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1.
Anal Chem ; 96(14): 5349-5356, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38554084

RESUMO

The patterning of hydrophilic paper with hydrophobic materials has emerged as an interesting method for the fabrication of paper-based devices (PADs). Herein, we demonstrate a digitally automated, easy, low-cost, eco-friendly, and readily available method to create highly hydrophobic barriers on paper that can be promptly employed with PADs by simply using a bioink made with rosin, a commercially available natural resin obtained from conifer trees. The bioink can be easily delivered with the use of a ballpoint pen to produce water- and organic solvent-resistant barriers, showing superior properties when compared to other methods such as wax-printing or permanent markers. The approach enables the pen to be attached to a commercially available cutting printer to perform the semiautomated fabrication of hydrophobic barriers for PADs. With the aid of digitally controlled optimization, together with features of machine learning and design of experiments, we show a thorough investigation on the barrier strength that can be further adjusted to the desired application's needs. Then, we explored the barrier sturdiness across various uses, such as wide range aqueous pH sensing and the harsh acidic/organic conditions needed for the colorimetric detection of cholecalciferol.


Assuntos
Papel , Água , Solventes , Impressão/métodos , Impressão Tridimensional
2.
Anal Bioanal Chem ; 415(18): 4391-4400, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36773069

RESUMO

This paper describes the design and construction of dual microfluidic paper-based analytical devices (dual-µPADs) as a lab-on-paper platform involving a "do-it-yourself" fabrication protocol. The device comprises a colorimetric and electrochemical module to obtain a dual-mode signal readout sensing strategy. A 3D pen polymeric resin was used to prepare graphite carbon-based electrodes and hydrophobic barriers on paper substrates. The proposed carbon-based ink was employed to manufacture electrodes on paper based on a stencil-printing approach, which were further characterized by electrochemical and morphological analyses. The analytical performance of the dual-µPADs was simultaneously evaluated for lactate, pH, nitrite, and salivary amylase (sAA) analysis. To demonstrate the proof-of-concept, saliva samples collected from both healthy individuals and those with periodontitis were successfully tested to demonstrate the feasibility of the proposed devices. Samples collected from individuals previously diagnosed with periodontitis showed high levels of nitrite and sAA (> 94 µmol L-1 and > 610 U mL-1) in comparison with healthy individuals (≤ 16 µmol L-1 and 545 U mL-1). Moreover, periodontitis saliva resulted in acid solution and almost null lactate levels. Notably, this protocol supplies a simple way to manufacture dual-µPADs, a versatile platform for sensitive detecting of biomarkers in saliva playing a crucial role towards the point-of-care diagnosis of periodontal disease.


Assuntos
Técnicas Analíticas Microfluídicas , Doenças Periodontais , Periodontite , Humanos , Nitritos/análise , Dispositivos Lab-On-A-Chip , Colorimetria/métodos , Carbono , Papel
3.
J Sep Sci ; 46(19): e2300442, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37582647

RESUMO

A capillary electrophoresis-mass spectrometry method was used to analyze naphthenic acids in produced water samples. It was possible to detect cyclopentanecarboxylic, benzoic, cyclohexanebutyric, 1-naphthoic, decanoic, 3,5-dimethyladamantane-1-carboxylic, 9-anthracenecarboxylic, and pentadecanoic acids within ca. 13 min using a buffer composed of 40 mmol/L ammonium hydroxide, 32 mmol/L acetic acid and 20% v/v isopropyl alcohol, pH 8.6. The proposed method showed good repeatability, with relative standard deviation (RSD) values of 6.6% for the sum of the peak areas and less than 2% for the analysis time. In the interday analysis, the RSD values for the sum of the peak areas and migration time were 10.3% and 10%, respectively. The developed method demonstrated linear behavior in the concentration range between 5 and 50 mg/L for benzoic, decanoic, 3,5-dimethyladamantane-1-carboxylic and 9-anthracenecarboxylic acids, and between 10 and 50 mg/L for cyclopentanecarboxylic, cyclohexanebutyric, 1- naphthoic, and pentadecanoic acids. The detection limits values ranged from 0.31 to 1.64 mg/L. Six produced water samples were analyzed and it was possible to identify and quantify cyclopentanecarboxylic, benzoic, cyclohexanebutyric, and decanoic acids. The concentrations varied between 4.8 and 98.9 mg/L, proving effective in the application of complex samples.

