Embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate in patients with hemoptysis: A retrospective single-center study.

OBJECTIVES: To evaluate the safety and efficacy of the embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate (NBCA) in patients with hemoptysis. METHODS: We analyzed a total of 55 consecutive patients with hemoptysis (14 mild, 31 moderate, and 10 massive) treated with the embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate between November 2013 and January 2020. The main variables analyzed were the rates of technical success, of clinical success, of recurrence, and of complications. Statistics included a descriptive analysis and Kaplan-Meier survival curves. RESULTS: Embolization was a technical success in 55 (100%) and a clinical success in 54 (98.2%). During follow-up (mean, 23.8 months; interquartile range, 9.7-38.2 months), hemoptysis recurred in 5 (9.3%) patients. The nonrecurrence rate was 91.9% one year after the initial procedure and 88.7% two years and four years after the initial procedure. Minor complications related with the procedure occurred in 6 (10.9%); no major complications occurred. CONCLUSIONS: The embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate is safe and efficacious for controlling hemoptysis, resulting in low recurrence rates.

Embolización de arterias bronquiales y arterias sistémicas no bronquiales con n-butil-cianoacrilato en pacientes con hemoptisis: un estudio monocéntrico y retrospectivo / Embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate in patients with hemoptysis: a retrospective single-center study

Objetivos Evaluar la seguridad y la eficacia de la embolización de arterias bronquiales y arterias sistémicas no bronquiales con n-butil-cianoacrilato en pacientes con hemoptisis. Métodos Se han analizado un total de 55 pacientes consecutivos con hemoptisis (14 leves, 31 moderadas y 10 masivas) tratados mediante embolización de arterias bronquiales y arterias sistémicas no bronquiales con n-butil- cianoacrilato entre noviembre de 2013 y enero de 2020. Las variables principales estudiadas son tasa de éxito técnico, tasa de éxito clínico, tasas de recurrencia y complicaciones. Se ha realizado un análisis estadístico descriptivo y un análisis de supervivencia mediante el método de Kaplan-Meier. Resultados En 55 (100%) pacientes se ha realizado la embolización con éxito técnico y en 54 (98,2%), con éxito clínico. Durante el seguimiento (media, 23,8 meses; rango intercuartílico, 9,7-38,2) ha recurrido en 5 de los 54 (9,3%) pacientes. La tasa de no recurrencia al año ha sido del 91,9%, y a los 2 y 4 años, del 88,7% después del procedimiento inicial. Ha habido 6 (10,9%) complicaciones menores relacionadas con el procedimiento y ninguna mayor. Conclusiones La embolización de arterias bronquiales y arterias sistémicas no bronquiales con n-butil-cianoacrilato es segura y eficaz para controlar la hemoptisis con tasas de recurrencia bajas (AU)

Objectives To evaluate the safety and efficacy of the embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate (NBCA) in patients with hemoptysis. Methods We analyzed a total of 55 consecutive patients with hemoptysis (14 mild, 31 moderate, and 10 massive) treated with the embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate between November 2013 and January 2020. The main variables analyzed were the rates of technical success, of clinical success, of recurrence, and of complications. Statistics included a descriptive analysis and Kaplan-Meier survival curves. Result Embolization was a technical success in 55 (100%) and a clinical success in 54 (98.2%). During follow-up (mean, 23.8 months; interquartile range, 9.7 – 38.2 months), hemoptysis recurred in 5 (9.3%) patients. The nonrecurrence rate was 91.9% one year after the initial procedure and 88.7% two years and four years after the initial procedure. Minor complications related with the procedure occurred in 6 (10.9%); no major complications occurred. Conclusions The embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate is safe and efficacious for controlling hemoptysis, resulting in low recurrence rates (AU)

Phenological and seismological impacts on airborne pollen types: A case study of Olea pollen in the Region of Murcia, Mediterranean Spanish climate.

