Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230096
Olívia Moreira, Bruna Berlande, Jéssica Cordeiro Queiroz de Souza, J. Candido, Lauren H. Jaeger, L. H. Adriano, Marco Antônio e Brito, Maria Patrícia do Nascimento, Patrícia Geraldo, P. Chellini, M. D. de Oliveira
Capillary electromigration techniques can be understood as the ones used to separate neutral compounds, solvated ions and ionized species, considering the differentiated migration among them when an electrical field is applied within a capillary column filled with a background electrolyte. Several existing capillary electrophoresis setups provides the possibility of developing reliable quantitative assays of inorganic ions, organic acids, fatty acids, amino acids, carbohydrates, nucleic acids, proteins, hormones, vitamins, macromolecules, and more. Therefore, given the chemical complexity of bodily fluid matrices, capillary electrophoresis (CE) and its variations present themselves as an advantageous strategy for enhancing traditional clinical diagnostic methods and for the development of new ones. The recent advances in the study of the human metabolome associated with technological improvements towards medical applications make CE a very useful and versatile technique for clinical laboratory assays. Within this context, this review has the purpose of presenting some traditional methods used for exams of blood, urine, saliva, feces, and sweat, and how CE can be implemented as a real alternative to enable faster, automated, and cost-effective analysis with a comprehensive perspective that shall result in better diagnostic possibilities for patients, being a powerful tool for helping the physicians on the precision medicine achievements.
{"title":"Capillary Electromigration Techniques Applied to Clinical Chemistry Investigations and Alternative Diagnostic Assays: Possibilities and Perspectives","authors":"Olívia Moreira, Bruna Berlande, Jéssica Cordeiro Queiroz de Souza, J. Candido, Lauren H. Jaeger, L. H. Adriano, Marco Antônio e Brito, Maria Patrícia do Nascimento, Patrícia Geraldo, P. Chellini, M. D. de Oliveira","doi":"10.21577/0103-5053.20230096","DOIUrl":"https://doi.org/10.21577/0103-5053.20230096","url":null,"abstract":"Capillary electromigration techniques can be understood as the ones used to separate neutral compounds, solvated ions and ionized species, considering the differentiated migration among them when an electrical field is applied within a capillary column filled with a background electrolyte. Several existing capillary electrophoresis setups provides the possibility of developing reliable quantitative assays of inorganic ions, organic acids, fatty acids, amino acids, carbohydrates, nucleic acids, proteins, hormones, vitamins, macromolecules, and more. Therefore, given the chemical complexity of bodily fluid matrices, capillary electrophoresis (CE) and its variations present themselves as an advantageous strategy for enhancing traditional clinical diagnostic methods and for the development of new ones. The recent advances in the study of the human metabolome associated with technological improvements towards medical applications make CE a very useful and versatile technique for clinical laboratory assays. Within this context, this review has the purpose of presenting some traditional methods used for exams of blood, urine, saliva, feces, and sweat, and how CE can be implemented as a real alternative to enable faster, automated, and cost-effective analysis with a comprehensive perspective that shall result in better diagnostic possibilities for patients, being a powerful tool for helping the physicians on the precision medicine achievements.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68339504","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230140
F. Costa, P. Maia, F. D. da Silva, C. Nobre, Renata Silva, M. Milhome
The tomato (Solanum lycopersicon L.) crop has great economic relevance, being one of the most processed agricultural products worldwide. Some pesticides are chemically stable and can remain in food even after processing. In this context, the objective of this work was to analyze food products derived from tomatoes (extract, sauce and ketchup), regarding the levels of pesticide residues. Fifteen samples were acquired from Vale do Jaguaribe, Ceará, Brazil. Six pesticides (bifenthrin, chlorothalonil, chlorpyrifos, cyfluthrin, pyriproxyfen, trifluralin) authorized by Agência Nacional de Vigilância Sanitária (Anvisa) for tomato cultivation were selected for the study. QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction and gas chromatography coupled to mass spectrometry (GC-MS) were used in method validation, according to the recommendations of SANTE 11312/2021 guidelines. Statistical analyzes of linearity show that the six pesticides studied were classified as heterocesdastic. Limits of detection (LOD) and quantification (LOQ) values (0.01-0.03 and 0.03-0.10 mg kg-1, respectively) were below the established maximum residue limits (MRLs) for tomatoes. Accuracy and precision (78-121 and 2.3-16.7%, respectively) were satisfactory. The results indicated that among the 15 analyzed samples, one active ingredient was detected (0.05 mg kg-1) in a tomato sauce sample, lower than MRLs (Anvisa 0.15 mg kg-1 and FAO 0.3 mg kg-1). The results show the relevance of monitoring pesticide residues in tomato-derived products and the validation of new methodologies for food control.
