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In this work, the influence of laser ablation and lamination parameters in the fabrication of embedded microstructures using Low Temperature Co-Fired Ceramics, have been studied. First, the influence of laser ablation parameters in the dimensions of fabricated microchannels in Low Temperature Co-Fired Ceramics substrates was characterized and strategies for tailoring the microchannels aspect ratios are described. The influence of lamination conditions on the fabrication of monolithically embedded microstructures is presented. Thereafter, a ceramic microfluidic platform, was constructed using a multilayer approach. The ceramic microfluidic platforms incorporate three independent inlet channels and a microfluidic chamber with an monolithically integrated transparent optical windows. The construction procedure used ensures monolithic ceramic devices with homogeneous surface chemistry as well as homogeneous physical properties. Fluorescence dyes were used in order to characterize the hydrodynamic focusing as a function of flow rate ratio of the microfluidic chamber inlets. The results obtained open the possibility of studying chemical process, in static or flow conditions using fluorescence imaging, within the traditional fields of LTCC technology, such as high-temperature or organic solvents applications, while using a simple fabrication procedure suitable for low cost mass production.

meso-Bromosubstituted indodicarbocyanine dyes produce dimeric molecules, together with the debrominated species, under acid catalysis. The relationship between the dimerization and hydrodebromination routes depends on the aryl substitution of the dyes. A possible reaction mechanism is also proposed.

A microanalyzer prototype for copper(II) ion monitoring in mining industrial processes is presented. The microanalyzer is designed as an assembly of different modules, each module being responsible for a unit operation. In order to optimize the industrial processes, the microanalyzer can automate all sample management, signal processing, and mathematical calculations and wirelessly transfer data to a control room. The determination of copper(II) ion is done using a colorimetric reaction and the microanalyser performs autocalibration by in situ dilution of a stock solution, matching the higher analyte concentration of the working range defined for the sample to be determined, using a multicommutation approach. The performance of the microanalyzer for monitoring copper(II) ion in water effluents of mining facilities was optimized in the working range from 1 to 10 mg/L to match Mexican environmental law regulations, which allow a maximum concentration of 4 mg/L of copper(II) ion in these circumstances.

The design, construction and evaluation of a low-cost cyclic olefin copolymer (COC)-based continuous flow microanalyzer with optical detection to determine the titratable acidity content of wine is here presented. The analysis method is based on the monitoring of the blue coloration decrease of a buffered bromothymol blue (BTB) solution in the presence of the acidic compounds of wine. The microanalyzer monolithically integrates the required microfluidic motifs as well as an optical flow cell where the measurements are performed by using a miniaturized and versatile photometric detection system. Fluid management is totally automated by the use of computer-controlled microvalves, permitting the automatic calibration of the system as well as the automatic sampling, including in-line dilution and analysis. The reduced size of the whole system along with its high simplicity and automation make it suitable for its application to the on-line monitoring of titratable acidity during wine-making processes. With the optimal conditions, a linear range up to 0.50 g L−1 tartaric acid, a quantification limit (LOQ) of 0.01 g L−1 and a detection limit (LOD) of 0.004 g L−1 were obtained, covering the most common acidity content of musts and wines. A sampling rate up to 26 h−1 could be achieved, consuming less than 3 mL of inexpensive reagents per analysis and requiring no pretreatment of the sample. The microsystem has been successfully applied to the quantification of the titratable acidity content of several wine samples, being the results in excellent agreement with the ones obtained by the reference method.

The analysis of soluble reactive phosphate (SRP) in water is key to control water quality. In order to continuous monitor orthophosphate content in water during treatment processes and in the effluents of wastewater treatment plants, conventional procedures, usually performed in a laboratory, must be adapted. This means pursuing efforts on miniaturizing systems to operate in situ and automating analytical methods to work on-line. The design, construction and evaluation of an automatic and low cost cyclic olefin copolymer (COC)-based spectrophotometric microanalyzer, capable of operating in unattended conditions, is presented to monitor soluble reactive phosphorous, as orthophosphate ion, in wastewater samples coming from sewage treatment plants. The microsystem, constructed by CNC micromilling and using a multilayer approach, integrates microfluidics to carry out the phosphomolybdenum blue (PMB) reaction and an optical flow-cell for the spectrophotometric orthophosphate determination in a single polymeric substrate smaller than a credit card. It is connected to a compact optical detection system composed by a LED emitting at 660 nm and a PIN-photodiode, both integrated in a PCB. Flow management is automatically performed by programmed microvalves and micropumps, which control autocalibration processes and allow unattended operation. Analytical features after the optimization of the microfluidic platform and the chemical and the hydrodynamic variables, were a linear range from 0.09 to 32 mg L−1 P and a detection limit of 0.03 mg L−1 P with a sampling rate of 24 samples h−1, demonstrating the microanalyzer suitability for SRP monitoring in water. Moreover, real samples were analyzed obtaining promising results.

The design, construction and evaluation of a low cost, cyclic olefin copolymer (COC)-based continuous flow microanalyzer, with optical detection, to monitor carbon dioxide in bottled wines and beers as well as in fermentation processes, is presented. The microsystem, constructed by computer numerically controlled (CNC) micromilling and using a multilayer approach, integrates microfluidics, gas-diffusion module and an optical flow-cell in a single polymeric substrate. Its size is slightly bigger than a credit card, exactly 45 × 60 × 4 mm in the microfluidic and diffusion module zone and 22.5 × 40 × 3 mm in the flow-cell zone. The gas-diffusion module is based on a hydrophobic polyvinylidene fluoride (PVDF) membrane, which allows the transfer of the carbon dioxide present in the sample to a bromothymol blue (BTB) pH-sensitive acceptor solution, where the color change is measured optically. The detection system consisted of a LED with an emission peak at 607 nm and a photodiode integrated in a printed circuit board (PCB). The obtained analytical features after the optimization of the microfluidic platform and hydrodynamic variables are a linear range from 255 to 10000 mg L−1 of CO2 and a detection limit of 83 mg L−1 with a sampling rate of 30 samples h−1.

