Low-Cost Pocket Fluorometer and Chemometric Tools for Green and Rapid Screening of Deoxynivalenol in Durum Wheat Bran.

Cereal crops are frequently contaminated by deoxynivalenol (DON), a harmful type of mycotoxin produced by several Fusarium species fungi. The early detection of mycotoxin contamination is crucial for ensuring safety and quality of food and feed products, for preventing health risks and for avoiding economic losses because of product rejection or costly mycotoxin removal. A LED-based pocket-size fluorometer is presented that allows a rapid and low-cost screening of DON-contaminated durum wheat bran samples, without using chemicals or product handling. Forty-two samples with DON contamination in the 40-1650 µg/kg range were considered. A chemometric processing of spectroscopic data allowed distinguishing of samples based on their DON content using a cut-off level set at 400 µg/kg DON. Although much lower than the EU limit of 750 µg/kg for wheat bran, this cut-off limit was considered useful whether accepting the sample as safe or implying further inspection by means of more accurate but also more expensive standard analytical techniques. Chemometric data processing using Principal Component Analysis and Quadratic Discriminant Analysis demonstrated a classification rate of 79% in cross-validation. To the best of our knowledge, this is the first time that a pocket-size fluorometer was used for DON screening of wheat bran.

Smartphone-Enabled Colorimetry.

A smartphone is used as a colorimeter. The performance characterization for colorimetry is presented using both the built-in camera and a clip-on dispersive grating. Certified colorimetric samples provided by Labsphere® are considered as test samples. Color measurements directly performed utilizing the smartphone camera only are obtained using the RGB Detector app, downloaded from the Google Play Store. More precise measurements are achieved using the commercially available GoSpectro grating and related app. In both cases, to quantify the reliability and sensitivity of smartphone-based color measurements, the CIELab color difference ΔE between the certified and smartphone-measured colors is calculated and is reported in this paper. In addition, as an example of a practical application of interest for the textile industry, several samples of cloth fabrics with a palette of the most common colors are measured, and the comparison with the certified color values is presented.

Bluetooth-Connected Pocket Spectrometer and Chemometrics for Olive Oil Applications.

Unsaturated fatty acids are renowned for their beneficial effects on the cardiovascular system. The high content of unsaturated fatty acids is a benefit of vegetable fats and an important nutraceutical indicator. The ability to quickly check fat composition of an edible oil could be advantageous for both consumers and retailers. A Bluetooth-connected pocket spectrometer operating in NIR band was used for analyzing olive oils of different qualities. Reference data for fatty acid composition were obtained from a certified analytical laboratory. Chemometrics was used for processing data, and predictive models were created for determining saturated and unsaturated fatty acid content. The NIR spectrum also demonstrated good capability in classifying extra virgin and non-extra virgin olive oils. The pocket spectrometer used in this study has a relatively low cost, which makes it affordable for a wide class of users. Therefore, it may open the opportunity for quick and non-destructive testing of edible oil, which can be of interest for consumer, retailers, and for small/medium-size producers, which lack easy access to conventional analytics.

Novel Probe for Thermally Controlled Raman Spectroscopy Using Online IR Sensing and Emissivity Measurements.

Temperature rise during Raman spectroscopy can induce chemical alterations of the material under analysis and seriously affect its characterization. Thus, such photothermal side effects can represent a serious problem to be carefully controlled in order to safeguard the integrity of the material and its spectral features. In this work, an innovative probe for thermally controlled portable Raman spectroscopy (exc. 785 nm) equipped with infrared sensing lines was developed. It included an infrared source and two thermopile sensors, which allowed to perform real-time measurements of the local emissivity of the material surface under laser excitation. The emissivity, which is needed in order to monitor the temperature of the irradiated surface through infrared radiation measurements, represents the complementary component of the reflectance in the radiative energy balance. Thus, total reflectance, temperature measurements and Raman spectroscopy were integrated in the present probe. After independently assessing the reliability of the former in order to derive the emissivity of variety of materials, the probe was successfully applied on pigments, paint layers, and a painting on canvas. The results achieved evidence the significant exploitation potential of the novel tool.

Quantitative Compositional Analyses of Calcareous Rocks for Lime Industry Using LIBS.

Here, the potential of laser-induced breakdown spectroscopy (LIBS) in grading calcareous rocks for the lime industry was investigated. In particular, we developed a system equipped with non-intensified detectors operating in scanning mode, defined a suitable data acquisition protocol, and implemented quantitative data processing using both partial least squares regression (PLS-R) and a multilayer perceptron (MLP) neural network. Tests were carried out on 32 samples collected in various limestone quarries, which were preliminarily analyzed using traditional laboratory X-ray fluorescence (XRF); then, they were divided into two groups for calibration and validation. Particular attention was dedicated to the development of LIBS methodology providing a reliable basis for precise material grading. The congruence of the results achieved demonstrates the capability of the present approach to precisely quantify major and minor geochemical components of calcareous rocks, thus disclosing a concrete application perspective within the lime industry production chain.

A Study of Overripe Seed Byproducts from Sun-Dried Grapes by Dispersive Raman Spectroscopy.

