for the clustering of the species. Cultivars, landraces and wild forms of S. melongena were practically identical in terms of their taxonomic position. The results confirmed high and statistically significant distinctiveness of all African eggplant species from the brinjal eggplant. The latter was characterized mostly by abundant long chain hydrocarbons in the range of 34-37 carbon atoms. The differences between both African eggplant species were, however, also statistically significant; S. aethiopicum displayed the highest contribution of 2-methylalkanes to the total cuticular hydrocarbons, while S. macrocarpon was characterized by elevated n-alkanes in the range of 25-32 carbon atoms. Wild ancestors of both African eggplant species were identical with their cultivated relatives. Concluding, high usefulness of the chemotaxonomic approach in classification of this important group of plants was confirmed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Available ecotoxicological data for anti-cancer drugs and their metabolites are incomplete, and only some studies have been accompanied by chemical analysis. Therefore, the main aim of this study was to evaluate the acute toxicity of the six most commonly used cytostatics, namely cyclophosphamide (CF), ifosfamide (IF), 5-fluorouracil (5-FU), imatinib (IMT), tamoxifen (TAM) and methotrexate (MET) and its metabolite - 7-hydroxymethotrexate (7-OH-MET), towards selected aquatic organisms, namely bacteria Vibrio fischeri, algae Raphidocelis subcapitata, crustaceans Daphnia magna and duckweed Lemna minor. All ecotoxicological tests were accompanied by chemical analysis to determine the differences between nominal and actual concentrations of investigated compounds and their stability under test conditions. For unstable compounds, tests were performed in static and semi-static conditions. It was observed that L. minor was the most sensitive organism. The compounds that were most toxic to aquatic organisms were 5-FU (highly toxic to algae, EC 50  = 0.075 mg L -1 ), MET and TAM (very toxic to highly toxic to duckweed depending on the test conditions; EC 50MET 0.08-0.16 mg L -1 , EC 50TAM 0.18-0.23 mg L -1 ). It is suspected that MET and 5-FU mainly affected algae and plants most probably because the exposure time was long enough for them to cause a specific effect (they inhibit DNA replication and act predominantly on actively dividing cells). Furthermore, the obtained results also suggest that the toxicity of the metabolites/potentially produced degradation products of MET towards duckweed is lower than that of the parent form, whereas the toxicity of TAM degradation products is in the same range as that of TAM., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Routine laboratory lipid assays include simple measurements of total cholesterol, triacylglycerols and HDL. However, lipids are a large group of compounds involved in many metabolic pathways, and their alterations may have serious health consequences. In this study, we used 1 H NMR to analyze lipids extracted from sera of 16 obese patients prior to and after bariatric surgeries. We observed a post-surgery decrease in serum concentrations of lipids from various groups. The hereby presented findings imply that 1 H NMR is suitable for rapid, simple and non-invasive detection of lipids from 30 structural groups, among them triacylglycerols, phosphatidylcholine, phosphatidylethanolamine, sphingomyelin, total phospholipids, total, free and esterified cholesterol, total and unsaturated fatty acids. NMR-based analysis of serum lipids may contribute to a substantial increase in the number of routinely determined markers from this group; therefore, it may find application in clinical assessment of obese subjects prior to and after bariatric surgeries, as well as in the examination of patients with other metabolic diseases.

Patients with chronic kidney disease (CKD) are at increased risk of cardiovascular mortality. Lipid disorders, a constant feature of CKD, might contribute to this state. The aim of this study was to evaluate n-3 polyunsaturated fatty acids (PUFA) composition in CKD patients treated with dialysis, in comparison to the general population and to assess possible associations between the n-3 PUFA profile and anthropometric variables. Thirty-three prevalent dialysis patients were studied and compared with an age- and sex-adjusted control group of 22 patients. Fatty acid composition in serum was analyzed by gas chromatography with a mass spectrometer detector (GC-MS) and anthropometric measures were assessed by bioimpedance spectroscopy. The fatty acid profile of dialyzed patients was characterized by a significantly lower percentage content of n-3 PUFA. For α-linolenic acid (ALA), it was 0.21 ± 0.09% in dialysis patients versus 0.33 ± 0.11% in the control group (p < .001). For eicosapentanoic acid (EPA), 0.59 ± 0.23% versus 1.15 ± 0.87% (p < .001), and for docosahexaenoic acid (DHA) 1.11 ± 0.50% versus 1.75 ± 0.87% (p < .001), respectively. The amount of n-3 PUFA decreased with time on dialysis and it correlated positively with body fat mass. For DHA, this correlation was r = .48 (p < .01) and for EPA r = .40 (p < .05). Patients with CKD have a relatively low content of n-3 PUFA which may contribute to their high cardiovascular risk. Patients with a higher content of body fat are characterized by a favorable fatty acid composition.

Gas chromatography-mass spectrometry is a preferred method for fatty acid (FA) analysis in biofluids from patients with metabolic diseases. Complex characteristics of FAs make their analysis particularly challenging. Selection of an appropriate chromatographic column is particularly important component of the process as it provides optimal separation and detection of possibly all FAs present in the sample. However, no accurate protocol for comparative evaluation of capillary columns for the analysis of whole serum FA profile in patients with chronic kidney disease (CKD) has been developed thus far. Therefore, in the present study four columns were examined to select the one providing optimal separation and determination of FA profiles in this group of patients. Moreover, serum FA profiles obtained with the selected column in CKD patients subjected to peritoneal dialysis and healthy controls were compared. Thirty-seven component FAME Mix and sera from CKD patients were used to optimize chromatographic conditions and to select the most appropriate column. The ZB-5 column turned out to be the most appropriate for the analysis of whole FA profile in CKD patients' sera. Then, this column was used to compare FA profiles in patients subjected to peritoneal dialysis and in healthy controls. The analysis demonstrated many abnormalities in the FA profile of CKD patients. Further studies involving larger groups of patients presenting with other stages of CKD are required to explain the impact of the disease progression on composition of serum FAs., (Copyright © 2017 John Wiley & Sons, Ltd.)

Among the wide range of compounds reaching the soil are the veterinary antimicrobials. Since no regulations regarding acceptable levels of drug concentrations in the environment exist, monitoring tests, particularly concerning soils, are carried out very rarely. This study presents a preliminary assessment of the contamination of agricultural soils in Northern Poland with seven antimicrobial veterinary medicines which has never been carried out before. Veterinary drugs were detected in 54% of the examined soil samples; the most commonly detected drugs were sulfonamides and trimethoprim. The highest indicated concentrations refer to enrofloxacin (57.0 μg kg -1 ) and trimethoprim (47.8 μg kg -1 ). The presence of these target drugs in the soil environment confirms the need for further monitoring studies. The analytical methods developed in this study are an excellent tool to achieve this goal and allow an estimation of the risk connected with the presence of veterinary antimicrobials in soils.