The progress made in recent years in the area of micro total analysis system (μ-TAS) has allowed the development of analytical tools for determination and measurement of elements and compounds that previously required bench laboratory equipment for such purposes. μ-TAS provides a high degree of sensitivity and they are simple and affordable. This work details a process by which classical colorimetric methodologies used in analysis have been adapted from discontinuous to continuous flow systems, for determination of cobalt in aqueous solutions in real time. The purpose of this adaptation is the subsequent system miniaturization using low temperature co-fired ceramics (LTCC). The adapted methodology for the colorimetric determination of cobalt uses 3-Hydroxy-4-nitroso-2,7-naphtalene disulfonic acid disodium salt or nitroso-R salt (NRS) as the main reagent, in an environment of acetate and sodium citrate which favors the reaction. The carrier solution is prepared with sulfuric acid. The system encompasses a microfluidic structure in LTCC, a peristaltic pump to maintain the continuous flow, a six-way valve for sample injection, and an issuer of light of 540 nm based on a multiled. Using the integrated circuit TCS3414, the signal is sent to the computer wirelessly through zigbee protocol, and at the end a LabVIEW-based application shows the absorbance for a range of concentrations between 0.5 and 10 mg/L.

A boron trifluoride–methanol complex demonstrated remarkable deprotection selectivity against commonly used amino-protecting groups in the deacetylation of acetanilides and high sensitivity to the steric hindrance of substrates. The scope and limitations of the reaction were explored.

A novel and versatile optical reader for microfluidic platforms is presented. The reader includes a modular insertion port based on the lock and key concept for reproducible alignment with a miniaturized optical detection system comprising an interchangeable light emitting diode (LED) and a photodiode. The modular nature of the insertion port allows the use of microfluidic platforms in variable shapes and fluidic configurations. Three different analytical methodologies based on absorbance or fluorescence measurements were used to demonstrate the flexibility and reproducibility of the proposed experimental setup.

This work is focused on the design and implementation of a microsystem for continuous colorimetric determination of cobalt in aqueous solutions in real time. The main goal is the colorimetric determination of cobalt by adapting colorimetric methodologies used in discontinuous analysis systems to a continuous flow system and its subsequent miniaturization using the LTCC (Low Temperature Co-fired Ceramics) technology. The measure absorbance was recorded using an optical detection system based on a LED (Light Emitting Diode) with a wavelength of 540 nm.

Assisted reproductive technology (ART) can benefit from the features of microfluidic technologies, such as the automation of time-consuming labor-intensive procedures, the possibility to mimic in vivo environments, and the miniaturization of the required equipment. To date, most of the proposed approaches are based on polydimethylsiloxane (PDMS) as platform substrate material due to its widespread use in academia, despite certain disadvantages, such as the elevated cost of mass production. Herein, we present a rapid fabrication process for a cyclic olefin copolymer (COC) monolithic microfluidic device combining hot embossing—using a low-temperature cofired ceramic (LTCC) master—and micromilling. The microfluidic device was suitable for trapping and maturation of bovine oocytes, which were further studied to determine their ability to be fertilized. Furthermore, another COC microfluidic device was fabricated to store sperm and assess its quality parameters over time. The study herein presented demonstrates a good biocompatibility of the COC when working with gametes, and it exhibits certain advantages, such as the nonabsorption of small molecules, gas impermeability, and low fabrication costs, all at the prototyping and mass production scale, thus taking a step further toward fully automated microfluidic devices in ART.

The construction and evaluation of a Cyclic Olefin Copolymer (COC)-based continuous flow potentiometric microanalyzer to simultaneously monitor potassium, chloride and nitrate ions in samples from an on-board water recycling process expected to be installed in future manned space missions is presented. The main goals accomplished in this work address the specific required characteristics for a miniaturized on-line monitoring system to control water quality in such missions. To begin with, the integration of three ion-selective electrodes (ISEs) and a reference electrode in a compact microfluidic platform that incorporates a simple automatic autocalibration process allows obtaining information about the concentration of the three ions with optimal analytical response characteristics, but moreover with low reagents consumption and therefore with few waste generation, which is critical for this specific application. By a simple signal processing (signal removal) the chloride ion interference on the nitrate electrode response can be eliminated. Furthermore, all fluidics management is performed by computer-controlled microvalves and micropumps, so no manual intervention of the crew is necessary. The analytical features provided by the microsystem after the optimization process were a linear range from 6.3 to 630 mg L−1 and a detection limit of 0.51 mg L−1 for the potassium electrode, a linear range from 10 to 1000 mg L−1 and a detection limit of 1.58 mg L−1 for the chloride electrode and a linear range from 10 to 1000 mg L−1 and a detection limit of 3.37 mg L−1 for the nitrate electrode with a reproducibility (RSD) of 4%, 2% and 3% respectively. Sample throughput was 12 h−1 with a reagent consumptions lower than 2 mL per analysis.

The synthesis of a set of open-chain bis-aminosubstituted cyanine dyes as well as others with cyclic fragments in the polymethine chain is presented. These dyes are suitable for the development of polymeric compositions with variable optical characteristics as they can be covalently incorporated into the polymer.