The rationale of this paper was to investigate whether earthquakes impact airborne pollen concentrations, considering some meteorological parameters. Atmospheric pollen concentrations in the Region of Murcia Aerobiological Network (Spain) were studied in relation to the occurrence of earthquakes of moment magnitude (up to Mw = 5.1) and intensity (intensity up to grade VII on the European Macroseismic Scale). In this study, a decade (2010-2019) was considered across the cities of the network. Earthquakes were detected in 12 out of 1535 days in the Olea Main Pollen Season in Cartagena, 49 out of 1481 days in the Olea Main Pollen Season in Lorca, and 39 out of 1441 days in the Olea Main Pollen Season in Murcia. The Olea pollen grains in this network were attributed to the species Olea europaea, i.e., the olive tree, a taxon that appears widely in the Mediterranean basin, in both cultivated and wild subspecies. Differences between the Olea concentration on days with and without earthquakes were only found in Lorca (Kruskal-Wallis: p-value = 0.026). The low frequency and intensity of the earthquakes explained these results. The most catastrophic earthquake felt in Lorca on May 11th, 2011 (IVII, Mw = 5.1, 9 casualties) did not result in clear variations in pollen concentrations, while meteorology (e.g., African Dust Outbreak) might have conditioned these pollen concentrations. The research should be broadened to other active seismological areas to reinforce the hypothesis of seismological impact on airborne pollen concentrations.

Monitoring of pesticide residues in crops irrigated with reclaimed water by a multiresidue method based on modified QuEChERS.

In this study, we aimed to validate and apply a quick and easy extraction method for the simultaneous determination of 27 pesticide residues at trace levels in agricultural samples (soil, fruit, and leaf) to monitor the presence of these contaminants released from reclaimed water. The procedure was based on a salting-out extraction method with acidified acetonitrile, followed by a dispersive solid-phase extraction (d-SPE) clean-up step applying the C18 sorbent. Ultra-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC-MS/MS) was used for identification and quantification of the target analytes. This methodology provided recovery values higher than 70%, for all pesticides and matrices evaluated in the study, except for propamocarb in soil samples (35%). Repeatability and reproducibility results, calculated as relative standard deviations (RSD, %), ranged between 1% and 18% in both cases. No remarkable matrix effects were observed for vegetable samples, except for thiamethoxam in red cabbage, and hexythiazox in carrot and leaves (between 30 and 40%). Soil samples showed a moderate matrix effect (between 21 and 35%) for more than 80% of the compounds. Monitoring pesticide residues found in agricultural samples irrigated with contaminated reclaimed water under controlled conditions revealed the efficacy of the proposed method. Three common vegetables were grown to evaluate the different migration and distribution rates in crops and soil. Pesticide accumulation in the different parts of the crop (soil, fruit, and leaves) and the potential human exposure to pesticides through daily intake were also discussed.

The effects of continentality, marine nature and the recirculation of air masses on pollen concentration: Olea in a Mediterranean coastal enclave.

Olea pollen concentrations have been studied in relation to the typology of air masses, pollen grain sources and marine nature during advections in a coastal enclave in the south-eastern Iberian Peninsula. Since Spain is the world's leading olive producer, and olive growing extends throughout the Mediterranean basin, this location is ideal for the study of long-distance transport events (LTD) during the main pollen season (MPS). The air masses were classified using the calculation of 48-h back trajectories at 250, 500 and 750 m above ground level using the HYSPLIT model. After that, the frequency of LDT events from Africa and Europe was found to be 8.7% of the MPS days. In contrast, regional air masses were found in 38.6% of the MPS days. This was reflected in pollen concentrations, with significantly higher concentrations (p-value <0.05) on days with regional air masses compared to days with European air masses. Regarding the source areas, the importance of nearby sources with intense olive cultivation was confirmed (i.e., Andalusia). This proximity was relevant beyond the attenuations observed when the advections acquired a marine nature as the air mass back trajectories moved over the sea (p-value <0.001). The review of air mass typologies, source areas and pollen concentrations resulted in establishing peak dates and the detection of LDT associated with these peak dates. Distortions in the typical path of each air mass explained alterations in pollen concentrations on consecutive days. The recirculation and loops of the air mass back trajectories varied the pollen load that every type of air mass could originally contain.

Embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate in patients with hemoptysis: a retrospective single-center study. / Embolización de arterias bronquiales y arterias sistémicas no bronquiales con n-butil-cianoacrilato en pacientes con hemoptisis: un estudio monocéntrico y retrospectivo.

OBJECTIVES: To evaluate the safety and efficacy of the embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate (NBCA) in patients with hemoptysis. METHODS: We analyzed a total of 55 consecutive patients with hemoptysis (14 mild, 31 moderate, and 10 massive) treated with the embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate between November 2013 and January 2020. The main variables analyzed were the rates of technical success, of clinical success, of recurrence, and of complications. Statistics included a descriptive analysis and Kaplan-Meier survival curves. RESULTS: Embolization was a technical success in 55 (100%) and a clinical success in 54 (98.2%). During follow-up (mean, 23.8 months; interquartile range, 9.7 - 38.2 months), hemoptysis recurred in 5 (9.3%) patients. The nonrecurrence rate was 91.9% one year after the initial procedure and 88.7% two years and four years after the initial procedure. Minor complications related with the procedure occurred in 6 (10.9%); no major complications occurred. CONCLUSIONS: The embolization of bronchial arteries and nonbronchial systemic arteries with n-butyl-cyanoacrylate is safe and efficacious for controlling hemoptysis, resulting in low recurrence rates.

Solid phase extraction of pesticides from environmental waters using an MSU-1 mesoporous material and determination by UPLC-MS/MS.

This paper describes the synthesis of a silica based MSU-1 mesoporous solid and its application as sorbent in solid-phase extraction to pre-concentrate thirteen pesticides of low-high polarity (methomyl, cymoxanil, carbofuran, monolinuron, isoproturon, methidathion, methiocarb, malathion, phosalone, diazinon, penconazole, neburon and chlorotoluron) in ground and river water. The synthesis was based in an H-bonding interaction assembling (I0N0) between two non-ionic components (the inorganic silica surface, I0 and the polyethylene oxide template, N0) by adding tetraethoxysilane to the non-ionic surfactant Brij®100, the latter previously dissolved in HCl 1 M. 50 mL water samples adjusted at pH= 3.5 were passed, at a flow rate of 5 mL/min, through a home-made cartridge containing 50 mg of MSU-1 sorbent, pre-conditioned with 5 mL of ultrapure water; then, the cartridge was washed with 5 mL of ultrapure water. Following elution with 5 mL of acetonitrile, the pesticides were determined by ultra performance liquid chromatography coupled to triple quadrupole-mass spectrometry. Two selected reaction monitoring transitions were monitored per compound, the most intense one being used for quantification and the second one for confirmation. Three points were used for identification, as established in the Directive 96/23/EC for LC-MS/MS analysis, which deals with confirmatory methods for organic residues and contaminants listed in the Group B (veterinary drugs and contaminants). Medium matrix effect (|20%||50%|). Therefore, the standard addition methodology was applied by adding an adequate amount of the pesticide standard mixture to the final sample extract. All pesticides were quantified using this approach for practical reasons, thus avoiding two different calibrations. The method quantification limit (MQL) of pesticides was 0.01 µg/L for all of them, except for diazinon (0.1 µg/L). Recoveries of the target pesticides at MQL and 0.25 µg/L concentration levels in blank river water were in the range 70.1-113.5% and 86.7-107.3%, respectively, with RSDs lower than 16.3% and 15.7%, respectively. Four ground water samples and three river water samples, taken from Almería (Spain), were analyzed by the proposed method and only phosalone at a concentration level of 0.05 µg/L was found in one river water sample.

Group Psychotherapy Could Improve Depression in Cirrhotic Patients on the Liver Transplant Waiting List.

