Beyond helium: hydrogen as a carrier gas in multiresidue pesticide analysis in fruits and vegetables by GC-MS/MS.

In this comprehensive study, we evaluated the feasibility of using hydrogen instead of helium as a carrier gas in a GC-MS/MS system for pesticide residue analysis, spanning three matrices: pepper, tomato, and zucchini. Initial assessments focused on the ion source's chemical inertness, employing nitrobenzene as a benchmark to monitor the hydrogenation process. A method with a duration of less than 12 minutes was developed, achieving good chromatographic peak resolution attributable to the enhanced chromatographic performance of hydrogen as a carrier gas. The study emphasized the optimization of system parameters, testing various ion source temperatures, detector voltages, and injection volumes. Sensitivity assessments, based on the DG-SANTE criteria, indicated that the majority of compounds were identifiable at a concentration of 5 µg kg-1 (81% in tomato, 84% in pepper and 73% in zucchini). Detailed validation for reproducibility, matrix effects, and linearity across 150 pesticides unveiled generally favorable outcomes, with a notable majority of compounds displaying low matrix effects, satisfactory linearity ranges and good reproducibility with most compounds returning a relative standard deviation (RSD) below 10%. When applied to 15 real samples, the hydrogen-based system's performance was juxtaposed against a helium-based counterpart, revealing that results are very comparable between both systems. This comparative approach highlights hydrogen's potential as a reliable and efficient carrier gas in pesticide residue analysis for routine food control laboratories, overcoming difficulties resulting from the lack of helium supplies.

Human Leukocyte Antigen Signatures as Pathophysiological Discriminants of Microscopic Colitis Subtypes.

BACKGROUND AND AIMS: Microscopic colitis [MC] is currently regarded as an inflammatory bowel disease that manifests as two subtypes: collagenous colitis [CC] and lymphocytic colitis [LC]. Whether these represent a clinical continuum or distinct entities is, however, an open question. Genetic investigations may contribute important insight into their respective pathophysiologies. METHODS: We conducted a genome-wide association study [GWAS] meta-analysis in 1498 CC, 373 LC patients, and 13 487 controls from Europe and the USA, combined with publicly available MC GWAS data from UK Biobank and FinnGen [2599 MC cases and 552 343 controls in total]. Human leukocyte antigen [HLA] alleles and polymorphic residues were imputed and tested for association, including conditional analyses for the identification of key causative variants and residues. Genetic correlations with other traits and diagnoses were also studied. RESULTS: We detected strong HLA association with CC, and conditional analyses highlighted the DRB1*03:01 allele and its residues Y26, N77, and R74 as key to this association (best p = 1.4 × 10-23, odds ratio [OR] = 1.96). Nominally significant genetic correlations were detected between CC and pneumonia [rg = 0.77; p = 0.048] and oesophageal diseases [rg = 0.45, p = 0.023]. An additional locus was identified in MC GWAS analyses near the CLEC16A and RMI2 genes on chromosome 16 [rs35099084, p = 2.0 × 10-8, OR = 1.31]. No significant association was detected for LC. CONCLUSION: Our results suggest CC and LC have distinct pathophysiological underpinnings, characterised by an HLA predisposing role only in CC. This challenges existing classifications, eventually calling for a re-evaluation of the utility of MC umbrella definitions.

Mediating effect of job crafting dimensions on influence of burnout at self-efficacy and performance: revisiting health-impairment process of JD-R theory in public administration.

Introduction: In recent years, job crafting has greatly interested Work and Organizational Psychology. Different research studies have shown its positive impact on people and organizational performance. However, it knows little about the differential effect of the two dimensions that make up this variable (prevention-focused and promotion-focused) and its role in the health-impairment spiral process of the job demand-resources theory (JD-R). Method: This research aims to analyze the mediating effect of the different dimensions of job crafting on the influence of burnout on performance and self-efficacy in the workplace. The study used a sample of 339 administrative employees of a university. Results: The results indicate that promotion-focused job crafting is a mediating variable in the relationship between the influence of burnout on performance and self-efficacy. Unexpectedly, prevention-focused job crafting does not have this mediating role in the same relationship. Discussion: These findings confirm the adverse impact of burnout on personal and organizational improvement, while showing the absence of prevention/protection responses of employees when they are burned out. The theoretical and practical implications show an advance in knowledge about the process of health deterioration and about the spiral of health deterioration in the JD-R theory.

