Correction: Inkjet-printed O2 gas sensors in intelligent packaging.

Correction for 'Inkjet-printed O2 gas sensors in intelligent packaging' by M. D. Fernández-Ramos et al., Analyst, 2021, 146, 3177-3184, https://doi.org/10.1039/D1AN00295C.

Correction: An optical sensor for the sensitive determination of formaldehyde gas based on chromotropic acid and 4-aminoazobenzene immobilized in a hydrophilic membrane.

Correction for 'An optical sensor for the sensitive determination of formaldehyde gas based on chromotropic acid and 4-aminoazobenzene immobilized in a hydrophilic membrane' by M. D. Fernández-Ramos et al., Analyst, 2023, 148, 4533-4538, https://doi.org/10.1039/D3AN01056B.

An optical sensor for the sensitive determination of formaldehyde gas based on chromotropic acid and 4-aminoazobenzene immobilized in a hydrophilic membrane.

Formaldehyde is a common contaminant in occupational and environmental atmospheres, prolonged exposure leads to health risks, and its determination is necessary to protect health. There is a great demand for portable, rapid, and sensitive methods that can be used in resource-limited settings. In this respect, a colorimetric sensor has been developed based on the colour change from pink to purple of co-immobilized chromotropic acid and 4-aminoazobenzene in hydroxypropyl methylcellulose when it is exposed to different concentrations of formaldehyde. The concentration of formaldehyde in the gas phase was quantified by measuring the change of the appropriate colour coordinates in response to the concentration of formaldehyde. A calibration curve was obtained for formaldehyde, with a useful concentration range from 0.08 to 0.6 ppmv. The detection limit was 0.016 ppmv, which is lower than the maximum exposure concentrations recommended by both the World Health Organization (WHO) and the Occupational Safety and Health Administration (OSHA). The optical sensor was found to have good reproducibility, with a relative standard deviation of 2.3 and 1.7% at 0.08 and 0.25 ppmv, respectively. The sensor can operate at room temperature and environmental humidity, 25 °C, and 50% RH, respectively. In addition, a study of interferents (acetaldehyde, toluene, methanol, ethyl acetate, acetone, acetic acid, carbon dioxide and ammonia) showed high selectivity for formaldehyde, which indicates that this membrane is a simple, fast, and economical alternative for quantifying the concentration of formaldehyde in different environments.

Design of colorimetric nanostructured sensor phases for simple and fast quantification of low concentrations of acid vapors.

Two colorimetric nanostructured sensor phases (Color-NSPs) for the determination of low concentrations of acid vapors in the atmosphere of paper storage rooms have been designed and characterized. The acid vapor determination is based on the color change that occurs in polyaniline (PANI) in the presence of acids when it goes from its emeraldine base form (blue) to its emeraldine salt form (green). To synthesize the Color-NSPs, two methods have been used, a one-step method performed by grafting polyaniline onto a cellulose membrane (Cellu-PANI) and a two-step method in which in the first step, polyaniline is grafted onto the surface of polymeric nanoparticles (NPs-PANI), and in a second step, NPs-PANI are immobilized into the pores of a nylon membrane (Nylon-NPs PANI). The response of the sensors versus acid vapor was measured by color coordinates with a photographic camera. A linear response range from 1 ppmv to 7 ppmv was found for both sensors, and the detection limits were 0.95 ppmv (1.2 % RSD) and 0.40 ppmv (0.8 % RSD) for Cellu-PANI and Nylon-NPs PANI, respectively. In addition, both sensors showed complete reversibility and a short exposition time (5 min). The potential applicability of the Color-NSPs in the control of the exposure of paper heritage collections to outdoor- and indoor-generated gaseous pollutants was demonstrated by determining acid vapors in museums. The method was validated with an external reference method; the paired test was applied, and p-values greater than 5% were obtained, indicating an excellent correlation and showing that the Color-NSPs reported are simple, fast, and an economical alternative to control and protect cultural heritage materials in indoor environments.

Point-of-care assay platform for uric acid, urea, and triglycerides with a microfluidic paper device (µPAD) controlled by stimulus-sensitive valves.

A microfluidic biosensor paper-based analytical device, or µPAD, was developed as a point-of-care assay platform for the simultaneous determination of three clinically important markers: uric acid, urea, and triglycerides. To achieve a simultaneous determination, thermosensitive valves based on N-isopropylacrylamide polymers controlled the flow of fluid in the µPAD. The evaluation of the analytical characteristics of the µPAD was done using a photographic camera at room temperature. The detection limits were 4.5·10-5, 2.5·10-3, and 1.5·10-3 mg mL-1, for uric acid, urea, and triglycerides, respectively, and the precision expressed as relative standard deviation (% RSD) 3.2, 1.2, and 1.6%. The obtained µPAD devices were validated with real human plasma samples, demonstrating high accuracy and precision. Multiple analyte point-of-care tests such as those developed here have excellent characteristics, being easy to manufacture, cost-effective, easy to use, and highly sensitive.