4.
Mikrochim Acta ; 190(8): 324, 2023 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-37493852

RESUMO

The development of a disposable electrochemical paper-based analytical device (ePAD) is described using a novel formulation of conductive ink that combines graphite powder, polyester resin, and acetone. As a proof of concept, the proposed sensor was utilized for paracetamol (PAR) sensing. The introduced ink was characterized via morphological, structural, and electrochemical analysis, and the results demonstrated appreciable analytical performance. The proposed ePAD provided linear behavior (R2 = 0.99) in the concentration range between 1 and 60 µmol L-1, a limit of detection of 0.2 µmol L-1, and satisfactory reproducibility (RSD ~ 7.7%, n = 5) applying a potential of + 0.81 V vs Ag at the working electrode. The quantification of PAR was demonstrated in different pharmaceutical formulations. The achieved concentrations revealed good agreement with the labeled values, acceptable accuracy (101% and 106%), and no statistical difference from the data obtained by HPLC at the 95% confidence level. The environmental impact of the new device was assessed using AGREE software, which determined a score of 0.85, indicating that it is eco-friendly. During the pharmacokinetic study of PAR, it was found that the drug has a maximum concentration of 23.58 ± 0.01 µmol L-1, a maximum time of 30 min, and a half-life of 2.15 h. These results are comparable to other studies that utilized HPLC. This suggests that the combination of graphite powder and polyester resin can transform conductive ink into an effective ePAD that can potentially be used in various pharmaceutical applications.


Assuntos
Acetaminofen , Grafite , Acetaminofen/análise , Grafite/química , Tinta , Reprodutibilidade dos Testes , Pós , Técnicas Eletroquímicas/métodos , Poliésteres
5.
Electrophoresis ; 43(20): 2044-2048, 2022 10.
Artigo em Inglês | MEDLINE | ID: mdl-35948488

RESUMO

A low-cost and straightforward hybrid NOA (Norland optical adhesive) 81-glass microchip electrophoresis device was designed and developed for protein separation using indirect fluorescence detection. This new microchip was first characterized in terms of surface charge density via electroosmotic mobility measurement and stability over time. A systematic determination of the electroosmotic mobility (µeo ) over a wide pH range (2-10) and at various ionic strengths (20-50 mM) was developed for the first time via the neutral marker approach in an original simple frontal methodology. The evolution of µeo was proved consistent with the silanol and thiol functions arising from the glass and the NOA materials, respectively. The repeatability and reproducibility of the measurements on different microchips (RSD < 14%) and within 15 days (less than 5% decrease) were successfully demonstrated. The microchip was then applied for the efficient electrophoretic separation of proteins in a zonal mode coupled with indirect fluorescence detection, which is, to our knowledge, the first proof of concept of capillary zone electrophoresis in this hybrid microsystem.


Assuntos
Eletroforese em Microchip , Eletroforese Capilar/métodos , Eletroforese em Microchip/métodos , Vidro/química , Proteínas/análise , Reprodutibilidade dos Testes , Compostos de Sulfidrila
6.
Mikrochim Acta ; 189(6): 235, 2022 05 28.
Artigo em Inglês | MEDLINE | ID: mdl-35633399

