Data-Driven Virtual Sensing for Electrochemical Sensors.

In recent years, the application of machine learning for virtual sensing has revolutionized the monitoring and management of information. In particular, electrochemical sensors generate large amounts of data, allowing the application of complex machine learning/AI models able to (1) reproduce the measured data and (2) predict and manage faults in the measuring sensor. In this work, data-driven models based on an autoregressive model and an artificial neural network have been identified and used to (i) evaluate sensor redundancy and (ii) predict and manage faults in the context of electrochemical sensors for the measurement of ethanol. The approach shows encouraging results in terms of both performance and sensitivity analyses, allowing for the reconstruction of the values measured by two sensors in a series of six sensors with different dopant levels and to reproduce their values after a fault.

Leuconostoc performance in soy-based fermentations - Survival, acidification, sugar metabolism, and flavor comparisons.

Leuconostoc spp. is often regarded as the flavor producer, responsible for the production of acetoin and diacetyl in dairy cheese. In this study, we investigate seven plant-derived Leuconostoc strains, covering four species, in their potential as a lyophilized starter culture for flavor production in fermented soy-based cheese alternatives. We show that the process of lyophilization of Leuconostoc can be feasible using a soy-based lyoprotectant, with survivability up to 63% during long term storage. Furthermore, the storage in this media improves the subsequent growth in a soy-based substrate in a strain specific manner. The utilization of individual raffinose family oligosaccharides was strain dependent, with Leuconostoc pseudomesenteroides NFICC99 being the best consumer. Furthermore, we show that all investigated strains were able to produce a range of volatile flavor compounds found in dairy cheese products, as well as remove certain dairy off-flavors from the soy-based substrate like hexanal and 2-pentylfuran. Also here, NFICC99 was strain producing most cheese-related volatile flavor compounds, followed by Leuconostoc mesenteroides NFICC319. These findings provide initial insights into the development of Leuconostoc as a potential starter culture for plant-based dairy alternatives, as well as a promising approach for generation of stable, lyophilized cultures.

Nanotechnology and E-Sensing for Food Chain Quality and Safety.

Nowadays, it is well known that sensors have an enormous impact on our life, using streams of data to make life-changing decisions. Every single aspect of our day is monitored via thousands of sensors, and the benefits we can obtain are enormous. With the increasing demand for food quality, food safety has become one of the main focuses of our society. However, fresh foods are subject to spoilage due to the action of microorganisms, enzymes, and oxidation during storage. Nanotechnology can be applied in the food industry to support packaged products and extend their shelf life. Chemical composition and sensory attributes are quality markers which require innovative assessment methods, as existing ones are rather difficult to implement, labour-intensive, and expensive. E-sensing devices, such as vision systems, electronic noses, and electronic tongues, overcome many of these drawbacks. Nanotechnology holds great promise to provide benefits not just within food products but also around food products. In fact, nanotechnology introduces new chances for innovation in the food industry at immense speed. This review describes the food application fields of nanotechnologies; in particular, metal oxide sensors (MOS) will be presented.

Volatile Olfactory Profiles of Umbrian Extra Virgin Olive Oils and Their Discrimination through MOX Chemical Sensors.

Extra virgin olive oil (EVOO) is the best vegetable oil worldwide but, at the same time, is one of the product victims of fraud in the agri-food sector, and the differences about quality within the extra-virgin olive oil category are often missed. Several scientific techniques were applied in order to guarantee the authenticity and quality of this EVOO. In the present study, the volatile compounds (VOCs) by gas chromatography-mass spectrometry with solid-phase micro-extraction detection (GC-MS SPME), organoleptic analysis by the official Slow Food panel and the detection by a Small Sensor System (S3) were applied. Ten EVOOs from Umbria, a central Italian region, were selected from the 2021 Slow Food Italian extra virgin olive oil official guide, which includes hundreds of high-quality olive oils. The results demonstrated the possibility to discriminate the ten EVOOs, even if they belong to the same Italian region, by all three techniques. The result of GC-MS SPME detection was comparable at the discrimination level to the organoleptic test with few exceptions, while the S3 was able to better separate some EVOOs, which were not discriminated perfectly by the other two methods. The correlation analysis performed among and between the three methodologies allowed us to identify 388 strong associations with a p value less than 0.05. This study has highlighted how much the mix of VOCs was different even among few and localized EVOOs. The correlation with the sensor detection, which is faster and chipper compared to the other two techniques, elucidated the similarities and discrepancies between the applied methods.