Overripe seeds from sun-dried grapes submitted to postharvest dehydration constitute a scarcely investigated class of vinification byproduct with limited reports on their phenolic composition and industrial applications. In this study, Raman spectroscopy was applied to characterize a selection of overripe seed byproducts from different white grapes (cv. Moscatel, cv. Pedro Ximénez and cv. Zalema) submitted to postharvest sun drying. The Raman measurements were taken using a 1064 nm excitation laser in order to mitigate the fluorescent effect and the dispersive detection scheme allowed a compactness of the optical system. Spectroscopic data were processed by a principal component analysis to reduce the dimensionality and partner recognition. The evolution of the Raman spectrum during the overripening process was compared with the phenolic composition of grape seeds, which was determined by rapid resolution liquid chromatography/mass spectrometry (RRLC/MS). A multivariate processing of the spectroscopic data allowed the classification of overripe seeds according to the grape variety and the monitoring of stages of the postharvest sun drying process.

High Energy Double Peak Pulse Laser Induced Plasma Spectroscopy for Metal Characterization Using a Passively Q-Switched Laser Source and CCD Detector.

Here, the development and testing of a portable double peak pulse laser induced plasma spectroscopy (DPP-LIPS) based on passively Q-switched Nd:YAG (Neodymium-doped Yttrium Aluminum Garnet) laser excitation is reported. The latter delivered structured laser pulses at a repetition rate of up to 20 Hz, including two energy peaks of about 100 mJ each with a relative temporal spacing of about 80 µs. Plasma spectra were collected using a low-cost Czerny-Turner spectrometer equipped with a non-intensified CCD (Charge-Coupled Device) array. Such a DPP-LIPS setup is technologically simpler and cheaper than the usual ones. Despite the relatively large temporal separation between the mentioned laser peaks, significant spectral intensity enhancements with respect to the usual single peak pulse configuration were observed. The amplification factor measured ranged between 2 and 10, depending on the specific emission peaks and the Q-switched configuration, and a consequent significant improvement of the detection limit of trace elements was observed. The instrument was calibrated for the quantitative analysis of copper alloy through systematic measurements carried out on reference samples and was then tested in an example archaeometric characterization of a statuette from the Egyptian Museum of Florence.

Raman spectrometer for the automated scan of large painted surfaces.

In this work, a novel Raman scanner capable of performing point-to-point mapping of relatively large surface of paintings is presented. This device employs an excitation wavelength of 1064 nm, and it is equipped with a high efficiency probe in order to collect the back-scattered light from each point of analysis. The use of long depth-of-field optics as well as an autofocus system allowed maintaining the best conditions for the Raman signal acquisition during the scanning, regardless of the surface irregularities. The small dimension of the optical components and the reasonable size of mechanical parts made this instrumentation particularly suitable for on-site measurements. Finally, the Raman scanner was also equipped with an online temperature control using a thermal sensor, which allows modulating automatically the output power of the laser source in order to prevent overheating and alteration effects during the scanning process. The capabilities of the Raman scanner were evaluated scanning two valuable paintings one attributed to Ambrogio Lorenzetti and the other to Duccio da Buoninsegna of the fourteenth century.

Comparison of lycopene changes between open-field processing and fresh market tomatoes during ripening and post-harvest storage by using a non-destructive reflectance sensor.

BACKGROUND: Accumulation and stability of tomato lycopene markedly depends on the cultivar, plant growing and storage conditions. To estimate lycopene in open-field cultivated processing and fresh market tomatoes, we used a calibrated spectral reflectance portable sensor. RESULTS: Lycopene accumulation in fruits attached to the plant, starting from the Green ripening stage, followed a sigmoidal function. It was faster and reached higher levels in processing (cv. Calista) than fresh market (cv. Volna) tomatoes (90 and 62 mg kg-1 fresh weight, respectively). During storage at 12, 20 and 25 °C, Red tomatoes retained about 90% of harvest lycopene for three weeks. Pink tomatoes increased lycopene during the first week of storage, but never reached the lycopene values of Red tomatoes ripened on the vine. Storability at 12 °C retaining the highest quality in red tomatoes was limited to 14 and 7 days for Calista and Volna cultivars, respectively. CONCLUSION: Significant differences in lycopene accumulation and stability between processing and fresh market tomatoes were established by examining with time the very same fruits by a non-destructive optical tool. It can be useful in agronomical and post-harvest physiological studies and can be of interest for producers oriented to the niche nutraceutical market. © 2018 Society of Chemical Industry.

Prediction Models for Assessing Lycopene in Open-Field Cultivated Tomatoes by Means of a Portable Reflectance Sensor: Cultivar and Growing-Season Effects.

