Colorimetric determination of formaldehyde in air using a hanging drop of chromotropic acid

A simple and sensitive method to determine parts per billion (ppb) of atmospheric formaldehyde in situ, using chromotropic acid, is described. A colorimetric sensor, coupled to a droplet of 15.5 muL chromotropic acid, was constructed and used to sample and quantify formaldehyde. The sensor was set up with two optical fibers, a right emitting diode (LED) and two photodiodes. The reference and transmitted light were measured by a photodetection arrangement that converts the signals into units of absorbance. Air was sampled around the chromotropic acid droplet. A purple product was formed and measured after the sampling terminated (typically 7 min). The response is proportional to the sampling period, analyte concentration and sample flow rate. The detection limit is similar to2 ppb and can be improved by using longer sampling times and/or a sampling flow rate higher than that used in this work, 200 mL min(-1). The present technique affords a simple, inexpensive near real-time measurement with very little reagent consumption. The method is selective and highly sensitive. This sensor could be used either for outdoor or indoor atmospheres.

Colorimetric determination of ammonia in air using a hanging drop

A simple and sensitive method for determining atmospheric ammonia (NH3), using a hanging drop, is described. A colorimetric sensor is composed of two optical fibers and the source of monochromatic light implemented was a red light emitting diode (LED) (635 nm). Preliminary experiments were carried out in order to optimize the geometry of the sensor. These tests showed that the best signal absorbance was obtained using a 22 muL deionized water drop for sampling the gas and as addition of 4 muL of each of the reactants to form the blue dye (indophenol). Some important analytical parameters were also studied, including sampling time and flow rate. The analytical curve was constructed with a concentration range of 3-20 ppbv of gaseous NH3 standard. The detection limit reached was of ca 0.5 ppbv. It was observed that formaldehyde and diethylamine did not interfere. However, studies showed that hydrogen sulfide caused a negative interference of 20%, when present in the atmosphere in a concentration equal to that of NE3. The method considered here was shown to be easy to apply, making it possible to make a determination every 17 min.

Colorimetric determination of ambient ozone using indigo blue droplet

A simple and sensitive method based on a liquid droplet is described for the measurement of atmospheric ozone. A 30 μL drop of indigo blue solution is suspended in a flowing-air sampling stream. The ozone collected reacts with the indigo solution resulting in its decolorization. The colorimetric sensor is composed of two optical fibers and the source of monochromatic light was a red LED (625 nm). The calibration curve was constructed with ozone standard concentrations ranging from 37 - 123 ppbv. The detection limit achieved was 7.3 ppbv. The method considered here showed itself to be easy to apply with a fast response and a total analysis time of only 5 minutes.

Seeing smells: development of an optoelectronic nose

The development of an array of chemically-responsive dyes on a porous membrane and in its use as a general sensor for odors and volatile organic compounds (VOCs) is reviewed. These colorimetric sensor arrays (CSA) act as an "optoelectronic nose" by using an array of multiple dyes whose color changes are based on the full range of intermolecular interactions. The CSA is digitally imaged before and after exposure and the resulting difference map provides a digital fingerprint for any VOC or mixture of odorants. The result is an enormous increase in discriminatory power among odorants compared to prior electronic nose technologies. For the detection of biologically important analytes, including amines, carboxylic acids, and thiols, high sensitivities (ppbv) have been demonstrated. The array is essentially non-responsive to changes in humidity due to the hydrophobicity of the dyes and membrane.

