Use of Mass Spectrometry for the Determination of Formaldehyde in Samples Potentially Toxic to Humans: A Brief Review

The chemical characteristics of formaldehyde make it widely used and important in the global economy. It has applications in the health area and in various industrial sectors. However, formaldehyde is considered toxic substance and is classifed as a persistent organic pollutant. Direct and prolonged contact with formaldehyde can cause serious damage to the body and may even lead to death. It is classifed by several agencies as a human carcinogen and may exhibit mutagenic/teratogenic efects and/or damage the endocrine system. Various matrices have been found to contain formaldehyde at concentrations higher than those permited by global health regulatory agencies. To this end, mass spectrometry can provide a very useful tool, enabling the identifcation and quantifcation of formaldehyde. Although various analytical techniques can be used for the determination and quantifcation of volatile organic compounds, chromatography is one of the most widely used methods due to its precision. Coupled to a detection system such as mass spectrometry, it can be employed for the determination of compounds potentially toxic to humans, including formaldehyde. The purpose of this chapter is to summarize some recent and important studies concerning the quantifcation of formaldehyde using mass spectrometry as a powerful analytical tool

Arbustus unedo essence: morphological and genetic characterization of the strawberry tree of Castelo de Paiva

O medronheiro é um arbusto da região mediterrânica que pode ser encontrada por todo o país. Ao contrário do que verifica na região sul do país, no concelho de Castelo de Paiva é atribuída uma reduzida importância económica a esta espécie. Com o intuito de preservar e potenciar a produção desta espécie e contribuir para a dinamização da economia do concelho, procedeu-se à caracterização morfológica e genética de uma amostra da população de medronheiros de Castelo de Paiva. A caracterização morfológica e genética foi realizada para um total de 10 genótipos. Para tal recolheram-se 70 folhas aleatoriamente em cada árvore. Em 40 folhas mediu-se o comprimento, largura, comprimento do pedúnculo, peso fresco, peso seco e determinou-se a área foliar. Dos caracteres morfológicos analisados, aqueles que se revelaram mais úteis na distinção dos vários genótipos foram: comprimento do pedúnculo, peso fresco e peso seco. As restantes 30 folhas foram utilizadas para a caracterização genética. Esta caracterização foi realizada recorrendo a um marcador de DNA, ISSR. Os 5 primeiros exemplaresutilizados na técnica de ISSR demonstraram-se polimórficos. Os resultados da caracterização genética sugerem que a variabilidade genética na população é média a alta.The strawberry tree is a shrub native in the Mediterranean region and it can be found throughout Portugal. Unlike the case in the southern region of the country, in Castelo de Paiva a minor economic importance is given to this species. In order to preserve, to enhance the production of this species and to contribute to the boosting of the economy of the region, we proceeded to the characterization of a small sample population of this fruit tree of Castelo de Paiva in what concerns to its morphology and genetics. The morphological and genetic characterization was performed for a total of 10 genotypes. For this, 70 leaves were randomly collected from each tree. For 40 leaves, it was measured the length, the width, the peduncle length, the wet weight, the dry weight and determined the leaf area. Of the morphological characteristics analyzed, the ones that proved most useful in distinguishing the various genotypes were: the length peduncle, the wet weight and the dry weight. The remaining 30 leaves were used in the genetic characterization. This characterization was performed using a DNA marker, the ISSR. The 5 primers used in the ISSR technique proved to be polymorphic. The results from the genetic characterization suggest that variability in population genetics is medium to high

Mortality from gastrointestinal congenital anomalies at 264 hospitals in 74 low-income, middle-income, and high-income countries: a multicentre, international, prospective cohort study