Reflectance spectroscopy represents a useful tool for the nondestructive assessment of tomato lycopene, even in the field. For this reason, a compact, low-cost, light emitting diode-based sensor has been developed to measure reflectance in the 400-750 nm spectral range. It was calibrated against wet chemistry and evaluated by partial least squares (PLS) regression analyses. The lycopene prediction models were defined for two open-field cultivated red-tomato varieties: the processing oblong tomatoes of the cv. Calista (average weight: 76 g) and the fresh-consumption round tomatoes of the cv. Volna (average weight: 130 g), over a period of two consecutive years. The lycopene prediction models were dependent on both cultivar and season. The lycopene root mean square error of prediction produced by the 2014 single-cultivar calibrations validated on the 2015 samples was large (33 mg kg-1) in the Calista tomatoes and acceptable (9.5 mg kg-1) in the Volna tomatoes. A more general bicultivar and biyear model could still explain almost 80% of the predicted lycopene variance, with a relative error in red tomatoes of less than 20%. In 2016, the in-field applications of the multiseasonal prediction models, built with the 2014 and 2015 data, showed significant ( P < 0.001) differences in the average lycopene estimated in the crop on two sampling dates that were 20 days apart: on August 19 and September 7, 2016, the lycopene was 98.9 ± 9.3 and 92.2 ± 10.8 mg kg-1 FW for cv. Calista and 54.6 ± 13.2 and 60.8 ± 6.8 mg kg-1 FW for cv. Volna. The sensor was also able to monitor the temporal evolution of lycopene accumulation on the very same fruits attached to the plants. These results indicated that a simple, compact reflectance device and PLS analysis could provide adequately precise and robust (through-seasons) models for the nondestructive assessment of lycopene in whole tomatoes. This technique could guarantee tomatoes with the highest nutraceutical value from the production, during storage and distribution, and finally to consumers.

Innovative Sensors for Environmental Monitoring in Museums.

Different physical and chemical factors, such as light, temperature, relative humidity, pollutants and so on, can affect works of art on display. Each factor does not act individually, but its effect can be enhanced or accelerated by the presence of other factors. Accordingly, an evaluation of the impact of the whole environment on art objects is recognized as an essential requirement for conservation purposes. To meet the most up-todate guidelines on preventive conservation, in recent years several scientific projects supported by the EC were aimed at developing innovative tools that could complement the standard methods for environmental monitoring in museums. These research projects produced a new generation of passive sensors that are capable of taking into account the overall environmental effects by mimicking in some way the behaviour of real works of art. The main goal of the present paper is to provide a survey of these sensors, which represent a new frontier in the environmental control in museums. Furthermore, the use of optical fibres, as both intrinsic sensors and devices for interrogating sensors, will also be illustrated, and examples of their use in the cultural heritage field will be reported.

Optical sensor for interstitial pH measurements.

An optical fiber sensor for measuring the pH in interstitial fluid is described. Microdialysis is the approach followed for extracting the sample from the subcutaneous adipose tissue. The interstitial fluid drawn flows through a microfluidic circuit formed by a microdialysis catheter in series with a pH glass capillary. The pH indicator (phenol red) is covalently immobilized on the internal wall of the glass capillary. An optoelectronic unit that makes use of LEDs and photodetectors is connected to the sensing capillary by means of optical fibers. Optical fibers are used to connect the interrogating unit to the sensing capillary. A resolution of 0.03 pH units and an accuracy of 0.07 pH units are obtained. Preliminary in vivo tests are carried out in pigs with altered respiratory function.

Mathematical model for the analytical signal of an herbicide sensor based on the reaction centre of Rhodobacter sphaeroides.

This paper introduces a mathematical model which makes it possible both to determine the concentration of photosynthetic herbicides and to obtain a quantitative parameter in order to compare their activity using a previously described sensing system. The working principle involves the changes in absorption properties at 860nm of the reaction centre (RC) isolated from the bacteria Rhodobacter sphaeroides when photosynthetic herbicides are present. The method has been used for the determination and activity comparison of five photosynthetic herbicides: diuron, atrazine, terbutryn, terbuthylazine and simazine. Detection limits obtained were 2.2, 0.75, 0.046, 0.25, and 1.4muM, respectively. The resulting order for the different herbicides according to their action on RC was: terbutryn > terbuthylazine > atrazine > simazine > diuron.

Antibody immobilisation on fibre optic TIRF sensors.

A study of antibody immobilisation techniques on quartz and fibre optic surfaces for immunosensors has been carried out. Methods of covalent antibody immobilisation which have not previously been applied to optical fibres were investigated, and compared with classical methods found in the literature. Preliminary experiments on covalent immobilisation methods on planar quartz surfaces were conducted to enable us to choose the most suitable protein immobilisation technique for sensor applications. The immobilisation studies were directed in particular towards obtaining a high density of binding sites for the analyte of interest. Two of the most promising methods, antibody immobilisation on surfaces coated with dextran based hydrogel and F(ab')-SH fragments bound to silanised glass, which resulted in surface densities of active sites of above 0.45 pmol/cm2, were selected for further experiments on a fibre optic total internal reflection fluorescence immunosensor and gave satisfactory responses to changes in analyte concentrations of the order of 10(-8) M. The efficiency of polar organic solvents, such as dimethylsulfoxide, in dissociating the antigen-antibody complex and hence to regenerate the immunosensor surface was also evaluated.