BACKGROUND: It is well-known that there is a high incidence of depression in patients on the liver transplant (LT) waiting list. However, there have been few studies of psychological intervention on these patients. OBJECTIVES: To determine symptoms of depression in patients on the LT waiting list and the impact of group psychotherapy. METHODS: Study population: patients on the LT waiting list who received group psychotherapy (n = 15). CONTROL GROUP: patients who did not receive psychotherapy (n = 10). Measurement instrument: Beck's depression test, which was provided before psychotherapy was initiated and after it was completed (after 6 months). The control group was given the questionnaire at the same 2 points in time as the study group. The psychotherapeutic method consisted of discussing patients' feelings, which dealt with several matters related to transplantation. Different coping strategies were considered. RESULTS: More than half of those surveyed initially had depressive symptoms. When the second survey was administered to the study population, all the patients improved in their psychopathological assessment. When the survey was administered to the control group, a worse psychopathological assessment was obtained in all cases. CONCLUSIONS: Our data suggest an improvement in depressive symptoms in patients on the LT waiting list after receiving group psychotherapy.

Quality of Life and Group Psychological Intervention in Patients With Cirrhosis on Liver Transplant Waiting List.

BACKGROUND: The patients on the liver transplant (LT) waiting list usually present with deterioration in their quality of life. Previous studies on psychological intervention have shown how the quality of life can be improved. OBJECTIVE: To analyze preliminary results of the influence of group psychotherapy on the quality of life of patients on the LT waiting list. METHOD: Fifteen patients on the LT waiting list who accepted receiving group psychotherapy were selected. The development of each 1 of these sessions was carried out at fortnightly periods for 6 months (12 sessions). Those patients who received a transplant and those patients who did not attend more than 6 group psychotherapy sessions were excluded. The Nottingham Health Profile was used to assess the quality of life. It consists of 38 items belonging to 6 health dimensions: energy, pain, physical mobility, emotional reaction, sleep, and social isolation. The study population was given a questionnaire before starting group psychotherapy and after it was finished. RESULTS: Of the 15 patients selected from the study population, 3 patients were given a transplant before the psychotherapy had finished, and 5 patients were excluded for not having attended more than 50% of the sessions. Therefore, the study was completed on 7 patients (n = 7). Overall, a better assessment can be seen in the second questionnaire. CONCLUSIONS: Group psychotherapy might favorably influence the quality of life of patients on the LT waiting list; therefore, it might be interesting to carry out studies on a larger scale in order to confirm these results.

Novel Mapping Method for the Intraoperative Neurophysiologic Monitoring of Sexual Function During Prostate Surgery.

PURPOSE: The occurrence of urinary incontinence and erectile dysfunction after surgical treatment for prostate cancer is a significant and lingering problem. The aim of this study is to revise and improve older techniques of intraoperative cavernous nerve mapping already in use to improve accuracy and reliability. METHODS: We prospectively studied this technique in 12 patients suffering from prostate cancer. Inhalation or intravenous anesthetic regimen was used with nondepolarizing muscle relaxants. Stimulation protocol was 30 Hz, 0.2 ms, 10 to 20 mA intensity and a maximum duration of 30 seconds. Recording was performed with a system for measuring pressure changes using a stainless steel needle electrode inside the cavernous bodies. Stimulation was systematically performed at three distinct moments during the surgery at various points. An increase or decrease in pressure of 4 cm of H20 in the cavernous bodies was considered a positive result and negative response when no changes occurred after 30 seconds of continuous stimulation. RESULTS: Of patients, 91.6% had positive responses to initial stimulation. The anesthetic regimen did not appear to significantly influence the responses in our series. CONCLUSIONS: In light of the results of this study, the stimulation of the cavernous nerves may be a viable technique in the right context, which includes good patient selection (young patients with a localized tumor and with preserved potency). The major limitation is that mapping techniques are useful to localize functional nerves, but not to monitor function in a continuous manner.

A Multicentric Brazilian Investigative Study of Copy Number Variations in Patients with Congenital Anomalies and Intellectual Disability.

Genomic imbalances are the most common cause of congenital anomalies (CA) and intellectual disability (ID). The aims of this study were to identify copy number variations (CNVs) in 416 patients with CA and ID from 5 different genetics centers within 4 different states by using the Multiplex Ligation-dependent Probe Amplification (MLPA) technique and to apply the chromosomal microarray (CMA) methodology in selected cases. The samples were analyzed by MLPA kits P064, P036, P070 and P250. Positive results were found in 97/416 (23.3%) patients. CMA was applied in 14 selected cases. In 6/14 (42.85%) patients, CMA detected other copy number variations not detected by the MLPA studies. Although CMA is indispensable for genotype refinement, the technique is still unfeasible in some countries as a routine analysis due to economic and technical limitations. In these cases, clinical evaluation followed by karyotyping and MLPA analysis is a helpful and affordable solution for diagnostic purposes.