{"title":"Analysis of Residues of Pesticides in Tomato Processed Foods","authors":"F. Costa, P. Maia, F. D. da Silva, C. Nobre, Renata Silva, M. Milhome","doi":"10.21577/0103-5053.20230140","DOIUrl":"https://doi.org/10.21577/0103-5053.20230140","url":null,"abstract":"The tomato (Solanum lycopersicon L.) crop has great economic relevance, being one of the most processed agricultural products worldwide. Some pesticides are chemically stable and can remain in food even after processing. In this context, the objective of this work was to analyze food products derived from tomatoes (extract, sauce and ketchup), regarding the levels of pesticide residues. Fifteen samples were acquired from Vale do Jaguaribe, Ceará, Brazil. Six pesticides (bifenthrin, chlorothalonil, chlorpyrifos, cyfluthrin, pyriproxyfen, trifluralin) authorized by Agência Nacional de Vigilância Sanitária (Anvisa) for tomato cultivation were selected for the study. QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction and gas chromatography coupled to mass spectrometry (GC-MS) were used in method validation, according to the recommendations of SANTE 11312/2021 guidelines. Statistical analyzes of linearity show that the six pesticides studied were classified as heterocesdastic. Limits of detection (LOD) and quantification (LOQ) values (0.01-0.03 and 0.03-0.10 mg kg-1, respectively) were below the established maximum residue limits (MRLs) for tomatoes. Accuracy and precision (78-121 and 2.3-16.7%, respectively) were satisfactory. The results indicated that among the 15 analyzed samples, one active ingredient was detected (0.05 mg kg-1) in a tomato sauce sample, lower than MRLs (Anvisa 0.15 mg kg-1 and FAO 0.3 mg kg-1). The results show the relevance of monitoring pesticide residues in tomato-derived products and the validation of new methodologies for food control.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68340748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230125
T. Nakamura, Enoc Lima do Rego, J. D. de Souza, Paulo Diniz, J. D. Da Silva
Fresh coconut (Cocos nucifera) water, a popular beverage in tropical countries, is often exposed to pesticide contamination due to agricultural practices. Thus, this work proposed the simultaneous determination of 36 pesticides in fresh coconut water samples using liquid-liquid extraction, drying assisted by a household microwave oven, and gas gas chromatography-mass spectrometry (GC-MS) analysis. Limits of detection varied from 5.4 (disulfoton) to 9.6 ng L-1 (parathion-methyl). Nine pesticides residues were detected (dimethoate, γ-HCH, β-HCH, 4,4’-dichlorodiphenyldichloroethylene, endosulfan II, 4,4’-dichlorodiphenyldichloroethane, 4,4’-dichlorodiphenyltrichloroethane, endrin ketone, and methoxychlor) with concentrations from < limit of quantification to 5,768.34 ± 1.64 ng L-1. Dimethoate was quantified in all samples, indicating its recent use. The proposed methodology offers several advantages, including the use of small sample volumes and solvent extraction, which eliminates the need for costly cartridges and reduces waste production. Additionally, the obtained results can be valuable for regulatory agencies, aiding in the mitigation of environmental damage and the protection of human health.
