Rapid Authentication and Detection of Olive Oil Adulteration Using Laser-Induced Breakdown Spectroscopy.

The adulteration of olive oil is a crucial matter for food safety authorities, global organizations, and consumers. To guarantee olive oil authenticity, the European Union (EU) has promoted the labeling of olive oils with the indices of Protected Designation of Origin (PDO) and Protected Geographical Identification (PGI), while food security agencies are also interested in newly emerging technologies capable of operating reliably, fast, and in real-time, either in situ or remotely, for quality control. Among the proposed methods, photonic technologies appear to be suitable and promising for dealing with this issue. In this regard, a laser-based technique, namely, Laser-Induced Breakdown Spectroscopy (LIBS), assisted via machine learning tools, is proposed for the real-time detection of olive oil adulteration with lower-quality oils (i.e., pomace, soybean, sunflower, and corn oils). The results of the present work demonstrate the high efficiency and potential of the LIBS technique for the rapid detection of olive oil adulteration and the detection of adulterants.

Exceptional ultrafast nonlinear optical response of functionalized silicon nanosheets.

The present work reports on the ultrafast saturable absorption (SA), optical limiting (OL), and the nonlinear refractive response of hydride-terminated silicon nanosheets (SiNS-H) differently functionalized with styrene and tert-butyl methacrylate (tBuMA), namely, SiNS-styrene and SiNS-tBuMA, using 50 fs, 400 nm and 70 fs, 800 nm laser pulses. SiNS-styrene and SiNS-tBuMA exhibit dramatically enhanced nonlinear optical (NLO) responses compared to SiNS-H, with their absorptive nonlinearity strongly dependent on the laser excitation wavelength. More specifically, the studied functionalized SiNSs reveal strong SA behavior under 400 nm laser excitation, with NLO absorption coefficients, saturable intensities, and modulation depths comparable to various two-dimensional (2D) materials, known to exhibit strong SA, such as graphene, black phosphorous (BP), some transition metal dichalcogenides (TMDs), and some MXenes. On the other hand, under 800 nm laser excitation, SiNS-styrene and SiNS-tBuMA show highly efficient OL performance with OL onset values of about 0.0045 and 0.0065 J cm-2, respectively, which are significantly lower than those of other 2D nanostructures. In addition, it is shown that both SiNS samples have great potential in already existing Si-based optoelectronic devices for optical-switching applications since they exhibit very strong NLO refraction comparable to that of bulk Si. The results of the present work demonstrate that the chemical functionalization of SiNSs provides a highly efficient strategy for the preparation of 2D Si-based nanostructures with enhanced NLO response in view of several optoelectronic and photonic applications, such as OL, SA, and all-optical switching.

2D Non-van der Waals Nanoplatelets of Hematene and Magnetene: Nonlinear Optical Response and Optical Limiting Performance from UV to NIR.

Recently, the preparation of some hematene and magnetene ultrathin non van der Waals (non-vdW) 2D nanoplatelets was reported starting from hematite and magnetite natural iron ores. The present work reports on the determination and evaluation of the nonlinear optical response and the optical limiting (OL) action of these 2D nanoplatelets dispersed in water under ns laser excitation. The obtained results show that both hematene and magnetene exhibit strong nonlinear absorption and refraction, comparable and even larger than those of other van der Waals (vdW) 2D counterpart materials. In addition, due to their strong nonlinear absorption, both hematene and magnetene show exceptional OL performance from the UV to visible, attaining very low values of optical limiting onset (OLon ), comparable and even lower than that of vdW 2D nanomaterials, such as graphene, graphene oxide, other transition metal dichalcogenides like MoS2 , WS2 and MoSe2 , black phosphorous and antimonene. Moreover, hematene was found to exhibit more efficient OL action than magnetene for all the excitation wavelengths studied, attributed to more efficient ligand to metal charge transfer. The present findings open new possibilities for the potential use of these non-vdW 2D materials in photonics and optoelectronics, e. g., as optical limiters and optical switchers.