Analysis of airborne Olea pollen in Cartagena (Spain).

Olive cultivation is of great importance in Southern Europe but olive pollen is the leading cause of allergy in many regions where it is grown. The best preventive measure for allergic patients is to avoid exposure. Thus, aerobiological monitoring networks must supply realistic pollen classes for the different types of allergic pollen. Even though those pollen classes are defined, they do not necessarily fit local data. Altogether, they should use predictive models to assess flowering intensity in advance. In this study, the Olea pollen degree of exposure classes (OPDEC) are defined based on percentiles and a predictive model is suggested for Cartagena, Spain. 24year (1993-2016) Olea pollen counts series was used to characterize the Main Pollen Season (MPS). The aerobiological samples were processed following the methodology proposed by Hirst and developed by the Spanish Aerobiology Network. The aerobiological database was completed with the meteorological data supplied by AEMET (Spanish State Meteorological Agency). MPS evolution over time, and its relation with temperature and rainfall, has been analysed. The study showed an increase in MPS duration and the amount of Olea pollen grains collected both in MPS and the peak day. The OPDEC should fit local data to improve preventive measures. Based on the 24year series, the proposed OPDEC for Cartagena are: Low (≤10grains/m3), Medium (between 10 and 50grains/m3), High (between 51 and 100grains/m3) and Very High (≥100grains/m3). Olea pollen estimations in the MPS and in the peak day were obtained by means of three Regression Methods and climatic factors. The analysis reveals that the Bagging for Regression Trees (BRT) method is a good predictive alternative and stablishes the importance for each meteorological variable.

Large multiresidue analysis of pesticides in edible vegetable oils by using efficient solid-phase extraction sorbents based on quick, easy, cheap, effective, rugged and safe methodology followed by gas chromatography-tandem mass spectrometry.

The aim of this research was to adapt the QuEChERS method for routine pesticide multiresidue analysis in edible vegetable oil samples using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Several clean-up approaches were tested: (a) D-SPE with Enhanced Matrix Removal-Lipid (EMR-Lipid™); (b) D-SPE with PSA; (c) D-SPE with Z-Sep; (d) SPE with Z-Sep. Clean-up methods were evaluated in terms of fat removal from the extracts, recoveries and extraction precision for 213 pesticides in different matrices (soybean, sunflower and extra-virgin olive oil). The QuEChERS protocol with EMR-Lipid d-SPE provided the best reduction of co-extracted matrix compounds with the highest number of pesticides exhibiting mean recoveries in the 70-120% range, and the lowest relative standard deviations values (4% on average). A simple and rapid (only 5min) freeze-out step with dry ice (CO2 at -76°C) prior to d-SPE clean-up ensured much better removal of co-extracted matrix compounds in compliance of the necessity in routine analysis. Procedural Standard Calibration was established in order to compensate for recovery losses of certain pesticides and possible matrix effects. Limits of quantification were 10µgkg(-1) for the majority of the pesticides. The modified methodology was applied for the analysis of different 17 oil samples. Fourteen pesticides were detected with values lower than MRLs and their concentration ranged between 10.2 and 156.0µgkg(-1).

Mesoporous silica based MCM-41 as solid-phase extraction sorbent combined with micro-liquid chromatography-quadrupole-mass spectrometry for the analysis of pharmaceuticals in waters.

