Measurement errors and implications for preprocessing in miniaturised near-infrared spectrometers: Classification of sweet and bitter almonds as a case of study.

Near-infrared (NIR) spectroscopy is a well-established analytical technique that has been used in many applications over the years. Due to the advancements in the semiconductor industry, NIR instruments have evolved from benchtop instruments to miniaturised portable devices. The miniaturised NIR instruments have gained more interest in recent years because of the fast and robust measurements they provide with almost no sample pretreatments. However, due to the very different configurations and characteristics of these instruments, they need a dedicated optimization of the measurement conditions, which is crucial for obtaining reliable results. To comprehensively grasp the capabilities and potentials offered by these sensors, it is imperative to examine errors that can affect the raw data, which is a facet frequently overlooked. In this study, measurement error covariance and correlation matrices were calculated and then visually inspected to gain insight into the error structures associated with the devices, and to find the optimal preprocessing technique that may result in the improvement of the models built. This strategy was applied to the classification of sweet and bitter almonds, which were measured with the three portable low-cost NIR devices (SCiO, FlameNIR+ and NeoSpectra Micro Development Kit) after removing the shelled, since their classification is of utmost importance for the almond industry. The results showed that bitter almonds can be classified from sweet almonds using any of the instruments after selecting the optimal preprocessing, obtained through inspection of covariance and correlation matrices. Measurements obtained with FlameNIR + device provided the best classification models with an accuracy of 98 %. The chosen strategy provides new insight into the performance characterization of the fast-growing miniaturised NIR instruments.

Biosensors and Smart Analytical Systems in Food Quality and Safety: Status and Perspectives.

The primary focus of research in food production revolves around ensuring food quality and safety [...].

Seafood consumption as a source of exposure to high production volume chemicals: A comparison between Catalonia and the Canary Islands.

Seafood plays an important role in diet because of its health benefits. However, the fact that chemical compounds such as high production volume chemicals may be present in seafood means that its consumption can be a potential risk for population. To assess the occurrence of HPVs and estimate the exposure and risk associated with their consumption, specimens of the most consumed seafood species in Catalonia and the Canary Islands, Spain, were collected and analysed. Results showed higher levels of HPVs in samples from Catalonia and a prevalence of phthalate esters and benzenesulfonamides over the other target compounds in samples from both locations. Multivariate analysis showed spatial differences between the mean concentration profiles of HPVs for the samples from Catalonia and the Canary Islands. Exposures were higher for the samples from Catalonia, although the intake of HPVs via seafood was not of any real concern in either of the locations.

Exploring the Analytical Complexities in Insect Powder Analysis Using Miniaturized NIR Spectroscopy.

Insects have been a food source for humans for millennia, and they are actively consumed in various parts of the world. This paper aims to ascertain the feasibility of portable near-infrared (NIR) spectroscopy as a reliable and fast candidate for the classification of insect powder samples and the prediction of their major components. Commercially-available insect powder samples were analyzed using two miniaturized NIR instruments. The samples were analyzed as they are and after grinding, to study the effect of the granulometry on the spectroscopic analyses. A homemade sample holder was designed and optimized for making reliable spectroscopic measurements. Classification was then performed using three classification strategies, and partial least squares (PLS) regression was used to predict the macronutrients. The results obtained confirmed that both spectroscopic sensors were able to classify insect powder samples and predict macronutrients with an adequate detection limit.

Potentiometric detection of creatinine in the presence of nicotine: Molecular recognition, sensing and quantification through multivariate regression.

Systematic errors in the calix [4] pyrrole-based potentiometric detection of creatinine have been observed in heavy smokers. This work further characterizes the interactions between the nicotinium cation and the cavitand as well as the resulting interference produced during the potentiometric detection. It is found that the nicotinium cation binds the electronic rich aromatic cavity defined by the pyrrole rings of the receptor's cone conformation with an estimated binding constant higher than 10-4 M-1 in methylene chloride. On the other hand, the creatininium cation is preferentially included in the hydrophobic aromatic cavity of the ionophore by establishing hydrogen bond interactions with the pyrrole NHs groups. Potentiometric calibrations confirmed the detection of the nicotinium cation at neutral and acidic pH, respectively. Due to the lower pka of creatinine, a methodology to quantify creatinine in presence of nicotine by using an array of three sensors at two pH values is proposed. A partial least squares regression was performed and reported recoveries of 103% with a standard deviation of 20%. The improved determination of creatinine was therefore discussed. This approach represents a step forward in the development of effective approaches to improve the measurement of creatinine in decentralized settings.

