Analysis of adulteration chemical markers of balsamic vinegars by silica plate laser desorption/ionization mass spectrometry (SP-LDI-MS)

Orientador: Rodrigo Ramos CatharinoDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Ciências MédicasResumo: O Vinagre Balsâmico é um produto italiano de grande valor, bastante apreciado em todo o mundo devido ao seu sabor característico e aos seus potenciais benefícios à saúde. Ao longo dos últimos anos, diversos pesquisadores realizaram estudos que avaliaram a sua composição físico-química, microbiana e suas propriedades benéficas. Devido ao alto número de estudos que confirmam o seu caráter antioxidante e suas propriedades anti-hipertensivas e antiglicêmicas, o vinagre balsâmico é um produto alvo de fraudes e adulterações. Desta forma, há uma preocupação acerca dos balsâmicos autênticos, que possuam certificação tanto para sua origem (região ou país), como para suas condições de processamento, garantindo sua qualidade e originalidade. Por isso, o esforço para a redução de fraudes, bem como a garantia da qualidade dos balsâmicos são de grande interesse tanto para saúde do consumidor, quanto do ponto de vista econômico. Buscando encontrar estratégias analíticas confiáveis, capazes de avaliar rapidamente a qualidade do vinagre balsâmico, este trabalho emprega a técnica de Espectrometria de Massas por Ionização/Dessorção a Laser em Placa de Sílica (SP-LDI-MS) para a rápida caracterização química de amostras de vinagres balsâmicos comercial e com indicação geográfica protegida (IGP), e identificação de suas amostras adulteradas com vinagres de baixo custo, provenientes de maçã, álcool e vinhos branco e tintoAbstract: The Balsamic Vinegar is a valuable Italian product, very popular worldwide due to its distinctive flavor and potential health benefits. Several studies have been conducted to assess physicochemical and microbial compositions as well as with respect to its beneficial properties. Due to the high number of studies that confirm its antioxidant character and their antihypertensive and antiglycemic properties, balsamic vinegar is a potential target for frauds and adulterations. Thus, there is growing concern about the search for authenticated balsamics, so make sure your origin (region or country) as well as their processing conditions, which guarantee quality and originality of balsamic vinegar. Striving for fraud reduction and ensuring the quality and safety of food through reliable analytical strategies to quickly assess the quality of balsamic vinegar are of great interest to health and the economic point of view. In this context, this work employs the technique of Silica Plate Laser Desorption/Ionization Mass Spectrometry (SP-LDI-MS) for rapid chemical characterization of samples of commercial balsamic vinegars and with protected geographical indications (PGI) and identification their samples adulterated with inexpensive vinegars from apple, alcohol and red and white winesMestradoFisiopatologia MédicaMestra em Ciência

Rationale, study design, and analysis plan of the Alveolar Recruitment for ARDS Trial (ART): Study protocol for a randomized controlled trial

Background: Acute respiratory distress syndrome (ARDS) is associated with high in-hospital mortality. Alveolar recruitment followed by ventilation at optimal titrated PEEP may reduce ventilator-induced lung injury and improve oxygenation in patients with ARDS, but the effects on mortality and other clinical outcomes remain unknown. This article reports the rationale, study design, and analysis plan of the Alveolar Recruitment for ARDS Trial (ART). Methods/Design: ART is a pragmatic, multicenter, randomized (concealed), controlled trial, which aims to determine if maximum stepwise alveolar recruitment associated with PEEP titration is able to increase 28-day survival in patients with ARDS compared to conventional treatment (ARDSNet strategy). We will enroll adult patients with ARDS of less than 72 h duration. The intervention group will receive an alveolar recruitment maneuver, with stepwise increases of PEEP achieving 45 cmH(2)O and peak pressure of 60 cmH2O, followed by ventilation with optimal PEEP titrated according to the static compliance of the respiratory system. In the control group, mechanical ventilation will follow a conventional protocol (ARDSNet). In both groups, we will use controlled volume mode with low tidal volumes (4 to 6 mL/kg of predicted body weight) and targeting plateau pressure <= 30 cmH2O. The primary outcome is 28-day survival, and the secondary outcomes are: length of ICU stay; length of hospital stay; pneumothorax requiring chest tube during first 7 days; barotrauma during first 7 days; mechanical ventilation-free days from days 1 to 28; ICU, in-hospital, and 6-month survival. ART is an event-guided trial planned to last until 520 events (deaths within 28 days) are observed. These events allow detection of a hazard ratio of 0.75, with 90% power and two-tailed type I error of 5%. All analysis will follow the intention-to-treat principle. Discussion: If the ART strategy with maximum recruitment and PEEP titration improves 28-day survival, this will represent a notable advance to the care of ARDS patients. Conversely, if the ART strategy is similar or inferior to the current evidence-based strategy (ARDSNet), this should also change current practice as many institutions routinely employ recruitment maneuvers and set PEEP levels according to some titration method.Hospital do Coracao (HCor) as part of the Program 'Hospitais de Excelencia a Servico do SUS (PROADI-SUS)'Brazilian Ministry of Healt