Smart facemask for wireless CO2 monitoring.

The use of facemasks by the general population is recommended worldwide to prevent the spread of SARS-CoV-2. Despite the evidence in favour of facemasks to reduce community transmission, there is also agreement on the potential adverse effects of their prolonged usage, mainly caused by CO2 rebreathing. Herein we report the development of a sensing platform for gaseous CO2 real-time determination inside FFP2 facemasks. The system consists of an opto-chemical sensor combined with a flexible, battery-less, near-field-enabled tag with resolution and limit of detection of 103 and 140 ppm respectively, and sensor lifetime of 8 h, which is comparable with recommended FFP2 facemask usage times. We include a custom smartphone application for wireless powering, data processing, alert management, results displaying and sharing. Through performance tests during daily activity and exercise monitoring, we demonstrate its utility for non-invasive, wearable health assessment and its potential applicability for preclinical research and diagnostics.

Inkjet-printed O2 gas sensors in intelligent packaging.

An inkjet printed membrane is presented as a colorimetric sensor for oxygen for use in smart packaging, in order to quickly inform the consumer about possible degradation reactions in modified atmosphere products (MAP). The colorimetric sensor is based on the redox dye, toluidine blue (TB), a sacrificial electron donor, glycerol, and, hydroxypropyl methylcellulose, as the hydrophilic polymeric matrix. The UVC-wavelength activated TB is photoreduced by SnO2 nanoparticle ink. This colorimetric oxygen indicator stays colourless upon exposure in nitrogen atmosphere to 7 min UVC light (6 W·cm-2). The photoreduced TB to leuco TB recovers its original colour upon exposure to oxygen for 55 min under ambient conditions (∼21 °C, ∼55%RH, 21% O2). The characteristics of the sensor have been evaluated, including its functionality through the colorimetric response to different oxygen concentrations as well as the influence of experimental variables such as humidity and temperature using a digital camera as the detector. The results obtained show that: (1) the colorimetric sensor remains stable in the absence of oxygen; (2) relative humidity greater than 60% significantly affects the reoxidation process; and (3) the temperature has a significant influence on the colour recovery, although the stability increases considerably when the sensor is kept refrigerated at 4 °C. A real application to packaged ham was performed, demonstrating that the printed colorimetric sensor is stable for at least 48 hours once activated and when the container deteriorates upon the entrance of oxygen, the sensor returns to its original blue colour, demonstrating its utility as a UVC-activated colorimetric oxygen sensor.

Bioactive microfluidic paper device for pesticide determination in waters.

This work presents a new optical microfluidic paper biosensor for the detection of organophosphate pesticides and carbamate pesticides. The assay strip is composed of a paper support (1 × 17.6 mm) onto which acetylcholine esterase (AChE) and acetylcholine chloride (AChCl) are deposited, in such a way that there is a small hole between them that ensures that they only come into contact in the reaction zone when they are carried by a solution of the sample by lateral flow to the reaction zone containing bromocresol purple (BCP) as the pH indicator, immobilized by sol-gel. The sensor operates at room temperature and the rate of the inhibited reaction serves as an analytical signal, which is measured using a camera by quantifying the appropriate colour coordinate. Calibration curves were obtained for chlorpyrifos and carbaryl, with a useful concentration range from 0.24 to 20 µg L-1 for carbaryl and from 2.00 to 45 µg L-1 for chlorpyrifos. The detection limits were 0.24 and 2.00 µg L-1, respectively, and with reproducibility around 4.2-5.5%. The method was applied to the determination of pesticides in different water samples, with no sample preparation.

Optical portable instrument for the determination of CO2 in indoor environments.

