An Alternative Strategy for Screening and Confirmation of 330 Pesticides in Ground- and Surface Water Using Liquid Chromatography Tandem Mass Spectrometry.

The presence of pesticide residues in water is a huge worldwide concern. In this paper we described the development and validation of a new liquid chromatography tandem mass spectrometric (LC-MS/MS) method for both screening and quantification of pesticides in water samples. In the sample preparation stage, the samples were buffered to pH 7.0 and pre-concentrated on polymeric-based cartridges via solid-phase extraction (SPE). Highly sensitive detection was carried out with mobile phases containing only 5 mM ammonium formate (pH of 6.8) as an eluent additive and using only positive ionization mode in MS/MS instrument. Hence, only 200-fold sample enrichment was required to set a screening detection limit (SDL) and reporting limit (RL) of 10 ng/L. The confirmatory method was validated at 10 and 100 ng/L spiking levels. The apparent recoveries obtained from the matrix-matched calibration (5-500 ng/L) were within the acceptable range (60-120%), also the precision (relative standard deviation, RSD) was not higher than 20%. During the development, 480 pesticides were tested and 330 compounds fulfilled the requirements of validation. The method was successfully applied to proficiency test samples to evaluate its accuracy. Moreover, the method robustness test was carried out using higher sample volume (500 mL) followed by automated SPE enrichment. Finally, the method was used to analyze 20 real samples, in which some compounds were detected around 10 ng/L, but never exceeded the assay maximum level.

A Dilute and Shoot Strategy for Determining Alternaria Toxins in Tomato-Based Samples and in Different Flours Using LC-IDMS Separation.

Alternaria toxins are emerging mycotoxins whose regulation and standardization are in progress by the European Commission and the European Committee for Standardization. This paper describes a dilute and shoot approach to determine five Alternaria toxins in selected food samples using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The strategy involves sample extraction with acidified aqueous methanol, followed by a solvent change accomplished via sample evaporation and reconstitution. The quantification is based on isotope dilution, applying all corresponding isotopically labeled internal standards to compensate possible matrix effects of the analysis. The main advantages of the present method over other existing methods includes simple and effective sample preparation, as well as detection with high sensitivity. The five-fold sample dilution can decrease matrix effects, which were evaluated with both external and internal standard methods. The results demonstrated a limit of quantification lower than 1.0 µg/kg for all five analytes for the first time. The newly presented method showed acceptable accuracy (52.7-111%) when analyzing naturally contaminated and spiked standard samples at the described levels. The method was validated for tomato-based and flour samples (wheat, rye, and maize). The absolute recovery ranged from 66.7% to 91.6% (RSD < 10%). The developed method could be an alternative approach for those laboratories that exclude sample cleanup and pre-concentration of state-of-the-art instruments with enhanced sensitivity.

Physical activity in European adolescents and associations with anxiety, depression and well-being.

In this cross-sectional study, physical activity, sport participation and associations with well-being, anxiety and depressive symptoms were examined in a large representative sample of European adolescents. A school-based survey was completed by 11,110 adolescents from ten European countries who took part in the SEYLE (Saving and Empowering Young Lives in Europe) study. The questionnaire included items assessing physical activity, sport participation and validated instruments assessing well-being (WHO-5), depressive symptoms (BDI-II) and anxiety (SAS). Multi-level mixed effects linear regression was used to examine associations between physical activity/sport participation and mental health measures. A minority of the sample (17.9 % of boys and 10.7 % of girls; p < 0.0005) reported sufficient activity based on WHO guidelines (60 min + daily). The mean number of days of at least 60 min of moderate-to-vigorous activity in the past 2 weeks was 7.5 ± 4.4 among boys and 5.9 days ± 4.3 among girls. Frequency of activity was positively correlated with well-being and negatively correlated with both anxiety and depressive symptoms, up to a threshold of moderate frequency of activity. In a multi-level mixed effects model more frequent physical activity and participation in sport were both found to independently contribute to greater well-being and lower levels of anxiety and depressive symptoms in both sexes. Increasing activity levels and sports participation among the least active young people should be a target of community and school-based interventions to promote well-being. There does not appear to be an additional benefit to mental health associated with meeting the WHO-recommended levels of activity.

Pathological Internet use among European adolescents: psychopathology and self-destructive behaviours.