Desenvolvimento de um sensor óptico para determinação de Norfloxacina

A presente dissertação descreve o desenvolvimento e a caracterização de sensores ópticos com base em membranas de poli(cloreto de vinilo), PVC, para determinação de Norfloxacina em amostras do sector da aquacultura. Estes sensores basearam-se na reacção colorimétrica entre um metal imobilizado em PVC e a Norfloxacina. O metal foi escolhido com base em ensaios prévios de reacção colorimétrica entre a Norfloxacina e várias espécies metálicas, nomeadamente, Fe(III), Al(III), Pb(II), Aluminon, Mo(II), Mn(II), Ni(II), Cu(II), Co(II), Sn(II) e V(V). A reacção mais intensa foi obtida com o Fe(III). Neste sentido, numa primeira fase foram desenvolvidos sensores baseados em Fe(III). O efeito de alguns parâmetros experimentais na resposta desses sensores foi avaliado de modo univariado. Incluem-se aqui o efeito do pH, avaliado entre 2,00 e 6,00, e o da concentração de Fe(III), variada entre cerca de 1,00x10-5 M e 2,00x10-4 M. Os melhores valores foram obtidos a pH 3, para o qual se verificou um comportamento linear entre cerca de 1,00x10-5 M e 1,70x10-4 M de Fe(III). Utilizando as condições seleccionadas anteriormente, procedeu-se à caracterização do complexo sob ponto de vista químico. Os valores obtidos apontaram para a necessidade de um excesso de Fe(III) de, pelo menos, 10 vezes, no sentido de garantir a máxima extensão de complexação. O complexo referido apresentou, nestas condições, um comportamento linear ao longo do intervalo de concentrações de cerca de 7,00x10-5 M a 7,00x10-4 M em NOR. O complexo formado foi estável ao longo de 90 minutos. As condições óptimas para análise desse complexo numa superfície sólida foram obtidas após avaliação do efeito da quantidade de Fe(III) e do tipo e quantidade de solvente mediador (o-nitrofenil octil éter, di-n-octilftalato, dibutilftalato, bis(etilhexil)sebacato, bis(etilhexil)ftalato). O bis(etilhexil)sebacato foi o solvente mediador escolhido e a relação de quantidade entre o PVC e o solvente mediador foi igual a 1:2. O procedimento de preparação do sensor sólido e subsequente optimização foi aplicado a outras espécies metálicas, para além do Fe(III), tais como, Cu(II), Mn(II) e aluminon. A conjugação de todos estes metais permitiu desenvolver um array de sensores para despistagem de Norfloxacina em águas de aquacultura. Algumas membranas sensoras foram aplicadas com sucesso no controlo de Norfloxacina em amostras de águas ambientais dopadas. Os resultados obtidos com membranas de Fe(III) e Cu(II) foram exactos, tendo-se registado valores de concentração próximos dos reais. O método proposto permitiu, por isso, a despistagem rápida e eficaz da presença de um antibiótico em águas ambientais, permitindo ainda o seu doseamento a um baixo custo. Numa perspectiva de rotina, e tendo em vista a despistagem deste antibiótico, este método revelou-se mais rápido e mais barato do que os demais métodos descritos na literatura para este efeito.

Design and development of a microfluidic platform for use with colorimetric gold nanoprobe assays

Due to the importance and wide applications of the DNA analysis, there is a need to make genetic analysis more available and more affordable. As such, the aim of this PhD thesis is to optimize a colorimetric DNA biosensor based on gold nanoprobes developed in CEMOP by reducing its price and the needed volume of solution without compromising the device sensitivity and reliability, towards the point of care use. Firstly, the price of the biosensor was decreased by replacing the silicon photodetector by a low cost, solution processed TiO2 photodetector. To further reduce the photodetector price, a novel fabrication method was developed: a cost-effective inkjet printing technology that enabled to increase TiO2 surface area. Secondly, the DNA biosensor was optimized by means of microfluidics that offer advantages of miniaturization, much lower sample/reagents consumption, enhanced system performance and functionality by integrating different components. In the developed microfluidic platform, the optical path length was extended by detecting along the channel and the light was transmitted by optical fibres enabling to guide the light very close to the analysed solution. Microfluidic chip of high aspect ratio (~13), smooth and nearly vertical sidewalls was fabricated in PDMS using a SU-8 mould for patterning. The platform coupled to the gold nanoprobe assay enabled detection of Mycobacterium tuberculosis using 3 8l on DNA solution, i.e. 20 times less than in the previous state-of-the-art. Subsequently, the bio-microfluidic platform was optimized in terms of cost, electrical signal processing and sensitivity to colour variation, yielding 160% improvement of colorimetric AuNPs analysis. Planar microlenses were incorporated to converge light into the sample and then to the output fibre core increasing 6 times the signal-to-losses ratio. The optimized platform enabled detection of single nucleotide polymorphism related with obesity risk (FTO) using target DNA concentration below the limit of detection of the conventionally used microplate reader (i.e. 15 ng/μl) with 10 times lower solution volume (3 μl). The combination of the unique optical properties of gold nanoprobes with microfluidic platform resulted in sensitive and accurate sensor for single nucleotide polymorphism detection operating using small volumes of solutions and without the need for substrate functionalization or sophisticated instrumentation. Simultaneously, to enable on chip reagents mixing, a PDMS micromixer was developed and optimized for the highest efficiency, low pressure drop and short mixing length. The optimized device shows 80% of mixing efficiency at Re = 0.1 in 2.5 mm long mixer with the pressure drop of 6 Pa, satisfying requirements for the application in the microfluidic platform for DNA analysis.