An optical microfluidic system based on the use of modified gold nanoparticles for monitoring Hg(II) is presented. The system is based on the specific recognition of the heavy metal by a new synthesized ionophore based on a modified thiourea, which is attached to the gold nanoparticles. This interaction generates a change on the gold Surface Plasmon Resonance (SPR) band. The sensitivity and selectivity of the procedure is firstly studied in batch. The obtained results demonstrate the mercury selective response over the different tested ions that can be found in environmental water samples. Due to the remarkable unusual rapid signal change observed during the interaction of the metal and the modified gold nanoparticles, the reaction can be easily performed in a microfluidic system. Results obtained by using the microfluidic system revealed improved analytical features compared to batch experiments such as a lower detection limit (11 ppb), higher sensitivity and faster analysis time, all this with an easy and automated procedure. Therefore, the approach has shown great potential for designing low cost instrumentation for automatic in-field discrete or continuous measurements of Hg(II).

An automated flow analyzer based on low temperature co-fired ceramic (LTCC), a solid-phase reactor (SPR) and a low-cost photometer was designed for ascorbic acid (AA) determination in pharmaceutical formulations. It consists of a peristaltic pump, three-way solenoid valves, SPR to chemically convert Cu(II) into Cu(I), and a LTCC device for mixing the liberated copper with bathocuproine and detection. The flow cell in the LTCC employed an ultrabright LED — photodiode photometer. The analyzer successfully determined AA in pharmaceutical formulations. The analytical curve from 8.5×10−6 to 7.0×10−4 M gave a detection limit of 7.0×10−7 M and a RSD of 2.1% for a 2.0×10−4 M AA solution (n = 10). A high sampling frequency of 102 h−1 and low reagent and sample consumption (150 µL) resulted.

This work describes the development of a fully integrated Low Temperature Co-fired Ceramic (LTCC) microreactor for the synthesis of carbon dots (CDots). The microreactor integrates fluidics, a heating resistor and an optical window for fluorescence imaging of the reaction progress in a monolithic, all ceramic device, ensuring homogeneous surface chemistry and physical properties. A pool of different CDots was synthesized at high temperature and pressure using a hydrothermal method, demonstrating the robustness of the microreactor. The synthesis was monitored by following the photoluminescence of the produced CDots, and the reaction conditions were optimized according to their Quantum Yield (QY) and the flow pattern inside the microchannel. The obtained CDots exhibited blue photoluminescence upon irradiation with UV light with QYs of up to 0.77. The CDots were screened as metal nanoprobes and bioimaging contrast agents.

The construction and evaluation of a Low Temperature Co-fired Ceramics (LTCC)-based continuous flow potentiometric microanalyzer prototype to simultaneously monitor the presence of two ions (potassium and nitrate) in samples from the water recycling process for future manned space missions is presented. The microsystem integrates microfluidics and the detection system in a single substrate and it is smaller than a credit card. The detection system is based on two ion-selective electrodes (ISEs), which are built using all-solid state nitrate and potassium polymeric membranes, and a screen-printed Ag/AgCl reference electrode. The obtained analytical features after the optimization of the microfluidic design and hydrodynamics are a linear range from 10 to 1000 mg L−1 and from 1.9 to 155 mg L−1 and a detection limit of 9.56 mg L−1 and 0.81 mg L−1 for nitrate and potassium ions respectively.

A boron trifluoride–methanol complex demonstrated remarkable deprotection selectivity against commonly used amino-protecting groups in the deacetylation of acetanilides and high sensitivity to the steric hindrance of substrates. The scope and limitations of the reaction were explored.

Monitoring organic environmental contaminants is of crucial importance to ensure public health. This requires simple, portable and robust devices to carry out on-site analysis. For this purpose, a low-temperature co-fired ceramics (LTCC) microfluidic potentiometric device (LTCC/ POT) was developed for the first time for an organic compound: sulfamethoxazole (SMX). Sensory materials relied on newly designed plastic antibodies. Sol–gel, self-assembling monolayer and molecular-imprinting techniques were merged for this purpose. Silica beads were amine-modified and linked to SMX via glutaraldehyde modification. Condensation polymerization was conducted around SMX to fill the vacant spaces. SMX was removed after, leaving behind imprinted sites of complementary shape. The obtained particles were used as ionophores in plasticized PVC membranes. The most suitable membrane composition was selected in steady-state assays. Its suitability to flow analysis was verified in flow-injection studies with regular tubular electrodes. The LTCC/ POT device integrated a bidimensional mixer, an embedded reference electrode based on Ag/AgCl and an Ag-based contact screen-printed under a micromachined cavity of 600 m depth. The sensing membranes were deposited over this contact and acted as indicating electrodes. Under optimum conditions, the SMX sensor displayed slopes of about −58.7 mV/decade in a range from 12.7 to 250 g/mL, providing a detection limit of 3.85 g/mL and a sampling throughput of 36 samples/h with a reagent consumption of 3.3 mL per sample. The system was adjusted later to multiple analyte detection by including a second potentiomet-ric cell on the LTCC/ POT device. No additional reference electrode was required. This concept was applied to Trimethoprim (TMP), always administered concomitantly with sulphonamide drugs, and tested in fish-farming waters. The biparametric microanalyzer displayed Nernstian behaviour, with aver-age slopes −54.7 (SMX) and +57.8 (TMP) mV/ decade. To demonstrate the microanalyzer capabilities for real applications, it was successfully applied to single and simultaneous determination of SMX and TMP in aquaculture waters. The authors acknowledge the financial support from FCT, Fundacão para a Ciência e Tecnologia/FEDER (project PTDC/AGR-AAM/68359/2006). Oneofus (Almeida SAA) is grateful to FCT for the PhD Grant (SFRH/BD/42509/2007). Publicado