Iridium-Based Nanohybrids: Synthesis, Characterization, Optical Limiting, and Nonlinear Optical Properties.

The present work reports on the synthesis and characterization of iridium (Ir)-based nanohybrids with variable chemical compositions. More specifically, highly stable polyvinylpyrrolidone (PVP) nanohybrids of the PVP-IrO2 and PVP-Ir/IrO2 types, as well as non-coated Ir/IrO2 nanoparticles, are synthesized using different synthetic protocols and characterized in terms of their chemical composition and morphology via X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM), respectively. Furthermore, their nonlinear optical (NLO) response and optical limiting (OL) efficiency are studied by means of the Z-scan technique, employing 4 ns laser pulses at 532 and 1064 nm. The results demonstrate that the PVP-Ir/IrO2 and Ir/IrO2 systems exhibit exceptional OL performance, while PVP-IrO2 presents very strong saturable absorption (SA) behavior, indicating that the present Ir-based nanohybrids could be strong competitors to other nanostructured materials for photonic and optoelectronic applications. In addition, the findings denote that the variation in the content of IrO2 nanoparticles by using different synthetic pathways significantly affects the NLO response of the studied Ir-based nanohybrids, suggesting that the choice of the appropriate synthetic method could lead to tailor-made NLO properties for specific applications in photonics and optoelectronics.

Strong Ultrafast Saturable Absorption and Nonlinear Refraction of Some Non-van der Waals 2D Hematene and Magnetene Nanoplatelets for Ultrafast Photonic Applications.

In the present work, some non-van der Waals (non-vdW) 2D materials, namely, hematene and magnetene nanoplatelets, were synthesized starting from hematite and magnetite ores, respectively, using a green synthesis method, and they were dispersed in water. Then, their ultrafast nonlinear optical (NLO) response was studied under 50 fs, 400 nm laser excitation. Both non-vdW 2D materials revealed strong saturable absorption with NLO absorption coefficient ß, saturable intensity, and modulation depth of about -33.2 × 10-15 m/W, 320 GW/cm2, and 19%, respectively, for hematene, and about -21.4 × 10-15 m/W, 500 GW/cm2, and 17% for magnetene. These values are comparable to those of other vdW 2D materials, such as graphene, transition metal dichalcogenides (TMDs) like MoS2, WS2, and MoSe2, black phosphorus (BP), and some MXenes (Ti3C2Tx), recently reported as efficient saturable absorbers. In addition, both hematene and magnetene dispersions displayed strong Kerr type NLO refraction with nonlinear refractive index parameters γ' comparable and even larger than those of van der Waals 2D materials. In all cases, hematene was found exhibiting significantly larger optical nonlinearities than magnetene, most probably due to the formation of a more efficient charge transfer system. The results of the present work are strongly suggesting that hematene and magnetene can have applications in a wide range of photonic and optoelectronic applications.

A new class of third-order nonlinear optical materials: laser pulse-duration dependant saturable absorption and nonlinear refraction in platinum(II) diimine-dithiolate complexes.

The third-order nonlinear optical (NLO) properties of a series of platinum diimine-dithiolate complexes [Pt(N^N)(S^S)] were investigated by means of Z-scan measurements, revealing second hyperpolarizability values up to 10-29 esu, saturable absorption properties, and nonlinear refractive behaviour, which were rationalized also by means of DFT calculations.

Nanocomposites Based on Spin-Crossover Nanoparticles and Silica-Coated Gold Nanorods: A Nonlinear Optical Study.