RESUMO

The 3D printing is described of a complete and portable system comprising a batch injection analysis (BIA) cell and an electrochemical platform with eight sensing electrodes. Both BIA and electrochemical cells were printed within 3.4 h using a multimaterial printer equipped with insulating, flexible, and conductive filaments at cost of ca. ~ U$ 1.2 per unit, and their integration was based on a threadable assembling without commercial component requirements. Printed electrodes were exposed to electrochemical/Fenton pre-treatments to improve the sensitivity. Scanning electron microscopy and electrochemical impedance spectroscopy measurements upon printed materials revealed high-fidelity 3D features (90 to 98%) and fast heterogeneous rate constants ((1.5 ± 0.1) × 10-3 cm s-1). Operational parameters of BIA cell were optimized using a redox probe composed of [Fe(CN)6]4-/3- under stirring and the best analytical performance was achieved using a dispensing rate of 9.0 µL s-1 and an injection volume of 2.0 µL. The proof of concept of the printed device for bioanalytical applications was evaluated using adrenaline (ADR) as target analyte and its redox activities were carefully evaluated through different voltammetric techniques upon multiple 3D-printed electrodes. The coupling of BIA system with amperometric detection ensured fast responses with well-defined peak width related to the oxidation of ADR applying a potential of 0.4 V vs Ag. The fully 3D-printed system provided suitable analytical performance in terms of repeatability and reproducibility (RSD ≤ 6%), linear concentration range (5 to 40 µmol L-1; R2 = 0.99), limit of detection (0.61 µmol L-1), and high analytical frequency (494 ± 13 h-1). Lastly, artificial urine samples were spiked with ADR solutions at three different concentration levels and the obtained recovery values ranged from 87 to 118%, thus demonstrating potentiality for biological fluid analysis. Based on the analytical performance, the complete device fully printed through additive manufacturing technology emerges as powerful, inexpensive, and portable tool for electroanalytical applications involving biologically relevant compounds.


Assuntos
Espectroscopia Dielétrica , Fuligem , Eletrodos , Impressão Tridimensional , Reprodutibilidade dos Testes
7.
Analyst ; 146(11): 3463-3473, 2021 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-34075939

RESUMO

Heavy metals are the main pollutants present in aquatic environments and their presence in human organisms can lead to many different diseases. While many methods exist for analysis, colorimetric and electrochemistry are particularly attractive for on-site analysis and their integration on a single platform can improve multiplexed metals analysis. This report describes for the first time a "plug-and-play" (PnP) assembly for coupling a microfluidic paper-based device (µPAD) and a screen-printed electrochemical paper-based device (ePAD) using a vertical and reversible foldable mechanism for multiplexed detection of Fe, Ni, Cu, Zn, Cd and Pb in river water samples. The integration strategy was based on a reversible assembly, allowing the insertion of a pretreatment zone to minimize potential chemical interfering agents and providing a better control of the aspirated sample volume as well as to a lower sample evaporation rate. In comparison with lateral flow and electrochemical assays performed using independent devices, the integrated prototype proved that the reversible coupling mechanism does not interfere on the analytical performance (95% confidence interval). The limit of detection (LOD) values calculated for metals determined varied from 0.1 to 0.3 mg L-1 (colorimetric) and from 0.9 to 10.5 µg L-1 (electrochemical). When compared to other integrated devices based on horizontal designs, the use of a foldable coupling mechanism offered linear response in a lower concentration range and better LOD values for Fe, Ni and Cu. The proposed method successfully measured heavy metals in river water samples with concentrations ranging from 16 to 786 µg L-1, with recovery studies ranging from 76 to 121%. The new method also showed good correlation with conventional atomic absorption spectroscopic methods (95% significance level). Thus, the integration of µPADs and ePADs by a vertical folding mechanism was efficient for multiplexed heavy metal analysis and could be exploited for environmental monitoring.

8.
Anal Bioanal Chem ; 413(12): 3201-3208, 2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-33665673

RESUMO

Entomotoxicology allows the detection and analysis of substances such as poisons, drugs, and metals in necrophagous insects using analytical protocols. In a forensic situation related to death by gunshot, the gunshot residue (GSR) is dispersed at the crime scene and may be consumed by necrophagous insects. Lead (Pb) is the most abundant metal in GSR samples and it can be determined using non-portable methods. However, the toxicity effects of GSR samples on Lucilia cuprina (Diptera: Calliphoridae) and the detection of Pb via portable electrochemical methods have not been investigated. This study describes for the first time the toxicity analysis of Pb on immature L. cuprina through their survival rate and influence of Pb on immature development. In addition, the bioaccumulation of Pb in the larvae samples was determined based on square wave anodic stripping voltammetry (SWASV) measurements. The results revealed a low limit of detection to Pb (6.5 µg L-1) and the analytical performance was satisfactory because it measures Pb levels in larvae exposed to a diet containing 50 µg Pb g-1. Furthermore, the levels of Pb influenced the survival rate and development time of the immature L. cuprina. Larvae exposed to a high concentration of the metal (50 µg Pb g -1) showed statistically significant changes (p < 0.05). The presence of Pb in immature L. cuprina can be used to estimate the post-mortem interval; thus, the present study provides important information in forensic entomology.