High-throughput Analysis By Sp-ldi-ms For Fast Identification Of Adulterations In Commercial Balsamic Vinegars.

Balsamic vinegar (BV) is a typical and valuable Italian product, worldwide appreciated thanks to its characteristic flavors and potential health benefits. Several studies have been conducted to assess physicochemical and microbial compositions of BV, as well as its beneficial properties. Due to highly-disseminated claims of antioxidant, antihypertensive and antiglycemic properties, BV is a known target for frauds and adulterations. For that matter, product authentication, certifying its origin (region or country) and thus the processing conditions, is becoming a growing concern. Striving for fraud reduction as well as quality and safety assurance, reliable analytical strategies to rapidly evaluate BV quality are very interesting, also from an economical point of view. This work employs silica plate laser desorption/ionization mass spectrometry (SP-LDI-MS) for fast chemical profiling of commercial BV samples with protected geographical indication (PGI) and identification of its adulterated samples with low-priced vinegars, namely apple, alcohol and red/white wines.83886-9

An LDI-MSI approach for targeted and untargeted differentiation and assessment of pharmaceutical formulations

Falsified, counterfeit and adulterated medicines are an endemic problem worldwide that results in both monetary and health-related losses. Developing fast and reliable methods that are able to present a timely result based on the drug's spectral profile is an effort that is sure to benefit those involved in the whole distribution chain. We propose herein a Laser Desorption/Ionization imaging-based method that provides simple and minimal sample preparation; this method is capable of providing specific markers that characterize adulterations, using as proof of concept one of the most adulterated drug products for oral use, sildenafil. Our approach is able to provide quality markers, which can be applied in the fast screening of any product within the same molecular class. This same strategy may be a useful alternative to provide accurate measurements with high specificity for unraveling contaminants and/or byproducts in virtually any given pharmaceutical product1979297CAPES - Coordenação de Aperfeiçoamento de Pessoal e Nível SuperiorFAPESP – Fundação de Amparo à Pesquisa Do Estado De São Paulo88887.137889/2017-00; 14897402011/50400-0; 2015/06809-1; 2016/17066-

New Approach of QuEChERS and GC-MS Triple-Quadrupole for the Determination of Ethyl Carbamate Content in Brazilian cachaças

Cachaça is a popular spirit produced in Brazil, obtained by distillation of fermented sugar cane. Among the contaminants arising from production, ethyl carbamate is a carcinogenic compound that occurs naturally in fermented foods and beverages; in Brazil, the maximum limit established by current legislation is 150 µg L−1. Quality control is usually performed using gas chromatography; however, robustness and reproducibility of quantitative results may be severely impaired, as the addition of 6–30 g L−1 of sucrose is a common procedure for taste standardization, directly interfering in the results. This work describes the development of a novel method to improve ethyl carbamate quantification in cachaças using a new approach of QuEChERS extraction based on salting-out phenomenon, to effectively separate ethanol from sugar-containing water. Eighteen different brands of cachaça were analyzed. The proposed methodology was able to eliminate components that contaminate the sample flow path in the gas chromatography system, while improving precision and accuracy by using a triple-quadrupole approach, in comparison with the methodology usually employed: direct analysis of cachaça samples with no sample prep. Results indicate that this approach is more effective due to the removal of sugar content, with no impact in costs per analysis