Real Time Monitoring of Wine Vinegar Supply Chain through MOX Sensors.

Vinegar is a fermented product that is appreciated world-wide. It can be obtained from different kinds of matrices. Specifically, it is a solution of acetic acid produced by a two stage fermentation process. The first is an alcoholic fermentation, where the sugars are converted in ethanol and lower metabolites by the yeast action, generally Saccharomyces cerevisiae. This was performed through a technique that is expanding more and more, the so-called "pied de cuve". The second step is an acetic fermentation where acetic acid bacteria (AAB) action causes the conversion of ethanol into acetic acid. Overall, the aim of this research is to follow wine vinegar production step by step through the volatiloma analysis by metal oxide semiconductor MOX sensors developed by Nano Sensor Systems S.r.l. This work is based on wine vinegar monitored from the grape must to the formed vinegar. The monitoring lasted 4 months and the analyses were carried out with a new generation of Electronic Nose (EN) engineered by Nano Sensor Systems S.r.l., called Small Sensor Systems Plus (S3+), equipped with an array of six gas MOX sensors with different sensing layers each. In particular, real-time monitoring made it possible to follow and to differentiate each step of the vinegar production. The principal component analysis (PCA) method was the statistical multivariate analysis utilized to process the dataset obtained from the sensors. A closer look to PCA graphs affirms how the sensors were able to cluster the production steps in a chronologically correct manner.

Internet of Food (IoF), Tailor-Made Metal Oxide Gas Sensors to Support Tea Supply Chain.

Tea is the second most consumed beverage, and its aroma, determined by volatile compounds (VOCs) present in leaves or developed during the processing stages, has a great influence on the final quality. The goal of this study is to determine the volatilome of different types of tea to provide a competitive tool in terms of time and costs to recognize and enhance the quality of the product in the food chain. Analyzed samples are representative of the three major types of tea: black, green, and white. VOCs were studied in parallel with different technologies and methods: gas chromatography coupled with mass spectrometer and solid phase microextraction (SPME-GC-MS) and a device called small sensor system, (S3). S3 is made up of tailor-made metal oxide gas sensors, whose operating principle is based on the variation of sensor resistance based on volatiloma exposure. The data obtained were processed through multivariate statistics, showing the full file of the pre-established aim. From the results obtained, it is understood how supportive an innovative technology can be, remotely controllable supported by machine learning (IoF), aimed in the future at increasing food safety along the entire production chain, as an early warning system for possible microbiological or chemical contamination.

Chemical Gas Sensors Studied at SENSOR Lab, Brescia (Italy): From Conventional to Energy-Efficient and Biocompatible Composite Structures.

In this paper, we present the investigations on metal oxide-based gas sensors considering the works performed at SENSOR lab, University of Brescia (Italy). We reported the developments in synthesis techniques for the preparation of doped and functionalized low-dimensional metal oxide materials. Furthermore, we discussed our achievements in the fabrication of heterostructures with unique functional features. In particular, we focused on the strategies to improve the sensing performance of metal oxides at relatively low operating temperatures. We presented our studies on surface photoactivation of sensing structures considering the application of biocompatible materials in the architecture of the functional devices as well.

Nanostructured MOS Sensor for the Detection, Follow up, and Threshold Pursuing of Campylobacter Jejuni Development in Milk Samples.

Food poisoning is still the first cause of hospitalization worldwide and the most common microbial agent, Campylobacter jejuni, is the most commonly reported gastrointestinal disease in humans in the EU (European Union) as is reported by the European Union One Health 2018 Zoonoses Report styled by the EFSA (European Food Safety Authority) and ECDC (European Center for Disease Prevention and Control). One of the vehicles of transmission of this disease is milk. Nanostructured MOS (Metal Oxide Semiconductor) sensors have extensively demonstrated their ability to reveal the presence and follow the development of microbial species. The main objective of this work was to find a set up for the detection and development follow up of C. jejuni in milk samples. The work was structured in two different studies, the first one was a feasibility survey and the second one was to follow up the development of the bacteria inside milk samples. The obtained results of the first study demonstrate the ability of the sensor array to differentiate the contaminated samples from the control ones. Thanks to the second study, it has been possible to find the limit of microbial safety of the contaminated milk samples.