Summary Background Congenital anomalies are the fifth leading cause of mortality in children younger than 5 years globally. Many gastrointestinal congenital anomalies are fatal without timely access to neonatal surgical care, but few studies have been done on these conditions in low-income and middle-income countries (LMICs). We compared outcomes of the seven most common gastrointestinal congenital anomalies in low-income, middle-income, and high-income countries globally, and identified factors associated with mortality. Methods We did a multicentre, international prospective cohort study of patients younger than 16 years, presenting to hospital for the first time with oesophageal atresia, congenital diaphragmatic hernia, intestinal atresia, gastroschisis, exomphalos, anorectal malformation, and Hirschsprung’s disease. Recruitment was of consecutive patients for a minimum of 1 month between October, 2018, and April, 2019. We collected data on patient demographics, clinical status, interventions, and outcomes using the REDCap platform. Patients were followed up for 30 days after primary intervention, or 30 days after admission if they did not receive an intervention. The primary outcome was all-cause, in-hospital mortality for all conditions combined and each condition individually, stratified by country income status. We did a complete case analysis. Findings We included 3849 patients with 3975 study conditions (560 with oesophageal atresia, 448 with congenital diaphragmatic hernia, 681 with intestinal atresia, 453 with gastroschisis, 325 with exomphalos, 991 with anorectal malformation, and 517 with Hirschsprung’s disease) from 264 hospitals (89 in high-income countries, 166 in middleincome countries, and nine in low-income countries) in 74 countries. Of the 3849 patients, 2231 (58·0%) were male. Median gestational age at birth was 38 weeks (IQR 36–39) and median bodyweight at presentation was 2·8 kg (2·3–3·3). Mortality among all patients was 37 (39·8%) of 93 in low-income countries, 583 (20·4%) of 2860 in middle-income countries, and 50 (5·6%) of 896 in high-income countries (p<0·0001 between all country income groups). Gastroschisis had the greatest difference in mortality between country income strata (nine [90·0%] of ten in lowincome countries, 97 [31·9%] of 304 in middle-income countries, and two [1·4%] of 139 in high-income countries; p≤0·0001 between all country income groups). Factors significantly associated with higher mortality for all patients combined included country income status (low-income vs high-income countries, risk ratio 2·78 [95% CI 1·88–4·11], p<0·0001; middle-income vs high-income countries, 2·11 [1·59–2·79], p<0·0001), sepsis at presentation (1·20 [1·04–1·40], p=0·016), higher American Society of Anesthesiologists (ASA) score at primary intervention (ASA 4–5 vs ASA 1–2, 1·82 [1·40–2·35], p<0·0001; ASA 3 vs ASA 1–2, 1·58, [1·30–1·92], p<0·0001]), surgical safety checklist not used (1·39 [1·02–1·90], p=0·035), and ventilation or parenteral nutrition unavailable when needed (ventilation 1·96, [1·41–2·71], p=0·0001; parenteral nutrition 1·35, [1·05–1·74], p=0·018). Administration of parenteral nutrition (0·61, [0·47–0·79], p=0·0002) and use of a peripherally inserted central catheter (0·65 [0·50–0·86], p=0·0024) or percutaneous central line (0·69 [0·48–1·00], p=0·049) were associated with lower mortality. Interpretation Unacceptable differences in mortality exist for gastrointestinal congenital anomalies between lowincome, middle-income, and high-income countries. Improving access to quality neonatal surgical care in LMICs will be vital to achieve Sustainable Development Goal 3.2 of ending preventable deaths in neonates and children younger than 5 years by 2030

Desenvolvimento e valida??o de um m?todo para determina??o de formalde?do em esmaltes utilizando QUERCHERS/SPE e GC/MS.