Colorimetric determination of sulfur dioxide in air using a droplet collector of malachite green solution

The measurement of sulfur dioxide in air at the parts-per-billion level is described. The experimental arrangement consists of two optical fibers placed on opposite sides of a liquid droplet of malachite green solution. After light has been passed through the droplet, the transmitted light is measured by a referenced photodetection arrangement. The light used in this absorption process is from a monochromatic source (lambda(max) 625 nm). This arrangement permits the variation of color in the droplet to be measured. The sulfur dioxide in the sample is collected by the droplet; it reacts with malachite green resulting in a colorless dye. The decoloration of the solution is proportional to the concentration of sulfur dioxide sampled. The signal depends on the sample flow rate. The present technique is simple, inexpensive, and permits a fast and near real time measurement while consuming very little reagent, (C) 1999 Academic Press.

Desenvolvimento de método analítico para determinação de ozônio residual em água utilizando a ténica de fluorescência e estudo da viabilidade da construção de um sensor fluorimétrico em uma gota de solução para determinação de ozônio em ar

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novel temperature-activated, humidity-sensitive optical sensor

A novel, colorimetric, temperature-activated humidity indicator is presented, with a colour change based on the semi-reversible aggregation of thiazine dyes (esp. methylene blue, MB) encapsulated within the polymer, hydroxypropyl cellulose (HPC). The initially purple MB/HPC film is activated by heat treatment at 370 °C for 4 s, at which point the film (with a colour associated with a highly aggregated form of MB; λmax = 530 nm) becomes blue (indicating the presence of monomeric and dimeric MB; i.e. with λmax = 665; 605 nm respectively). The blue, heat-treated MB/HPC films respond to an ambient environment with a relative humidity (RH) exceeding 70% at 21 °C within seconds, returning to their initial purple colour. This colour change is irreversible until the film is heat-treated once more. When exposed to a lower RH of up to ca. 47%, the film is stable in its blue form. In contrast, a MB/HPC film treated only at 220 °C for 15 s also turns a blue colour and responds in the same way to a RH value of ca. 70%, but it is unstable at moderate RH 37-50% values, so that it gradually returns to its purple form over a period of approximately 6 hours. The possible use of the high heat-treated MB/HPC humidity indicator in the packaging of goods that cannot tolerate high RH, such as dry foods and electronics, is discussed.

The Use of a Pressure-Indicating Sensor Film to Provide Feedback upon Hydrogel-Forming Microneedle Array Self-Application In Vivo

PURPOSE:
To evaluate the combination of a pressure-indicating sensor film with hydrogel-forming microneedle arrays, as a method of feedback to confirm MN insertion in vivo.
METHODS:
Pilot in vitro insertion studies were conducted using a Texture Analyser to insert MN arrays, coupled with a pressure-indicating sensor film, at varying forces into excised neonatal porcine skin. In vivo studies involved twenty human volunteers, who self-applied two hydrogel-forming MN arrays, one with a pressure-indicating sensor film incorporated and one without. Optical coherence tomography was employed to measure the resulting penetration depth and colorimetric analysis to investigate the associated colour change of the pressure-indicating sensor film.
RESULTS:
Microneedle insertion was achieved in vitro at three different forces, demonstrating the colour change of the pressure-indicating sensor film upon application of increasing pressure. When self-applied in vivo, there was no significant difference in the microneedle penetration depth resulting from each type of array, with a mean depth of 237 μm recorded. When the pressure-indicating sensor film was present, a colour change occurred upon each application, providing evidence of insertion.
CONCLUSIONS:
For the first time, this study shows how the incorporation of a simple, low-cost pressure-indicating sensor film can indicate microneedle insertion in vitro and in vivo, providing visual feedback to assure the user of correct application. Such a strategy may enhance usability of a microneedle device and, hence, assist in the future translation of the technology to widespread clinical use.