Multidisciplinary Approach to Characterizing the Fingerprint of Italian EVOO.

Extra virgin olive oil (EVOO) is characterized by its aroma and other sensory attributes. These are determined by the geographical origin of the oil, extraction process, place of cultivation, soil, tree varieties, and storage conditions. In the present work, an array of metal oxide gas sensors (called S3), in combination with the SPME-GC-MS technique, was applied to the discrimination of different types of olive oil (phase 1) and to the identification of four varieties of Garda PDO extra virgin olive oils coming from west and east shores of Lake Garda (phase 2). The chemical analysis method involving SPME-GC-MS provided a complete volatile component of the extra virgin olive oils that was used to relate to the S3 multisensory responses. Furthermore, principal component analysis (PCA) and k-Nearest Neighbors (k-NN) analysis were carried out on the set of data acquired from the sensor array to determine the best sensors for these tasks and to assess the capability of the system to identify various olive oil samples. k-NN classification rates were found to be 94.3% and 94.7% in the two phases, respectively. These first results are encouraging and show a good capability of the S3 instrument to distinguish different oil samples.

Application of a Novel S3 Nanowire Gas Sensor Device in Parallel with GC-MS for the Identification of Rind Percentage of Grated Parmigiano Reggiano.

Parmigiano Reggiano cheese is one of the most appreciated and consumed foods worldwide, especially in Italy, for its high content of nutrients and taste. However, these characteristics make this product subject to counterfeiting in different forms. In this study, a novel method based on an electronic nose has been developed to investigate the potentiality of this tool to distinguish rind percentages in grated Parmigiano Reggiano packages that should be lower than 18%. Different samples, in terms of percentage, seasoning and rind working process, were considered to tackle the problem at 360°. In parallel, GC-MS technique was used to give a name to the compounds that characterize Parmigiano and to relate them to sensors responses. Data analysis consisted of two stages: Multivariate analysis (PLS) and classification made in a hierarchical way with PLS-DA ad ANNs. Results were promising, in terms of correct classification of the samples. The correct classification rate (%) was higher for ANNs than PLS-DA, with correct identification approaching 100 percent.

Metal Oxide Gas Sensors, a Survey of Selectivity Issues Addressed at the SENSOR Lab, Brescia (Italy).

This work reports the recent results achieved at the SENSOR Lab, Brescia (Italy) to address the selectivity of metal oxide based gas sensors. In particular, two main strategies are being developed for this purpose: (i) investigating different sensing mechanisms featuring different response spectra that may be potentially integrated in a single device; (ii) exploiting the electronic nose (EN) approach. The former has been addressed only recently and activities are mainly focused on determining the most suitable configuration and measurements to exploit the novel mechanism. Devices suitable to exploit optical (photoluminescence), magnetic (magneto-optical Kerr effect) and surface ionization in addition to the traditional chemiresistor device are here discussed together with the sensing performance measured so far. The electronic nose is a much more consolidated technology, and results are shown concerning its suitability to respond to industrial and societal needs in the fields of food quality control and detection of microbial activity in human sweat.

Nanostructured metal oxide gas sensors, a survey of applications carried out at SENSOR lab, Brescia (Italy) in the security and food quality fields.

In this work we report on metal oxide (MOX) based gas sensors, presenting the work done at the SENSOR laboratory of the CNR-IDASC and University of Brescia, Italy since the 80s up to the latest results achieved in recent times. In particular we report the strategies followed at SENSOR during these 30 years to increase the performance of MOX sensors through the development of different preparation techniques, from Rheotaxial Growth Thermal Oxidation (RGTO) to nanowire technology to address sensitivity and stability, and the development of electronic nose systems and pattern recognition techniques to address selectivity. We will show the obtained achievement in the context of selected applications such as safety and security and food quality control.

An Array of MOX Sensors and ANNs to Assess Grated Parmigiano Reggiano Cheese Packs' Compliance with CFPR Guidelines.