Assuntos
Calliphoridae/efeitos dos fármacos , Custos e Análise de Custo , Técnicas Eletroquímicas/métodos , Medicina Legal/métodos , Chumbo/toxicidade , Animais , Bioensaio , Biomarcadores/metabolismo , Calliphoridae/crescimento & desenvolvimento , Técnicas Eletroquímicas/economia , Medicina Legal/economia , Larva/efeitos dos fármacos , Larva/metabolismo , Chumbo/análise , Limite de Detecção
9.
Electrophoresis ; 41(7-8): 434-448, 2020 04.
Artigo em Inglês | MEDLINE | ID: mdl-31793007

RESUMO

The use of organic solvents as electrolytic medium in electrophoresis has become an important alternative for the analysis of compounds that exhibit low or no solubility in water. In recent years, nonaqueous electrophoresis has been extensively explored in conventional capillary systems for different applications. On the other hand, this separation strategy is still not as popular as free solution electrophoresis on chip-based platforms due to the effects of solvent in the background electrolyte on the sample injection, detection performance, and microfluidic platform compatibility. In this way, this review summarizes the main achievements on nonaqueous microchip electrophoresis (NAME). To the best of our knowledge, this is the first review dedicated to discuss exclusively nonaqueous electrophoresis on chip-based systems. For this purpose, some important theoretical aspects involved when separations are performed in organic medium, such as equilibrium, interactions and electrophoretic considerations, are included in the review. In addition, the main challenges, advantages and influences of nonaqueous media on the sample injection, detection as well as the choice of the substrate to fabricate chip-based electrophoresis devices are highlighted. Last, examples showing the feasibility of nonaqueous microchip electrophoresis for applications exploiting different methodologies, operational, and instrumental conditions are summarized and discussed. We hope this review can be useful to spread the huge potential of nonaqueous electrophoresis on microfluidic platforms.


Assuntos
Eletroforese em Microchip , Compostos Orgânicos/química , Solventes/química
10.
Electrophoresis ; 41(18-19): 1641-1650, 2020 10.
Artigo em Inglês | MEDLINE | ID: mdl-32726462

RESUMO

This study describes an inexpensive and nonconventional soft-embossing protocol to produce microfluidic devices in poly(methyl methacrylate) (PMMA). The desirable microfluidic structure was photo-patterned in a poly(vinyl acetate) (PVAc) film deposited on glass substrate to produce a low-relief master. Then, this template was used to generate a high-relief pattern in stiffened PDMS by increasing of curing agent /monomer ratio (1:5) followed by thermal aging in a laboratory oven (200°C for 24 h). The stiffened PDMS masters were used to replicate microfluidic devices in PMMA based on soft embossing at 220-230°C and thermal sealing at 140°C. Both embossing and sealing stages were performed by using binder clips. The proposed protocol has ensured the replication of microfluidic devices in PMMA with great fidelity (>94%). Examples of MCE devices, droplet generator devices and spot test array were successfully demonstrated. For testing MCE devices, a mixture containing inorganic cations was selected as model and the achieved analytical performance did not reveal significant difference from commercial PMMA devices. Water droplets were successfully generated in an oil phase at rate of ca. 60 droplets/min (fixing the continuous phase flow rate at 100 µL/h) with size of ca. 322 ± 6 µm. Glucose colorimetric assay was performed on spot test devices and good detectability level (5 µmol/L) was achieved. The obtained results for two artificial serum samples revealed good agreement with the certified concentrations. Based on the fabrication simplicity and great analytical performance, the proposed soft-embossing protocol may emerge as promising approach for manufacturing PMMA devices.