Ihwg-μnir: A Miniaturised Near-infrared Gas Sensor Based On Substrate-integrated Hollow Waveguides Coupled To A Micro-nir-spectrophotometer.

A miniaturised gas analyser is described and evaluated based on the use of a substrate-integrated hollow waveguide (iHWG) coupled to a microsized near-infrared spectrophotometer comprising a linear variable filter and an array of InGaAs detectors. This gas sensing system was applied to analyse surrogate samples of natural fuel gas containing methane, ethane, propane and butane, quantified by using multivariate regression models based on partial least square (PLS) algorithms and Savitzky-Golay 1(st) derivative data preprocessing. The external validation of the obtained models reveals root mean square errors of prediction of 0.37, 0.36, 0.67 and 0.37% (v/v), for methane, ethane, propane and butane, respectively. The developed sensing system provides particularly rapid response times upon composition changes of the gaseous sample (approximately 2 s) due the minute volume of the iHWG-based measurement cell. The sensing system developed in this study is fully portable with a hand-held sized analyser footprint, and thus ideally suited for field analysis. Last but not least, the obtained results corroborate the potential of NIR-iHWG analysers for monitoring the quality of natural gas and petrochemical gaseous products.

Measuring air pressure with a polymeric gas sensor

In this communication we describe the application of a conductive polymer gas sensor as an air pressure sensor. The device consists of a thin doped poly(4'-hexyloxy-2,5-biphenylene ethylene) (PHBPE) film deposited on an interdigitated metallic electrode. The sensor is cheap, easy to fabricate, lasts for several months, and is suitable for measuring air pressures in the range between 100 and 700 mmHg.

Active waveguide effects from porous anodic alumina: An optical sensor proposition

We present in this paper an active waveguide effect observed in porous anodic alumina (PA), which can be applied in optical sensors. The spectral position, shape, and polarization effect of the narrow waveguide modes is described. An analytical test with a commercial pesticide was performed. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3447375]

Chromic materials for responsive surface-enhanced resonance Raman scattering systems: a nanometric pH sensor

The use of chromic materials for responsive surface-enhanced resonance Raman scattering (SERRS) based nanosensors is reported. The potential of nano-chromic SERRS is demonstrated with the use of the halochrome methyl yellow to fabricate an ultrasensitive pH optical sensor. Some of the challenges of the incorporation of chromic materials with metal nanostructures are addressed through the use of computational calculations and a comparison to measured SERRS and surface-enhanced Raman scattering (SERS) spectra is presented. A strong correlation between the measured SERRS and the medium's proton concentration is demonstrated for the pH range 2-6. The high sensitivity achieved by the use of resonance Raman conditions is shown through responsive SERRS measurements from only femtolitres of volume and with the concentration of the reporting molecules approaching the single molecule regime.

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

This work describes the coupling of a biomimetic sensor to a flow injection system for the sensitive determination of paracetamol. The sensor was prepared as previously described in the literature (M. D. P. T. Sotomayor, A. Sigoli, M. R. V. Lanza, A. A. Tanaka and L. T. Kubota, J. Braz. Chem. Soc., 2008, 19, 734) by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz), a biomimetic catalyst of the P450 enzyme. The performance of the sensor for paracetamol detection was investigated and optimized in a flow injection system (FIA) using a wall jet electrochemical cell. Under optimized conditions a wide linear response range (1.0 x 10(-5) to 5.0 x 10(-2) mol L(-1)) was obtained, with a sensitivity of 2579 (+/- 129) mu A L mu mol(-1). The detection and quantification limits of the sensor for paracetamol in the FIA system were 1.0 and 3.5 mu mol L(-1), respectively. The analytical frequency was 51 samples h(-1), and over a period of five days (320 determinations) the biosensor maintained practically the same response. The system was successfully applied to paracetamol quantification in seven pharmaceutical formulations and in water samples from six rivers in Sao Paulo State, Brazil.