新鲜椰子水是热带国家的一种流行饮料，由于农业实践，它经常受到农药污染。为此，本研究提出了液液萃取、家用微波炉辅助干燥、气相色谱-质谱联用(GC-MS)同时测定新鲜椰子水样品中36种农药的方法。检出限从5.4(二硫顿)到9.6 ng L-1(甲基对硫磷)不等。共检出9种农药残留(乐果、γ-HCH、β-HCH、4,4′-二氯二苯二氯乙烯、硫丹II、4,4′-二氯二苯二氯乙烷、4,4′-二氯二苯三氯乙烷、endrin酮和甲氧氯)，浓度范围<定量限至5,768.34±1.64 ng L-1。所有样品中都定量检测了乐果，表明其最近使用过。所提出的方法具有几个优点，包括使用小样本量和溶剂萃取，从而消除了对昂贵的墨盒的需要并减少了废物的产生。此外，所获得的结果对监管机构可能很有价值，有助于减轻环境损害和保护人类健康。
{"title":"Pesticide Determination in Fresh Coconut Water (Cocos nucifera Linn.) by GC-MS Using Microwave-Assisted Liquid-Liquid Extraction","authors":"T. Nakamura, Enoc Lima do Rego, J. D. de Souza, Paulo Diniz, J. D. Da Silva","doi":"10.21577/0103-5053.20230125","DOIUrl":"https://doi.org/10.21577/0103-5053.20230125","url":null,"abstract":"Fresh coconut (Cocos nucifera) water, a popular beverage in tropical countries, is often exposed to pesticide contamination due to agricultural practices. Thus, this work proposed the simultaneous determination of 36 pesticides in fresh coconut water samples using liquid-liquid extraction, drying assisted by a household microwave oven, and gas gas chromatography-mass spectrometry (GC-MS) analysis. Limits of detection varied from 5.4 (disulfoton) to 9.6 ng L-1 (parathion-methyl). Nine pesticides residues were detected (dimethoate, γ-HCH, β-HCH, 4,4’-dichlorodiphenyldichloroethylene, endosulfan II, 4,4’-dichlorodiphenyldichloroethane, 4,4’-dichlorodiphenyltrichloroethane, endrin ketone, and methoxychlor) with concentrations from < limit of quantification to 5,768.34 ± 1.64 ng L-1. Dimethoate was quantified in all samples, indicating its recent use. The proposed methodology offers several advantages, including the use of small sample volumes and solvent extraction, which eliminates the need for costly cartridges and reduces waste production. Additionally, the obtained results can be valuable for regulatory agencies, aiding in the mitigation of environmental damage and the protection of human health.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68340493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230060
A. D. dos Santos, Ana Nadja L. Lucas, Iuri D. P. da Mota, Jaderson Schneider, A. Polidoro, A. Pinho, F. Mendes, E. Caramão
Bio-oils from biomass pyrolysis have a highly promising potential as biofuels or sources of chemicals. The quantitative analysis of bio-oils is quite difficult and requires many standards. In this study, we developed a methodology using only 16 standards for determining the concentration of 49 compounds, representatives of the main chemical classes commons in bio-oils, using relative response factors (RRF) and analytical curves. Five Pinus sawdust bio-oils were analyzed using a GC-MS-DB-5 capillary column (60 m). SCAN mode (from 45 to 450 Daltons) and retention indices (LPTRI) were used for qualitative analysis. For quantitative analysis, SIM mode was preferred, and analytical curves were constructed from an initial solution at 400 mg g-1 of each of the 16 standards, with concentrations ranging from 1 to 150 mg g-1 added to the internal standard (methyl hexanoate) at 70 mg g-1. After the positive identification and quantification of 9 compounds (among the 16 standards used), the other compounds were quantified using the RRF obtained from a standard solution at 30 mg g-1, considering the similarities with those identified standards. 196 compounds were identified, while 49 compounds were quantified, highlighting the monoaromatic hydrocarbons, naphthalenes, benzofurans, alkyl phenols, and catechols.