A multicommutation-based flow system with photometric detection was developed, employing an analytical microsystem constructed with low temperature co-fired ceramics (LTCC) technology, a solid-phase reactor containing particles of Canavalia ensiformis DC (urease source) immobilized with glutaraldehyde, and a mini-photometer coupled directly to the microsystem which monolithically integrates a continuous flow cell. The determination of urea in milk was based on the hydrolysis of urea in the solid-phase reactor and the ammonium ions produced were monitored using the Berthelot reaction. The analytical curve was linear in the urea concentration range from 1.0 x 10(-4) to 5.0 x 10(-3) mol L(-1) with a limit of detection of 8.0 x 10(-6) mol L(-1). The relative standard deviation (RSD) for a 2.0 x 10(-3) mol L(-1) urea solution was lower than 0.4% (n = 10) and the sample throughput was 13 h(-1). To check the reproducibility of the flow system, calibration curves were obtained with freshly prepared solutions on different days and the RSD obtained was 4.7% (n = 6). Accuracy was assessed by comparing the results of the proposed method with those from the official procedure and the data are in close agreement, at a 95% confidence level.

Low-temperature cofired ceramics (LTCC) technology is a versatile fabrication technique used to construct microflow systems. It permits the integration of several unitary operations (pretreatment, separation, (bio)chemical reaction, and detection stage) of an analytical process in a modular or monolithic way. Moreover, because of its compatibility with biological material, LTCC is adequate for analytical applications based on enzymatic reactions. Here we present the design, construction, and evaluation of a LTCC microfluidic system that integrates a microreactor (internal volume, 24.28 microL) with an immobilized beta-galactosidase from Escherichia coli (0.479 activity units) and an optical flow cell to measure the product of the enzymatic reaction. The enzyme was immobilized on a glyoxal-agarose support, maintaining its activity along the time of the study. As a proof of concept, the LTCC-beta-galactosidase system was tested by measuring the conversion of ortho-nitrophenyl beta-D-galactopyranoside, the substrate usually employed for activity determinations. Once packed in a monolithically integrated microcolumn, the miniaturized flow system was characterized, the operational conditions optimized (flow rate and injection volume), and its performance successfully evaluated by determining the beta-galactosidase substrate concentration at the millimolar level.

A novel fluorescence dip-probe POF (Polymer Optical Fiber) sensor that allows performing in situ chemical determinations has been fabricated. The dip-probe sensor design has been optimized by simulations in order to improve the fluorescence collection. To demonstrate its possibilities, it has been chemically activated with a lead-selective plasticized PVC (polyvinylchloride) membrane containing a new synthesized suitable fluoroionophore and a commercial lead ionophore. The analytical response of the dip-probe sensor has been characterized and it shows a fully reversible response with a sensitivity of −35.10 mV/dec C and a Pb2+ detection limit of 7 × 10−6 M, which can be appropriate for monitoring contamination episodes. No significant interferences with other metal ions have been found. The device has been finally tested to determine the lead content in contaminated natural samples with promising results.

In this work, selective chemical sensors of phosphorus (PO4 3−) installed in PVC probes and their associated instrumentation were evaluated in soil solution phosphorous monitoring. The evaluation was carried out with the addition of a 0.1 mol L−1 P‐PO4 3− solution in the soil, followed by data acquisition supplied by the probes; by collecting soil samples in the region where the probes were installed; and by phosphorus determination through conventional laboratory techniques. The phosphorus amounts were determined by spectrophotometry after the following extraction methodologies: Mehlich 1, Mehlich 3, and ionic exchange resin. The results, compared with the potentials registered by the probes, express the best correlation with the results obtained with the resin method. The results indicate good response of the sensors and the potential applicability of these probes to assist in the monitoring of soil nutrients, helping to establish rational processes in the use of fertilizers in crops.

A miniaturized and robust optical fluorosensor, designed as a portable instrumentation for the in situ analysis of ions in water samples by using optodes has been constructed with low cost discrete optical components. The chemical recognition element of the device consists of a plasticized PVC-based fluorescent optode, which includes a new hexamethine–hemicyanine dye as a fluorophore. The signal can be attributed to a certain analyte depending on the ionophore employed. In this work, a commercial potassium ionophore (valinomycin) has been used to formulate a model membrane selective to potassium. The sensor has been fully characterized using a simple flow injection analysis (FIA) system and analytical parameters such as sensitivity (0.71 mV dec −1 ), limit of detection (2.2 × 10 −5 M K + ), repeatability (R.S.D. = 4.2%), reproducibility, lifetime and ionic interferences have been determined. The developed miniaturized system has been applied to the potassium concentration determination in spiked tap water samples. The obtained results have been compared to those acquired by the ICP-OES reference method and the suitability of the experimental setup for the determination of ions in water samples by the miniaturized fluorescence proposal has been demonstrated.

The integration of optical detection methods in continuous flow microsystems can highly extend their range of application, as long as some negative effects derived from their scaling down can be minimized. Downsizing affects to a greater extent the sensitivity of systems based on absorbance measurements than the sensitivity of those based on emission ones. However, a careful design of the instrumental setup is needed to maintain the analytical features in both cases. In this work, we present the construction and evaluation of a simple miniaturized optical system, which integrates a novel flow cell configuration to carry out chemiluminescence (CL) measurements using a simple photodiode. It consists of a micromixer based on a vortex structure, which has been constructed by means of the low-temperature cofired ceramics (LTCC) technology. This mixer not only efficiently promotes the CL reaction due to the generated high turbulence but also allows the detection to be carried out in the same area, avoiding intensity signal losses. As a demonstration, a flow injection system has been designed and optimized for the detection of cobalt(II) in water samples. It shows a linear response between 2 and 20 muM with a correlation of r > 0.993, a limit of detection of 1.1 muM, a repeatability of RSD = 12.4 %, and an analysis time of 17 s. These results demonstrate the suitability of the proposal to the determination of compounds involved in CL reactions by means of an easily constructed versatile device based on low-cost instrumentation. This work was supported by the Spanish "Comisión Interministerial de Ciencia y Tecnología" through Projects CICYT-TEC2006-13907-C04/MIC and PTR1995-0770-OP and Project MEC (PHB2004-0105-PC)-CAPES. Publicado