Evaluation of automated clean-up for large scope pesticide multiresidue analysis by liquid chromatography coupled to mass spectrometry.

Clean-up step is essential during the multiresidue sample preparation process to remove undesired matrix components that may cause analytical interferences or suppression effect. However, its application generally by specific sorbents entails time-consuming work producing low recoveries for some compounds. Moreover, it usually needs to be adapted to the different co-extractives from the matrix present in the samples by using different chemical sorbents increasing the number of validation procedures. Therefore, the development of a more efficient and automated and unified clean-up procedure means a significant time reduction and laboratory work with improved performance. In this study, extracts from different matrices (tomato, orange, rice, avocado and black tea) were purified by manual dispersive clean-up (different procedures according to the matrix group) in parallel with an automated µSPE clean-up workflow, in both cases based on QuEChERS extraction. The latter procedure employed clean-up cartridges containing a mixture of sorbent materials (anhydrous MgSO4/PSA/C18/CarbonX) suitable for multiple matrices. All the samples were analysed by liquid chromatography mass spectrometry and the results obtained from both procedures have been compared in terms of the extract cleanness, performance, interferences, and sample workflow. At the levels studied, similar recoveries were achieved by both techniques (manual and automated) except for reactive compounds when PSA was used as the sorbent material producing low recoveries. However, the µSPE recoveries were between 70-120%. Furthermore, closer calibration line slopes were provided when µSPE was applied to the different matrix groups studied. It is important to note that up to 30% more samples per day can be analysed using an automated µSPE compared to the manual method (which requires shaking, centrifuging, then taking the supernatant and adding formic acid in ACN); it also provides good repeatability - an RSD (%) < 10%. Consequently, this technique is a very useful option for routine analyses, greatly simplifying the work of muti-residue methods.

COVID-19 nosocomial. Estudio prospectivo en un hospital de referencia / Nosocomial COVID-19. Prospective study in a referral hospital

Antecedentes y ObjetivoEl objetivo fue describir las características clínicas y el pronóstico de los pacientes con infección nosocomial por SARS-CoV-2.MétodosSe realizó un estudio observacional y prospectivo en un hospital de referencia. Se incluyeron todos los pacientes adultos diagnosticados de infección por SARS-CoV-2 nosocomial en octubre de 2020, definida como una PCR para SARS-CoV-2 negativa al ingreso y positiva a partir de los siete días de hospitalización.ResultadosSe diagnosticaron 66 casos de infección por SARS-CoV-2 nosocomial: 39 (59%) hombres, edad mediana al diagnóstico de 74,5 años (RIC 56,8-83,1) y mediana del índice de comorbilidad de Charlson de 3 puntos (RIC 1-5). Veintisiete (41%) presentaron neumonía y 13 (20%) fallecieron durante el ingreso. La mortalidad a los 28 días fue del 33% (22 pacientes). La mortalidad a los 28 días en los 242 pacientes con infección por SARS-CoV-2 adquirida en la comunidad y hospitalizados durante el mismo periodo fue del 10%.ConclusionesSe deben extremar las medidas de prevención y detección precoz de brotes nosocomiales de COVID-19 para minimizar el impacto negativo de esta infección. (AU)

Background and objectiveThe objective was to describe the clinical characteristics and prognosis of patients with nosocomial SARS-CoV-2 infection.MethodsAn observational and prospective study was performed in a referral hospital. We included all adult patients diagnosed with nosocomial SARS-CoV-2 infection in October 2020. Nosocomial infection was defined as a negative PCR for SARS-CoV-2 on admission and a positive PCR after 7 days of hospitalization.ResultsWe included 66 cases of nosocomial SARS-CoV-2 infection: 39 (59%) men, median age at diagnosis was 74.5 years (IQR 56.8–83.1) and median Charlson comorbidity index was 3 points (IQR 1–5). Twenty-seven (41%) developed pneumonia and 13 (20%) died during admission. Mortality at 28 days was 33% (22 patients). Mortality at 28 days in the 242 patients with community-acquired SARS-CoV-2 infection who were hospitalized during the same period was 10%.ConclusionsPreventive measures and early detection of nosocomial outbreaks of COVID-19 should be prioritized to minimize the negative impact of this infection. (AU)

Nosocomial COVID-19. Prospective study in a referral hospital.