Analytical Chemistry Strategies in the Use of Miniaturised NIR Instruments: An Overview.

Miniaturized NIR instruments have been increasingly used in the last years, and they have become useful tools for many applications on a broad variety of samples. This review focuses on miniaturized NIR instruments from an analytical point of view, to give an overview of the analytical strategies used in order to help the reader to set up their own analytical methods, from the sampling to the data analysis. It highlights the uses of these instruments, providing a critical discussion including current and future trends.

Measurement Strategies for the Classification of Edible Oils Using Low-Cost Miniaturised Portable NIR Instruments.

Miniaturised near-infrared (NIR) instruments have been increasingly used in the last few years, and they have become useful tools for many applications on different types of samples. The market already offers a wide variety of these instruments, each one having specific requirements for the correct acquisition of the instrumental signal. This paper presents the development and optimisation of different measuring strategies for two miniaturised NIR instruments in order to find the best measuring conditions for the rapid and low-cost analysis of olive oils. The developed strategies have been applied to the classification of different samples of olive oils, obtaining good results in all cases.

Fabrication and modification of homemade paper-based electrode systems.

This work reports the simple and inexpensive fabrication of homemade paper-based carbon-printed electrodes (HP C-PEs), aiming to produce an alternative way to generate electrochemical biosensors to all and promoting their wide use. This is especially important in times of pandemics, considering the excellent features of electrochemical biosensing, which may ensure portability, low-cost and quick responses. HP C-PEs were fabricated using a standard cellulose filter paper that was first modified with wax, to make it hydrophobic. Then, the electrodes were manually printed on top of this cellulose/wax substrate. The electrodes were designed by having standard configurations for potentiometric and electrochemical readings, combining two or three electrodes. In general, both electrode systems showed excellent electrochemical and mechanical features, which were better in specific cases than commercial devices. The 3-electrode system displayed high current levels with low peak-to-peak potential separation, yielding highly stable signals after consecutive electrode bending that corresponded to high active areas. The possibility of modifying the devices with polymers produced in-situ was also explored and proven successful, providing also advantageous features when compared to other devices. The 2-electrode system was also proven highly stable and capable of subsequent use in potentiometric sensing development. Overall, the fabrication process of the 2- and 3-electode systems described herein may be employed in laboratories to produce successful electrochemical biosensors, with the final devices displaying excellent electrochemical and mechanical features. This procedure offers the advantages of being simple and inexpensive, when compared to other commercial devices, while using materials that are promptly available and that may undergo a worldwide use.

The Use of Conducting Polymers for Enhanced Electrochemical Determination of Hydrogen Peroxide.

The role of hydrogen peroxide in a wide range of biological processes has led to a steady increase in research into hydrogen peroxide determination in recent years, and conducting polymers have attracted much interest in electrochemistry as promising materials in this area. We present an overview of electrochemical devices for hydrogen peroxide determination using conducting polymers, either as a target or as a byproduct of redox reactions. We describe different combinations of electrode modifications through the incorporation of conducting polymers as the main component along with other materials or nanomaterials. We critically compare the analytical performances cited and highlight some of the future challenges for the feasible application of such devices.

Rapid Analysis of Milk Using Low-Cost Pocket-Size NIR Spectrometers and Multivariate Analysis.

The miniaturisation of analytical devices, reduction of analytical data acquisition time, or the reduction of waste generation throughout the analytical process are important requirements of modern analytical chemistry, and in particular of green analytical chemistry. Green analytical chemistry has fostered the development of a new generation of miniaturized near-infrared spectroscopy (NIR) spectrometric systems. However, one of the drawbacks of these systems is the need for a compromise between the performance parameters (accuracy and sensitivity) and the aforementioned requirements of green analytical chemistry. In this paper, we evaluated the capabilities of two recently developed portable NIR instruments (SCiO and NeoSpectra) to achieve a rapid, simple and low-cost quantitative determination of commercial milk macronutrients. Commercial milk samples from Italy, Switzerland and Spain were chosen, covering the maximum range of variability in protein, carbohydrate and fat content, and multivariate calibration was used to correlate the recorded spectra with the macronutrient content of milk. Both SCiO and NeoSpectra can provide a fast and reliable analysis of fats in commercial milk, and they are able to correctly classify milk according to fat level. SCiO can also provide predictions of protein content and classification according to presence or absence of lactose.

Computer-operated analytical platform for the determination of nutrients in hydroponic systems.

