Claudimir Lucio do Lago

Toner and paper‐based fabrication techniques for microfluidic applications

The interest in low‐cost microfluidic platforms as well as emerging microfabrication techniques has increased considerably over the last years. Toner‐ and paper‐based techniques have appeared as two of the most promising platforms for the production of disposable devices for on‐chip applications. This review focuses on recent advances in the fabrication techniques and in the analytical/bioanalytical applications of toner and paper‐based devices. The discussion is divided in two parts dealing with (i) toner and (ii) paper devices. Examples of miniaturized devices fabricated by using direct‐printing or toner transfer masking in polyester‐toner, glass, PDMS as well as conductive platforms as recordable compact disks and printed circuit board are presented. The construction and the use of paper‐based devices for off‐site diagnosis and bioassays are also described to cover this emerging platform for low‐cost diagnostics.

Contactless conductivity detection for capillary electrophoresis: Hardware improvements and optimization of the input-signal amplitude and frequency

A new prototype of contactless conductivity detector, smaller and easier to operate than the former version, is described. For a fused-silica capillary with 142-microm wall thickness and voltages up to 25 kV, it can be placed at the low- or high-voltage end of the column. This feature allowed implementation of an apparatus with sample introduction at the grounded end of the column. The input signal is an important parameter for determining the signal-to-noise ratio (S/N) of the detection system. An optimization procedure of its amplitude and frequency is proposed. Although the SIN must be determined by introduction of actual samples, the operating conditions can be optimized merely by changing the signal parameters and by using a mathematical procedure. Thus, an easy and fast optimization routine can be carried out. Mathematical and instrumental backgrounds are discussed, and experimental support of the techniques effectiveness is presented.

A compact and high-resolution version of a capacitively coupled contactless conductivity detector

An all‐in‐one version of a capacitively coupled contactless conductivity detector is introduced. The absence of moving parts (potentiometers and connectors) makes it compact (6.5 cm3) and robust. A local oscillator, working at 1.1 MHz, was optimized to use capillaries of id from 20 to 100 μm. Low noise circuitry and a high‐resolution analog‐to‐digital converter (ADC) (21 bits effective) grant good sensitivities for capillaries and background electrolytes currently used in capillary electrophoresis. The fixed frequency and amplitude of the signal generator is a drawback that is compensated by the steady calibration curves for conductivity. Another advantage is the possibility of determining the inner diameter of a capillary by reading the ADC when air and subsequently water flow through the capillary. The difference of ADC reading may be converted into the inner diameter by a calibration curve. This feature is granted by the 21‐bit ADC, which eliminates the necessity of baseline compensation by hardware. In a typical application, the limits of detection based on the 3σ criterion (without baseline filtering) were 0.6, 0.4, 0.3, 0.5, 0.6, and 0.8 μmol/L for K+, Ba2+, Ca2+, Na+, Mg2+, and Li+, respectively, which is comparable to other high‐quality implementations of a capacitively coupled contactless conductivity detector.

Capacitively coupled contactless conductivity detection on microfluidic systems—ten years of development

The use of capacitively coupled contactless conductivity detection (C4D) on miniaturized systems has increased considerably over the last few years. Since the first report, 10 years ago, several advances on the detection cell geometry, strategies for increasing the sensitivity and a wide range of applications have been reported. This review intends to cover the main features related to the instrumental setup of this detection method for analytical and bioanalytical assays on microfluidic chips.

A toner-mediated lithographic technology for rapid prototyping of glass microchannels

A simple, fast, and inexpensive masking technology without any photolithographic step to produce glass microchannels is proposed in this work. This innovative process is based on the use of toner layers as mask for wet chemical etching. The layouts were projected in graphic software and printed on wax paper using a laser printer. The toner layer was thermally transferred from the paper to cleaned glass surfaces (microscope slides) at 130 degrees C for 2 min. After thermal transference, the glass channel was etched using 25% (v/v) hydrofluoric acid (HF) solution. The toner mask was then removed by cotton soaked in acetonitrile. The etching rate was approximately 7.1 +/- 0.6 microm min(-1). This process is economically more attractive than conventional methods because it does not require any sophisticated instrumentation and it can be implemented in any chemical/biochemical laboratory. The glass channel was thermally bonded against a flat glass cover and its analytical feasibility was investigated using capacitively coupled contactless conductivity detection (C(4)D) and laser-induced fluorescence (LIF) detection.

Conductivity detection of aliphatic alcohols in micellar electrokinetic chromatography using an oscillometric detector.

Although conductivity is usually applied to detect ionic species in capillary electrophoresis (CE), nonionic species can also be detected by their indirect effects on the conductivity of the running electrolyte. This approach was used for detection of aliphatic alcohols in micellar electrokinetic chromatography (MEKC) with an oscillometric detector. Although the detector operates at 600 kHz, for the range of electrolyte concentration used in CE, the response is mainly due to variations of conductivity. A 50 mM phosphate and 50 mM SDS solution was used as running electrolyte and as the solvent for mixtures of some isomers of propanol, butanol, and pentanol. A set of negative peaks was obtained and assigned to the components by spiking the samples. The limits of detection (LOD) ranged from 2.1 mM for 2-methyl-2-propanol to 5.3 mM for 1-pentanol. Due to the high affinity for the interior of the micelles, 1-hexanol could not be easily-detected, but by the addition of 10% methanol to the running electrolyte it was possible. For this electrolyte, the LOD was improved, ranging from 0.8 mM for 2-methyl-2-propanol to 1.5 mM for 1-pentanol. Calibration plots were linear up to 40 mM at least. These results indicate that conductivity may be useful for detection of nonionic species in CE, especially when optical methods can not be conveniently applied.