An agrarian sensorial system based on temperature, moisture, and all solid-state ion-selective potentiometric sensors was developed with the objective of monitoring the behavior of H+ and Ca2+ ions in soil and in real conditions, contributing with a new tool that tries to complement the current precision agriculture technology. The evaluation of the sensorial system to pH monitoring presented a good correlation between the results obtained by the system and the standard methodology, allowing us to notice the soil buffer capacity at different soil depths. With regard to calcium, the sensor system also presented an agreement between its results and those obtained by flame atomic absorption spectrometry, using a calibration model based on multiple linear regressions that allows the correct determination of Ca2+ concentrations in soil depths where the relative moisture is different. In this way, using well-known potentiometric sensors in a complex, discontinued, and heterogeneous matrix, such as soil, the sensorial system proved to be a useful task for agrochemical field applications.

Among the several fabrication techniques used to construct microflow systems, the low-temperature cofired ceramics (LTCC) technology, taking advantage of its multilayer approach, is one of the most versatile ones. It permits the integration of several unitary operations of an analytical process in a modular or monolithic way. Moreover, due to its perfect compatibility with screen-printing techniques, it also permits the integration of electronic components used to control the whole system setup. In this work the design, construction, and evaluation of a miniaturized analyzer for pesticide determination that integrates a pretreatment stage, based on two mixers or reactors, and an amperometric detection system to measure the product of an enzymatic inhibition reaction are presented. The detection system was monolithically integrated in the microfluidic platform, and it consisted of a screen-printed reference electrode and two platinum sheets, acting as auxiliary and working electrodes, which were embedded within the ceramic structure. The miniaturized system was characterized and successfully evaluated by determining carbofuran at the nanomolar level.

New norcyanine dyes were characterised for their use as long wavelength chromoionophores in optodes. Different membrane compositions were formulated for pH determination in water and their response in terms of sensitivity, linear range, response time and reversibility was examined with the aim to apply them in planar optochemical sensors. Their absorbance maxima are located in the NIR region (785–830 nm), which is very appropriate for applications using common low cost telecommunication components. The characterised optodes showed good analytical features. Hence, fully reversible, reproducible, fast, and sensitive bulk optodes were obtained. The photostability of dyes in the plasticised matrices and their tendency to leach from the membrane phase were also evaluated at different conditions.

New far-visible absorbing anilino-cyanine dyes have been synthesised for future application as chromoionophores in integrated waveguide absorbance optodes based on bulk optodes. The effect of the heterocycle, of the substitution of the heterocyclic nitrogen and of the type of heptamethine central ring on the pKa values (4.3–8.2 in ethanol–water solutions and 9.5–11.0 in plasticised PVC membranes), on the spectroscopic characteristics of the dye and on photostability is discussed. pH-selective bulk optodes have been formulated as a first approach to develop ion-selective optodes, and sensitivity, repeatability, lifetime and response time have been determined. The dyes show good analytical behaviour for use as chromoionophores for the development of ion-selective optodes. Reversible (80–87%), fast (tr90% = 0.94–2.28 min) and pH-sensitive membranes (slopes of 0.09–0.23 ΔAbs·pHdec–1, absorbance range 0.19–0.53) have been obtained. Moreover, they exhibit good spectroscopic features for employment with integrated optochemical sensors: absorption maxima of the acidic species in plasticised PVC membranes matched those of 650–670-nm LEDs, high molar absorption coefficients (\( \varepsilon _{{{\text{acidic}}}} = 3.5 \times 10^{4} - 9.3 \times 10^{4} \) L mol–1 cm–1 and \( \varepsilon _{{{\text{basic}}}} = 1.9 \times 10^{4} - 6.7 \times 10^{4} \) L mol−1 cm−1) and fluorescence.

New nor-based cyanine dyes have been characterised for their use as long wavelength chromoionophores in optochemical sensors. Since common quaternary cyanine dyes present optimum spectroscopic characteristics but with high basicities, three kinds of molecules (nortricarbocyanine dyes, norindosquarocyanine dyes and norindocrococyanine dyes), based on an acid–base equilibrium, where the proton attached to the indolic nitrogen is involved, have been designed, expecting to obtain lower p K a values. For comparison purposes, every type of dye has been synthesised with a different central group and molecules with the same heterocyclic substituents have been proposed. The acid forms of the norcyanine dyes present sharp and intense absorption bands from the far visible to the NIR region, with absorption maxima between 648 and 821 nm, allowing the use of non-expensive semiconductor based optical sources and detectors. Relationships between the optical properties, the basicity and the molecular structure are discussed.

This paper describes the development of a new flow system by substituting the injection valve of a FIA system with an automatic microburette controlled by a PC via an RS-232 interface to introduce flexibility into the system. Initially, the response of the system was characterized without a chemical reaction by using a reference system (6-port valve) and a modified system (automatic microburette). The response vs. flow rate and injected volume were studied. The statistic analysis and comparison of the dispersion coefficients obtained for both systems showed no significant difference between them. Comparative studies with chemical reactions were also performed using a reverse Flow Injection Analysis (r-FIA) technique and the Griess-Ilosvay model reaction for nitrite ions. Finally, the system based on the automatic microburette was validated for the analysis of nitrite in two complementary concentration ranges (0.0–0.1 and 0.0–3.0 mg · L−1) using 25 and 350 µL of reactant, respectively. The detection limits obtained were 0.009 and 0.024 mg · L−1, respectively. High repeatability was obtained for both concentration ranges (RSD: 0.52 and 1.35%, respectively).