Background and objective: The objective was to describe the clinical characteristics and prognosis of patients with nosocomial SARS-CoV-2 infection. Methods: An observational and prospective study was performed in a referral hospital. We included all adult patients diagnosed with nosocomial SARS-CoV-2 infection in October 2020. Nosocomial infection was defined as a negative PCR for SARS-CoV-2 on admission and a positive PCR after 7 days of hospitalization. Results: We included 66 cases of nosocomial SARS-CoV-2 infection: 39 (59%) men, median age at diagnosis was 74.5 years (IQR 56.8-83.1) and median Charlson comorbidity index was 3 points (IQR 1-5). Twenty-seven (41%) developed pneumonia and 13 (20%) died during admission. Mortality at 28 days was 33% (22 patients). Mortality at 28 days in the 242 patients with community-acquired SARS-CoV-2 infection who were hospitalized during the same period was 10%. Conclusions: Preventive measures and early detection of nosocomial outbreaks of COVID-19 should be prioritized to minimize the negative impact of this infection.

Antecedentes y Objetivo: El objetivo fue describir las características clínicas y el pronóstico de los pacientes con infección nosocomial por SARS-CoV-2. Métodos: Se realizó un estudio observacional y prospectivo en un hospital de referencia. Se incluyeron todos los pacientes adultos diagnosticados de infección por SARS-CoV-2 nosocomial en octubre de 2020, definida como una PCR para SARS-CoV-2 negativa al ingreso y positiva a partir de los siete días de hospitalización. Resultados: Se diagnosticaron 66 casos de infección por SARS-CoV-2 nosocomial: 39 (59%) hombres, edad mediana al diagnóstico de 74,5 años (RIC 56,8-83,1) y mediana del índice de comorbilidad de Charlson de 3 puntos (RIC 1−5). Veintisiete (41%) presentaron neumonía y 13 (20%) fallecieron durante el ingreso. La mortalidad a los 28 días fue del 33% (22 pacientes). La mortalidad a los 28 días en los 242 pacientes con infección por SARS-CoV-2 adquirida en la comunidad y hospitalizados durante el mismo periodo fue del 10%. Conclusiones: Se deben extremar las medidas de prevención y detección precoz de brotes nosocomiales de COVID-19 para minimizar el impacto negativo de esta infección.

Nosocomial COVID-19. Prospective study in a referral hospital. / COVID-19 nosocomial. Estudio prospectivo en un hospital de referencia.

BACKGROUND AND OBJECTIVE: The objective was to describe the clinical characteristics and prognosis of patients with nosocomial SARS-CoV-2 infection. METHODS: An observational and prospective study was performed in a referral hospital. We included all adult patients diagnosed with nosocomial SARS-CoV-2 infection in October 2020. Nosocomial infection was defined as a negative PCR for SARS-CoV-2 on admission and a positive PCR after 7 days of hospitalization. RESULTS: We included 66 cases of nosocomial SARS-CoV-2 infection: 39 (59%) men, median age at diagnosis was 74.5 years (IQR 56.8-83.1) and median Charlson comorbidity index was 3 points (IQR 1-5). Twenty-seven (41%) developed pneumonia and 13 (20%) died during admission. Mortality at 28 days was 33% (22 patients). Mortality at 28 days in the 242 patients with community-acquired SARS-CoV-2 infection who were hospitalized during the same period was 10%. CONCLUSIONS: Preventive measures and early detection of nosocomial outbreaks of COVID-19 should be prioritized to minimize the negative impact of this infection.

Cutting-edge approach using dual-channel chromatography to overcome the sensitivity issues associated with polarity switching in pesticide residues analysis.