{"title":"Quantitative GC-MS Analysis of Sawdust Bio-Oil","authors":"A. D. dos Santos, Ana Nadja L. Lucas, Iuri D. P. da Mota, Jaderson Schneider, A. Polidoro, A. Pinho, F. Mendes, E. Caramão","doi":"10.21577/0103-5053.20230060","DOIUrl":"https://doi.org/10.21577/0103-5053.20230060","url":null,"abstract":"Bio-oils from biomass pyrolysis have a highly promising potential as biofuels or sources of chemicals. The quantitative analysis of bio-oils is quite difficult and requires many standards. In this study, we developed a methodology using only 16 standards for determining the concentration of 49 compounds, representatives of the main chemical classes commons in bio-oils, using relative response factors (RRF) and analytical curves. Five Pinus sawdust bio-oils were analyzed using a GC-MS-DB-5 capillary column (60 m). SCAN mode (from 45 to 450 Daltons) and retention indices (LPTRI) were used for qualitative analysis. For quantitative analysis, SIM mode was preferred, and analytical curves were constructed from an initial solution at 400 mg g-1 of each of the 16 standards, with concentrations ranging from 1 to 150 mg g-1 added to the internal standard (methyl hexanoate) at 70 mg g-1. After the positive identification and quantification of 9 compounds (among the 16 standards used), the other compounds were quantified using the RRF obtained from a standard solution at 30 mg g-1, considering the similarities with those identified standards. 196 compounds were identified, while 49 compounds were quantified, highlighting the monoaromatic hydrocarbons, naphthalenes, benzofurans, alkyl phenols, and catechols.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68338432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230074
M. Pinto, I. D. de Souza, L. F. Miranda, M. E. Queiroz
Parkinson’s disease is a neurodegenerative disorder characterized by progressive loss of dopaminergic neurons. There is substantial evidence that the endocannabinoid system modulates the dopaminergic activity in the basal ganglia, a forebrain system that integrates cortical information to coordinate motor activity regulating signals. In this article, a fused-silica capillary with a molecularly imprinted polymer was developed for in-tube solid-phase microextraction of the endocannabinoid anandamide in plasma samples from Parkinson’s disease patients and further analysis by ultra-high-performance liquid chromatography with tandem mass spectrometry. The molecularly imprinted polymer capillary presented recognition sites with complementary shape, size, and functionality to anandamide. Scanning electron micrographs and Fouriertransform infrared spectra illustrated the physical and chemical modification of the printed and non-printed capillary surface. The in-tube solid-phase microextraction ultra-high-performance liquid chromatography with tandem mass spectrometry method presented a linear range from 0.1 to 20 ng mL-1, precision with coefficient of variation values ranging from 1.2 to 13%, and relative standard deviation accuracy ranging from -3.6 to 7.5%. The method developed herein can adequately determine anandamide in plasma samples from Parkinson’s disease patients. By applying the standard addition approach, the anandamide plasmatic concentration in these samples was found to range from 0.2 to 0.4 ng mL-1.
帕金森氏病是一种以多巴胺能神经元进行性丧失为特征的神经退行性疾病。有大量证据表明，内源性大麻素系统调节基底神经节中的多巴胺能活动，基底神经节是一个整合皮质信息以协调运动活动调节信号的前脑系统。本文研究了一种分子印迹聚合物融合二氧化硅毛细管，用于在管内固相微萃取帕金森病患者血浆样品中的内源性大麻素anandamide，并通过超高效液相色谱-串联质谱法进一步分析。分子印迹聚合物毛细血管呈现出与苯胺具有互补形状、大小和功能的识别位点。扫描电子显微镜和傅里叶变换红外光谱说明了印刷和非印刷毛细管表面的物理和化学修饰。管内固相微萃取超高效液相色谱串联质谱法的线性范围为0.1 ~ 20 ng mL-1，精密度为1.2 ~ 13%，相对标准偏差精度为-3.6 ~ 7.5%。本文所建立的方法可以充分测定帕金森病患者血浆样品中的阿南达明。应用标准添加法，发现这些样品中的anandamide血浆浓度在0.2 ~ 0.4 ng mL-1之间。
{"title":"A New Molecularly Imprinted Polymer for In-Tube SPME/UHPLC-MS/MS of Anandamide in Plasma Samples","authors":"M. Pinto, I. D. de Souza, L. F. Miranda, M. E. Queiroz","doi":"10.21577/0103-5053.20230074","DOIUrl":"https://doi.org/10.21577/0103-5053.20230074","url":null,"abstract":"Parkinson’s disease is a neurodegenerative disorder characterized by progressive loss of dopaminergic neurons. There is substantial evidence that the endocannabinoid system modulates the dopaminergic activity in the basal ganglia, a forebrain system that integrates cortical information to coordinate motor activity regulating signals. In this article, a fused-silica capillary with a molecularly imprinted polymer was developed