Some new symmetrical and unsymmetrical near-infrared absorbing acidochromic dyes are synthesised by a simple one-step reaction. Such indicators belong to the ketocyanine dyes type and as well as their full characterisation as the relationship between their structure and optical properties are discussed. They are mainly tested for their future application as pH or solvent polarity sensors. The absorption maxima of the long-wavelength absorbing acidic form span the region from 715 to 750 nm, nearly matching the emission wavelength of the 780 nm laser diode. p K a values in ethanol cover the range between 1.7 and 4.3, and reversible absorption spectra are observed while pH is changed forth and back. As merocyanine dyes, the synthesised ketocyanine dyes show a positive solvatochromism. Since one of the requirements for a solvatochromic molecule to be useful to establish a solvent polarity scale is its stability, the photostability of the dyes is tested in ethanolic solution as well.

Twenty ketocyanine dyes are evaluated as potential pH fluoroionophores to be used in the development of new integrated waveguide fluorescence optodes (IWFOs). Its fluorescence characterization, as well as the pH response is first undertaken in ethanolic solution and then in plasticized PVC membranes with a conventional spectrofluorimeter. Analytical parameters such as basicity, reversibility, leaching and calibration curves are determined in both media and finally, photostability is also measured. Besides, some photophysical fluorescent parameters, such as the emission wavelength, are evaluated for both species, the acidic and the basic form, and quantum yields are calculated in ethanolic solution. Ketocyanine dyes have demonstrated their suitability for being used as acidochromic fluoroionophores in bulk optodes for the development of new IWFOs. They exhibit high fluorescence intensities in the far-visible region, an adequate photostability and an optimum pH response.

In this paper, the low-temperature co-fired ceramics (LTCC) technology, which has been commonly used for electronic applications, is presented as a useful alternative to construct continuous flow analytical microsystems. This technology enables not only the fabrication of complex three-dimensional structures rapidly and at a realistic cost but also the integration of the elements needed to carry out a whole analytical process, such as pretreatment steps, mixers, and detection systems. In this work, a simple and general procedure for the integration of ion-selective electrodes based on liquid ion exchanger is proposed and illustrated by using ammonium- and nitrate-selective membranes. Additionally, a screen-printed reference electrode was easily incorporated into the microfluidic LTCC structure allowing a complete on-chip integration of the potentiometric detection. Analytical features of the proposed systems are presented.

A set of near-infrared absorbing tricarbocyanine dyes has been synthesised and characterised for their future application as chromoionophores in optochemical sensors. Their absorption maxima are localised in the NIR region, where matrix interferences are minimal and the use of suitable and inexpensive optical communication components gives great advantages. The acid form of the synthesised dyes in pure ethanol spans the region from 675 to 815 nm and the molar absorptivities are up to 3.3 × 10 5 l/mol cm. The calculated p K a values in ethanol lie between 11.4 and more than 13. The effect of the introduction of substituents on the p K a values and on the spectroscopic characteristics of the dyes is also discussed. Moreover, pH-sensitive aggregation processes have been observed in aqueous solution.

Acyclic Pd–diaminocarbene complex showed high catalytic activity in Suzuki arylation of meso-chlorine-substituted tricarboindocyanine dyes. Arylated dyes were obtained in 57–83% yields in the presence of 5 × 10−4 equiv of catalyst.

The present report describes the development of a thick-film sensor with intended applications for soil analysis. A probe incorporates three sensors, each at a different depth and featuring a copper plate as the reference electrode. In addition, the probe also contains all necessary instrumentation required for processing the sensor signal and to transmit it via radio. The developed sensors were calibrated in situ using two different soil compositions by adding standard solutions. Results show a quasi-Nernstian response in soil, in response to the addition of fertilisers. Extracts of soil samples analysed by the Kjeldahl method were compared with results from the probe. This comparison confirms that the sensors are capable or measuring chemical parameters in situ in an automated fashion.

The first prototype of a technologically improved integrated waveguide absorbance optode (IWAO) was developed and tested with a membrane based on a new H+-selective ketocyanine dye and a cadmium ionophore. It was designed with curved instead of rectilinear planar waveguides. Results demonstrated the suitability of the new IWAOs to be employed as sensing platforms, which confer versatility, robustness, and mass production capabilities besides high sensitivity on conventional bulk optodes, as well as the usefulness of such dyes in developing ion-selective membranes in combination with a selective ionophore. The sensor integration as a detector in a flow injection system (FIA) was proposed to obtain an automated, simple, and sufficiently reproducible (RSD5%) analytical methodology with a sample throughput of 55 h(-1). Very sensitive optodes were obtained, and detection limits on the order of 20 ppb were achieved. Because of the ionophore employed, the optode system showed excellent selectivity over alkali and alkaline-earth metals with the exception of samples containing lead and cadmium ions, where the membrane responded to both analytes. The proposed procedure combines all the advantages of the FIA systems, the simplicity of optical detection, ion recognition selectivity, and sensitivity of ketocyanine dyes, and the features achieved using the integrated device, which comprise an improved sensitivity and short response times as well as robustness, easy handling, and mass production.