The main advantage of alkylimidazolium cation-based ionic liquids (ILs) as phase additives in RP-HPLC is believed to be the suppression of deleterious residual free silanols in chemically modified silica stationary phases. However, up to now, the influence of ILs was usually evaluated having in mind a particular IL salt as one compound, not as a specific mixture of cations and anions. This in fact led to some misinterpretation of observed results, very often related to the suppression effect, while in fact caused by the nature of IL anions, which contribute to the elevated chaotropicity of the separation phases. In the present study, we have attempted to consider the effect gained due to the presence of both ionic liquid entities in the mobile phase used for the separation of basic compounds. Tri-cyclic antidepressants (TCAs) were taken as representative analytes. The effect of ILs on the chromatographic separation of TCAs was investigated in comparison to common mobile phase additives and by the presentation of retention factors, tailing factors and theoretical plates. In addition, an overloading study was performed for the IL-based phases for the first time. In general, it was found that the effect of chaotropic hexafluorophosphate anions in ILs is much stronger and opposite to that caused by imidazolium cations. The overloading study gives interesting information on how imidazolium cations affect the separation of cationic analytes. Finally, the usefulness of imidazolium-based ILs as mobile phase modifiers in the RP-HPLC separation of basic compounds was discussed., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Passive sampling is one of the most efficient methods of monitoring pharmaceuticals in environmental water. The reliability of the process relies on a correctly performed calibration experiment and a well-defined sampling rate (R s ) for target analytes. Therefore, in this review the state-of-the-art methods of passive sampler calibration for the most popular pharmaceuticals: antibiotics, hormones, β-blockers and non-steroidal anti-inflammatory drugs (NSAIDs), along with the sampling rate variation, were presented. The advantages and difficulties in laboratory and field calibration were pointed out, according to the needs of control of the exact conditions. Sampling rate calculating equations and all the factors affecting the R s value - temperature, flow, pH, salinity of the donor phase and biofouling - were discussed. Moreover, various calibration parameters gathered from the literature published in the last 16 years, including the device types, were tabled and compared. What is evident is that the sampling rate values for pharmaceuticals are impacted by several factors, whose influence is still unclear and unpredictable, while there is a big gap in experimental data. It appears that the calibration procedure needs to be improved, for example, there is a significant deficiency of PRCs (Performance Reference Compounds) for pharmaceuticals. One of the suggestions is to introduce correction factors for R s values estimated in laboratory conditions.

Nowadays, residual amounts of many pharmaceuticals can be found in various environmental compartments including surface and ground waters, soils and sediments as well as biota. Even though they undergo degradability, their environmental discharge is relatively continuous, thus they may be regarded as quasi-persistent contaminants, and are also frequently regarded as emerging organic pollutants. Benzimidazoles, especially flubendazole (FLU) and fenbendazole (FEN), represent two anthelmintic drugs belonging to this group. Although their presence in environmental matrices has been reported, there is relatively little data concerning their (eco)toxicological impact. Furthermore, no data is available on their mixture toxicity. FLU and FEN have been found to have a strong impact on an environmentally important non-target organism - Daphnia magna. Moreover, these compounds are usually present in the environment as a part of pharmaceutical mixtures. Therefore, there is a need to evaluate their mixture toxicity, which was the main aim of this study. Single substance toxicity tests were carried out in parallel with mixture studies of FLU and FEN, with the application of two well established concepts of Concentration Addition (CA) and Independent Action (IA). As a result, both models (CA and IA) were found to underestimate the toxicity of mixtures, however CA yielded more accurate predictions., (Copyright © 2017 Elsevier GmbH. All rights reserved.)

In this publication, a new dispersive solid-phase extraction (dSPE) method combined with gas chromatography-mass spectrometry and atomic absorption spectrometry was developed for the simultaneous determination of 9 PAHs and chromium, cadmium, and lead ions in water samples. For this purpose, non-modified multi-walled carbon nanotubes (MWCNTs) and modified -MWCNTs (OH-MWCNTs and COOH-MWCNTs) were used as sorbents. Parameters affecting the extraction, such as the amount of sorbent, the pH of the sample, the composition and volume of eluents and the extraction time were optimized. Sequential elution was applied using 6mL of dichloromethane for the elution of PAHs and 5mL of 3M HNO 3 for cadmium, lead, and chromium. The optimal values of other parameters were as follows: 50mg of sorbent per 250mL of water sample, pH in a range from 6 to 7 and 30min of contact time between the sorbent and analytes. The results demonstrated the high extraction capability of modified MWCNTs with recoveries between 80 and 101% for cadmium, chromium, and lead ions and between 83 and 92% for PAHs. Finally, the optimized method was validated, and the matrix effects were determined., (Copyright © 2016. Published by Elsevier B.V.)