Rising global rates of pathological Internet use (PIU) and related psychological impairments have gained considerable attention in recent years. In an effort to acquire evidence-based knowledge of this relationship, the main objective of this study was to investigate the association between PIU, psychopathology and self-destructive behaviours among school-based adolescents in eleven European countries. This cross-sectional study was implemented within the framework of the European Union project: Saving and Empowering Young Lives in Europe. A representative sample of 11,356 school-based adolescents (M/F: 4,856/6,500; mean age: 14.9) was included in the analyses. PIU was assessed using the Young's Diagnostic Questionnaire. Psychopathology was measured using the Beck Depression Inventory-II, Zung Self-Rating Anxiety Scale and Strengths and Difficulties Questionnaire. Self-destructive behaviours were evaluated by the Deliberate Self-Harm Inventory and Paykel Suicide Scale. Results showed that suicidal behaviours (suicidal ideation and suicide attempts), depression, anxiety, conduct problems and hyperactivity/inattention were significant and independent predictors of PIU. The correlation between PIU, conduct problems and hyperactivity/inattention was stronger among females, while the link between PIU and symptoms of depression, anxiety and peer relationship problems was stronger among males. The association between PIU, psychopathology and self-destructive behaviours was stronger in countries with a higher prevalence of PIU and suicide rates. These findings ascertain that psychopathology and suicidal behaviours are strongly related to PIU. This association is significantly influenced by gender and country suggesting socio-cultural influences. At the clinical and public health levels, targeting PIU among adolescents in the early stages could potentially lead to improvements of psychological well-being and a reduction of suicidal behaviours.

Separation of fosetyl and phosphonic acid in food matrices with mixed-mode HPLC column coupled with tandem mass spectrometric detection and method application to other highly polar pesticides.

The aluminum salt of fosetyl (tris(ethyl phosphonate)) is an antifungal agrochemical. This paper presents a novel high performance liquid chromatography (HPLC) method for the simultaneous determination of fosetyl and the phosphonic acid, its main metabolite, in food samples. The method is based on an ion-displacement separation performed on the recently released Luna Omega PS C18 mixed-mode HPLC column. Baseline separation of fosetyl and phosphonic acid was feasible. This was achieved by optimizing the mobile phase composition and by introducing ethylenediaminetetraacetate for all matrices in the generally used extraction medium for polar pesticides and the injection solution. The binary mobile phase consisted of 10% (v/v) methanol in water and aqueous formate buffer (pH = 3.5) in gradient elution mode. The main advantages of the method over previous method include the stable retention time and peak resolution without the need for long column priming, conditioning or regeneration. Moreover, the approach was tested with other polar pesticides including glyphosate, glufosinate, and perchlorate and showed fit-for-purpose separation. The method was validated for spinach, cherry, and wheat flour samples, and was successfully applied on oat flour and arugula quality control samples. The results obtained for the five analytes met the requirements set by EU. The limit of quantifications was much lower than the maximum residue limits and ranged from 0.02 to 0.20 mg/kg.

Automation in quantifying phenoxy herbicides and bentazon in surface water and groundwater using novel solid phase extraction and liquid chromatography tandem mass spectrometry.

The occurrence of phenoxy herbicides is a financial and regulatory concern for drinking water treatment plants. This paper presents a new method of quantification for nine phenoxy-acids and bentazon in different water samples using liquid chromatography tandem mass spectrometry (LC-MS/MS). The method is based on an automated solid phase extraction (SPE) process that applied hydrophilic modified polystyrene and divinylbenzene cartridges at low pH (<2.0). Main advantages of the presented method include the reduced consumption of organic solvent in extraction and the fully automated sample pre-concentration. The method is thus more environmentally-friendly. In the quantification step, five stable isotopically labelled analogues were used as internal standards to account for the losses during sample preparation and to calibrate the ion source response under the mass spectrometric detection. The method was optimized in terms of sample preparation and subsequent LC-MS/MS separation to obtain reliable measurement of the analyte concentration during real sample analysis. The method quantification limit was between 1.5 and 10.0 ng/L for target compounds in surface water and groundwater samples. The method was validated at three fortification levels between 10.0 and 1000 ng/L, and the results showed fit-for-purpose recovery with appropriate precision at low concentration levels. The method was also utilized to analyse thirty-two actual water samples from different sources. Forty percent of the analysed samples contained detectable level of herbicides, ranging from 1.91 to 40.5 ng/L. The concentrations of targeted herbicides in our study were comparable to those found in water samples in other regions of world.

[Dysmotility-type dyspepsia and eructation. Introduction of a new gas-analytical method]. / Dysmotilitas típusú dyspepsia és bélgázok. Új gázanalitikai módszer bemutatása.