Assuntos
Desenho de Equipamento/métodos , Dispositivos Lab-On-A-Chip , Procedimentos Analíticos em Microchip/métodos , Polimetil Metacrilato/química , Glicemia/análise , Colorimetria/instrumentação , Eletroforese/instrumentação , Temperatura Alta , Limite de Detecção , Modelos Lineares , Modelos Biológicos , Reprodutibilidade dos Testes
11.
Electrophoresis ; 40(3): 462-468, 2019 02.
Artigo em Inglês | MEDLINE | ID: mdl-30411387

RESUMO

This study describes the development of an analytical methodology based on the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C4 D) for the separation and detection of inorganic anions in post-blast explosive residues. The best separation condition was achieved using a running buffer composed of 35 mmol/L lactic acid, 10 mmol/L histidine and 0.070 mmol/L cetyl(trimethyl ammonium) bromide. For C4 D measurements, the highest sensitivity was obtained applying a 700 kHz sinusoidal wave with excitation voltage of 20 Vpp . The separation of Cl- , NO3- , NO2- , SO42- , ClO4- and ClO3- was performed within ca. 150 s with baseline resolution and efficiencies between 4.4 × 104 and 1.7 × 105 plates/m. The found limits of detection ranged between 2.5 and 9.5 µmol/L. Last, real samples of post-blast explosive residues were analyzed on the ME-C4 D devices obtaining successfully the determination of Cl- , NO3- and SO42- . The achieved concentration values varied between 12.8-72.5 mg/L for Cl- , 1.7-293.1 mg/L for NO3- and 1.3-201.3 mg/L for SO42- . The data obtained using ME-C4 D devices were in good agreement with the concentrations found by ion chromatography. The approach reported herein has provided short analysis time, instrumental simplicity, good analytical performance and low cost. Furthermore, the ME-C4 D devices emerge as a powerful and portable analytical platform for on-site analysis demonstrating to be a promising tool for the crime scene investigation.


Assuntos
Eletroforese em Microchip/métodos , Substâncias Explosivas/isolamento & purificação , Ciências Forenses/métodos , Ânions/análise , Ânions/química , Ânions/isolamento & purificação , Cromatografia por Troca Iônica/métodos , Condutividade Elétrica , Substâncias Explosivas/análise , Substâncias Explosivas/química , Vidro , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes
12.
Electrophoresis ; 40(5): 693-698, 2019 03.
Artigo em Inglês | MEDLINE | ID: mdl-30597587

RESUMO

This study reports the separation of fructose, galactose, glucose, lactose and sucrose on glass microchip electrophoresis (ME) devices using a microfluidic platform adapted with external reservoirs for controlling the electrolysis phenomenon. The connections between external reservoirs and microfluidic platform were performed by saline bridges created using silicone tubing filled with BGE. The separation conditions were optimized and the best results were achieved using a BGE containing 75 mmol/L NaOH and 15 mmol/L trisodium phosphate. Electrophoretic separations were monitored using a capacitively coupled contactless conductivity detection system. The controlled electrolysis has successfully allowed the application of a higher voltage on the separation channel promoting the baseline separation of five carbohydrates within 180 s with great run-to-run repeatability (RSD < 1%). The achieved efficiencies ranged from 45 000 ± 6000 to 70 000 ± 3000 plates/m demonstrating a performance better than ME devices without controlled electrolysis. The proposed system offered good linearity from 1 to 10 mmol/L and LODs between 150 and 740 µmol/L. The use of external tubes for controlling the electrolysis phenomenon on ME devices has solved common problems associated to run-to-run repeatability and analytical reliability required for routine and quantitative analysis.


Assuntos
Eletroforese em Microchip/métodos , Açúcares/análise , Açúcares/isolamento & purificação , Condutividade Elétrica , Concentração de Íons de Hidrogênio , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes , Açúcares/química
13.
Anal Bioanal Chem ; 411(19): 4919-4928, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-30941478