A fast and sensitive method was validated for the analysis of pesticide residues in baby food. After an QuEChERS-based extraction, the samples were analysed with a dual-channel liquid chromatography instrument coupled to a triple quadrupole mass spectrometer. The method consisted of two independent injections per sample. In the first injection the sample was analysed with a mobile phase optimal for the positive polarity ionisation (water, methanol, formic acid, and ammonium formate), whereas in the second injection the mobile phase was optimised for the negative polarity ionisation (water, acetonitrile, acetic acid). The total number of pesticides was 264, out of which 238 were analysed with the methanol gradient and 26 with the acetonitrile gradient. The dual-channel instrument allowed for sample multiplexing. Thus, sample throughput was equivalent to that of a single-channel system. The limit of quantitation, determined according to the DG SANTE guidance document, was 0.003 mg/kg for 97% of the evaluated compounds. The validation study was followed by a real sample survey. In 42 samples, 16 positives were found.

Liquid chromatography versus supercritical fluid chromatography coupled to mass spectrometry: a comparative study of performance for multiresidue analysis of pesticides.

Abundant studies have been published evaluating different parameters of reverse-phase liquid chromatography (LC) and supercritical fluid chromatography (SFC), both coupled to electrospray (ESI)/mass spectrometry (MS) for pesticide residue analysis. However, there is a lack of a comprehensive comparative study that facilitates deep knowledge about the benefits of using each technique. In the present study, the same mass spectrometer was used coupled to both liquid and supercritical fluid chromatographies with a multiresidue method of 215 compounds, for the analysis of pesticide residues in food samples. Through the injection of the spiked extracts, separate experiments were conducted. A study of the optimum ion source temperature using the different chromatography modes was performed. The results were evaluated in terms of sensitivity with tomato, leek, onion, and orange as representative fruit and vegetable matrices. The compounds which reported the highest area values in each chromatography were evaluated through their substance groups and polarity values. The impact of matrix effects obtained in tomato matrix was similar for both cases; however, SFC clearly showed better results in analyzing matrices with a higher number of natural co-extracted compounds. This can be explained by the combination of two effects: (i) chromatography separation and (ii) ion source efficiency. The chromatographic elution presented different profiles of matrix components, which had diverse impact on the coelution with the analytes, being more beneficial when SFC was used in the matrices studied. The data showed that the best results obtained in SFC are also related to a higher ionization efficiency even when the ESI emitter tip was not optimized for SFC flow. In the present study a comprehensive evaluation of the benefits and drawbacks of these chromatography modes for routine pesticide residue analysis related to target compounds/commodities is provided.

Receptor-like cytoplasmic kinase MAZZA mediates developmental processes with CLAVATA1 family receptors in Arabidopsis.

The receptor-like kinases (RLKs) CLAVATA1 (CLV1) and BARELY ANY MERISTEMs (BAM1-BAM3) form the CLV1 family (CLV1f), which perceives peptides of the CLV3/EMBRYO SURROUNDING REGION (ESR)-related (CLE) family within various signaling pathways of Arabidopsis thaliana. CLE peptide signaling, which is required for meristem size control, vascular development, and pathogen responses, involves the formation of receptor complexes at the plasma membrane. These complexes comprise RLKs and co-receptors in varying compositions depending on the signaling context, and regulate expression of target genes, such as WUSCHEL (WUS). How the CLE signal is transmitted intracellularly after perception at the plasma membrane is not known in detail. Here, we found that the membrane-associated receptor-like cytoplasmic kinase (RLCK) MAZZA (MAZ) and additional members of the Pti1-like protein family interact in vivo with CLV1f receptors. MAZ, which is widely expressed throughout the plant, localizes to the plasma membrane via post-translational palmitoylation, potentially enabling stimulus-triggered protein re-localization. We identified a role for a CLV1-MAZ signaling module during stomatal and root development, and redundancy could potentially mask other phenotypes of maz mutants. We propose that MAZ, and related RLCKs, mediate CLV1f signaling in a variety of developmental contexts, paving the way towards understanding the intracellular processes after CLE peptide perception.

Are Job Demands Necessary in the Influence of a Transformational Leader? The Moderating Effect of Role Conflict.