This paper describes a new gas-analytical method used in a 55-year-old female patient with dyspepsia. Symptoms included epigastric fullness and inflation. Evaluation indicated an increased gas production in the proximal end of the small intestine that entered into the stomach via duodenogastric reflux. High CO2 content of eructed gas was confirmed in eructed gas samples using a tube in situ. Authors propose that this new analytical method of eructed gas may be applied in clinical practice in patients with dyspepsia.

Nickel/magnesium-lanthanum mixed oxide catalyst in the Kumada-coupling.

A new, heterogeneous, magnesium-lanthanum mixed oxide solid base-supported nickel(ii) catalyst was developed. The catalyst was used successfully in the Kumada coupling of aryl halides, especially aryl bromides. The optimal reaction conditions of the coupling were determined.

Simultaneous determination of thirteen different steroid hormones using micro UHPLC-MS/MS with on-line SPE system.

Ultratrace analysis of sample components requires excellent analytical performance in terms of limits of quantitation (LOQ). Micro UHPLC coupled to sensitive tandem mass spectrometry provides state of the art solution for such analytical problems. Using on-line SPE with column switching on a micro UHPLC-MS/MS system allowed to decrease LOQ without any complex sample preparation protocol. The presented method is capable of reaching satisfactory low LOQ values for analysis of thirteen different steroid molecules from human plasma without the most commonly used off-line SPE or compound derivatization. Steroids were determined by using two simple sample preparation methods, based on lower and higher plasma steroid concentrations. In the first method, higher analyte concentrations were directly determined after protein precipitation with methanol. The organic phase obtained from the precipitation was diluted with water and directly injected into the LC-MS system. In the second method, low steroid levels were determined by concentrating the organic phase after steroid extraction. In this case, analytes were extracted with ethyl acetate and reconstituted in 90/10 water/acetonitrile following evaporation to dryness. This step provided much lower LOQs, outperforming previously published values. The method has been validated and subsequently applied to clinical laboratory measurement.

Direct Self-Injurious Behavior (D-SIB) and Life Events among Vocational School and High School Students.

Although several studies have recently assessed direct self-injurious behavior (D-SIB) among adolescents, it is still understudied in adolescents attending vocational schools: an educational setting generally associated with lower socioeconomic status. After extending the "Saving and Empowering Young Lives in Europe" (SEYLE) project to a vocational school population, we examined their D-SIB and life event characteristics compared to the high school population. SEYLE's Hungarian randomly selected high school sample (N = 995) was completed with a randomly selected vocational school sample (N = 140) in Budapest, Hungary. Participants aged 14⁻17 years completed the SEYLE project's self-administered questionnaires. D-SIB lifetime prevalence was significantly higher (29.4%) in the vocational school group compared to the high school group (17.2%) (Χ²(1) = 12.231, p< 0.001). D-SIB was associated with suicidal ideation in the vocational school group. Different life events were more frequent in the high school than in the vocational school group, and associations between D-SIB and life events differed in the vocational school group compared to the high school group. In conclusion, vocational school students are a vulnerable population with a higher prevalence of D-SIB compared to high school students. Life events and their association with D-SIB also differ in vocational school students compared to high school students. Taking all these into account might contribute to prevention/intervention designed for this population.

[Psychology and psychosomatics of the orthodontic treatment]. / Pszichológia és pszichoszomatika a fogszabályozásban irodalmi áttekintés.

Psychosomatic problems related to orthodontic treatment are a special group of oral psychosomatic disorders. The most frequent complaints are related to aesthetics and occlusion. Most of the patients are children, adolescence or young adults, with special emotional problems. Authors reviewed the most important knowledge related to this specific field, but some general aspects of oral psychosomatics are also discussed.

[Time parameters of dental hypnosis]. / A fogászati hipnózis idóparaméterei.

Dental treatments of high dental anxiety patients (n = 20) under hypnotic conditions were investigated. Time need of main hypnotic events like rapport; induction: deepening; calming: developing imagination; dehypnosis; discussion was measured. Total time was significantly higher (p < or = 0.05) than pure dental treatment time, but the time the patients percepted was significantly less then total (p < or = 0.05), even somewhat less then pure dental treatment time. Time distortion correlated significantly (negative Pearson's correlation; p < or = 0.05) with the time need of rapport (-0.50), calming (-0.51) and dehipnosis (-0.46), and with the time need of developing delightful imagination (+0.57) (positive Pearson's correlation; p < or = 0.05). There was no significant correlation between time distortion and the time need of hypnotic induction, deepening, total time need of hypnosis, or pure dental treatment time.