Parmigiano Reggiano cheese is one of the most appreciated Italian foods on account of its high nutrient content and taste. Due to its high cost, these characteristics make this product subject to counterfeiting in different forms. In this study, an approach based on an array of gas sensors has been employed to assess if it was possible to distinguish different samples based on their aroma. Samples were characterized in terms of rind percentage, seasoning, and rind working process. From the responses of the sensors, five features were extracted and the capability of these parameters to recognize target classes was tested with statistical analysis. Hence, the performance of the sensors' array was quantified using artificial neural networks. To simplify the problem, a hierarchical approach has been used: three steps of classification were performed, and in each step one parameter of the grated cheese was identified (firstly, seasoning; secondly, rind working process; finally, rind percentage). The accuracies ranged from 88.24% to 100%.

UV-Enhanced Humidity Sensing of Chitosan-SnO2 Hybrid Nanowires.

The surface of SnO2 nanowires was functionalized by chitosan for the development of room-temperature conductometric humidity sensors. SnO2 nanowires were synthesized by the seed-mediated physical-vapor-deposition (PVD) method. Chitosan layers were deposited on top of the SnO2 nanowires by spin coating. Surface morphology, crystal structure, and optical properties of the synthesized hybrid nanostructure were investigated by scanning electron microscope, grazing incidence X-ray diffraction, and UV-Vis absorption measurements. During electrical conductivity measurements, the hybrid nanostructure showed unusual behavior towards various relative humidity (RH) concentrations (25%, 50%, 75%), under UV-light irradiation, and in dark conditions. The highest sensor responses were recorded towards an RH level of 75%, resulting in 1.1 in the dark and 2.5 in a UV-irradiated chamber. A novel conduction mechanism of hybrid nanowires is discussed in detail by comparing the sensing performances of chitosan film, SnO2 nanowires, and chitosan@SnO2 hybrid nanostructures.

Metabolomics fingerprint of Philippine coffee by SPME-GC-MS for geographical and varietal classification.

Volatile metabolites of Philippine Arabica and Robusta coffee beans in both forms standard (not-eaten by the Asian palm civet) and civet coffee grown in different Philippine regions were identified using the hyphenated technique headspace-solid phase microextraction-gas chromatography-mass spectrometry. A great number of volatile metabolites with a wide variety of functional groups were extracted and forty-seven prominent compounds were identified. The volatile metabolomics (volatilomics) fingerprint of Arabica coffees considerably differed from Robusta coffee and geographical origin slightly altered the fingerprint profile of coffee samples. Chemometric analysis such as principal component analysis (PCA) displayed a good classification between Arabica and Robusta coffee samples. Although Arabica coffee samples from different geographical origins were clustered separately from each other, the proximity of clusters between Arabica coffee samples which could be classified into one large group, indicated their close similarity of headspace metabolites. The distinction between Arabica samples and Robusta coffees was attributed through the PCA to several key volatile metabolites, in particular, higher quantities of acetic acid, furfural, 5-methylfurfural, 2-formylpyrrole and maltol and lower concentrations of 4-ethylguaiacol and phenol. These discriminating metabolites could represent useful quality markers to differentiate Arabica from Robusta coffee. Results revealed that the headspace metabolites in coffee provide significant information on its inherent aroma quality. Also, the findings suggested that the overall quality of Philippine coffee is variety and region-specific.

Innovative Sensor Approach to Follow Campylobacter jejuni Development.

Campylobacter spp infection affects more than 200,000 people every year in Europe and in the last four years a trend shows an increase in campylobacteriosis. The main vehicle for transmission of the bacterium is contaminated food like meat, milk, fruit and vegetables. In this study, the aim was to find characteristic volatile organic compounds (VOCs) of C. jejuni in order to detect its presence with an array of metal oxide (MOX) gas sensors. Using a starting concentration of 10³ CFU/mL, VOCs were analyzed using Gas-Chromatography Mass-Spectrometry (GC-MS) with a Solid-Phase Micro Extraction (SPME) technique at the initial time (T0) and after 20 h (T20). It has been found that a Campylobacter sample at T20 is characterized by a higher number of alcohol compounds that the one at T0 and this is due to sugar fermentation. Sensor results showed the ability of the system to follow bacteria curve growth from T0 to T20 using Principal Component Analysis (PCA). In particular, this results in a decrease of ΔR/R0 value over time. For this reason, MOX sensors are a promising technology for the development of a rapid and sensitive system for C. jejuni.