for in-tube solid-phase microextraction of the endocannabinoid anandamide in plasma samples from Parkinson’s disease patients and further analysis by ultra-high-performance liquid chromatography with tandem mass spectrometry. The molecularly imprinted polymer capillary presented recognition sites with complementary shape, size, and functionality to anandamide. Scanning electron micrographs and Fouriertransform infrared spectra illustrated the physical and chemical modification of the printed and non-printed capillary surface. The in-tube solid-phase microextraction ultra-high-performance liquid chromatography with tandem mass spectrometry method presented a linear range from 0.1 to 20 ng mL-1, precision with coefficient of variation values ranging from 1.2 to 13%, and relative standard deviation accuracy ranging from -3.6 to 7.5%. The method developed herein can adequately determine anandamide in plasma samples from Parkinson’s disease patients. By applying the standard addition approach, the anandamide plasmatic concentration in these samples was found to range from 0.2 to 0.4 ng mL-1.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68338863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230084
R. Vitek, Fernando H. do Nascimento, J. Masini
This study describes reversed-phase liquid chromatography (RPLC) methods to quantify urinary myoglobin using polymer monolithic columns produced by copolymerization of stearyl methacrylate (SMA) and ethylene glycol dimethacrylate (EDMA). The columns were prepared in the coffins of 1.5 mm internal diameter (i.d.) ethylene tetrafluoroethylene (ETFE) tubing for use in sequential injection chromatography (SIC) and solid phase extraction (SPE), and inside 1.0 mm i.d. Silcosteel ® tube for use in narrow-bore liquid chromatography. The monoliths inside the ETFE were produced via UV, whereas thermal polymerization formed the monoliths inside the Silcosteel ® tube. The separation of carbonic anhydrase, lysozyme, and myoglobin was demonstrated because they may occur simultaneously in urine samples. Quantification was undertaken by external calibration, and the accuracy was evaluated by the spiking/recovery strategy. The methods exhibited linearity from 5.0 to 60 µ g mL -1 (SIC), 2.5 to 50 µ g mL -1 (high-performance liquid chromatography (HPLC)), and 1.0 to 7.5 µ g mL -1 for an SPE-HPLC method. The lowest limits of detection and quantification were 0.13 and 0.43 µg L -1 , respectively, obtained after concentrating myoglobin by SPE. Recoveries ranged from 98 to 105%. The low cost, simplicity, reusability, and analytical features provided by these polymeric stationary phases make them affordable alternatives to routine analyses of urinary myoglobin.
本研究介绍了使用由甲基丙烯酸硬脂酯（SMA）和乙二醇二甲基丙烯酸酯（EDMA）共聚而成的聚合物整体柱定量检测尿肌红蛋白的反相液相色谱（RPLC）方法。这些色谱柱是在内径为 1.5 毫米的乙烯-四氟乙烯（ETFE）管（用于顺序进样色谱法（SIC）和固相萃取（SPE））和内径为 1.0 毫米的 Silcosteel ® 管（用于窄孔液相色谱法）的容器中制备的。ETFE 内的单体是通过紫外线产生的，而 Silcosteel ® 管内的单体则是通过热聚合形成的。由于碳酸酐酶、溶菌酶和肌红蛋白可能同时存在于尿液样本中，因此对它们的分离进行了演示。定量是通过外部校准进行的，准确度则是通过加标/回收策略进行评估的。这些方法的线性范围分别为 5.0 至 60 µ g mL -1 （SIC）、2.5 至 50 µ g mL -1 （高效液相色谱法）和 1.0 至 7.5 µ g mL -1 （SPE-高效液相色谱法）。采用 SPE 法浓缩肌红蛋白后，最低检测限和定量限分别为 0.13 和 0.43 µg L -1 。回收率为 98% 至 105%。这些聚合固定相成本低、操作简单、可重复使用且具有分析功能，是尿肌红蛋白常规分析的经济型替代品。
{"title":"Reversed-Phase Liquid Chromatography Methods Based on C18 Polymer Monoliths for the Determination of Urinary Myoglobin","authors":"R. Vitek, Fernando H. do Nascimento, J. Masini","doi":"10.21577/0103-5053.20230084","DOIUrl":"https://doi.org/10.21577/0103-5053.20230084","url":null,"abstract":"This study describes reversed-phase liquid chromatography (RPLC) methods to quantify urinary myoglobin using polymer monolithic columns produced by copolymerization of stearyl methacrylate (SMA) and ethylene glycol dimethacrylate (EDMA). The columns were prepared in the coffins of 1.5 mm internal diameter (i.d.) ethylene tetrafluoroethylene (ETFE) tubing for use in sequential injection chromatography (SIC) and solid phase extraction (SPE), and inside 1.0 mm i.d. Silcosteel ® tube for use in narrow-bore liquid chromatography. The monoliths inside the ETFE were produced via UV, whereas thermal polymerization formed the monoliths inside the Silcosteel ® tube. The separation of carbonic anhydrase, lysozyme, and myoglobin was demonstrated because they may occur simultaneously in urine samples. Quantification was undertaken by external calibration, and the accuracy was evaluated by the spiking/recovery strategy. The methods exhibited linearity from 5.0 to 60 µ g mL -1 (SIC), 2.5 to 50 µ g mL -1 (high-performance liquid chromatography (HPLC)), and 1.0 to 7.5 µ g mL -1 for an SPE-HPLC method. The lowest limits of detection and quantification were 0.13 and 0.43 µg L -1 , respectively, obtained after concentrating myoglobin by SPE. Recoveries ranged from 98 to 105%. The low cost, simplicity, reusability, and analytical features provided by these polymeric stationary phases make them affordable alternatives to routine analyses of urinary myoglobin.