A portable device based on a colorimetric sensor to determine the atmospheric level of CO2 gas is presented in this work. The system is based on a low-cost, low-power System on a Chip (SoC) microcontroller with integrated Wi-Fi. A user-friendly application was developed to monitor and log the CO2 measurements when the system is connected to a Wi-Fi network. The sensing membrane is directly deposited on the surface of the colour detector, thus reducing the complexity of the system. This sensing membrane is formed by a pH indicator α-naphtholphthalein, tetramethylammonium hydroxide pentahydrate, 1-ethyl-3-methylimidazolium tetrafluoroborate, Tween 20 and hydroxypropyl methylcellulose as the hydrophilic polymer. The system has been fully characterized, obtaining response and recovery times of 1.3 and 2.5 s, respectively, a limit of detection of 51 ppm, and an average resolution of 6.3 ppm. This portable device was applied for the in-situ determination of CO2 gas in the atmosphere inside classrooms in several secondary schools. The measurements were taken during complete workdays and the results were statistically compared with the same measurements taken using a commercially available non-dispersive infra-red (NDIR) device. No significant statistical differences were found between the results obtained using both devices. A complete statistical treatment of the measurements made with the proposed portable device was carried out. The obtained results show that the concentration of CO2 gas in some schools was higher than the desired concentration, with regard to influencing the student's health, safety, productivity and comfort. This demonstrates the need to control this parameter to ensure appropriate indoor environmental quality (IEQ).

NIR optical carbon dioxide gas sensor based on simple azaBODIPY pH indicators.

Two simple boron-dipyrromethene-type fluorophore (azaBODIPYs) dyes are synthesized and tested for the determination of CO2 gas by an inner filter process. The indicators are noncovalently entrapped in suitable polymers according to their polarity, featuring absorption maxima at 620 nm and fluorescent emission maxima in the range 675-720 nm. Molar absorptivity and fluorescence quantum yield data were determined for these two synthesized azaBODIPYs. These indicators have high molar absorption coefficients of 7.1 × 104 and 2.1 × 104 M-1 cm-1 and quantum yields of 21 and 9%. The pKa values of the indicators are determined from absorbance and fluorescence measurements with values of 7.9 and 8.5, depending on the positioning of the substitution pattern of the electron-donating functionalities. The two azaBODIPYs present excellent photostability, making them suitable for long duration measurements. These azaBODIPY dyes act as fluorescent pH indicators in a polymeric sensing membrane along with microcrystalline powder of chromium-doped gadolinium aluminium borate as the luminophore, a transfer phase agent (tetraoctyl or tetramethyl ammonium hydroxide) and a plasticizer or surfactant to improve membrane permeability to gaseous CO2. The response time ranges from 42 to 60 s and recovery time from 103 to 120 s, with a detection limit of 0.04 and 0.57% CO2. The store time of the sensing membranes is longer than 570 days in the best case, and it does not need to be kept in any special atmosphere other than darkness.

Ionic liquids on optical sensors for gaseous carbon dioxide.

This work presents a study on the influence of eight different ionic liquids (ILs) in the composition of dry membranes used for gaseous CO2 optical sensing. The presence of CO2 causes a displacement of a colorimetric pH indicator toward its acid form that increases the emission intensity of the luminophore by an inner filter process. The influence of ILs in the membrane on the stability and dynamic behavior-usually the main drawbacks of these sensors-of the membranes is studied. The characterization of the different membranes prepared was carried out and the discussion of the results is presented. In all cases, the response and recovery times improved considerably, with the best case being response times of only 10 s and recovery times of 48 s, compared to response and recovery times of 41 and 100 s, respectively, for membranes without IL. The useful life of the detection membranes is also considerably longer than that of membranes that do not include IL, at least 292 days in the best case. The sensing membrane without luminophore and only containing the pH indicator is proposed for the color-based measurement of CO2 using a digital camera for possible use in food-packaging technology. Graphical abstract ᅟ.

Optical sensor for carbon dioxide gas determination, characterization and improvements.

A study of different alternatives to improve the stability and lifetime of sensors for the determination of gaseous CO2 has been performed. It includes the characterization of different sensing membranes, a discussion of the results obtained and possibilities for the future. The solid sensor membrane for gaseous CO2 based on changes in the luminiscence of a luminophore immobilized on O2-insensitive film, concurrent with the displacement of a pH indicator, has some drawbacks, such as the loss of efficiency over time and the need to maintain the sensor in special atmospheric conditions. As a solution to these drawbacks, two alternatives were tested, the first alternative was replacing the newly proposed tetraoctyl ammonium hydroxide (TOAOH ) phase transfer agent with other basic agents that did not undergo a Hoffman degradation reaction, and the second alternative was the use of hydrophilic polymers that could retain water needed for CO2 sensing more efficiently. The different membranes tested indicated that the use of tetramethyl ammonium (TMAOH) instead of TOAOH as the phase transfer agent produced better results regarding stability and sensitivity. In addition, replacing the membrane polymer with hydrophilic polymers improved the sensing characteristics in terms of response time and stability over hydrophobic polymers. With a detection limit of 0.006%, the response time is 19s and the recovery time is 100s. The lifetime of the sensing membranes, which do not need to be held in any special atmosphere other than darkness, is longer than at least 300 days for membranes with TMAOH in hydrophilic polymer and 515 days for membranes with TMAOH in ethyl cellulose.