RESUMO

Microfluidic paper-based devices (µPADs) and wearable devices have been highly studied to be used as diagnostic tools due to their advantages such as simplicity and ability to provide instrument-free fast results. Diseases such as periodontitis and diabetes mellitus can potentially be detected through these devices by the detection of important biomarkers. This study describes the development of µPADs through craft cutter printing for glucose and nitrite salivary diagnostics. In addition, the use of µPADs integrated into a mouthguard as a wearable sensor for glucose monitoring is also presented. µPADs were designed to contain two detection zones for glucose and nitrite assays and a sampling zone interconnected by microfluidic channels. Initially, the analytical performance of the proposed µPADs was investigated and it provided linear behavior (r2 ≥ 0.994) in the concentration ranges between 0 to 2.0 mmol L-1 and 0 to 400 µmol L-1 for glucose and nitrite, respectively. Under the optimized conditions, the limits of detection achieved for glucose and nitrite were 27 µmol L-1 and 7 µmol L-1, respectively. Human saliva samples were collected from healthy individuals and patients previously diagnosed with periodontitis or diabetes and then analyzed on the proposed µPADs. The results found using µPADs revealed higher glucose concentration values in saliva collected from patients diagnosed with diabetes mellitus and greater nitrite concentrations in saliva collected from patients diagnosed with periodontitis, as expected. The results obtained on µPADs did not differ statistically from those measured by spectrophotometry. With the aim of developing paper-based wearable sensors, µPADs were integrated, for the first time, into a silicone mouthguard using a 3D-printed holder. The proof of concept was successfully demonstrated through the monitoring of the glucose concentration in saliva after the ingestion of chocolate. According to the results reported herein, paper-based microfluidic devices offer great potential for salivary diagnostics, making their integration into a silicone mouthguard possible, generating simple, low-cost, instrument-free, and powerful wearable sensors.


Assuntos
Glucose/metabolismo , Técnicas Analíticas Microfluídicas/instrumentação , Saliva/metabolismo , Dispositivos Eletrônicos Vestíveis , Estudos de Casos e Controles , Colorimetria/métodos , Diabetes Mellitus/metabolismo , Humanos , Limite de Detecção , Nitritos/metabolismo , Papel , Periodontite/metabolismo , Estudo de Prova de Conceito , Reprodutibilidade dos Testes
14.
Anal Chem ; 90(20): 11949-11954, 2018 10 16.
Artigo em Inglês | MEDLINE | ID: mdl-30188682

RESUMO

This study describes the use of mass spectrometry imaging with matrix-assisted laser desorption/ionization (MALDI) and desorption electrospray ionization (DESI) to understand the color gradient generation commonly seen in microfluidic paper-based analytical devices (µPADs). The formation of color gradients significantly impacts assay sensitivity and reproducibility with µPADs but the mechanism for formation is poorly understood. The glucose enzymatic assay using potassium iodide (KI) as a chromogenic agent was selected to investigate the color gradient generated across a detection spot. Colorimetric measurements revealed that the relative standard deviation for the recorded pixel intensities ranged between 34 and 40%, compromising the analytical reliability. While a variety of hypotheses have been generated to explain this phenomenon, few studies have attempted to elucidate the mechanisms associated with its formation. Mass spectrometry imaging using MALDI and DESI was applied to understand the nonuniform color distribution on the detection zone. MALDI experiments were first explored to monitor the spatial distribution of the glucose oxidase and horseradish peroxidase mixture, before and after lateral flow assay with and without KI. MALDI(+)-TOF data revealed uniform enzyme distribution on the detection spots. On the other hand, after the complete assay DESI(-) measurements revealed a heterogeneous shape indicating the presence of iodide and triiodide ions at the zone edge. The reaction product (I3-) is transported by lateral flow toward the zone edge, generating the color gradient. Mass spectrometry imaging has been used for the first time to prove that color gradient forms as result of the mobility small molecules and not the enzyme distribution on µPAD surface.