(1) Background: The objective of this manuscript is to propose the necessity of job demands to ensure the positive influence of policies in stimulating employees' engagement and performance. If the policies related to the intellectual stimulation of employees implemented by team leaders are to have positive effects on employee performance, they must induce emotional engagement in the employees. Furthermore, to achieve this positive influence on emotions, the organization must offer an environment that challenges the employees in the organization. Here, we analyze a moderate mediation model to examine the moderating, positive effect of role conflict on the intellectual engagement and performance of employees. (2) Methods: This study involved 705 employees of a multinational private company based in Spain. (3) Results: We confirm the positive moderating effect of role conflict between the intellectual stimulation of employees and intellectual engagement, and the mediating effect of intellectual engagement between leadership behavior and employee performance. (4) Conclusions: Organizational leader stimulation practices necessitate an environment of moderate job demands in order to improve the intellectual engagement of employees, thereby increasing their performance. The implications of the findings in terms of theory, research and practice are discussed.

Improving the simultaneous target and non-target analysis LC-amenable pesticide residues using high speed Orbitrap mass spectrometry with combined multiple acquisition modes.

The use of high-resolution mass spectrometry (HRMS) for the simultaneous target and non-target analysis of pesticide residues in food control is a subject that has been studied over the last decade. However, proving its efficacy compared to the more established triple quadrupole mass spectrometers (QQQ-MS2) is challenging. Various HRMS platforms have been evaluated, seemingly showing this approach not to be as effective as QQQ-MS2 for quantitative analysis, especially in routine food testing laboratories. The two main reasons are (i) the lower sensitivity especially in the case of the fragment ions produced and (ii) the lack of familiarity and an understanding of the most appropriate combination of HRMS acquisition modes to use. In fact, the number of different acquisition modes can appear as a puzzle to inexperienced users. This work was therefore focused on obtaining experimental data to gain a better understanding of the extended acquisition capabilities of a new Q-Orbitrap platform. Experimental data were obtained for 244 pesticides and their degradation products in commodities of varying matrix complexity (tomato, onion, avocado, and orange) using various combinations of acquisition modes. The best results for targeted analysis were obtained with a combination of full scan (FS), all-ions fragmentation (AIF) and target MS2 (tMS2) modes, and for non-target analysis using full scan (FS) and data-dependent MS2 (ddMS2) modes. All these acquisition modes (FS, AIF, tMS2, and ddMS2) could be applied simultaneously with cycle times ≤ 1 s. The tMS2 especially, proved to be a very powerful approach to increase sensitivity for MS2 fragments and identification rates. Overall, the results for the various pesticide-commodity combinations were fully satisfactory in terms of limit of quantitation (LOQ) repeatability and identification when considered against the SANTE EU Guideline criteria. In addition, the screening capabilities were evaluated for a non-target survey with the use of spectral libraries, the presence of non-target compounds was detected, thus proving the efficacy of the proposed approach. Another issue often overlooked is the optimization of use of spectral libraries, but in our experiments the compounds present in these libraries were not blindly sought in the screening analyses. To minimize the potential for false positives detects in our study, the extractability of the compounds present in the libraries, was also taken into account. The extractability of compounds using a QuEChERS acetonitrile procedure was estimated based on the physicochemical properties of target compounds. By removing compounds that will not be extracted, reduces the occurrences of false detects, reducing the time required for data processing and thus improving the efficiency of the overall screening workflow.

Overcoming difficulties in the evaluation of captan and folpet residues by supercritical fluid chromatography coupled to mass spectrometry.