Since humans and ecosystems are continually exposed to a very complex and permanently changing mixture of chemicals, there is increasing concern in the general public about the potential adverse effects they may cause. Among all "emerging pollutants", pharmaceuticals in particular have raised great environmental concern. For these reasons the aim of our study was to evaluate the mixture toxicity of six antimicrobial sulfonamides (SAs) and their two most commonly identified degradation products - sulfanilic acid (SNA) and sulfanilamide (SN) - to limnic green algae Scenedesmus vacuolatus and duckweed Lemna minor. The ecotoxicological data for the single toxicity of SNA and SN towards selected organisms are presented. The concept of Concentration Addition (CA) was applied to estimate the effects, and less than additive effects were observed. In general terms, it seems sufficiently precautionary for the aquatic environment to consider the toxicity of a sulfonamide mixture as additive. The Concentration Addition model proves to be a reasonable worst-case estimation. Such a comparative study on the mixture toxicity of sulfonamides and their transformation products has been presented for the first time., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Nowadays, carbon nanotubes, as commercially available materials, have attracted great attention because of their unique physicochemical properties, especially their strong adsorption abilities. This paper deals with the possibilities and limitations of the application of multi-walled carbon nanotubes as an alternative sorbent in passive sampling devices for the isolation of selected pharmaceuticals and phenolic compounds directly in water samples. Compounds with different properties, including sulfapyridine, sulfamethoxazole, carbamazepine, p-nitrophenol, 17-β-estradiol, 3,5-dichlorophenol and diclofenac were selected as model compounds. Firstly, the influence of several parameters on the extraction efficiency was defined, then the matrix effect and standard validation parameters were established. Under optimized conditions, the proposed analytical methods exhibited good validation parameters, including excellent linearity with R 2 >0.999, the LODs were found to be between 0.01-0.5μgL -1 and the LOQ ranged from 0.05 to 1.5μgL -1 . Recovery values obtained for model compounds were 79,8±0.2% for sulfapyridine, 41,5±0.1% for sulfamethoxazole, 96,6±1,5% for carbamazepine, 70,5±0.1% for p-nitrophenol, 77,1±0.5% for 17-β-estradiol, 103,1±1.8% for 3,5-dichlorophenol and 76,3±1.4% for diclofenac. This study provides useful data regarding the sorption process on MWCNTs and definitely evaluates the application potential of these types of sorbents in passive sampling devices., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Tropane alkaloids are toxic secondary metabolites produced by Solanaceae plants. Among them, plants from Datura genus produce significant amounts of scopolamine and hyoscyamine; the latter undergoes racemization to atropine during isolation. Because of their biological importance, toxic properties and commonly reported food and animal feed contamination by different Datura sp. organs, there is a constant need for reliable methods for the analysis of tropane alkaloids in many matrices. In the current study, three extraction and sample-clean up procedures for the determination of scopolamine and atropine in plant material were compared in terms of their effectiveness and repeatability. Standard liquid-liquid extraction (LLE) and EXtrelut ® NT 3 columns were used for the sample clean-up. Combined ultrasound-assisted extraction and 24h static extraction using ethyl acetate, followed by multiple LLE steps was found the most effective separation method among tested. However, absolute extraction recovery was relatively low and reached 45-67% for atropine and 52-73% for scopolamine, depending on the compound concentration. The same method was also the most effective one for the isolation of target compounds from Datura stramonium leaves. EXtrelut ® columns, on the other hand, displayed relatively low effectiveness in isolating atropine and scopolamine from such a complex matrix and hence could not be recommended. The most effective method was also applied to the extraction of alkaloids from roots and stems of D. stramonium. Quantitative analyses were performed using validated method based on gas chromatography with flame ionization detector (GC-FID). Based on the results, the importance of the proper selection of internal standards in the analysis of tropane alkaloids was stressed out., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Continous renal replacement therapy (CRRT) is particularly recommended for septic shock patients in intensive care units. The CRRT technique used most frequently is high volume continuous veno-venous haemofiltration. It provides a high rate of clearance of uremic toxins and inflammatory cytokines. However, it should also be taken into account that substances important for homeostasis may be concurrently unintentionally removed. Accordingly, water-soluble vitamins can be removed during continuous renal replacement therapy, and the estimate of the loss is critical to ensure appropriate supplementation. The aim of this work was to develop a simple methodology for a purification step prior to the LC-MS/MS determination of water-soluble vitamins in ultrafiltrate samples. For this purpose, two types of resin and a mix of resins were used as sorbents for the purification step. Moreover, parameters such as the amount of resin and the extraction time were optimized. The LC-MS/MS method was developed and validated for final determination of 11 vitamins. The results demonstrated the high purification capability of DEAE Sephadex resin with recoveries between 65 and 101% for water-soluble vitamins from ultrafiltrate samples. An optimized method was applied to assess the loss of B-group vitamins in patients after 24h of renal replacement therapy. The loss of vitamins B2, B6 pyridoxamine, B6 pyridoxal, B7, B1, and B5 in ultrafiltrates was similar in all patients. In the native ultrafiltrates, vitamins B6 pyridoxine, B9 and B12 were not detected., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Cushing's syndrome (CS) is a disease which results from excessive levels of cortisol in the human body. The disorder is associated with various signs and symptoms which are also common for the general population not suffering from compound hypersecretion. Thus, more sensitive and selective methods are required for the diagnosis of CS. This follow-up study was conducted to determine which steroid metabolites could serve as potential indicators of CS and possible subclinical hypercortisolism in patients diagnosed with so called non-functioning adrenal incidentalomas (AIs). Urine samples from negative controls ( n = 37), patients with CS characterized by hypercortisolism and excluding iatrogenic CS ( n = 16), and patients with non-functioning AIs with possible subclinical Cushing's syndrome ( n = 25) were analyzed using gas chromatography-mass spectrometry (GC/MS) and gas chromatograph equipped with flame ionization detector (GC/FID). Statistical and multivariate methods were applied to investigate the profile differences between examined individuals. The analyses revealed hormonal differences between patients with CS and the rest of examined individuals. The concentrations of selected metabolites of cortisol, androgens, and pregnenetriol were elevated whereas the levels of tetrahydrocortisone were decreased for CS when opposed to the rest of the study population. Moreover, after analysis of potential confounding factors, it was also possible to distinguish six steroid hormones which discriminated CS patients from other study subjects. The obtained discriminant functions enabled classification of CS patients and AI group characterized by mild hypersecretion of cortisol metabolites. It can be concluded that steroid hormones selected by applying urinary profiling may serve the role of potential biomarkers of CS and can aid in its early diagnosis.

Carbon nanotubes (CNTs) are currently one of the most promising groups of materials with some interesting properties, such as lightness, rigidity, high surface area, high mechanical strength in tension, good thermal conductivity or resistance to mechanical damage. These unique properties make CNTs a competitive alternative to conventional sorbents used in analytical chemistry, especially in extraction techniques. The amount of work that discusses the usefulness of CNTs as a sorbent in a variety of extraction techniques has increased significantly in recent years. In this review article, the most important feature and different applications of solid-phase extraction (SPE), including, classical SPE and dispersive SPE using CNTs for pesticides isolation from different matrices, are summarized. Because of high number of articles concerning the applicability of carbon materials to extraction of pesticides, the main aim of proposed publication is to provide updated review of the latest uses of CNTs by covering the period 2006-2015. Moreover, in this review, the recent papers and this one, which are covered in previous reviews, will be addressed and particular attention has been paid on the division of publications in terms of classes of pesticides, in order to systematize the available literature reports.

The use of veterinary pharmaceuticals (VPs) is a result of growing animal production. Manure, a great crop fertilizer, contains a significant amount of VPs. The investigation of VPs in manure is prevalent, because of the potential risk for environmental organisms, as well as human health. A re-evaluation of the impact of veterinary pharmaceuticals on the agricultural environment is needed, even though several publications appear every year. The aim of this review was to collate the data from fields investigated for the presence of VPs as an inevitable component of manure. Data on VP concentrations in manure, soils, groundwater and plants were collected from the literature. All of this was connected with biotic and abiotic degradation, leaching and plant uptake. The data showed that the sorption of VPs into soil particles is a process which decreases the negative impact of VPs on the microbial community, the pollution of groundwater, and plant uptake. What was evident was that most of the data came from experiments conducted under conditions different from those in the environment, resulting in an overestimation of data (especially in the case of leaching). The general conclusion is that the application of manure on crop fields leads to a negligible risk for plants, bacteria, and finally humans, but in future every group of compounds needs to be investigated separately, because of the high divergence of properties.

Backgrounds/aims: Colorectal cancer (CRC) cells show some alterations of lipid metabolism. Elongation of fatty acids (FA) has not been studied in CRC tissues thus far. The aim of this study was to verify if CRC specimens and normal colon mucosa differ in terms of their levels of very long-chain FAs, a product of FA elongation. Moreover, the expression of elongase genes has been studied in normal tissue and CRC. Finally, we searched for some specific products of FA elongation in serum of CRC patients., Methods: The specimens of normal colon mucosa and CRC were obtained from nineteen CRC patients differ in terms of FA elongation. We also searched for some specific products of FA elongation in serum of CRC patients and from healthy volunteers. Tissue and serum FA profiles were determined by means of gas chromatography-mass spectrometry (GC/MS), and the tissue expression of elongases (ELOVLs) was analyzed with real-time PCR., Results: Compared to normal colon tissue, CRC specimens showed significantly higher levels of 22-, 24- and 26-carbon FAs, stronger expressions of ELOVL1 and ELOVL6 (4- and 9-fold elevated respectively), and higher values of 18: 0/16: 0 elongation index. We also demonstrated presence of cerotic acid (26: 0) in serum of all CRC patients but in none of the healthy controls., Conclusions: CRC tissue seems to be characterized by enhanced FA elongation (hyper-elongation). Presence of cerotic acid in CRC patients sera and absence of this FA in healthy subjects points to this compound as a strong candidate for specific metabolic marker of colorectal malignancies., (© 2017 The Author(s)Published by S. Karger AG, Basel.)