In this paper, the universal determination of non-ionic surfactants (NIS) of the polyethoxylate type is attempted using flow-injection potentiometry. Two systems are proposed which use specifically developed tubular flow-through ion selective electrodes (ISEs). These are sensitive to NIS with an hydrophilic chain between 6 and 18 ethoxylate units, which are predominant species in the environment. An on-line pre-concentration system is designed with the aim of a possible application for the unattended monitoring of NIS in surface waters. This on-line pre-concentration is achieved by employing a column packed with a commercial solid phase extraction (SPE) sorbent for the enrichment and purification of the target analytes. The procedure outlined improves the detection limit of a direct system, decreasing it from 1×10 −4 to 3×10 −6 M by use of a pre-concentration volume of 40.0 ml and 200 μl of 75% acetonitrile in water as the eluent. Precision was estimated as 4% relative standard deviation (R.S.D.) ( n =25) for a 1×10 −6 M (0.7 ppm) nonylphenol polyethoxylate with 12 ethoxylate units when 10.0 ml of sample are pre-concentrated. Finally, the on-line pre-concentration system is applied for the total NIS determination in environmental samples from Llobregat river basin of Barcelona area (NE Spain).

The design, construction and evaluation of a versatile cyclic olefin copolymer (COC)-based continuous flow potentiometric microanalyzer to monitor the presence of ammonium ion in recycling water processes for future manned space missions is presented. The microsystem integrates microfluidics, a gas-diffusion module and a detection system in a single substrate. The gas-diffusion module was integrated by a hydrophobic polyvinylidene fluoride (PVDF) membrane. The potentiometric detection system is based on an all-solid state ammonium selective electrode and a screen-printed Ag/AgCl reference electrode. The analytical features provided by the analytical microsystem after the optimization process were a linear range from 0.15 to 500 mg L−1 and a detection limit of 0.07 ± 0.01 mg L−1. Nevertheless, the operational features can be easily adapted to other applications through the modification of the hydrodynamic variables of the microfluidic platform.

A centrifugal microfluidic platform prototype with an integrated membrane for gas diffusion is presented for the first time. The centrifugal platform allows multiple and parallel analysis on a single disk and integrates at least ten independent microfluidic subunits, which allow both calibration and sample determination. It is constructed with a polymeric substrate material and it is designed to perform colorimetric determinations by the use of a simple miniaturized optical detection system. The determination of three different analytes, sulfur dioxide, nitrite and carbon dioxide, is carried out as a proof of concept of a versatile microfluidic system for the determination of analytes which involve a gas diffusion separation step during the analytical procedure.

Standard methods to measure nutrient levels in soil are complex and time consuming due to the extraction and pre-treatment processes involved. The instrumentation used for these measurements is also expensive. Therefore, the use of chemical sensors would be interesting since they can be applied directly to the soil. Thus, it would provide results in real or quasi real time at a moderate cost. The control of these nutrients will permit an optimisation of the overall production process of the crop. Besides, this approach will be useful for reducing the environmental impact caused by excess of nutrients in crop soils. In this work, the use of chemical sensors based on Ion Sensitive Field Effect Transistors (ISFETs) for soil analysis is proposed. These devices are fabricated with microelectronic technology -providing this fact some important advantages- but their mechanism of response are similar to that of Ion selective electrodes (ISEs). Fabrication of pH, Ca 2+ , K + and NO 3 - ISFETs and their evaluation in aqueous solutions is reported. From the preliminary results of their application in soils it is possible to confirm their feasibility as sensors for in-soil monitoring and the promising future applications they have.

A method is described for the conductimetric determination of CO 2 . The proposed system was constructed with a pervaporator chamber coupled to a flow system comprised of a six-way solenoid valve, a conductivity cell, a conductivimeter and a PC microcomputer for data acquisition and external controls. An amount of 2 g of dry soil samples were directly weighted in the donor compartment of the pervaporation chamber. The CO 2 was determined from an analytical curve within 5.0 x 10 -3 -5.0 x 10 -2 mol kg -1 CaCO 3 . This curve was constructed with the matrix matching approach and presented a linear regression of y = 13.58 + 584.77r (r = 0.9962). Soils with different lime amounts were analyzed by the proposed methodology and with the official method, that uses the calcium difference between the total, extracted with HCl 1 mol l -1 and exchangeable, extracted with the KCl 1 mol l -1 After paired t-test application, no significant difference between the methods was found at the 95% probability level. The proposed method presented sampling rate of 17 h -1 , detection limit of 8.0 x 10 -4 mol kg -1 CaCO 3 , and R.S.D. < 3%. The use of the pervaporator allowed the in situ soil pretreatment for the residual lime determination.

A flow injection system for the determination of polyethoxylated nonionic surfactants is described. Potentiometric detection based on tubular flow-through ion-selective electrodes (ISEs) sensitive to this type of surfactants was used. As ion-exchanger, the plasticised PVC membrane incorporates the ion pair between the adduct of a nonionic surfactant with barium and tetraphenylborate. Two different membrane compositions were studied. They differed in the nonionic surfactant used in the ion-exchanger preparation: either nonylphenoxypolyethoxylate with 5 (Ig5) or 12 (Ig12) ethylene oxide units were used. Experimental results showed that the use of Ig5 membrane with a barium salt adjusting solution allowed lower detection limits, while Ig12 ISE with potassium salt solution presented enhanced sensitivity. Both FI systems were evaluated employing three different polyethoxylate standards, which could be determined down to ca. 10 −5 M. Precision was 3% R.S.D. for n = 50 using repetitive injections of a 3 × 10 −4 M Ig12 standard. Preliminary tests of an on-line preconcentration flow system employing the developed sensing devices are also shown. © 2001 Elsevier Science B.V. All rights reserved.