Assuntos
Cor , Colorimetria , Glucose/análise , Técnicas Analíticas Microfluídicas , Papel , Aspergillus niger/enzimologia , Glucose/metabolismo , Glucose Oxidase/metabolismo , Imagem Óptica , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Propriedades de Superfície
15.
Electrophoresis ; 39(17): 2188-2194, 2018 09.
Artigo em Inglês | MEDLINE | ID: mdl-29947145

RESUMO

This study describes the development of a new analytical method for the separation and detection of cocaine (COC) and its adulterants, or cutting agents, using microchip electrophoresis (ME) devices coupled with capacitively coupled contactless conductivity detection (C4 D). All the experiments were carried out using a glass commercial ME device containing two pairs of integrated sensing electrodes. The running buffer composed of 20 mmol/L amino-2-(hydroxymethyl) propane-1,3-diol and 10 mmol/L 3,4-dimethoxycinnamic acid provided the best separation conditions for COC and its adulterants with baseline resolution (R > 1.6), separation efficiencies ranging from (2.9 ± 0.1) to (3.2 ± 0.2) × 105 plates/m, and estimated LOD values between 40 and 150 µmol/L. The quantification of COC was successfully performed in four samples seized by the Brazilian Federal Police Department and all predicted values agree with values estimated by the reference method. Some other interfering species were detected in the seized samples during the screening procedure on ME-C4 D devices. While lidocaine was detected in sample 3, the presence of levamisole was observed in samples 2 and 4. However, their concentrations were estimated to be below the LOQ. ME-C4 D devices have proved to be quite efficient for the identification and quantification of COC with errors lower than 10% when compared to the data obtained by a reference method. The approach herein reported offers great potential to be used for on-site COC screening in seized samples.


Assuntos
Cocaína/análise , Eletroforese em Microchip/métodos , Detecção do Abuso de Substâncias/métodos , Cocaína/química , Contaminação de Medicamentos , Condutividade Elétrica , Modelos Lineares , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
16.
Analyst ; 144(1): 180-185, 2018 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-30379147

RESUMO

S-nitrosothiols (RSNOs) are very important biomolecules that play crucial roles in many physiological and physiopathological processes. They act as NO-donors and are candidates for future medicines. Their identification and quantitation are therefore important for biomedical applications. One, two or more RSNOs can then be combined to design a drug and therefore, the quantification of each is important to establish an acceptable quality control process. Till date, miniaturized devices have been used to detect RSNOs based on their total quantitation without a preceding separation step. This study reports on an original and integrated microdevice allowing for the successive electrokinetic separation of low molecular weight RSNOs, their decomposition under metal catalysis, and their quantitation by amperometric detection of the produced nitrite in the end-channel arrangement, leading to their quantitation in a single run. For this purpose, a commercial SU-8/Pyrex microfluidic system was coupled to a portable and wireless potentiostat. Different operating and running parameters were optimized to achieve the best analytical data, allowing for an LOD equal to 20 µM. The simultaneous separation of S-nitrosoglutathione and S-nitrosocysteine was successfully obtained within 75 s. The proposed methodology using SU-8/Pyrex microfluidic devices opens new possibilities to investigate future drug candidates for NO-donors.


Assuntos
Cisteína/análogos & derivados , Dispositivos Lab-On-A-Chip , Técnicas Analíticas Microfluídicas/métodos , S-Nitrosoglutationa/análise , S-Nitrosotióis/análise , Catálise , Cobre/química , Cisteína/análise , Cisteína/síntese química , Cisteína/química , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Limite de Detecção , Técnicas Analíticas Microfluídicas/instrumentação , S-Nitrosoglutationa/síntese química , S-Nitrosoglutationa/química , S-Nitrosotióis/síntese química , S-Nitrosotióis/química
17.
J Sep Sci ; 41(16): 3310-3317, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29956462

RESUMO

We describe the assembly of a hybrid electrophoresis device that contains fused silica capillaries interconnected to a microfabricated interface in a cross format for the determination of inorganic cations in biological samples. The sample transport in the proposed hybrid device was performed under gated injection mode and the separations were monitored with a capacitively coupled contactless conductivity detector. The capillary extremities were inserted into polypropylene tubes to create solution reservoirs. Sensing electrodes were produced using stainless-steel hypodermic needles previously cut with 2.0 mm length. The running composition and injection time were optimized and the best results were found using 50 mmol/L lactic acid, 20 mmol/L histidine and 3 mmol/L 18-crown-6 ether, and an electrokinetic injection time of 15 s. The separation of six inorganic cations was achieved with baseline resolution, and efficiencies were between 9.1 × 103 and 5.4 × 104 plates/m. The proposed hybrid device was explored for determining the concentration levels of inorganic cations in urine, saliva, and tear samples, employing Li+ as an internal standard. The achieved results were in good agreement with the data reported in the literature. The reliability of the proposed method ranged from 93 to 98%, thus suggesting satisfactory accuracy for bioanalytical applications.