Serious difficulties in evaluating the fungicides captan and folpet by the usual chromatography systems coupled to mass spectrometry are well known. These compounds are highly prone to degradation due to different conditions into tetrahydrophthalimide (THPI) and phthalimide (PHI). Such an effect can be produced at different stages of the analytical procedure or during the growing crop, making their evaluation troublesome. As a consequence, the quantification of captan and folpet is typically performed through or together these metabolites. However, imide ring metabolites can be produced by other unknown sources, including other phthalimide derived pesticides enabling false positive results. For this reason, in the last decade, laboratories demand a robust method to quantify captan and folpet, that overcomes such a situation. In the present work, various operational parameters were optimized to ensure the no degradation of captan and folpet facilitated by supercritical fluid chromatography coupled to mass spectrometry (SFC-MS/MS). A direct comparison with reverse-phase LC-MS/MS and GC-MS/MS was conducted for comparative purposes. The representative commodities selected for this evaluation were pepper and tomato. Furthermore, possible oxidative degradation during the sample milling step was also evaluated and avoided by the application of crio-milling conditions and ascorbic acid addition. By the proposed procedure, captan and folpet were recovered in both matrices at the 84%-105% range and with an RSD below 8% at two concentration levels: 10 and 50 µg/kg. On the contrary, with GC-MS/MS, captan and folpet were not recovered, and, as a consequence, their evaluation was possible only by THPI and PI. In the case of LC-MS/MS a significant decrease in the sensitivity was observed compared to SFC-MS/MS. Other validation parameters evaluated were satisfactory. This new approach can assess the correct analysis of captan and folpet at low concentrations in fruits and vegetables.

Presence of anthraquinone in coffee and tea samples. An improved methodology based on mass spectrometry and a pilot monitoring programme.

Anthraquinone has been linked to potential adverse effects on human health and the environment. The most commonly employed methods for the analysis of coffee and tea cause the extraction of matrix interferents such as the methylxanthines caffeine and theobromine, which hinder the analysis of anthraquinone. A new manual extraction method - using ethyl acetate as the extraction solvent with a dispersive solid-phase extraction clean-up step based on primary-secondary amines - has been developed. The new developed method allows for the quantitation of anthraquinone at 5 µg kg-1 concentration levels, four times lower than the current maximum residue limit for coffee and tea in the European Union (20 µg kg-1). Alongside, a new automated extraction method has also been developed. Finally, a pilot monitoring programme of 90 coffee and tea samples from several countries within the European Union has been performed, in which anthraquinone has been detected in a concentration range of 5.1-18.8 µg kg-1 in 32% of the monitored samples, below the current 20 µg kg-1 maximum residue limit, and in 48% of the monitored tea samples, revealing the need for including anthraquinone in a more extensive monitoring programme of tea.

Inclusión social de las personas con discapacidad: estudio piloto en el contexto laboral del papel mediador de la autodeterminación entre el conflicto de rol y la inclusión social / Social Inclusion of People with Disability: Pilot Study in the Workplace of the Mediating Role of Self-Determination between Role Conflict and Social Inclusion

En este estudio se pretende conocer la calidad de vida que tienen los trabajadores con discapacidad respecto a la inclusión social, así como si los problemas existentes en el trabajo (conflicto de rol) consideran que son determinantes en dicha inclusión. Además, proponemos un modelo donde se plantea que la autodeterminación tiene un efecto mediador entre el conflicto de rol y la inclusión social. El trabajo se ha realizado con un total de 51 trabajadores con discapacidad pertenecientes a un Centro Especial de Empleo que prestan un servicio de limpieza en la Administración Pública. Los resultados indican que los trabajadores valoran la inclusión social y que el conflicto de rol puede afectar a su inclusión social. Además, los hallazgos respaldan el modelo propuesto, ofreciendo una orientación para conseguir la inclusión social del colectivo con discapacidad. Al final planteamos las implicaciones prácticas del presente trabajo y, también, se debate en torno al relevante papel que desempeña el trabajo en la inclusión social

This study aims to know the perception that workers with disability have regarding social inclusion, as well as whether the problems at work (role conflict) consider them to be determinants in such inclusion. In addition, we propose a mediation model that states that self-determination has effect between role conflict and social inclusion. The work has been carried out with a total of 51 workers with disability from a Special Employment Center that they perform a cleaning job in the Public Administration. The results indicate that workers value social inclusion and that role conflict can affect their social integration. In addition, the findings support the proposed model, offering guidance to achieve social inclusion of the group with disability. In the end we propose the practical implications of this work and, also, we discuss the relevant role that work plays in social inclusion

Supercritical fluid chromatography separation of chiral pesticides: Unique capabilities to study cyhalothrin and metalaxyl as examples.