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139315398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230097
P. Alves, Jhonyson Guedes, L. Serrano, M. Martins, Debora Bezerra de Sousa, G. Silva, Paulo Ribeiro, D. Zampieri, G. Zocolo
Investigating specialized plant metabolites, traditionally referred to as ‘secondary metabolites’ present in leaf extracts of cashew trees (Anacardium occidentale) resistant and susceptible to anthracnose disease was carried out using metabolomics combined with chemometric tools. We used clones of dwarf-cashew with the following variations of characteristics: resistant and healthy (CCP 76, BRS 226, BRS 189), susceptible and healthy (BRS 265), and another clone also susceptible but affected by the disease (BRS 265). The UPLC-QTOF-MSE (ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry) analysis of the leaves of Anacardium clones allowed us annotation a total of 39 metabolites. The multiple orthogonal partial discriminant analysis of the least-squares (OPLS-DA) allowed twelve metabolites to be potential biomarkers of differentiation among the clones studied. Namely, the triene-(17:3)-anacardic acid found on CCP 76 and BRS 189 clones, respectively, is the main candidate for biomarker of resistance. While catechin, B-type procyanidin isomers, and procyanidin dimer monogallate identified in BRS 265 are significant potential biomarkers of susceptibility.
{"title":"UPLC-QTOF-MSE-Based Metabolic Profile to Screening Candidates of Biomarkers of Dwarf-Cashew Clones Resistant and Susceptible to Anthracnose (Colletotrichum gloeosporioides (Penz) Penz. & Sacc.)","authors":"P. Alves, Jhonyson Guedes, L. Serrano, M. Martins, Debora Bezerra de Sousa, G. Silva, Paulo Ribeiro, D. Zampieri, G. Zocolo","doi":"10.21577/0103-5053.20230097","DOIUrl":"https://doi.org/10.21577/0103-5053.20230097","url":null,"abstract":"Investigating specialized plant metabolites, traditionally referred to as ‘secondary metabolites’ present in leaf extracts of cashew trees (Anacardium occidentale) resistant and susceptible to anthracnose disease was carried out using metabolomics combined with chemometric tools. We used clones of dwarf-cashew with the following variations of characteristics: resistant and healthy (CCP 76, BRS 226, BRS 189), susceptible and healthy (BRS 265), and another clone also susceptible but affected by the disease (BRS 265). The UPLC-QTOF-MSE (ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry) analysis of the leaves of Anacardium clones allowed us annotation a total of 39 metabolites. The multiple orthogonal partial discriminant analysis of the least-squares (OPLS-DA) allowed twelve metabolites to be potential biomarkers of differentiation among the clones studied. Namely, the triene-(17:3)-anacardic acid found on CCP 76 and BRS 189 clones, respectively, is the main candidate for biomarker of resistance. While catechin, B-type procyanidin isomers, and procyanidin dimer monogallate identified in BRS 265 are significant potential biomarkers of susceptibility.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68339567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230118
Carmen Cardoso, M. D. de Moraes, Q. Cass
This review deals with two-dimensional liquid chromatography (2D-LC) separations encompassing target heart-cut (LC-LC), multiple heart-cut (mLC-LC), non-targeted comprehensive (LC × LC), and selective comprehensive (sLC × LC) analysis. It presents an overview of basic concepts and emphasizes the versatility of the applications gained by going from one-(1D) to two-dimensional (2D) separations. This review also discusses target analysis of achiral and chiral drugs for different applications and the use of 2D-LC in zonal bioaffinity chromatography. Advances in instrumental and column technologies have widened the application of LC × LC and sLC × LC separations, and we will discuss some of them.