Assuntos
Compostos de Amônio/análise , Líquidos Corporais/química , Metais Alcalinos/análise , Metais Alcalinoterrosos/análise , Cátions/análise , Condutividade Elétrica , Eletrodos , Eletroforese Capilar , Humanos , Dióxido de Silício/química
18.
Electrophoresis ; 38(2): 250-257, 2017 01.
Artigo em Inglês | MEDLINE | ID: mdl-27377397

RESUMO

This study describes a simple, rapid, and cost-effective fabrication of PDMS electrophoresis microchips using poly(vinyl acetate) (PVAc) emulsion as photoresist master. High-relief microfluidic structures were defined on poly(vinyl acetate) previously deposited on printed circuit boards surfaces without cleanroom facilities and sophisticated instrumentation. After a UV exposure, channels with heights ranging from 30 to 140 µm were obtained by controlling the emulsion mass deposited on the master surface. The developing stage was performed using water rather than the organic solvents that are applied for conventional masks. The surface morphology was characterized by optical imaging, profilometry, and SEM. Based on the achieved results, the proposed method offers suitable reproducibility for the prototyping of electrophoresis microchips in PDMS. The feasibility of the resulting PDMS electrophoresis chips was successfully demonstrated with the separation of major inorganic cations within 100 s using a contactless conductivity detection system. The separation efficiencies ranged from ca. 67 900 to 125 600 plates/m. Due to the satisfactory performance and simplified instrumentation, we believe this fabrication protocol presents potential to be implemented in any chemical, biochemical, or biological laboratory.


Assuntos
Dimetilpolisiloxanos/química , Eletroforese em Microchip/instrumentação , Desenho de Equipamento/métodos , Nylons/química , Polivinil/química , Condutividade Elétrica
19.
Anal Chem ; 88(10): 5145-51, 2016 05 17.
Artigo em Inglês | MEDLINE | ID: mdl-27103080

RESUMO

We report the development of a simple, portable, low-cost, high-throughput visual colorimetric paper-based analytical device for the detection of procaine in seized cocaine samples. The interference of most common cutting agents found in cocaine samples was verified, and a novel electrochemical approach was used for sample pretreatment in order to increase the selectivity. Under the optimized experimental conditions, a linear analytical curve was obtained for procaine concentrations ranging from 5 to 60 µmol L(-1), with a detection limit of 0.9 µmol L(-1). The accuracy of the proposed method was evaluated using seized cocaine samples and an addition and recovery protocol.


Assuntos
Colorimetria/instrumentação , Técnicas Eletroquímicas/instrumentação , Papel , Procaína/análise , Cocaína/química , Contaminação de Medicamentos , Concentração de Íons de Hidrogênio , Limite de Detecção
20.
Electrophoresis ; 37(21): 2891-2895, 2016 10.
Artigo em Inglês | MEDLINE | ID: mdl-27542656

RESUMO

This report describes for the first time the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C4 D) to investigate the authenticity of seized whiskey samples, which were probably adulterated by simple dilution with tap water. The proposed microfluidic platform was explored for the monitoring of anionic species (Cl- and F- ) in both original and tampered samples. The best separations were achieved within 70 s using a running buffer composed of lactic acid and histidine (pH = 5.9). ME-C4 D devices were used to analyze samples from three different brands (five samples each). Based on the presence of inorganic anions like Cl- , F- , SO42- and NO2- in different amounts, the authenticity of seized whiskeys was compared to original samples. According to the reported data, the proposed microfluidic platform can be useful to help regulatory authorities in the investigation and monitoring of authenticity of commercialized whiskey beverages.


Assuntos
Bebidas Alcoólicas/análise , Eletroforese em Microchip/métodos , Contaminação de Alimentos/análise , Condutividade Elétrica , Ciências Forenses
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