Hydroponics is a water, energy, space, and cost efficient system for growing plants in constrained spaces or land exhausted areas. Precise control of hydroponic nutrients is essential for growing healthy plants and producing high yields. In this article we report for the first time on a new computer-operated analytical platform which can be readily used for the determination of essential nutrients in hydroponic growing systems. The liquid-handling system uses inexpensive components (i.e., peristaltic pump and solenoid valves), which are discretely computer-operated to automatically condition, calibrate and clean a multi-probe of solid-contact ion-selective electrodes (ISEs). These ISEs, which are based on carbon nanotubes, offer high portability, robustness and easy maintenance and storage. With this new computer-operated analytical platform we performed automatic measurements of K(+), Ca(2+), NO3(-) and Cl(-) during tomato plants growth in order to assure optimal nutritional uptake and tomato production.

Graphene-based potentiometric biosensor for the immediate detection of living bacteria.

In this communication we present a potentiometric aptasensor based on chemically modified graphene (transducer layer of the aptasensor) and aptamers (sensing layer). Graphene oxide (GO) and reduced graphene oxide (RGO) are the basis for the construction of two versions of the aptasensor for the detection of a challenging living organism such as Staphylococcus aureus. In these two versions, DNA aptamers are either covalently (in the GO case) or non-covalently (in the RGO case) attached to the transducer layer. In both cases we are able to selectively detect a single CFU/mL of S. aureus in an assay close to real time, although the noise level associated to the aptasensors made with RGO is lower than the ones made with GO. These new aptasensors, that show a high selectivity, are characterized by the simplicity of the technique and the materials used for their construction while offering ultra-low detection limits in very short time responses in the detection of microorganisms.

Paper-based chemiresistor for detection of ultralow concentrations of protein.

A new paper-based chemiresistor composed of a network of single-wall carbon nanotubes (SWCNTs) and anti-human immunoglobulin G (anti-HIgG) is reported herein. SWCNTs act as outstanding transducers because they provide high sensitivity in terms of resistance changes due to immunoreaction. As a result, the resistance-based biosensor reaches concentration detection as low as picomolar. The resulting paper-based biosensor is sensitive, selective and employs low-cost substrate and simple manufacturing stages. Since chemiresistors require low-power equipment and are able to detect low concentrations with inexpensive materials, the present approach may pave the way for the development of resistive biosensors at very low-cost with high performances.

Carbon nanotube-based aptasensors for the rapid and ultrasensitive detection of bacteria.

In this paper we present a new generation of potentiometric biosensors based on carbon nanotubes (transducer layer of the biosensor) and aptamers (sensing layer of the biosensor) for the ultralow and selective detection of microorganisms. We show that with these aptasensors we were able to detect a few CFU of the target bacteria almost in real-time, both in buffered and in real samples.

Ultrasensitive and real-time detection of proteins in blood using a potentiometric carbon-nanotube aptasensor.

Potentiometric sensing represents the preferred technique in many routine measurements of pH and ions. Unfortunately, the simplicity of the technique has not been exploited so far in high throughput biomolecular sensing. In this work, we demonstrate the capabilities of the hybrid functional material carbon nanotubes/aptamer for the creation of a new generation of nuclease-resistant aptasensors using the potentiometric transduction capabilities of single-walled carbon nanotubes in combination with the recognition capabilities of a protein-specific RNA aptamer. The aptasensor was used to detect and identify disease-related proteins at attomolar concentration values in a rapid and non-expensive way. The variable surface glycoprotein from African Trypanosomes was chosen as an ideal model system for a pathogenic exoantigen protein in a clinical sample. Variations in the electromotive force are achieved in real-time upon the direct addition of diluted real blood samples containing the target protein thus eliminating the need of preliminary matrix removal. This work would open the door to real-time diagnostic assays for a wide range of diseases, but also to the rapid molecular detection of several proteins in truly customizable protein biosensing platforms.

Silicon photomultiplier detector for atmospheric lidar applications.

The viability and performance of using a silicon photomultiplier (SiPM) in atmospheric lidar applications is experimentally compared against the well-established use of photomultiplier tubes. By using a modified lidar setup for simultaneous data acquisition of both types of sensors, we demonstrate that a SiPM can offer appropriate qualities for this specific application where the detection of fast, extremely low light pulses and large dynamic range signals are essential capabilities. The experimental results show that the SiPM has an appropriate behaviour offering suitable capabilities for elastic, backscatter aerosol lidars. To the best of our knowledge, this is the first study showing SiPM for atmospheric lidar applications.

Label-free detection of Staphylococcus aureus in skin using real-time potentiometric biosensors based on carbon nanotubes and aptamers.