{"title":"The Versatility of Two-Dimensional Liquid Chromatography","authors":"Carmen Cardoso, M. D. de Moraes, Q. Cass","doi":"10.21577/0103-5053.20230118","DOIUrl":"https://doi.org/10.21577/0103-5053.20230118","url":null,"abstract":"This review deals with two-dimensional liquid chromatography (2D-LC) separations encompassing target heart-cut (LC-LC), multiple heart-cut (mLC-LC), non-targeted comprehensive (LC × LC), and selective comprehensive (sLC × LC) analysis. It presents an overview of basic concepts and emphasizes the versatility of the applications gained by going from one-(1D) to two-dimensional (2D) separations. This review also discusses target analysis of achiral and chiral drugs for different applications and the use of 2D-LC in zonal bioaffinity chromatography. Advances in instrumental and column technologies have widened the application of LC × LC and sLC × LC separations, and we will discuss some of them.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68339882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230098
Lucas Morés, R. Huelsmann, Gabrieli Bernardi, Josias Merib, E. Carasek
Lung cancer is one of the main causes of death for thousands of people yearly around the world. Biomarker aldehydes, such as hexanal and heptanal, are compounds related to the development of lung cancer, which can be detected in the early stages of this disease. A methodology was proposed to determine these aldehydes in urine, with a new configuration associated with the sample preparation step. A novel strategy with a parallel-disposable pipette extraction (DPX)-cork device was used, offering a fast and affordable extraction methodology with analysis performed by high performance liquid chromatography with diode array detector. In optimization steps, multivariate and univariate designs were applied, providing the following conditions: urine sample centrifuged at 3500 rpm for 15 min, 30 μL and 6 min of dinitrophenylhydrazine impregnation, 10× urine diluted in ultrapure water, pH adjusted to 4.8, 7 extraction cycles with 1.5 min each, 30 mg of cork, 2 desorption cycles and solvent acetonitrile with 300 μL. Limits of detection were 0.13 ng mL-1 for both analytes and limits of quantification were 0.40 and 0.41 ng mL-1 for hexanal and heptanal, respectively. Intraday and interday precisions ranged from 4 to 21%. Relative recoveries ranged from 86 to 107%, assessed at three concentrations. Urine samples were analyzed, but the presence of aldehydes was not detected.
肺癌是全世界每年成千上万人死亡的主要原因之一。生物标记醛，如己醛和庚醛，是与肺癌发展有关的化合物，可以在肺癌的早期阶段检测到。提出了一种方法来确定这些醛在尿液中，与一个新的配置相关的样品制备步骤。采用平行一次性移液管提取(DPX)-软木装置的新策略，提供了一种快速且经济实惠的提取方法，并使用二极管阵列检测器进行高效液相色谱分析。在优化步骤中，采用多因素和单因素设计，提供以下条件:尿样在3500 rpm离心15 min，二硝基苯肼浸渍30 μL和6 min, 10倍尿液在超纯水中稀释，pH调整为4.8,7次提取，每次1.5 min, 30 mg的cork, 2次解吸，溶剂乙腈300 μL。两种分析物的检出限分别为0.13 ng mL-1，己醛和庚醛的定量限分别为0.40和0.41 ng mL-1。日内及日间精确度介乎4%至21%。在三种浓度下，相对回收率为86% ~ 107%。对尿样进行了分析，但没有检测到醛类物质的存在。
{"title":"In situ Derivatization of Lung Cancer Biomarker Aldehydes by Parallel-DPX-Cork and Quantification by HPLC-DAD","authors":"Lucas Morés, R. Huelsmann, Gabrieli Bernardi, Josias Merib, E. Carasek","doi":"10.21577/0103-5053.20230098","DOIUrl":"https://doi.org/10.21577/0103-5053.20230098","url":null,"abstract":"Lung cancer is one of the main causes of death for thousands of people yearly around the world. Biomarker aldehydes, such as hexanal and heptanal, are compounds related to the development of lung cancer, which can be detected in the early stages of this disease. A methodology was proposed to determine these aldehydes in urine, with a new configuration associated with the sample preparation step. A novel strategy with a parallel-disposable pipette extraction (DPX)-cork device was used, offering a fast and affordable extraction methodology with analysis performed by high performance liquid chromatography with diode array detector. In optimization steps, multivariate