Determination of biogenic amines in beer and wine by capillary electrophoresis-tandem mass spectrometry

A capillary electrophoresis-tandem mass spectrometry (CE-MS/MS) method for the simultaneous assessment of nine biogenic amines (spermine, spermidine, putrescine, cadaverine, histamine, phenylethylamine, tryptamine, tyramine, and urocanic acid) in commercial samples of beer and wine is introduced. The samples were submitted to a simple clean-up step with poly(vinylpolypyrrolidone) followed by filtration. Electrophoretic separation in a polyvinyl alcohol (PVA)-coated capillary using 0.5 mol L(-1) acetic acid (pH 2.5) as background electrolyte and detection by electrospray-tandem mass spectrometry was employed. The range of the correlation coefficients of the calibration curves of the analyzed compounds was 0.996-0.999, and the limits of detection and limits of quantification were in the range of 1-2 μg L(-1) and 3-8 μg L(-1), respectively. The recovery values for samples spiked at three concentration levels (0.2, 0.5, and 1.0 mg L(-1)) ranged from 87 to 113% with standard deviation not greater than 5.8%. The use of a PVA-coated silica capillary allows suppressing the electroosmotic flow and, consequently, increasing of the separation efficiency. The method was successfully used to determine biogenic amines in commercial samples of beer and wine.

Environmental formaldehyde analysis by active diffusive sampling with a bundle of polypropylene porous capillaries followed by capillary zone electrophoretic separation and contactless conductivity detection

Compared to other volatile carbonylic compounds present in outdoor air, formaldehyde (CH(2)O) is the most toxic, deserving more attention in terms of indoor and outdoor air quality legislation and control. The analytical determination of CH(2)O in air still presents challenges due to the low-level concentration (in the sub-ppb range) and its variation with sampling site and time. Of the many available analytical methods for carbonylic compounds, the most widespread one is the time consuming collection in cartridges impregnated with 2,4-dinitrophenylhydrazine followed by the analysis of the formed hydrazones by HPLC. The present work proposes the use of polypropylene hollow porous capillary fibers to achieve efficient CH(2)O collection. The Oxyphan fiber (designed for blood oxygenation) was chosen for this purpose because it presents good mechanical resistance, high density of very fine pores and high ratio of collection area to volume of the acceptor fluid in the tube, all favorable for the development of air sampling apparatus. The collector device consists of a Teflon pipe inside of which a bundle of polypropylene microporous capillary membranes was introduced. While the acceptor passes at a low flow rate through the capillaries, the sampled air circulates around the fibers, impelled by a low flow membrane pump (of the type used for aquariums ventilation). The coupling of this sampling technique with the selective and quantitative determination of CH(2)O, in the form of hydroxymethanesulfonate (HMS) after derivatization with HSO(3)(-), by capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D) enabled the development of a complete analytical protocol for the CH(2)O evaluation in air.

Amperometric differential determination of ascorbic acid in beverages and vitamin C tablets using a flow cell containing an array of gold microelectrodes modified with palladium

A simple and attractive method for quantification of ascorbic acid (AA) in beers, soda, natural juices and commercial vitamin C tablets was achieved by combining flow injection analysis and amperometric detection. An array of gold microelectrodes electrochemically modified by deposition of palladium was employed as working electrode which was almost unaffected by fouling effects. Ascorbic acid was quantified in beverages and vitamin tablets using amperometric differential measurements. This method is based on three steps involving the flow injection of: (1) the sample plus a standard addition of AA, (2) the pure sample, and (3) the enzymatically-treated sample. The enzymatic treatment was carried out with Cucumis sativus tissue, which is a rich source of ascorbate oxidase, at pH 7. The calibration plots for freshly prepared ascorbic acid standards were very linear in the concentration range of 0.18–1.8 mg L−1 with a relative standard deviation (RSD) < 1%, while for real samples the deviations were between 2.7 % to 8.9 %.

Ionic mobility of the solvated proton and acid–base titration in a four-compartment capillary electrophoresis system

Although H+ and OH− are the most common ions in aqueous media, they are not usually observable in capillary electrophoresis (CE) experiments, because of the extensive use of buffer solutions as the background electrolyte. In the present work, we introduce CE equipment designed to allow the determination of such ions in a similar fashion as any other ion. Basically, it consists of a four-compartment piece of equipment for electrolysis-separated experiments (D. P. de Jesus et al., Anal. Chem., 2005, 77, 607). In such a system, the ends of the capillary are placed in two reservoirs, which are connected to two other reservoirs through electrolyte-filled tubes. The electrodes of the high-voltage power source are positioned in these reservoirs. Thus, the electrolysis products are kept away from the inputs of the capillary. The detection was provided by two capacitively coupled contactless conductivity detectors (C4D), each one positioned about 11 cm from the end of the capillary. Two applications were demonstrated: titration-like procedures for nanolitre samples and mobility measurements. Strong and weak acids (pKa < 5), pure or mixtures, could be titrated. The analytical curve is linear from 50 μM up to 10 mM of total dissociable hydrogen (r = 0.99899 for n = 10) in 10-nL samples. By including D2O in the running electrolyte, we could demonstrate how to measure the mixed proton/deuteron mobility. When H2O/D2O (9 : 1 v/v) was used as the solvent, the mobility was 289.6 ± 0.5 × 10−5 cm2 V−1 s−1. Due to the fast conversion of the species, this value is related to the overall behaviour of all isotopologues and isotopomers of the Zundel and Eigen structures, as well as the Stokesian mobility of proton and deuteron. The effect of neutral (o-phenanthroline) and negatively charged (chloroacetate) bases and aprotic solvent (DMSO) over the H+ mobility was also demonstrated.