Programa de P?s-Gradua??o em Qu?mica. Departamento de Qu?mica, Instituto de Ci?ncias Exatas e Biol?gicas, Universidade Federal de Ouro Preto.O formalde?do ? utilizado como agente firmador/endurecedor em esmaltes para unha, por?m, segundo as ag?ncias internacionais de controle do c?ncer e de prote??o ambiental, esse composto possui propriedades f?sico-qu?micas que o tornam carcinog?nico. Assim, no Brasil o seu controle ? feito pela ANVISA (Ag?ncia Nacional de Vigil?ncia Sanit?ria) que estabelece que os produtos cosm?ticos comerciais devem apresentar uma concentra??o m?xima de 0,2% m/m deste composto e identificar a presen?a dele com concentra??es superiores a 0,05% m/m. Devido ao seu uso constante por uma grande parte da popula??o, os esmaltes para unha podem se tornar uma fonte de preocupa??o, uma vez que a grande maioria possuem formalde?do em sua composi??o. Assim, este trabalho prop?s a extra??o do formalde?do derivatizado com 2,4-dinitrofenilhidrazina (2,4-DNPH) de amostras de esmalte para unha, pelo hifenamento dos m?todos de extra??o de QuEChERS e SPE, para a posterior an?lise por GC/MS. E devido ao grande n?mero de vari?veis que podem influenciar diretamente no sinal anal?tico deste trabalho, utilizou-se planejamentos experimentais multivariados para a obten??o de uma poss?vel condi??o ?tima de extra??o de formalde?do das amostras de esmalte de unha. Para avaliar sistematicamente a influ?ncia das vari?veis no sistema proposto, utilizou-se um planejamento fatorial 24, como triagem. As vari?veis estudadas foram: tempo, massa de derivatizante, massa de esmalte e massa de sal (MgSO4) no sistema de extra??o. Os resultados indicaram que somente a massa de derivatizante n?o ? significativa, mas suas intera??es com as demais vari?veis mostraram-se significativas. Assim, foram reestudadas todas as vari?veis da triagem em um planejamento composto central 24 esf?rico para a superf?cie de resposta. Tal estudo confirmou a signific?ncia de todas as vari?veis estudadas na triagem. N?o foi poss?vel obter um modelo quadr?tico sem falta de ajuste, no entanto, encontrou-se uma condi??o ?tima que proporcionou um aumento de 10.000 vezes na ?rea de pico cromatogr?fico por an?lise em GC/MS em rela??o aos estudos sem planejamento experimental multivariado. As melhores condi??es de extra??o foram: tempo de 5 min; 118,00 mg de massa de derivatizante; 730,00 mg de massa de esmalte e 2500,00 mg de massa de sal (MgSO4). O m?todo foi validado e apresentou os seguintes par?metros: LOD (Limite de detec??o) de 0,0005% m/v (massa de formalde?do/massa de esmaltes), LOQ (Limite de quantifica??o) de 0,005% m/v, e valores de recupera??o entre 90,00 - 99,33%. At? o momento n?o se tem o conhecimento de m?todos similares ao proposto aqui na literatura, embora esse estudo apresente acentuada relev?ncia, uma vez que possibilitar? informa??es ao consumidor e ag?ncias regulamentadoras sobre uma subst?ncia potencialmente t?xica, o formalde?do, em amostras de esmaltes para unha, produto altamente consumido pela popula??o. Assim este trabalho apresenta um m?todo anal?tico relativamente simples, de baixo gasto de reagentes para a an?lise de amostras de esmalte para unha.Formaldehyde is used as a firming agent/hardener in nail polish, however, according to international agencies cancer control and environmental protection, this compound has physicochemical properties that make it carcinogenic. Thus, in Brazil its control is done by ANVISA (National Sanitary Inspection Agency), which establishs that the commercial cosmetic products must carry a maximum concentration of 0.2% of this compound. Due to its constant use by a large part of the population, the nail polish can become a problem. However, it does not have the knowledge of sample preparation strategies for the formaldehyde in the literature analysis by gas chromatography coupled with mass spectrometry (GC/MS). This research proposed the extraction of formaldehyde derivatized with 2,4-dinitrophenylhydrazine (2,4- DNPH) in hypoallergenic nail polish samples (no formaldehyde in the final product), using hyphenate extraction methods of QuEChERS and SPE, for further analysis by GC/MS. Due to the large number of variables that can directly influence this method, was used a multivariate experimental design to obtain an optimum condition of formaldehyde extraction of nail polish samples. To evaluate systematically the influence of the variables in the proposed system, as tools for screening, was used a factorial design 24 with triplicate at the midpoint. The estudied variables were: time, mass derivatizing, mass of nail polish and mass of salt (MgSO4) in the extraction system. The results indicated that only the mass derivatizing is not significant in the system, but their interactions with the other variables were. So they were restudied all variables of screening in a central composite design 24 with triplicates the central point for the response surface. This study confirmed the significance of all the variables studied in the screening. For the analysis of ANOVA (analysis of variance) could not get a quadratic model without lack of fit. However, was found a great condition that provided an increase of 10,000 times the peak area chromatographic analysis by GC/MS in relation to studies without multivariate experimental design. Better extraction conditions were: 5 min, 118.00 mg of derivatizing mass, 730.00 mg of nail polish mass and 2500.00 mg of salt mass (MgSO4). The method was validated for a single sample R1, and presented the following parameters: LOD (Detection of limit) = 0.0005%, LOQ (limit of quantification) = 0.005%, cause this with% and recovery values between 90,00 - 99.33%. Until nowadays there is no knowledge about similar methods as the one proposed on this research in the literature, although this study presents relevance since it will enable information to consumers and regulators agengy about a potentially toxic substance (formaldehyde) in nail polish samples constantly used by population. So, this research becomes of immeasurable importance of presenting a relatively simple analytical method, low consumption of reagents for the analysis of nail polish samples