The tomato (Solanum lycopersicum L.) is one of the most important vegetables worldwide. Due to the limited genetic variability, wild related species are considered as potential gene pool for breeding cultivated plants with enriched genetic basis. Taxonomic relations between tomato species at the level of single groups and taxa still remain, however, not fully resolved. Hence, in addition to already reported classification based on the morphology of the plants and molecular markers, we proposed chemotaxonomic approach to unveil some aspects of tomato taxonomy. Cuticular hydrocarbons and surface sucrose esters (SEs) were used as chemotaxonomic markers. Classification based on the cuticular hydrocarbon profile was in good agreement with other taxonomic studies as long as between-species differences were taken into account. Clear separation of the common tomato and closely related species from the majority of S. pennellii accessions was obtained. In the same time, however, S. pennellii revealed broad variation: based on the results, three highly distinct types of these plants were proposed, among them one type was very similar to cultivated tomato and its relatives. Addition of SEs profiles to the dataset did not impair the classification, but clarified the position of S. pennellii. The results suggest possible hybrid origin of some of S. pennellii and wild S. lycopersicum accessions, and the approach proposed has a potential to identify such hybrid plant lines., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The presence of pharmaceutical residues in various environmental compartments is an issue of increasing concern. The widespread occurrence of these compounds in water and soil samples has been demonstrated in a number of analytical studies. However, the data about their concentrations in biota samples is scarce. Moreover, the trophic transfer of pharmaceuticals remains largely unexplored, despite increasing evidence of the potential bioaccumulation of those compounds. Therefore, the main aim of this review is to present an overview of the current state of data about the bioaccumulation and analytical methodologies used for the determination of pharmaceutical residues in biota samples. This work focuses on the most commonly found pharmaceuticals in the environment: antibiotics, analgesic and anti-inflammatory drugs, steroid hormones, antihypertensives and antidepressants. We do hope that the collected data will allow a better understanding of pharmaceutical pollution and the exposure of non-target organisms. However, although impressive progress has undoubtedly been made, in order to fully understand the behavior of these chemicals in the environment, there are still numerous gaps to be filled in our overall knowledge in this field., (Copyright © 2016 Elsevier B.V. All rights reserved.)

More than 100000 solid organ transplantations are performed every year worldwide. Calcineurin (cyclosporine A, tacrolimus), serine/threonine kinase (sirolimus, everolimus) and inosine monophosphate dehydrogenase inhibitor (mycophenolate mofetil), are the most common drugs used as immunosuppressive agents after solid organ transplantation. Immunosuppressive therapy, although necessary after transplantation, is associated with many adverse consequences, including the formation of secondary metabolites of drugs and the induction of their side effects. Calcineurin inhibitors are associated with nephrotoxicity, cardiotoxicity and neurotoxicity; moreover, they increase the risk of many diseases after transplantation. The review presents a study of the movement of drugs in the body, including the processes of absorption, distribution, localisation in tissues, biotransformation and excretion, and also their accompanying side effects. Therefore, there is a necessity to monitor immunosuppressants, especially because these drugs are characterised by narrow therapeutic ranges. Their incorrect concentrations in a patient's blood could result in transplant rejection or in the accumulation of toxic effects. Immunosuppressive pharmaceuticals are macrolide lactones, peptides, and high molecular weight molecules that can be metabolised to several metabolites. Therefore the two main analytical methods used for their determination are high performance liquid chromatography with various detection methods and immunoassay methods. Despite the rapid development of new analytical methods of analysing immunosuppressive agents, the application of the latest generation of detectors and increasing sensitivity of such methods, there is still a great demand for the development of highly selective, sensitive, specific, rapid and relatively simple methods of immunosuppressive drugs analysis., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Ionic liquids (ILs) are one of the very promising media for the passive sampling of organic contaminants in water. These compounds offer a wide range of interactions with various analytes and give possibilities to control analyte properties by altering their structures, but most of all, possess a high polarity independent of the water solubility. Recently, some ILs were successfully applied as the receiving phase in the passive sampling of polyaromatic hydrocarbons, and this approach was acronymized to PASSIL. In this paper, we aimed to verify the applicability of the PASSIL technique for the selective extraction and enrichment of polar and semi-polar compounds from aqueous environments. The test kit of analytes comprised selected pharmaceuticals and phenol-type compounds, while the applied ILs were alkylimidazolium- and alkylphosphonium entities with a variety of anions. The 14-day-long experiments were performed in static and semi-static no-renewal systems. The kinetics of the uptake process, the analyte extraction efficiency and the sampling rates for all analytes were determined. One of the tested ionic liquids [P666-14][N(CN)2] presented very promising properties both as a stable medium between polyethersulfone (PES) membranes as well as a highly effective extraction phase. The uptake kinetics of the analytes and the determined sampling rates confirm the better and faster efficiency of PASSIL extraction when compared to commercially available passive samplers. Additionally, some selectivity was observed during analyte extraction, which results from the specific interaction between the IL and analytes, but not from the lipophilicity or ionization state of the analytes. These very promising findings make the PASSIL approach a very promising and competitive analytical tool for the extraction of environmental contaminants over a wide polarity range., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Objective: While small amounts of odd-chain fatty acids (OCFAs) and branched-chain fatty acids (BCFAs) were known to be present in mammals, it was quite recently that they were shown to play an important role in human health. However, still little is known on OCFA and BCFA profiles in subjects who have obesity. The aim of this study was to verify whether obesity is associated with changes in serum OCFA and BCFA profiles., Methods: Serum content of fatty acids was determined by gas chromatography-mass spectroscopy in 23 patients with excess weight and 21 nonobese controls., Results: Six OCFAs and six BCFAs (three iso-BCFAs and three anteiso-BCFAs) were found in sera from the examined subjects. Patients with excess weight presented with significantly lower serum iso-BCFA levels than the controls. Total serum content of iso-BCFAs correlated inversely with serum insulin, triglycerides, and 18:1/18:0 desaturation index. Both OCFA and iso-BCFA levels correlated inversely with C-reactive protein concentration., Conclusions: Lower iso-BCFA content in patients with excess weight may be involved in elevation of serum concentration of triglycerides and inflammation. Decreased contents of iso-BCFAs in subjects with have obesity, and established anti-inflammatory, antidiabetic, and anticancer properties of these fatty acids, point to potential beneficial effects of an iso-BCFA-rich diet., (© 2016 The Obesity Society.)

Conidiobolus coronatus is an entomopathogenic fungus which has a potential as a biological control agent of insects. The cuticular and internal lipid composition of infected and noninfected Tettigonia viridissima males were analyzed by GC/MS. A total of 49 compounds were identified in the infected and noninfected males, including fatty acids, fatty acid methyl esters (FAMEs), n-alkanes, alcohols, sterols, and other organic compounds. The most abundant components of the cuticular and internal lipids of the insects were fatty acids. After exposure to C. coronatus, the cuticular lipids of the T. viridissima males contained 17 free fatty acids from C(8) to C(22), while the cuticular lipids of the noninfected insects contained only 15 fatty acids from C(12) to C(24). The cuticular and internal lipids of both the infected and the noninfected males also contained five FAMEs from C(15) to C(19), seven n-alkanes from C(25) to C(34), five alcohols from C(16) to C(25), five sterols, and the following six other organic compounds: azelaic acid, phenylacetic acid, glutaric acid, benzoic acid, sebacic acid, and glycerol. The compounds which were present only in the cuticular lipids of the infected males could be due to fungal infection., (© 2016 Wiley-VHCA AG, Zürich.)