Evaluation of chiral pesticides remains a frequently neglected matter in routine food control laboratories. This fact is due to the existence of many residue definitions but also due to the lack of robust instrumental methods for the evaluation of these isomeric compounds. However, supercritical fluid chromatography coupled to mass spectrometry (SFC-ESI-MS/MS) has been demonstrated to perform fast and highly efficient separations without the need to change the mobile phase employed in multiresidue pesticide analyses. Regarding chiral stationary phase columns, the polysaccharide-based ones clearly demonstrate the best separation technology. Two polysaccharide-based columns were tested in this study, and the robustness of their combination with SFC was verified. The enantiomers of lambda-cyhalothrin and metalaxyl were studied precisely due to their markedly distinct toxicity and enantioselectivity. Furthermore, the acute reference dose for gamma-cyhalothrin is half in comparison with its enantiomer (0.0025 and 0.005 mg/kg respectively), which is present in the lambda-cyhalothin residue definition. These enantiomers were analyzed in terms of linearity, reproducibility, and matrix effects in four representative matrices (tomato, orange, leek, and cayenne). Additionally, field tests under greenhouse conditions for these compounds were performed. The results obtained after different sample collections revealed a similar degradation in lambda-cyhalothrin enantiomers (R, S, S, and S, R, R) but not in the case of metalaxyl-M (mefenoxam) where the degradation in tomato was 2 to 6 times less in comparison with its S-enantiomer.

Pesticide residues evaluation of organic crops. A critical appraisal.

In the last decade, the consumption trend of organic food has increased dramatically worldwide. Since only a few pesticides are authorized in organic crops, concentrations are expected to range at zero or ultra-trace levels. In this context, the aim of the present study was to investigate the need for an improvement in the residue controls at very low concentrations (<0.010 mg kg-1) and to assess the impact of the scope of the analytical methods for this type of crops. For that purpose, a monitoring study for fruit and vegetable samples covering a wide range of pesticides (3 2 8) at low LOQs (0.002-0.005 mg kg-1) was developed. The results showed that the impact of applying analytical methods with low LOQs was not very relevant in the majority of the cases. However, a wide scope presented a high influence on this evaluation, especially regarding the inclusion of very polar compounds and metabolites.

Empleo de diente autógeno como material de regeneración ósea: revisión de la literatura a propósito de un caso clínico / Use Of Autogenous Teeth As Bone Regeneration Material: Case Report And Review

Introducción: El empleo de dientes autógenos, como material de injerto, es una opción terapéutica actual en casos de regeneración ósea. Su obtención se ha facilitado con la introducción de dispositivos capaces de procesar los dientes. El objetivo de este trabajo es realizar, a propósito de un caso clínico, una revisión de la literatura sobre el uso de dientes autólogos como material de injerto óseo y los dispositivos para su procesamiento. Caso clínico: Paciente varón de 18 años que acude a consulta presentando un cordal inferior retenido. El diagnóstico determinó la necesidad de extraer el diente y se informó al paciente de la posibilidad de utilizarlo como material de regeneración ósea. Tras la exodoncia, el diente procesado con el dispositivo Tooth Transformer(R) (Imbiodent), fue utilizado como material de injerto autólogo. El postoperatorio no presentó ninguna complicación y la evaluación radiográfica, tras 8 días y tras 10 semanas, mostró una evolución favorable del tratamiento. Discusión: La dentina desmineralizada es un material orgánico cuyo potencial reside en los factores de crecimiento que contiene para estimular la formación y reparación ósea. No obstante, no existe consenso sobre el grado de desmineralización o tamaño de partícula ideal. La reciente introducción de dispositivos, capaces de procesar dientes, facilita la obtención de un material de injerto dental para su uso en terapias de regeneración ósea. Conclusión: El uso de dientes autólogos constituye una alternativa prometedora en el campo de los injertos óseos. La técnica de transformación del diente es sencilla con el empleo de los dispositivos actuales