and univariate designs were applied, providing the following conditions: urine sample centrifuged at 3500 rpm for 15 min, 30 μL and 6 min of dinitrophenylhydrazine impregnation, 10× urine diluted in ultrapure water, pH adjusted to 4.8, 7 extraction cycles with 1.5 min each, 30 mg of cork, 2 desorption cycles and solvent acetonitrile with 300 μL. Limits of detection were 0.13 ng mL-1 for both analytes and limits of quantification were 0.40 and 0.41 ng mL-1 for hexanal and heptanal, respectively. Intraday and interday precisions ranged from 4 to 21%. Relative recoveries ranged from 86 to 107%, assessed at three concentrations. Urine samples were analyzed, but the presence of aldehydes was not detected.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68339629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2023-10-23DOI: 10.21577/0103-5053.20230093
A. Marinho, Bruno José Gonçalves da Silva
An extraction phase based on hydrogel disks of polyvinyl alcohol and pectin was developed, characterized, and evaluated for the extraction of four endocrine disruptors (methylparaben, ethylparaben, propylparaben and butylparaben) in free form in human urine samples with subsequent determination by liquid chromatography coupled with a diode array detector (LC-DAD). The proposed hydrogel showed easy synthesis, was made of low-cost and non-toxic polymers, and showed that it has an amphiphilic character. Gels with lower swelling indexes (175%) and more concentrated dispersions of polymers (P20PC2.0) showed lower relative standard deviation (RSD) values. Under optimized solid phase extraction (SPE) conditions, the LC-DAD method presented limits of quantification of 0.1 µg mL-1, accuracy values ranged from 101.3 to 118.2%, while the inter-assay precision ranged from 1.5 to 17.4%. In addition, the polyvinyl alcohol (PVOH)/pectin-based material presented the possibility of reuse of at least 15 times, without presenting carryover effect and physical degradation. In this way, the hydrogel shows promise for the extraction of organic compounds with different polarities in biological matrices.
{"title":"Polyvinyl Alcohol/Pectin-Based Hydrogel as Sorptive Phase for the Determination of Freely Dissolved Parabens in Urine Samples by LC-DAD","authors":"A. Marinho, Bruno José Gonçalves da Silva","doi":"10.21577/0103-5053.20230093","DOIUrl":"https://doi.org/10.21577/0103-5053.20230093","url":null,"abstract":"An extraction phase based on hydrogel disks of polyvinyl alcohol and pectin was developed, characterized, and evaluated for the extraction of four endocrine disruptors (methylparaben, ethylparaben, propylparaben and butylparaben) in free form in human urine samples with subsequent determination by liquid chromatography coupled with a diode array detector (LC-DAD). The proposed hydrogel showed easy synthesis, was made of low-cost and non-toxic polymers, and showed that it has an amphiphilic character. Gels with lower swelling indexes (175%) and more concentrated dispersions of polymers (P20PC2.0) showed lower relative standard deviation (RSD) values. Under optimized solid phase extraction (SPE) conditions, the LC-DAD method presented limits of quantification of 0.1 µg mL-1, accuracy values ranged from 101.3 to 118.2%, while the inter-assay precision ranged from 1.5 to 17.4%. In addition, the polyvinyl alcohol (PVOH)/pectin-based material presented the possibility of reuse of at least 15 times, without presenting carryover effect and physical degradation. In this way, the hydrogel shows promise for the extraction of organic compounds with different polarities in biological matrices.","PeriodicalId":17257,"journal":{"name":"Journal of the Brazilian Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2023-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"68339284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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