Insects are of growing significance in veterinary medicine and human healthcare; therefore, an understanding of their biology is very important. The cuticular and internal fatty acid compositions of Chorthippus brunneus males and females have been studied for the first time. The lipids of males and females were separated into classes of compounds using high-performance liquid chromatography with a laser light scattering detector. The free fatty acid (FFA) fractions obtained by HPLC were silylated and then analyzed by GC-MS. The cuticular lipids of males contained 15 saturated, four unsaturated with even-numbered and two unsaturated with odd-numbered carbon chains, FFAs ranging from C8 to C25. The major free fatty acids in males were C16 (20.8%), C18:2 (8.5%), C18:1 (32.9%) and C18 (24.4%). The cuticular lipids of females contained 17 saturated, four monounsaturated and two diunsaturated free fatty acids ranging from C8 to C30. The major cuticular fatty acids in females were C16 (25.1%), C18:2 (6.2%), C18:1 (23.7%) and C18:0 (33.2%). The internal FFAs of males consisted of 20 compounds ranging from C8 to C26. Four of these compounds were detected as major compounds: C16 (14.1%), C18:2 (21.6%), C18:1 (38.0%) and C18 (22.5%). Among 18 internal free fatty acids of females, C16 (22.3%), C18:2 (10.9%), C18:1 (40.2%) and C18 (20.5%) were the most abundant compounds. The following cuticular fatty acids present in the lipids of females were absent in the lipids of males: C26, C27 and C30. On the other hand, only C24 was absent from the cuticular lipids of females. Only C10 and C24 internal fatty acids present in the lipids of males were absent in the lipids of females. Copyright © 2016 John Wiley & Sons, Ltd., (Copyright © 2016 John Wiley & Sons, Ltd.)

Crop irrigation uses a majority of a total world water supply, at the same time displaying low efficiency. As the expected, future water requirements are higher than the current ones; there is a risk of a growing deficit of water for the agricultural use. Hence, there is an arising need for better understanding the effects of water deprivation on the crop plants. Eggplant (Solanum melongena L.) is a vegetable crop cultivated in arid and semi-arid parts of the world. Because of its high water demands, the eggplant is a convenient model organism for studies concerning the effects of water deficit on the plant growth. The objective of the study was to determine the impact of short-term water deficit on eggplant leaf cuticular waxes and total sterols. Water deprivation did not affect the amount and composition of aliphatic components of cuticular waxes. Significant decrease in the total cuticular sterols and the increase in cuticular cholesterol were observed as an effect of water deficit. In contrast, some of the free internal sterols were more abundant in water-deprived plants. The possible importance of these observations, including increased biosynthesis of defensive compounds and the need to maintain the cell membrane stability, was discussed., (© 2016 Verlag Helvetica Chimica Acta AG, Zürich.)

This paper presents the investigation of the influence of salinity variations on the toxicity of sulfapyridine, sulfamethoxazole, sulfadimethoxine and trimethoprim towards the green algae Chlorella vulgaris after exposure times of 48 and 72 h. In freshwater the EC50 values ranged from 0.98 to 123.22 mg L(-1) depending on the compound. The obtained results revealed that sulfamethoxazole and sulfapyridine were the most toxic, while trimethoprim was the least toxic pharmaceutical to the selected organism. Deviations between the nominal and real test concentrations were determined via instrumental analysis to support the interpretation of ecotoxicological data. The toxicity effects were also tested in saline water (3, 6 and 9 PSU). The tendency that the toxicity of selected pharmaceuticals decreases with increasing salinity was observed. Higher salinity implies an elevated concentration of inorganic monovalent cations that are capable of binding with countercharges available on algal surfaces (hydroxyl functional groups). Hence it can reduce the permeability of pharmaceuticals through the algal cell walls, which could be the probable reason for the observed effect. Moreover, for the classification of the mode of toxic action, the toxic ratio concept was applied, which indicated that the effects of the investigated drugs towards algae are caused by the specific mode of toxic action., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Recent developments and improvements in advanced instruments and analytical methodologies have made the detection of pharmaceuticals at low concentration levels in different environmental matrices possible. As a result of these advances, over the last 15 years residues of these compounds and their metabolites have been detected in different environmental compartments and pharmaceuticals have now become recognized as so-called 'emerging' contaminants. To date, a lot of papers have been published presenting the development of analytical methodologies for the determination of pharmaceuticals in aqueous and solid environmental samples. Many papers have also been published on the application of the new methodologies, mainly to the assessment of the environmental fate of pharmaceuticals. Although impressive improvements have undoubtedly been made, in order to fully understand the behavior of these chemicals in the environment, there are still numerous methodological challenges to be overcome. The aim of this paper therefore, is to present a review of selected recent improvements and challenges in the determination of pharmaceuticals in environmental samples. Special attention has been paid to the strategies used and the current challenges (also in terms of Green Analytical Chemistry) that exist in the analysis of these chemicals in soils, marine environments and drinking waters. There is a particular focus on the applicability of modern sorbents such as carbon nanotubes (CNTs) in sample preparation techniques, to overcome some of the problems that exist in the analysis of pharmaceuticals in different environmental samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The results of our research on the cuticular and internal lipids of Blattella germanica males provide new information on variation in the composition of the cuticular and internal lipids of B. germanica males after exposure to the presence of the insecticide. gas chromatography and gas chromatography-mass spectrometry analyses were used to identify and quantify the cuticular and internal lipid composition in males and males exposed to insecticide. There were significantly more acids having an even number of carbon atoms in the molecule, and these were also generally in higher concentrations. The following acids were in a higher concentration: C16:0 and C18:1, C18:2, C18:0. In both males and males exposed to insecticide, 24 fatty acids ranging from C6 to C22 were determined. However, there was a significantly higher content of fatty acids in the surface lipids of B. germanica males after exposure to insecticide. Our results indicate a higher content of n-alkanes, sterols, particularly cholesterol, fatty acids, and fatty acid methyl esters in the B. germanica surface after exposure to chlorpyrifos than in males that were not exposed., (© 2015 Institute of Zoology, Chinese Academy of Sciences.)