The fabrication of ion-sensitive electrochemical sensors for calcium is described in the present work. The membrane uses a photocurable polymer based on aliphatic diacrylated polyurethane. The use of photocurable polymers as the support matrix instead of PVC simplifies the preparation and the casting of the developed ion-sensitive membranes. Additionally, these polymers are compatible with the photolithographic fabrication techniques used in the microelectronics industry. This aspect permits the patterning of membranes on wafer level for semiconductor based sensors thus the automatization of the whole sensor fabrication. These polymer matrices show also better adhesion to silanised semiconductor surfaces, such as the gate surfaces of ion selective field effect transistors (ISFETs). Membranes sensitive to calcium ions were optimised according the type of plasticizer and the polymer/plasticizer ratio. Ion selective electrodes (ISEs) with a solid internal reference and ISFETs were used to evaluate the membrane. The resulting sensors were functional for periods of more than 8 months and the resulting sensitivities were quasi-Nernstian (26–27 mV/dec) in a range of 5×10 −6 –8×10 −2 M. These sensors were used to measure calcium activity in water samples extracted from agricultural soils. The results were compared with those yielded by standard methods, finding a good correlation between the two analytical procedures.

A new approach for developing absorbance optochemical sensors is presented in this paper. It is based on a planar microoptic circuit where an optochemically active membrane, which responds selectively to a compound, is deposited in the device, yielding a part of the guiding planar structure. Light is propagated through the membrane, which changes its spectral absorption properties and controls the selectivity of the measurements by means of several immobilised compounds. This way, high sensitivity of the device can be easily obtained due to relatively long light paths through the membrane, and low response times can be achieved as the analyte diffusion occurs perpendicularly to the light path and through a thin membrane. Experimental results on measurements of the concentration of a specific ion in solution using the fabricated sensors are also presented.

A new type of absorbance-based optical sensor is presented. It is based on a chemical transduction membrane that acts simultaneously as the sensing element and as the light guiding medium. This membrane is inserted between two micromachined waveguides in a silica on silicon structure. Light propagates longitudinally through the membrane, which changes its spectral properties accordingly while interacting with the analyte. As the path length corresponds to the membrane length, not its thickness, high sensitivity can be achieved without an increase of the response time. This paper summarizes the design, the construction, and the validation results obtained with integrated waveguide absorbance optode (IWAO) prototypes. The main advantages of the reported optode are its simple configuration, high sensitivity, and versatility. Experimental results obtained with this IWAO, using a potassium-selective bulk optode, are shown and compared to those obtained with a conventional absorbance device incorporating the sa...

A colorimetric flow injection-system for the determination of Cu(II) in waters based on complexation reaction with 4-(2-pyridylazo)-resorcinol, usually termed PAR, is described. Performing measurements in 0.25 mol l −1 HNO 3 medium allowed improved selectivity of the analytical method. The lack of sensitivity deriving from the low complex absorption under acidic conditions was balanced by the insertion of an immobilised poly(ethylenimine) (PEI) column where Cu(II) pre-concentration in neutral media occurs. Using sample volumes ranging from 2 to 4 ml, sampling rates of 24 and 12 samples h −1 within a detection limit of 25 and 13 μg l −1 , respectively, were accomplished. Accuracy of the developed methodology was assessed by comparison with atomic absorption spectrometry being the relationship [FIA] mg l −1 =1.00 (±0.03)×[AAS] mg l −1 +0.00 (±0.02) obtained after analysing 15 samples. Precision was also evaluated using two samples of 0.05 and 0.5 mg l −1 copper, and a relative standard deviation (R.S.D.) better than 3% was attained for both.

The authors present an automated flow injection analysis (FIA) system for the determination of low levels of anionic surfactants in river water and wastewater. The system uses especially constructed tubular flow-through ion-selective electrodes (ISEs) as potentiometric sensors and on-line preconcentration techniques. The anionic surfactant ISEs employed are of the all-solid-state type with a plasticized PVC membrane. They show a general response to anionic surfactants with a lower limit of linear response of ∼10(-)(5) M, when used in direct determinations. However, their specificity is limited, which hampers their direct use with environmental samples. Therefore, the FIA system presented here includes a solid-phase extraction procedure for purification and preconcentration of analytes. Breakthrough curves were constructed to characterize different sorbents and different eluents were tested to optimize the preconcentration process. The FIA system was first applied to the determination of different types of anionic surfactant standards. Potentially interfering substances such as chloride, nitrate, and nonionic surfactants were checked to verify that they did not interfere on the response of the system. Concentrations of ∼10(-)(7) M (0.03 ppm) of sodium dodecyl sulfate could be detected in the nonlinear response region when 3 mL of sample was preconcentrated and eluted with 50 μL of a 75% acetonitrile/water (v/v) solution. Precision was 2% RSD (n = 31) for a 1 × 10(-)(6) M sodium dodecyl sulfate standard solution and the sample throughput was 10 h(-)(1). The FIA system was then used for the determination of total anionic surfactants in river water and wastewater.

The development of a new electrochemical microsensor based on silicon technology with a photocurable enzyme membrane based on polyurethane acrylate is described. The use of photocurable polymers as the entrapping matrix for enzymes fulfils all the requirements expected for these materials without damaging the biological material. Additionally, the preparation of biosensor devices following this methodology is fast and simple, and this entails the main improvement shown by the new immobilisation method proposed here. The polymer used for enzyme immobilisation enhances the adhesion of the membrane to the previously silanised ion-sensitive field effect transistor (ISFET) gate and assures a long-term stability of more than one month. Additionally, this material provides a membrane deposition methodology compatible with photolithographic techniques allowing mass-production of low cost biosensors. The membrane has been optimised taking into account a good entrapment of the biological material and the effective transport of the substrate and the products through the membrane. After mixing the components of the prepolymer solution, a short exposure (30 s) to 365 nm UV-radiation produced a polymeric membrane without damaging the enzyme. The calibration parameters for the sensors prepared compared well with other methods yielding a slope of 58 mV/dec and a linear range of 0.04–36.0 mM urea in a NH4Cl pH 5.6 solution. The response time (t 95%) was approximately 2 min.