LED-LED portable oxygen gas sensor.

A portable instrument for oxygen determination, based on the quenching of phosphorescent octaethylporphyrin by gaseous O(2), has been developed using the fluorimetric paired emitter-detector diode technique (FPEDD). The instrument configuration consists of two light-emitting diodes (LEDs) facing each other, with an interchangeable support containing a phosphorescent membrane in between, in which one of the LEDs is used as the light source (emitter LED) and the other, working in reverse bias mode, as the light detector. The feasibility of using a LED as a luminescence detector is studied. Its small size enables integration of the instrument into a portable measurement system. A systematic study of the system capabilities as a portable instrument was performed to optimize range, sensitivity, short term and long term stability, dynamic behaviour, effect of temperature and humidity, and temporal drift.

An IUPAC-based approach to estimate the detection limit in co-extraction-based optical sensors for anions with sigmoidal response calibration curves.

An approach based on IUPAC methodology to estimate the limit of detection of bulk optode-based analytical methods for anions has been developed. The traditional IUPAC methodology for calculating the detection limit was modified to be adapted to particular cases where the calibration curves have a sigmoidal profile. Starting from the different full theoretical models for every co-extraction mechanism of the analyte in the membrane in bulk optodes, several particular simplified models at low analyte concentration were obtained and validated. The slope of the calibration curve at low analyte concentration was calculated from the first derivative of the simplified equation and, subsequently, the detection limit was estimated. This fitted-for-purpose estimation strategy was applied to anion quantification for in-house bulk optode-based analytical methods, and the estimated limits of detection were compared with those obtained by applying classical geometrical methodology. This way of establishing the detection limit yields values that maintain their true statistical and probabilistic aspects. It can be easily applied to any analytical system which yields non-linear calibration curves at low analyte concentration.

A new light emitting diode-light emitting diode portable carbon dioxide gas sensor based on an interchangeable membrane system for industrial applications.

A new system for CO(2) measurement (0-100%) based on a paired emitter-detector diode arrangement as a colorimetric detection system is described. Two different configurations were tested: configuration 1 (an opposite side configuration) where a secondary inner-filter effect accounts for CO(2) sensitivity. This configuration involves the absorption of the phosphorescence emitted from a CO(2)-insensitive luminophore by an acid-base indicator and configuration 2 wherein the membrane containing the luminophore is removed, simplifying the sensing membrane that now only contains the acid-base indicator. In addition, two different instrumental configurations have been studied, using a paired emitter-detector diode system, consisting of two LEDs wherein one is used as the light source (emitter) and the other is used in reverse bias mode as the light detector. The first configuration uses a green LED as emitter and a red LED as detector, whereas in the second case two identical red LEDs are used as emitter and detector. The system was characterised in terms of sensitivity, dynamic response, reproducibility, stability and temperature influence. We found that configuration 2 presented a better CO(2) response in terms of sensitivity.

Phosphorescent sensing of carbon dioxide based on secondary inner-filter quenching.

A study of different strategies to prepare phosphorescence-based sensors for gaseous CO(2) determination has been performed. It includes the characterization of different configurations tested, a discussion of the results obtained and possibilities for the future. The optical sensor for gaseous CO(2) is based on changes in the phosphorescence intensity of the platinum octaethylporphyrin (PtOEP) complex trapped both on oxygen-insensitive poly(vinylidene chloride-co-vinyl chloride) (PVCD) membranes and PVCD microparticles, due to the displacement of the alpha-naphtholphthalein acid-base equilibrium with CO(2) concentration. A secondary inner-filter mechanism was tested for the sensor and a full range linearized calibration was obtained by plotting (I(100)-I(0))/(I-I(0)) versus the inverse of the CO(2) concentration, where I(0) and I(100) are the detected luminescence intensities from a membrane exposed to 100% nitrogen and 100% CO(2), respectively, and I at a defined CO(2) concentration. The different configurations tested included the use of membranes containing luminophore and pH-sensitive dye placed on two opposite sides of a transparent support to prevent the observed degradation of the PtOEP complex in the presence of the tetraoctylammonium hydroxide (TOAOH) phase transfer agent, which produced better results regarding stability and sensitivity. The CO(2) gas sensor based on PtOEP homogeneous membranes presented better properties in terms of response time and sensitivity than that based on PtOEP microparticles. With a detection limit of 0.02%, the response time (10-90% maximum signal) is 9 s and the recovery time (90-10%) is 115 s. The lifetime of the membranes for CO(2) sensing preserved in a 94% RH atmosphere and dark conditions is longer than at least 4 months.