Anticancer drugs (ACDs) exhibit high biological activity, they are cytotoxic, genotoxic, and are constantly released into the environment as a result of incomplete metabolism. Consequently they pose a serious threat to the environment and human health due to their carcinogenic, mutagenic and/or reproductive toxicity properties. Knowledge of their bioavailability, including their sorption to soils and their impact on the soil-groundwater pathway, is crucial for their risk assessment. Laboratory batch and column leaching tests are important tools for determining the release potential of contaminants from soil or waste material. Batch and column tests were carried out with soils differing in physicochemical properties, each spiked with cyclophosphamide (CK) or ifosfamide (IF). Moreover, due to the fact that environmental pollutants may occur as coexisting compounds in the soil the mobility evaluation for ACDs in the mixture with metoprolol (MET; β-blocker) as a co-contaminant was performed. In order to assess appropriateness, the batch and column tests were compared. The release depended on the properties of both the soil and the presence of co-contaminants. The faster release was observed for coarse-grained soil with the smallest organic matter content (MS soil: 90% decrease in concentration until liquid-to-solid ratio (L/S) of 0.3 L kg(-1) for all tests' layout) than for loamy sand (LS soil: 90% decrease in concentration until ratio L/S of 0.75 L kg(-1)). ACDs are highly mobile in soil systems. Furthermore, the decrease of mobility of ifosfamide was observed with the presence of a co-contaminant (metoprolol) in both of the soils (in MS soil a decrease of 29%; in LS soil a decrease of 26%). The mobility of cyclophosphamide does not depend on the presence of a contaminant for MS soil, but also exhibits a decrease of 21% in LS soil., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This article presents an analysis of available literature data on metrological parameters of the amperometric gas sensors containing ionic liquids as an electrolyte. Four mechanism types of signal generation in amperometric sensors with ionic liquid are described. Moreover, this article describes the influence of selected physico-chemical properties of the ionic liquids on the metrological parameters of these sensors. Some metrological parameters are also compared for amperometric sensors with GDE and SPE electrodes and with ionic liquids for selected analytes.

Background: Abdominal aortic clamping during aneurysm repair may cause a decrease in splanchnic blood flow and deterioration of gut barrier integrity. Epidural blocks have beneficial effects on vital organs during abdominal surgery, but sparse data are available on the influence on gut permeability during open aortic surgery. The aim of this study was to verify the hypothesis that epidural blocks may have beneficial effects on intestine permeability changes., Methods: Seventy individuals undergoing elective open abdominal aortic aneurysm repair were randomly assigned to receive either balanced anaesthesia (continuous epidural and general anaesthesia, group E&G) or only general anaesthesia (group G). For group E&G, an epidural catheter was inserted into the epidural space before the induction of general anaesthesia. Ropivacaine was used for intraoperative and postoperative blocks. For both groups general anaesthesia was maintained with sevoflurane. For group G, analgesia was provided with remifentanil. The assessments of gut function were based on measurements of the absorption and percentages of urinary excretion of four sugars (m 3-O-methyl-D-glucose, D-xylose, L-rhamnose and lactulose) and the lactulose/rhamnose (L/R) ratio., Results: No intergroup differences were observed for sugar recovery or L/R ratio. Significant decreases in 3-O-methyl-D-glucose, D-xylose, and L-rhamnose recoveries were revealed in both examined groups when comparing the results obtained at 12 and 24 hours following the administration of anaesthesia. The rate of blood pressure decrease was significantly higher in group E&G., Conclusions: Aortic clamping during open abdominal aortic repair led to unfavorable changes in intestinal permeability. Epidural block did not attenuate this deterioration.

The aim of our study was to identify organic pollutants found in soil and sediment samples collected within the Jackson, MS metropolitan area. The chemical characterization of the organic compound fractions in soil and sediment samples was carried out by separating the organic fraction using column chromatography (CC) and quantitatively analyzing the polycyclic aromatic hydrocarbons (PAHs), n-alkanes and other organic compounds using gas chromatography-electron impact mass spectrometry (GC-MS). Fifty-six compounds were identified and quantified in the soil samples and 33 compounds were identified and quantified in the sediment samples. The PAHs, n-alkanes and other organic compound profiles in the soil and sediment samples were compared. The percentage contents of the organic compounds in the soil samples were very diverse (from traces to 12.44 ± 1.47%). The compounds present in the highest concentrations were n-alkanes: n-C31 (12.44 ± 1.47%), n-C29 (11.64 ± 1.21%), and n-C33 (8.95 ± 1.08%). The components occurring in smaller quantities (from 1% to 5%) were 2 PAHs (fluoranthene 1.28 ± 0.25%, pyrene 1.16 ± 0.20%), 10 n-alkanes from n-C21 (1.25 ± 0.29%) to n-C32 (2.67 ± 0.52%) and 11 other compounds (e.g., 2-pentanol, 4-methyl (3.33 ± 0.44%), benzyl butyl phthalate (4.25 ± 0.59%), benzenedicarboxylic acid (1.14 ± 0.08%), ethane, 1,1-diethoxy (3.15 ± 0.41) and hexadecanoic acid (2.52 ± 0.34). The soil samples also contained 30 compounds present in concentrations <1% (e.g., anthracene (0.13 ± 0.04%), n-C20 (0.84 ± 0.21%) and acetic acid (0.12 ± 0.04%). The compounds present in the highest concentrations in the sediment samples were PAHs: pyrene (7.73 ± 1.15%) and fluoranthene (6.23 ± 1.07%) and n-alkanes: n-C31 (6.74 ± 1.21%), n-C29 (6.65 ± 0.98%) and n-C27 (6.13 ± 1.09%). The remaining organic compounds were present in smaller quantities (< 5%).

The presence of pharmaceuticals in drinking water, even at very low concentrations, has raised concerns among stakeholders such as drinking-water regulators, governments, water suppliers and the public, with regard to the potential risks to humans. Despite this, the occurrence and the fate of pharmaceuticals in drinking waters of many countries (e.g. in Poland) remains unknown. There is a lack of sufficiently sensitive and reliable analytical methods for such analyses and a need for more in-depth hydrogeological analysis of the possible sources of drug residues in drinking water. In this paper, a multi-residual method for the simultaneous determination of seventeen human pharmaceuticals in drinking waters has been developed. Large-volume extractions using Speedisk extraction disks, and derivatization prior to GC-MS-SIM analysis using a new silylating agent DIMETRIS were applied. The method detection limits (MDLs) ranged from 0.9 to 5.7ng/L and the absolute recoveries of the target compounds were above 80% for most analytes. The developed method was successfully applied in the analysis of the target compounds in drinking water collected in Gdansk (Poland), and of the 17 pharmaceuticals, 6 compounds were detected at least once. During the investigation, the geomorphology of the site region was taken into account, possible sources of pharmaceuticals in the analysed drinking water samples were investigated, and the presence of the drugs in ground and surface waters, raw and treated drinking waters was determined. Concentrations were also compared with those observed in other countries. As a result, this study has not only developed a new analytical method for determining pharmaceuticals in drinking waters as well as rendering missing information for Poland (a country with one of the highest consumptions of pharmaceuticals in Europe), but it also presents a modelled in-depth hydrogeological analysis of the real sources of drugs in drinking waters., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) are promising platforms for the extraction and purification of proteins. In this work, a series of alternative and biocompatible ABS composed of cholinium-based ILs and polypropylene glycol were investigated. The respective ternary phase diagrams, tie-lines, tie-line lengths and critical points were determined at 25°C. The extraction performance of these systems for commercial bovine serum albumin (BSA) was then evaluated. The stability of BSA at the IL-rich phase was ascertained by size exclusion high-performance liquid chromatography and Fourier transform infrared spectroscopy. Appropriate ILs lead to the complete extraction of BSA for the IL-rich phase, in a single step, while maintaining the protein's native conformation. Furthermore, to evaluate the performance of these systems when applied to real matrices, the extraction of BSA from bovine serum was additionally carried out, revealing that the complete extraction of BSA was maintained and achieved in a single step. The remarkable extraction efficiencies obtained are far superior to those observed with typical polymer-based ABS. Therefore, the proposed ABS may be envisaged as a more effective and biocompatible approach for the separation and purification of other value-added proteins., (Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Although sulfonamides (SAs) are among the most commonly used veterinary drugs and their presence in the environment is well documented, knowledge of their fate and behavior in the soil environment is still limited, especially for sulfisoxazole (SSX) which is characterized by the lowest (among other SAs) pK a value associated with acid-base equilibrium of sulfonamide group. Thus, this work was focused on determining the sorption potential of SSX onto natural soils differing in physicochemical properties. All the results were modeled using linear, Freundlich, Langmuir, Dubinin-Radushkevich, and Temkin sorption isotherms. The established sorption coefficients (K(d)) for SSX were quite low (from 0.27 to 0.95 L kg(-1)), which indicated that this substance is highly mobile and has the potential to run off into surface waters and/or infiltrate ground water. The sorption data of SSX is well fitted to the Freundlich isotherm model (R(2) > 0.968). Moreover, we assessed the sorption mechanism of these compounds in the edaphic environment with respect to organic matter (OM) content, pH, and ionic strength. To clarify the current state of knowledge, these factors were examined much more thoroughly than in previous investigations concerning other SAs. The wide range of ionic strength examined showed positive correlation of this factor and sorption of SAs. The results also yielded new insight into dependency of sorption of SAs on organic matter content in soil.