This paper reports the first application of the silica based mesoporous material MCM-41 as a sorbent in solid phase extraction, to pre-concentrate pharmaceuticals of very different polarity (atenolol, nadolol, pindolol, timolol, bisoprolol, metoprolol, betaxolol, ketoprofen, naproxen, ibuprofen, diclofenac, tolfenamic acid, flufenamic acid and meclofenamic acid) in surface waters. The analytes were extracted from 100mL water samples at pH 2.0 (containing 10(-3) mol/L of sodium chloride) by passing the solution through a cartridge filled with 100 mg of MCM-41. Following elution, the pharmaceuticals were determined by micro-liquid chromatography and triple quadrupole-mass spectrometry. Two selected reaction monitoring transitions were monitored per compound, the most intense one being used for quantification and the second one for confirmation. Matrix effect was found in real waters for most analytes and was overcome using the standard addition method, which compared favorably with the matrix matched calibration method. The detection limits in solvent (acetonitrile:water 10:90, v/v) ranged from 0.01 to 1.48 µg/L and in real water extracts from 0.10 to 3.85 µg/L (0.001-0.0385 µg/L in the water samples). The quantitation limits in solvent were in the range 0.02-4.93 µg/L, whereas in real water extracts were between 0.45 and 10.00 µg/L (0.0045 and 0.1000 µg/L in the water samples). When ultrapure water samples were spiked at two concentration levels of each pharmaceutical (0.1 and 0.2 µg/L) and quantified using solvent based calibration graphs, recoveries were near 100%. However, recoveries for most pharmaceuticals were comparable or better than de described above, when river water samples (spiked at the same concentration levels) were quantified by the standard addition method and slightly worse using the matrix matched calibration method. Five real samples (two rivers, one dam and two fountain water samples) were analyzed by the developed method, atenolol, timolol, betaxolol, nadolol and diclofenac being found in some of them, at levels higher than their quantitation limits.

Full coding hepatitis E virus genotype 3 genome amplification method.

Hepatitis E virus (HEV) genotype 3 produces zoonotic infection associated with the consumption of infected animals. HEV infections can become chronic in immunocompromised (IC) patients. The viral genome has three well defined open reading frames (ORF1, ORF2 and ORF3) within which various domains and functions have been described. This paper (i) describes a new method of complete sequencing of the HEV coding region through overlapping PCR systems, (ii) establishes a consensus sequence and polymorphic positions (PP) for each domain, and (iii) analyzes the complete coding sequence of an IC patient. With regard to the consensus, a high percentage of PP was observed in protease (PP=19%) and the X domain (PP=22%) within ORF1, the N-terminal region of the S domain (PP=22%) in ORF2, and the P1 (PP=35%) and P2 (PP=25%) domains in ORF3. In contrast, the ORF1 Y, ORF2 S, ORF2 M and ORF3 D1 domains were conserved in the reference sequences (0.40, 1, 0.70 and 0% of PP, respectively). The sequence from the IC patient had more mutations in the RpRp (D1235G, Q1242R, S1454T, V1480I, I1502 V, K1511R, G1373 V, E1442D, V1693 M), the terminal ORF2 S- domain (F10L, S26T, G36S, S70P, A105 V, I113 V), the X domain (T938 M, T856 V, S898A) and the helicase (S1014N, S975T, Q1133 K).

Benefits of Group Psychotherapy in Cirrhotic Patients on the Liver Transplant Waiting List.

INTRODUCTION: It is well-known that patients on the liver transplant (LT) waiting list experience a high rate of psychopathologic symptoms. However, few studies have been published about the use of group psychotherapy for these patients. We sought to assess (1) the psychopathologic data in patients on the LT waiting list and (2) the attitude toward a group psychotherapy procedure and its efficacy. MATERIAL AND METHODS: In the pretransplant consultation phase, group therapy was offered to 20 patients on the LT waiting list. Patients who received psychotherapy were assessed previously using the Beck Depression Inventory. RESULTS: Fifteen patients were included in the study. Significant differences were found between the psychopathologic assessment and the level of hepatopathy. In the first session, we observed that patients with hepatocarcinoma were much more reluctant to participate in the group therapy. In the second session, the group showed a high level of anxiety connected with a fear of transplantation. In the third session, a transplant physician answered all their questions, and at the end of the session patient anxiety had decreased. During the following sessions, family bonds and sharing experiences with other transplant patients were emphasized. CONCLUSIONS: Patients were initially reluctant to participate in the group psychotherapy, although this changed as sessions proceeded. It is necessary to provide more information about the transplant procedure itself to decrease anxiety. Group therapy was valued positively by all patients who participated.