In this paper we report the first biosensor that is able to detect Staphylococcus aureus in real-time. A network of single-walled carbon nanotubes (SWCNTs) acts as an ion-to-electron potentiometric transducer and anti-S. aureus aptamers are the recognition element. Carbon nanotubes were functionalized with aptamers using two different approaches: (1) non-covalent adsorption of drop-casted pyrenil-modified aptamers onto the external walls of the SWCNTs; and (2) covalent bond formation between amine-modified aptamers and carboxylic groups previously introduced by oxidation at the ends of the SWCNTs. Both of these approaches yielded functional biosensors but there were large differences in the minimum detectable bacteria concentration and sensitivity values. With covalent functionalization, the minimum concentration detected was 8×10(2)colony-forming units (CFU)/mL and the sensitivity was 0.36 mV/Decade. With the non-covalent approach, the sensitivity was higher (1.52 mV/Decade) but the minimum concentration detected was greatly affected (10(7) CFU/mL). In both cases, potential as a function of Decade of bacteria concentration was linear. Functional biosensors were used to test real samples from freshly excised pig skin, contaminated with the target microorganism, as a surrogate for human skin.

Potentiometric strip cell based on carbon nanotubes as transducer layer: toward low-cost decentralized measurements.

In this study, we developed a potentiometric planar strip cell based on single-walled carbon nanotubes that aims to exploit the attributes of solid-contact ion-selective electrodes for decentralized measurements. That is, the ion-selective and reference electrodes have been simultaneously miniaturized onto a plastic planar substrate by screen-printing and drop-casting techniques, obtaining disposable strip cells with satisfactory performance characteristics (i.e., the sensitivity is 57.4 ± 1.3 mV/dec, the response time is ≤30 s within the linear range from log a(K+) = -5 to -2, and the limit of detection is -6.5), no need of maintenance during long dry storage, quick signal stabilization, and light insensitivity in short-term measurements. We also show how the new potentiometric strip cell makes it possible to perform decentralized and rapid determinations of ions in real samples, such as saliva or beverages.

Disposable planar reference electrode based on carbon nanotubes and polyacrylate membrane.

In this technical note, we report a new all-solid-state planar reference electrode based on single-walled carbon nanotubes and photocured poly(n-butylacrylate) (poly(nBA)) membrane containing the Ag/AgCl/Cl(-) ion system. Single-walled carbon nanotubes functionalized with octadecylamide (SWCNT-ODA) and deposited by drop-casting onto a disposable screen-printed electrode are an excellent all-solid-state transducer. The novel potentiometric planar reference electrode shows low potential variability (calibration slopes inferior to 2 mV/dec) for a wide range of chemical species (i.e., ions, small molecules, proteins) in a wide calibration range, redox pairs, changes in pH, and changes in ambient light. Potentiometric medium-term signal stability (-0.9 ± 0.2 mV/h) and electrochemical impedance characterization confirm the correct solid contact between the SWCNT-ODA layer and photocured poly(nBA) membrane. Overall, the materials used and the simple fabrication by screen-printing and drop-casting enable a high throughput and highly parallel and cost-effective mass manufacture of the new disposable reference electrode. Moreover, the reference electrode has a long shelf life, a characteristic that can be of special interest in decentralized and multiplexing potentiometric analysis.

Solid-state reference electrodes based on carbon nanotubes and polyacrylate membranes.

A novel potentiometric solid-state reference electrode containing single-walled carbon nanotubes as the transducer layer between a polyacrylate membrane and the conductor is reported here. Single-walled carbon nanotubes act as an efficient transducer of the constant potentiometric signal originating from the reference membrane containing the Ag/AgCl/Cl(-) ions system, and they are needed to obtain a stable reference potentiometric signal. Furthermore, we have taken advantage of the light insensitivity of single-walled carbon nanotubes to improve the analytical performance characteristics of previously reported solid-state reference electrodes. Four different polyacrylate polymers have been selected in order to identify the most efficient reservoir for the Ag/AgCl system. Finally, two different arrangements have been assessed: (1) a solid-state reference electrode using photo-polymerised n-butyl acrylate polymer and (2) a thermo-polymerised methyl methacrylate:n-butyl acrylate (1:10) polymer. The sensitivity to various salts, pH and light, as well as time of response and stability, has been tested: the best results were obtained using single-walled carbon nanotubes and photo-polymerised n-butyl acrylate polymer. Water transport plays an important role in the potentiometric performance of acrylate membranes, so a new screening test method has been developed to qualitatively assess the difference in water percolation between the polyacrylic membranes studied. The results presented here open the way for the true miniaturisation of potentiometric systems using the excellent properties of single-walled carbon nanotubes.