Green leafy vegetables are valuable secondary sources of nutrients, including lipids, commonly consumed in developing countries. However, method development for the analysis of fatty acids is usually focused on the animal lipid samples, rarely including natural plant extracts. Hence, the usefulness of four derivatization methods for the gas chromatographic analysis of plant lipids was studied. Methylation using 10% solution of BF3 in methanol and 2.0M solution of (trimethylsilyl)diazomethane (TMSD) in hexane, trimethylsilylation and tert-butyldimethylsilylation were compared using lipid standards and extracts from the leaves of Solanum macrocarpon and S. melongena after saponification. While silylation was found effective and precise using lipid standards, it initially did not perform well in the analysis of plant lipids due to the presence of transesterification products in samples. Optimization of the hydrolysis conditions resulted in an effective analysis of these derivatives, but poor separation of FA(18:0) from unsaturated FA(18:X) compounds and the presence of larger amounts of interferences disqualified the use silylation for the analysis of plant fatty acids in applied analytical conditions. Methylation using TMSD gave more precise quantitative results when compared to BF3/MeOH method. Also, it produced a significantly lower amount of interferences when applied to plant lipid samples. Additionally, the TMSD-based method is simple, safe and less time-consuming when compared to other procedures. Thus, we suggest using TMSD-based methylation as a method of choice in the GC analysis of plant-derived fatty acids., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Pharmaceuticals are continually being released into the environment. Because of their physical and chemical properties, many of them or their bioactive metabolites can accumulate in sediments, sludge and soils, and induce adverse effects in terrestrial organisms. However, due to the very limited methods permitting the detection of these low-level concentration compounds in such complex matrices, their concentrations in natural solids remain largely unknown. In this paper, an analytical method for the simultaneous determination of thirteen pharmaceuticals (eight non-steroidal anti-inflammatory drugs and five oestrogenic hormones) in solid matrices was developed. The proposed MAE-SPE-GC-MS(SIM) method has been successfully validated providing a linear response over a concentration range of 1(17)-1000(1200)ng/g, depending on the pharmaceuticals, with correlation coefficients above 0.991. The method detection limits were in the range of 0.3-5.7 ng/g, absolute recoveries above 50%, except estrone. The developed method was applied in the analysis of the target compounds in sediment, sludge and soils collected in Poland giving primary data on their concentrations in such matrices in Poland. The obtained results confirmed that the proposed method can be successfully used in the analysis of real environmental solid samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Flubendazole (FLU) and fenbendazole (FEN) belong to benzimidazoles-pharmaceuticals widely used in veterinary and human medicine for the treatment of intestinal parasites as well as for the treatment of systemic worm infections. In recent years, usage of these drugs increased, which resulted in a larger contamination of the environment and possible negative effects on biota. Hence, in our research, we investigated an aquatic ecotoxicity of these pharmaceuticals towards: marine bacteria (Vibrio fischeri), green algae (Scenedesmus vacuolatus), duckweed (Lemna minor) and crustacean (Daphnia magna). Ecotoxicity tests were combined with chemical analysis in order to investigate the actual exposure concentration of the compounds used in the experiment as well as to stability and adsorption studies. As a result, study evaluating sensitivity of different aquatic organisms to these compounds and new ecotoxicological data is presented. The strongest negative impact of FLU and FEN was observed to D. magna.