Nanomaterial Gas Sensors for Online Monitoring System of Fruit Jams.

Jams are appreciated worldwide and have become a growing market, due to the greater attention paid by consumers for healthy food. The selected products for this study represent a segment of the European market that addresses natural products without added sucrose or with a low content of natural sugars. This study aims to identify volatile organic compounds (VOCs) that characterize three flavors of fruit and five recipes using gas chromatography-mass spectrometry (GC-MS) and solid-phase micro-extraction (SPME) analysis. Furthermore, an innovative device, a small sensor system (S3), based on gas sensors with nanomaterials has been used; it may be particularly advantageous in the production line. Results obtained with linear discriminant analysis (LDA) show that S3 can distinguish among the different recipes thanks to the differences in the VOCs that are present in the specimens, as evidenced by the GC-MS analysis. Finally, this study highlights how the thermal processes for obtaining the jam do not alter the natural properties of the fruit.

Metal oxide nanostructures: preparation, characterization and functional applications as chemical sensors.

Preparation and characterization of different metal oxide (NiO, WO3, ZnO, SnO2 and Nb2O5) nanostructures for chemical sensing are presented. p-Type (NiO) and n-type (WO3, SnO2, ZnO and Nb2O5) metal oxide nanostructures were grown on alumina substrates using evaporation-condensation, thermal oxidation and hydrothermal techniques. Surface morphologies and crystal structures were investigated through scanning electron microscopy and Raman spectroscopy. Furthermore, different batches of sensors have been prepared, and their sensing performances towards carbon monoxide and nitrogen dioxide have been explored. Moreover, metal oxide nanowires have been integrated into an electronic nose and successfully applied to discriminate between drinking and contaminated water.

Validation of Parmigiano Reggiano Cheese Aroma Authenticity, Categorized through the Use of an Array of Semiconductors Nanowire Device (S3).

Parmigiano Reggiano (PR) cheese is one of the most important Italian Protected Designation of Origin (PDO) cheeses and it is exported worldwide. As a PDO, the product is supposed to have distinctive sensory characteristics. In this work we present the use of the Small Gas Sensor System (S3) device for the identification of specific PR markers, as compared to classical chemical techniques, such as Gas chromatography-mass spectrometry solid-phase microextraction (SPME-GC-MS). Markers are used to determine the percent of grated pulp and rind commercially utilized. The S3 device is equipped with an array of six metal oxide semiconductor (MOX) gas sensors, three of them with a nanowire (NW) morphology and the other three in the form of thin films. PDO can cover grated PR cheese as well, but only if made with whole cheese. Grated PR cheese must be characterized by the absence of additives and no more than 18% crust. The achieved results strongly encourage the use of S3 for a rapid identification of the percentage of grated PR.

A Novel MOS Nanowire Gas Sensor Device (S3) and GC-MS-Based Approach for the Characterization of Grated Parmigiano Reggiano Cheese.

To determine the originality of a typical Italian Parmigiano Reggiano cheese, it is crucial to define and characterize its quality, ripening period, and geographical origin. Different analytical techniques have been applied aimed at studying the organoleptic and characteristic volatile organic compounds (VOCs) profile of this cheese. However, most of the classical methods are time consuming and costly. The aim of this work was to illustrate a new simple, portable, fast, reliable, non-destructive, and economic sensor device S3 based on an array of six metal oxide semiconductor nanowire gas sensors to assess and discriminate the quality ranking of grated Parmigiano Reggiano cheese samples and to identify the VOC biomarkers using a headspace SPME-GC-MS. The device could clearly differentiate cheese samples varying in quality and ripening time when the results were analyzed by multivariate statistical analysis involving principal component analysis (PCA). Similarly, the volatile constituents of Parmigiano Reggiano identified were consistent with the compounds intimated in the literature. The obtained results show the applicability of an S3 device combined with SPME-GC-MS and sensory evaluation for a fast and high-sensitivity analysis of VOCs in Parmigiano Reggiano cheese and for the quality control of this class of cheese.