[Modification of the photo-acoustic stimulation in the psychotherapy of oral psychosomatic patients. Preliminary experiences]. / Módosítások a fény-hang stimuláció pszichoterápiás alkalmazásában. Elsó tapasztalatok oro-faciális kórképek terápiájában.

The possible use of a modified photo-acoustic stimulation technique was investigated in the explorative part of the psychotherapy of atypical oro-facial pain patients (n = 20; 13 females, 7 males; age between 39-59; psychiatric diagnostic categories in ICD-10: F41.2, F45.1) Since the stimulatory effects of this method cause difficulties to induce free imaginations, previously the main indication of this technique was the ego-strengthening of the patients, to help them to recognise and to verbalise emotions. In the modified technique, specific suggestions coming from detected changes of the patients' emotions, their symptoms, or their social activities are used. Our early results suggest that the modified technique advantageously speeded up the therapeutic process, but did not change the final therapeutic outcome.

[Effectiveness of standardized direct suggestions in dental hypnosis]. / Standard direkt szuggesztiók hatékonyságának vizsgálata fogászati hipnózisban.

The frequency of occurrence of amnesia, analgesia and time distortion during hypnotic dental treatments (n = 60) was investigated on high dental anxiety patients. Hypnosis with and without standardised direct suggestions related to amnesia, analgesia and time distortion were compared. Treatment of alert patients without direct suggestions (n = 10) were also used for comparison. Amnesia and time distortion was higher (p < or = 0.05) with the use of suggestions under hypnotic conditions, but analgesia was not significantly different. Alert appearance of the events were in all cases less (p < or = 0.01) than under hypnotic conditions.

[Effects of photo-acoustic stimulation combined with hypnotherapy on saliva secretion. A pilot study]. / A fény-hang stimulációval kombinált hipnoterápia hatásai a nyálszekrécióra. Elózetes klinikai vizsgálatok.

Effect of photo-acoustic stimulation on the flow rate and protein concentration of whole saliva was investigated. 10 medical students' and 11 edentulous patients' salivary volume and protein concentrations were measured before, during, and after stimulation. The flow rate of the students' group was significantly higher (p < or = 0.01) before and after the treatment, whereas the protein concentration was significantly lower (p < or = 0.05) before, during and after treatment comparing to the patients' group. The flow rate of the students' groups significantly decreased during stimulation (p < or = 0.05). Salivary protein concentration of the students' group significantly increased (p < or = 0.05) after stimulation. There were no significant changes in the group of patients. Repeated stimulation combined with hypnotic relaxation was used in the case of 4 psychosomatic patients. Resting salivary flow and protein concentration significantly increased in 2 cases (p < or = 0.05) as a result of the therapy.

Hsp70 is present in human saliva.

BACKGROUND: There is increasing evidence that chaperones are also present outside the cell, exerting cytokine-like effects and influencing immune recognition. Hsp70 has been found to be present in human blood sera. Chaperonins Cpn10 and Cpn60 are present in pancreatic juice, but Hsp70 is not. These observations raise the possibility that molecular chaperones may be present in other secretory fluids, such as human saliva. MATERIAL/METHODS: Human whole saliva was collected from six participants under resting conditions and secretory stimulation. The samples were precleared by centrifugation and sterile filtered. Salivary volume, protein concentration and amylase activity were determined. For detection of Hsp70 saliva proteins were separated on a 12.5% SDS-PAGE. Semi-dry Western blot analysis was used with a primary antibody against the inducible form of Hsp70. Hsp70 bands were detected with a horseradish peroxidase-linked secondary antibody and ECL-Western blotting analysis. RESULTS: A single band was recognized around 70 kDa in the saliva of all the participants. There was a significant decrease of Hsp70, and a non-significant decrease of total protein concentration during stimulation, whereas the activity of salivary amylase increased significantly. Stimulation significantly increased the Hsp70, total protein and amylase outputs as well as the amylase/protein ratio, and decreased the Hsp70/amylase and Hsp70/protein ratios. CONCLUSIONS: Hsp70 is secreted to saliva, but unlike amylase is not transported by the exocytotic secretory mechanisms of acinar cells. Passive transport mechanisms of Hsp70 from blood serum or from salivary gland cells may be major routes of salivary Hsp70 secretion.