A Metabolomic Overview of Follicular Fluid in Cows

Follicular fluid (FF) protects the oocyte against proteolysis and extrusion during ovulation, providing an appropriate microenvironment that favors proper embryonic development; thereby, FF plays a key role in embryo quality. Being directly related to cattle breeding, studying FF is extremely important in livestock science to measure cattle fertility. This may eventually help to assess the quality of both meat and milk, products widely consumed worldwide. There is an important commercial interest in the evaluation and characterization of compounds present in the FF of livestock that present greater likelihood of pregnancy. Mass spectrometry is a great ally for this type of analysis and can provide quick and efficient screening for molecular markers in biological samples. The present study demonstrated the potential of high-resolution mass spectrometry in analyzing FF samples from two distinct groups of Nellore cows (Bos indicus): high and low fertility, as determined by the number of oocytes produced. We were able to delineate markers of interest for each group, which may ultimately be related to biochemical pathways that lead to higher or lower reproductive performance

Comparative metabolomic profiling of women undergoing in vitro fertilization procedures reveals potential infertility-related biomarkers in follicular fluid

Abstract Infertility is a worldwide concern, affecting one in six couples throughout their reproductive period. Therefore, enhancing the clinical tools available to identify the causes of infertility may save time, money, and emotional distress for the involved parties. This study aims to annotate potential biomarkers in follicular fluid that are negatively affecting pregnancy outcomes in women suffering infertility-related diseases such as endometriosis, tuboperitoneal factor, uterine factor, and unexplained infertility, using a metabolomics approach through high-resolution mass spectrometry. Follicular fluid samples collected from women who have the abovementioned diseases and managed to become pregnant after in vitro fertilization procedures [control group (CT)] were metabolically compared with those from women who suffer from the same diseases and could not get pregnant after the same treatment [infertile group (IF)]. Mass spectrometry analysis indicated 10 statistically relevant differential metabolites in the IF group, including phosphatidic acids, phosphatidylethanolamines, phosphatidylcholines, phosphatidylinositol, glucosylceramides, and 1-hydroxyvitamin D3 3-d-glucopyranoside. These metabolites are associated with cell signaling, cell proliferation, inflammation, oncogenesis, and apoptosis, and linked to infertility problems. Our results indicate that understanding the IF’s metabolic profile may result in a faster and more assertive female infertility diagnosis, lowering the costs, and increasing the probability of a positive pregnancy outcome

Early developmental stages of ascaris lumbricoides featured by high-resolution mass spectrometry

Ascaris lumbricoides is responsible for a highly disseminated helminth parasitic disease, ascariosis, a relevant parasitosis that responds for great financial burden on the public health system of developing countries. In this work, metabolic fingerprinti11541074114COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPsem informação11/50400-0; 14/00084-2; 14/00302-0; 15/06809-1INNOVARE Biomarkers Laboratory would like to thank the Coordination for the Improvement of Higher Level (CAPES), the University of Campinas (Unicamp) and São Paulo Research Foundation (FAPESP, Process Nos. 11/50400-0, 14/00084-2, 14/00302-0 and 15/0680

A lipidomics approach in the characterization of zika-infected mosquito cells: potential targets for breaking the transmission cycle

Recent outbreaks of Zika virus in Oceania and Latin America, accompanied by unexpected clinical complications, made this infection a global public health concern. This virus has tropism to neural tissue, leading to microcephaly in newborns in a significant proportion of infected mothers. The clinical relevance of this infection, the difficulty to perform accurate diagnosis and the small amount of data in literature indicate the necessity of studies on Zika infection in order to characterize new biomarkers of this infection and to establish new targets for viral control in vertebrates and invertebrate vectors. Thus, this study aims at establishing a lipidomics profile of infected mosquito cells compared to a control group to define potential targets for viral control in mosquitoes. Thirteen lipids were elected as specific markers for Zika virus infection (Brazilian strain), which were identified as putatively linked to the intracellular mechanism of viral replication and/or cell recognition. Our findings bring biochemical information that may translate into useful targets for breaking the transmission cycle1110CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPSem informaçãoSem informação2011/50400-0; 2015/06809-1; 2014/00084-2; 2014/00302-0; 2013/11343-