Comparison of two ionic liquid dispersive liquid-liquid microextraction approaches for the determination of benzoylurea insecticides in wastewater using liquid chromatography-quadrupole-linear ion trap-mass spectrometry: evaluation of green parameters.

Two dispersive liquid-liquid microextraction (DLLME) approaches including temperature-controlled ionic liquid dispersive liquid-liquid microextraction (TCIL-DLLME) and ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) were compared for the extraction of six benzoylurea insecticides (diflubenzuron, triflumuron, hexaflumuron, teflubenzuron, lufenuron and flufenoxuron) from wastewater samples prior to their determination by high-performance liquid chromatography with a hybrid triple quadrupole-linear ion trap-mass spectrometer (LC-QqLIT-MS/MS). Influential parameters affecting extraction efficiency were systematically studied and optimized and the most significant green parameters were quantified and compared. The best results were obtained using the US-IL-DLLME procedure, which employed the IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) and methanol (MeOH) as extraction and disperser solvent, respectively. US-IL-DLLME procedure was fast, easy, low environmental toxicity and, it was also able to successfully extract all selected benzoylureas. This method was extensively validated with satisfactory results: limits of detection and quantification were in the range 0.5-1.0 ng L(-1) and 1.5-3.5 ng L(-1), respectively, whereas recovery rates ranged from 89 to 103% and the relative standard deviations were lower than 13.4%. The applicability of the method was assessed with the analysis of effluent wastewater samples from a wastewater treatment plant located in an agricultural zone of Almería (Spain) and the results indicated the presence of teflubenzuron at mean concentration levels of 11.3 ng L(-1). US-IL-DLLME sample treatment in combination with LC-QqLIT-MS/MS has demonstrated to be a sensitive, selective and efficient method to determine benzoylurea insecticides in wastewaters at ultra-trace levels.

Determination of drugs in river and wastewaters using solid-phase extraction by packed multi-walled carbon nanotubes and liquid chromatography-quadrupole-linear ion trap-mass spectrometry.

The present paper describes a solid-phase extraction by packed multi-walled carbon nanotubes, followed by liquid chromatography-mass spectrometry, method for the determination of some of the most consumed drugs including four ß-blockers and eight non-steroidal anti-inflammatory drugs, in river and wastewater samples. High extraction efficiency was found for most drugs due to the large specific surface area and high adsorption capacity of this nanomaterial compared with other conventional solid-phase extraction sorbents, and matrix effect was present only for two of the twelve studied drugs. Only 20mg of carbon nanotubes was enough to preconcentrate the analytes with recoveries from 68% to 107% for most of them. The pharmaceuticals were analyzed by liquid chromatography coupled to a hybrid triple quadrupole-linear ion trap-mass spectrometer at ultra-trace levels. Data acquisition was carried out in selected reaction monitoring mode, using two transitions for simultaneous identification and quantification of the analytes. Additionally, an information dependent acquisition scan was performed to carry out the identification of those analytes whose second transition was absent or was present at low intensity. The analytical performance of the whole method was evaluated in two environmental water matrices (river and wastewaters). Matrix effect was not found in river water, quantitation being carried out with calibration graphs built with solvent based standard. On the contrary, matrix effect was present in wastewater for some of the target drugs and, therefore, quantitation was carried out using the standard addition method. Limits of detection and quantitation in river waters were in the range of 9-36 and 23-121ngL(-1), respectively and the relative standard deviation of the full method was less than 17%. The proposed methodology was applied to the analysis of three river water and two wastewater (influent and effluent) samples, all of them from Almería (Spain). Some pharmaceuticals were found in river water at concentration levels near to or lower than their quantitation limits, whereas the most consumed pharmaceuticals were found at high concentration levels in influent wastewater and were not detected or were found at lower levels in the effluent wastewater sample.

Mucolipidosis II and III alpha/beta in Brazil: analysis of the GNPTAB gene.