Portable light-emitting diode-based photometer with one-shot optochemical sensors for measurement in the field.

This report describes the electronics of a portable, low-cost, light-emitting diode (LED)-based photometer dedicated to one-shot optochemical sensors. Optical detection is made through a monolithic photodiode with an on-chip single-supply transimpedance amplifier that reduces some drawbacks such as leakage currents, interferences, and parasitic capacitances. The main instrument characteristics are its high light source stability and thermal correction. The former is obtained by means of the optical feedback from the LED polarization circuit, implementing a pseudo-two light beam scheme from a unique light source with a built-in beam splitter. The feedback loop has also been used to adjust the LED power in several ranges. Moreover, the low-thermal coefficient achieved (-90 ppm/degrees C) is compensated by thermal monitoring and calibration function compensation in the digital processing. The hand-held instrument directly gives the absorbance ratio used as the analytical parameter and the analyte concentration after programming the calibration function in the microcontroller. The application of this photometer for the determination of potassium and nitrate, using one-shot sensors with ionophore-based chemistries is also demonstrated, with a simple analytical methodology that shortens the analysis time, eliminating some calibrating solutions (HCl, NaOH, and buffer). Therefore, this compact instrument is suitable for real-time analyte determination and operation in the field.

Oxygen-sensing film coated photodetectors for portable instrumentation.

A sensor configuration for oxygen determination based on luminescence quenching is presented in which the measured parameter is closely related to the luminescence lifetime. The sensing film is based on the dye platinum octaethylporphyrin complex immobilised in a polystyrene membrane and stabilised with the heterocyclic amine DABCO. In this report, we study the feasibility of using photodiodes as elements to be coated by this oxygen sensing film with the aim of obtaining a sensing device whose small size makes it possible to embed it into a portable measurement system. In addition to the concomitant sensor miniaturisation, several advantages have been demonstrated such as fast response, low energy consumption, the lack of any need for optical filter elements and less tendency to photobleaching than with previous configurations. A complete study of the coated photodetector preparation was carried out in order to optimise the specifications of the portable instrument where the photodetector is included, such as: repeatability, transient response and selectivity. We propose a preparation procedure for coating photodetectors with this film that has demonstrated the capacity to produce repetitive and reliable sensing devices.

A simplified measurement procedure and portable electronic photometer for disposable sensors based on ionophore-chromoionophore chemistry for potassium determination.

A field-portable photometer for potassium determination with disposable sensors has been developed. It can be applied to routine water and beverage analysis. The disposable sensor is based on ionophore-chromoionophore chemistry. A colour change in the sensing film is detected by measuring the transmitted intensity with a solid state photodetector. Optical excitation at 660 nm is emitted by a light-emitting diode (LED). Negative feedback for LED bias and thermal correction were included to improve system stability. Additionally, a measurement procedure is presented, characterized and validated for in situ photometer use and real-time results. This simplified procedure is based on prior preparation of the disposable sensor in its acidic form and on the use of an absorbance ratio as analytical parameter. The only requirement for analysis is prior equilibration with a buffered sample solution for 3 min and absorbance measurement before and after equilibration. Good sensitivity in the concentration range 5 muM to 100 mM and very good repetitively and stability were achieved that are comparable to those obtained with bulkier analytical instrumentation. Given the compact size, low weight, rapid response and low energy requirement of the electronic photometer developed here, this measurement system is suitable for potassium determination in the field.

Magnesium optical one-shot sensor based on a coumarin chromoionophore.

The characterization of a new irreversible optical absorption-based one-shot sensor for magnesium is described. The magnesium photoactive probe is 7-diethylamino-3-(3,4-ethylendioxybenzoyl)coumarin immobilized in a plasticized polymeric membrane. The magnesium selectivity can be explained in terms of size and charge density of magnesium and charge-separated resonance forms contribution in the excited state of coumarin. The selectivity obtained for magnesium over a variety of naturally occurring species in natural waters meets the requirements for the determination of this ion in water. The one-shot sensor responds between 0.14 and 14mgL(-1) with a sensor-to-sensor reproducibility of 1.3% as [Formula: see text] , at the medium level of the range. The performance of the optical one-shot sensor was tested in the analysis of magnesium in different types of natural waters and soft drinks validating results against a reference procedure.