Metronidazole (MNZ) is an antibacterial and antiprotozoal drug used in veterinary and human medicine. Its continual entry into the environment and its biological properties may have significant, long-term effects on the stability of ecosystems because MNZ and its metabolites possess mutagenic, carcinogenic and toxic properties. For this reason, the application of MNZ in food-producing species is prohibited in the EU, the USA and other countries. To ensure human food safety and to protect the environment, robust and reliable screening and confirmatory tests capable of the low-level detection of MNZ residues are required. The development of methods for MNZ determination in biological and environmental samples is thus an important analytical task in environmental and food science. This work focuses on the evaluation of a method for determining MNZ in water, sediment and fish tissue samples using liquid chromatography--ion trap mass spectrometry (LC-MS/MS). MNZ was extracted from waters on Strata XC cartridges using solid phase extraction (SPE), and from sediments and fish tissues by solid-liquid extraction (sediment: 15 mL 0.1 M HCl (pH=0.6), 15 min; fish tissue: 15 mL 1% CH3COOH in ACN, 1 min; drying: 5 g MgSO4(anhyd.; 30 s) with SPE purification of the extracts (from sediment: Strata XC cartridge; from fish tissue: Supelco NH2 cartridge). The optimal procedure that we developed was validated in order to confirm its reliability and sensitivity. Matrix effects (ME) were established. Absolute recoveries ranged from 89.3% to 97.2%, and the method detection limits were 3.4 ng L(-1) (water samples), 0.4 ng g(-1) (sediment samples) and 0.3 ng g(-1) (tissue samples). These methods were used to determine MNZ in surface waters, sediments and fish tissues from the Polish River Gościcina; MNZ was found in all these matrices. The highest concentrations in water, sediment and tissue were 136.2 ng L(-1), 12.0 ng g(-1) and 1.5 ng g(-1) respectively. The results confirmed that these methods are suitable for the simultaneous analysis of waters, sediments and fish tissues for the presence of MNZ., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In recent years, the number of analytical methods of target compound residues (such as pharmaceuticals) has grown rapidly. Most of them are based on high performance liquid chromatography (HPLC). From the economic point of view, it is usual to apply the conditions of available HPLC methods or to design extraction and chromatographic separation conditions using HPLC and transfer them subsequently to a more sensitive technique like liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). However, if such a transfer is planned, it is important to assess the quality of the newly-designed LC-MS/MS method. The determination of parameters like matrix effects (ME), extraction efficiency (EE) and absolute recovery (AR) is mandatory. These parameters can visualise the weakest step in the analytical method and enable methods based on different techniques to be compared. The aim of this work was to show how quality assessment should be carried out in order to transfer an optimised method from one technique to another. The representative compound used in our investigation was doramectin (DOR), an anthelmintic drug used in veterinary medicine. The quality of the suggested methods for determining this drug in three environmental matrices (water, sediment and fish tissue) using HPLC-UV and LC-MS/MS was evaluated on the basis of known values of absolute recovery (HPLC-UV) and matrix effect, extraction efficiency and absolute recovery (all LC-MS/MS). Finally, the suggested methods for determining DOR in water, sediment and fish tissue based on LC-MS/MS measurements were validated and applied to the analysis of real environmental samples., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Among the various pharmaceuticals regarded as emerging pollutants, benzimidazoles--represented by flubendazole and fenbendazole--are of particular concern because of their large-scale use in veterinary medicine and their health effects on aquatic organisms. For this reason, it is essential to have reliable analytical methods which can be used to simultaneously monitor their appearance in environmental matrices such as water, sediment and tissue samples. To date, however, such methods relating to these three matrices have not been available. In this paper we present a comprehensive approach to the determination of both drugs in the mentioned above matrices using liquid chromatography-ion trap mass spectrometry (LC-MS/MS). Special attention was paid to the sample preparation step. The optimal extraction methods were further validated by experiments with spiked water, sediment and fish tissue samples. Matrix effects were established. The following absolute recoveries of flubendazole and fenbendazole were achieved: 96.2% and 95.4% from waters, 103.4% and 98.3% from sediments, and 98.3% and 97.6% from fish tissue samples, respectively. Validation of the LC-MS/MS methods enable flubendazole and fenbendazole to be determined with method detection limits: 1.6 ng L(-1) and 1.7 ng L(-1) in water samples; 0.3 ng g(-1) for both compounds in sediment samples, and 3.3 ng g(-1) and 3.5 ng g(-1) in tissue samples, respectively. The proposed methods were successfully used for analysing selected pharmaceuticals in real samples collected in northern Poland. There is first data on the concentration in the environment of the target compounds in Poland., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Novel organic compounds found in the cuticular and internal lipids of medically important flies were identified. Uracil, 9-tricosene, 1-oleoyl glycerol, dimethyl suberate and butyl stearate were tested for their potential antifungal activity. Minimal inhibitory concentrations of the compounds against reference strains of fungi were determined. Uracil and dimethyl suberate slightly inhibited the growth of entomopathogenic fungi. The cuticular and internal lipids of Calliphora vicina, Calliphora vomitoria, Sarcophaga carnaria and Musca domestica were studied by gas chromatography (GC) combined with mass spectrometry (GC/MS). A comparison of the lipid extracts between the preimaginal and mature stages showed adults flies contained a higher total content of the identified components. Furthermore, their amounts distinctly predominated in the internal lipids of all the species. The amount of 9-tricosene was the highest in adults of C. vicina, while the larvae and pupae had a definitively lower amount of this compound. Uracil was found to be the most abundant component in extracts obtained from C. vomitoria especially in the internal lipids of adults. 1-oleoyl glycerol was detected in all of the examined species of flies. It was most abundant in the internal extracts isolated from the larvae of C. vicina and the pupae of C. vomitoria. Suberic acid dimethyl ester was found in the larval and pupal internal lipids of C. vicina and S. carnaria in low amounts. Butyl stearate was identified only in the internal lipids of the larvae and adults of houseflies., (Copyright © 2014 Elsevier GmbH. All rights reserved.)

The increasing consumption of beta-blockers (BB) has caused their presence in the environment to become more noticeable. Even though BB are safe for human and veterinary usage, ecosystems may be exposed to these substances. In this study, three selected BB: propranolol, metoprolol and nadolol were subjected to ecotoxicity study. Ecotoxicity evaluation was based on a flexible ecotoxicological test battery including organisms, representing different trophic levels and complexity: marine bacteria (Vibrio fischeri), soil/sediment bacteria (Arthrobacter globiformis), green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor). All the ecotoxicological studies were supported by instrumental analysis to measure deviation between nominal and real test concentrations. Based on toxicological data from the green algae test (S. vacuolatus) propranolol and metoprolol can be considered to be harmful to aquatic organisms. However, sorption explicitly inhibits the hazardous effects of BB, therefore the risks posed by these compounds for the environment are of minor importance., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Antibiotic consumption (e.g. fluoroquinolones (FQs)) and, as a consequence, their presence in the environment, have received a lot of attention in the last several years due to increasing numbers of diseases and infections that are becoming resistant to traditional treatments for both humans and animals. In addition, even though antibiotics are safe for human and veterinary usage, ecosystems may be exposed to these substances. In this study, analytical methods for determining enrofloxacin (ENR), norfloxacin (NOR) and ciprofloxacin (CIP) in water samples and fish tissue based on the LC-MS/MS technique were developed and validated. As there is no data available concerning the risks posed by antibiotics in Poland, the proposed methods were applied for monitoring drug presence in environmental samples collected from two rivers in northern Poland. Evaluations of the ecotoxicity of ENR, NOR and CIP towards four different species of aquatic organisms: marine bacteria (Vibrio fischeri), green algae (Scenedesmus vacuolatus), duckweed (Lemna minor) and crustacean (Daphnia magna), were also carried out. All the investigated compounds were detected at least once in the survey. NOR was found to be the most ubiquitous drug with concentrations of up to 442.8 ng L(-1). Moreover, it was established that L. minor is the most sensitive species to the investigated drugs (EC50NOR = 0.13 mg L(-1), EC50ENR = 0.22 mg L(-1) and EC50CIP = 0.34 mg L(-1)). The calculated risk quotient (RQ) values confirmed that the concentrations of the investigated FQs in the environmental samples were at a level of moderate environmental risk (1

Beta-blockers (BB) are one of the most widely used pharmaceuticals whose presence in different environmental compartments has already been proven in concentrations of even up to a few μg L(-1). However, our knowledge of their fate in the environment is still scarce. To obtain a better understanding on the environmental behavior of three selected BB comprehensive laboratory experiments assessing their mobility and hydrolytic stability has been conducted. Propranolol, metoprolol and nadolol--the most commonly consumed and detected in environmental samples--were selected as representatives of this group of pharmaceuticals. The objectives of our research were: (i) evaluation of the sorption potential and an explanation of the sorption mechanisms of these compounds onto soil and clay mineral (kaolinite); and (ii) investigation of the hydrolytic stability of these BB according to OECD 111. This comprehensive study supports the Environmental Risk Assessment of these pharmaceuticals., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na2SO4. The intermediates identified by LC-MS and GC-MS analysis suggested that the hydroxyl radicals attack mainly the SN bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test., (Copyright © 2014. Published by Elsevier B.V.)