UNLABELLED: Mucolipidosis II and III (MLII and MLIII) alpha/beta are rare autosomal recessive lysosomal storage diseases (LSDs) caused by pathogenic variations in the GNPTAB gene. GNPTAB gene codes for the α and ß subunits of phosphotransferase, the enzyme responsible for synthesis of the mannose-6-phosphate (M6P) marker that directs lysosomal enzymes to the lysosome. OBJECTIVES: The objective of this study is to identify sequence variations of the GNPTAB gene in Brazilian patients with MLII and MLIII alpha/beta. METHOD: Sequencing of the GNPTAB gene was performed in samples of gDNA extracted from the peripheral blood of patients with MLII/III diagnosed at a national reference center for LSDs. RESULTS: Twelve unrelated patients, from several regions of Brazil, were included in this study. Only one was born of consanguineous parents. All patients were found to carry at least one nonpathogenic variation. Nine causal sequence variations were found: c.242G>T (p.W81L); c.1123C>T (p.R375X); c.1196C>T (p.S399F); c.1208T>C (p.I403T); c.1514G>A (p.C505Y); c.1759C>T (p.R587X); c.2808A>G (p.Y937_M972del, novel mutation); c. 2269_2273delGAAAC (p.E757KfsX2, novel mutation); and c.3503_3504delTC (p.L1168QfsX5). Both pathogenic variations were identified in 8 of 12 patients; in four patients, only one pathogenic variation was identified. Mutation c.3503_3504delTC, located in exon 19, was the most frequent pathogenic variation found (n=11/24 alleles). The deleterious effect of the c.2808A>C mutation on splicing was confirmed by cDNA analysis. DISCUSSION/CONCLUSIONS: Our findings confirm that the GNPTAB gene presents broad allelic heterogeneity and suggests that, in Brazilian ML II and III patients, screening for mutations should begin at exon 19 of the GNPTAB gene. Further analyses will be conducted on patients in whom both pathogenic mutations have not been found in this study.

Ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction coupled with liquid chromatography-quadrupole-linear ion trap-mass spectrometry for simultaneous analysis of pharmaceuticals in wastewaters.

A simple, rapid, low environmental toxicity and sensitive ultrasound-assisted ionic liquid dispersive liquid-liquid microextraction (US-IL-DLLME) procedure was developed for the extraction of nine pharmaceuticals (paracetamol, metoprolol, bisoprolol, betaxolol, ketoprofen, naproxen, ibuprofen, flufenamic acid and tolfenamic acid) in wastewater, and their determination using high-performance liquid chromatography with a hybrid triple quadrupole-linear ion trap-mass spectrometer (LC-QqLIT-MS). The IL 1-octyl-3-methylimidazolium hexafluorophosphate ([C8MIM][PF6]) and acetonitrile (ACN) were used as extraction and disperser solvent, respectively, for the DLLME procedure, instead of using toxic chlorinated solvent. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, cooling in ice-water, sonication time, centrifuging time, sample pH and ionic strength, were optimized. The ultrasound-assisted process was applied to accelerate the formation of the fine cloudy solution using a small volume of disperser solvent (0.5mL of acetonitrile), which increased the extraction efficiency and reduced the equilibrium time. A slight increase in the recoveries of pharmaceuticals was observed when an ice-water bath extraction step was included in the analytical procedure. In this way, enrichment factors between 255 and 340 were obtained. Data acquisition in selected reaction monitoring mode (SRM), allowed the simultaneous identification and quantification of the analytes using two transitions (SRM1 and SRM2). Additionally, the information dependent acquisition (IDA) scan was performed to carry out the identification of those analytes whose second transition was absent or was present at low intensity, also providing extra confirmation for the other analytes. The optimized US-IL-DLLME-LC-QqLIT-MS method showed a good precision level, with relative standard deviation values between 1.1% and 11.3%. Limits of detection and quantification were in the range 0.2-60ngL(-1) and 1.0-142ngL(-1), respectively. Good enrichment factors (255-340) and recoveries (88-111%) were obtained for the extraction of the target analytes in wastewater samples. This method has been successfully applied to analyze effluent wastewater samples from a municipal wastewater treatment plant located in Almería (Spain) and the results indicated the presence of flufenamic acid and metoprolol in concentration levels of 0.1 and 1.3µgL(-1), respectively.