Introduction: The use of autogenous teeth, as graft material, is a current therapeutic option in cases of bone regeneration. Its obtention has been facilitated by the introduction of devices capable of processing teeth. The aim of this article is to perform, based on a clinical case, a review of the literature about the use of autologous teeth as bone graft material and the devices for its processing. Clinical case: Male patient, 18 years of age, who comes to the dental office presenting a lower wisdom retained. Extraction of the tooth was determined by diagnosis and the patient was informed about the possibility of using it as bone regeneration material. After the extraction, the tooth was processed by the Tooth Transformer(R) (Imbiodent) device and was used as autologous graft material. No postoperative complications were presented and the radiographic evaluation, at 8 days and 10 weeks, showed a favorable evolution of the treatment. Discusion: Demineralized dentin is a organic material whose potential relies in the growth factors it contains to stimulate bone formation and repair. However, there is no consensus on the degree of demineralization or the ideal particle size. The recent introduction of devices, capable of processing teeth, enables the obtention of a dental graft material for bone regeneration therapies. Conclusion: The use of autologous teeth is a promising alternative in the bonev grafts field. The technique of tooth transformation is simple with the use of the current devices

Selectivity enhancement using sequential mass isolation window acquisition with hybrid quadrupole time-of-flight mass spectrometry for pesticide residues.

The introduction of sequential mass isolation window acquisition mode in high-resolution quadrupole time-of-flight analysers undoubtedly represents an important improvement in the MS/MS spectra obtained when working in non-target analysis. However, the advantages and limitations of this approach have not been sufficiently defined and evaluated. The present work seeks to fill this gap by considering its application in non-target multiresidue pesticide analysis. This work focuses on the called SWATH® method, which combines both MS and MS/MS acquisition, dividing the entire mass range into smaller segments for the MS/MS mode. The effect of the number of mass isolation windows, the total cycle-time lapsed, the sensitivity obtained, the MS/MS spectra quality, the ion ratio stability as well as the identification and quantification capabilities has been evaluated. The use of ten mass isolation windows for data acquisition was selected as a compromise between the required points per chromatographic peak and the reduction in interferences achieved. An identification study was carried out on 141 pesticides in 20 vegetable matrices to check the false positives and false identifications found automatically, in accordance with the criteria set out in Document No. SANTE/11945/2015. Furthermore, special attention was given to certain issues that can make correct identification difficult, such as low fragment abundance due using of a generic collision energy, the matrix influence on the collision cell, the effect of the concentration level as well as deconvolution failure and mass window width. Finally, to verify the efficiency of the optimum parameters proposed, two proficiency samples were analysed, obtaining good results. This proved the benefits in terms of identification and quantification purposes.

Analysis of thermally labile pesticides by on-column injection gas chromatography in fruit and vegetables.

Thermally labile pesticides (captafol, captan, dicofol, and folpet) are highly prone to suffer thermal degradation during sample introduction into a gas chromatograph (GC) to tetrahydrophthalimide (THPI), 4,4'-dichlorobenzophenone (DCBP), and phthalimide (PI), respectively, mainly produced in the glass liner of the injector. This undesired behavior leads to inaccurate qualitative and quantitative results. Direct on-column injection (OCI) technique is evaluated as an alternative to avoid or minimize compound alteration during the analysis. This configuration was studied and evaluated for the determination of this group of thermally troublesome pesticides. The OCI inlet was operated in "track oven" temperature and connected to a wide-bore deactivated guard column that is itself connected to a capillary GC analytical column. This technique has demonstrated to be useful for avoiding degradation generated in the hot inlet. Limitations observed for OCI in routine analysis were injection volume, guard column length, and maintenance issues. Analytical standards spiked in vegetable solutions were injected in OCI, not observing any thermal degradation rate. On the contrary, classical splitless injection (SLI) produced high degradation rates in all cases. This OCI approach was validated in citrate QuEChERS extracts of tomato, apple, and orange matrices for these four compounds and their corresponding transformation products (THPI, DCBP, and PI), evaluating recoveries, repeatability, linearity, and matrix effect. This set-up enabled the correct identification and quantitation for most compounds at LOQs of 0.010 mg/kg in fruit and vegetable samples. The OCI grants evident differentiation between metabolites naturally occurring in food and thermal degradation products created during the analysis. Graphical abstract ᅟ.