Principais Microrganismos envolvidos na deterioração das características sensoriais de derivados cárneos

The meat products are easily contaminated by microorganisms during handling and processing. After being contaminated food is to provide conditions for the microorganisms multiply, they may change the physical and chemical characteristics of food, causing thus damage. The types of deterioration vary depending on weather conditions which involve the products and the storage temperature. It is concluded that the main microorganisms involved in the deterioration of the sensory characteristics of meat products are the bacteria, Pseudomonas, Acinetobacter / Moraxella, Shewanella putrefaciens, Brochotrix thermosphacta, Lactobacillus and some species of the Family Enterobacteriaceae, yeasts and molds. And that inadequate hygiene of food handlers and the environment favor the growth of microorganisms and some steps can be taken to minimize the changes caused in meat products. This present work aims at presenting the main sensory changes that can occur in meat products due to the action of spoilage microorganisms.Os produtos cárneos são facilmente contaminados por microrganismos durante a manipulação e o processamento. Após ter sido contaminado, se o alimento oferecer condições para que os microrganismos se multipliquem, estes podem alterar as características físicas e químicas dos alimentos, podendo causar, assim, a sua deterioração. Os tipos de deterioração variam de acordo com as condições atmosféricas que envolvem os produtos e com a temperatura de armazenamento. Os principais microrganismos envolvidos na deterioração das características sensoriais dos derivados cárneos são as bactérias Pseudomonas, Acinetobacter/Moraxella, Shewanella putrefaciens, Brochotrix thermosphacta, Lactobacillus e algumas espécies da Família Enterobacteriaceae, as leveduras e os bolores. E que as condições inadequadas de higiene dos manipuladores e do ambiente favorecem o crescimento destes microrganismos e algumas medidas podem ser tomadas para minimizar as alterações provocadas nos produtos cárneos. Este presente trabalho tem por objetivo apresentar as principais alterações sensoriais que podem ocorrer em derivados cárneos devido à ação de microrganismos deteriorantes

Otimiza??o multivariada de metodologia para digest?o de micropart?culas polim?ricas carreadoras de c?tions met?licos.

There are not reports in the literature of digestion processes of metallic cation carrier microparticles. Multivariate experimental designs were utilized to ensure an appropriate digestion for further analysis by atomic absorption spectroscopy. It was used a heater plate and the polimeric degradation was evaluated utilizing an analyzer of total organic carbon (TOC). For the total carbon (TC) content, the full factorial design 24 pointed the significance of sample volume (VAm), in relation to the variables acid volume (VAc), temperature (T) and digestion time (t). However, according to the normal distribution graph it was noted a possible significance of the T and t effects. The same was observed for TOC, including the VAm ? VAc ? T effect suggestive of complex behavior. In the central composite design all variables were again studied and the VAM was significant, promoting a TC decreasing at the lower evaluated level. By ANOVA a quadratic model without lack of fit was found, with the significant quadratic term. The best digestion condition was: 5.00 mL of sample, 10.00 mL of nitric acid, 60 ?C and 90 min. The multivariate optimization allowed an efficient digestion, with the initial carbon concentration of 4.60 mg L-1 decreased to 0.55 mg L-1

Polymeric microparticles for modified release of NPK in agricultural applications.

The aim of this work was to synthesize polymeric microparticles as carriers for nitrogen, phosphorus, and potassium (NPK fertilizer) for agricultural applications, using polyglycerol (PG) to improve the synthesis procedure. Multivariate experimental designs were employed to obtain a satisfactory synthesis. The desirability function identified the best conditions for preparation of the microparticles as being 100.00 mg of poly(e-caprolactone) (PCL), 825.00 mg of PG, 9.25 mL of chloroform, and 0.9% w/v of polyvinyl alcohol (PVA). This resulted in average encapsulation rates of 94.23% for N, 99.80% for P, and 65.00% for K. The profile of release from the microparticles was according to diffusion following Fick?s Law. These observations confirmed the capacity of the proposed microparticles to sustain a continuous and prolonged release of NPK for the purpose of plant fertilization