A nanocomposite based on silica-coated AuNRs with the aminated silica-covered spin-crossover nanoparticles (SCO NPs) of the 1D iron(II) coordination polymer with the formula [Fe(Htrz)2(trz)](BF4) is presented. For the synthesis of the SCO NPs, the reverse micelle method was used, while the gold nanorods (AuNRs) were prepared with the aspect ratio AR = 6.0 using the seeded-growth method and a binary surfactant mixture composed of cetyltrimethylammonium bromide (CTAB) and sodium oleate (NaOL). The final nanocomposite was prepared using the heteroaggregation method of combining different amounts of SCO NPs with the AuNRs. The nonlinear optical (NLO) properties of the hybrid AuNRs coated with different amounts of SCO NPs were studied in detail by means of the Z-scan technique, revealing that the third-order NLO properties of the AuNRs@SCO are dependent on the amount of SCO NPs grafted onto them. However, due to the resonant nature of the excitation, SCO-induced NLO switching was not observed.

Milk's inorganic content analysis via laser induced breakdown spectroscopy.

In the present work, the inorganic content of different milk samples is investigated by Laser Induced Breakdown Spectroscopy (LIBS) technique. Milk samples of different animal origin, in liquid, lyophilized powder, and ashed forms were studied using both infrared (1064 nm) and visible (532 nm) laser excitation conditions and the optimum experimental conditions for the measurement of the inorganic elements present in low concentration, were determined. Spectral features of major (Ca, Na, Mg and K) and minor minerals (P, Zn, Cu and Si) were detected and identified. The LIBS results for the different milk samples were found to correlate perfectly with the results obtained from atomic absorption measurements, demonstrating the potential of LIBS technique for the fast and in-situ qualitative characterization of the inorganic content of different animal origin milk samples.

Tailoring the Nonlinear Optical Response of Some Graphene Derivatives by Ultraviolet (UV) Irradiation.

In the present work the impact of in situ photoreduction, by means of ultraviolet (UV) irradiation, on the nonlinear optical response (NLO) of some graphene oxide (GO), fluorographene (GF), hydrogenated fluorographene (GFH) and graphene (G) dispersions is studied. In situ UV photoreduction allowed for the extended modification of the degree of functionalization (i.e., oxidization, fluorination and hydrogenation), leading to the effective tuning of the corresponding sp2/sp3 hybridization ratios. The nonlinear optical properties of the studied samples prior to and after UV irradiation were determined by means of the Z-scan technique using visible (532 nm), 4 ns laser excitation, and were found to change significantly. More specifically, while GO's nonlinear optical response increases with irradiation time, GF and GFH present a monotonic decrease. The graphene dispersions' nonlinear optical response remains unaffected after prolonged UV irradiation for more than an hour. The present findings demonstrate that UV photoreduction can be an effective and simple strategy for tuning the nonlinear optical response of these graphene derivatives in a controllable way, resulting in derivatives with custom-made responses, thus more suitable for different photonic and optoelectronic applications.

Laser-Induced Breakdown Spectroscopy: An Efficient Tool for Food Science and Technology (from the Analysis of Martian Rocks to the Analysis of Olive Oil, Honey, Milk, and Other Natural Earth Products).

Laser-Induced Breakdown Spectroscopy (LIBS), having reached a level of maturity during the last few years, is generally considered as a very powerful and efficient analytical tool, and it has been proposed for a broad range of applications, extending from space exploration down to terrestrial applications, from cultural heritage to food science and security. Over the last decade, there has been a rapidly growing sub-field concerning the application of LIBS for food analysis, safety, and security, which along with the implementation of machine learning and chemometric algorithms opens new perspectives and possibilities. The present review intends to provide a short overview of the current state-of-the-art research activities concerning the application of LIBS for the analysis of foodstuffs, with the emphasis given to olive oil, honey, and milk.

Laser-induced breakdown spectroscopy coupled with machine learning as a tool for olive oil authenticity and geographic discrimination.

Olive oil is a basic element of the Mediterranean diet and a key product for the economies of the Mediterranean countries. Thus, there is an added incentive in the olive oil business for fraud through practices like adulteration and mislabeling. In the present work, Laser Induced Breakdown Spectroscopy (LIBS) assisted by machine learning is used for the classification of 139 virgin olive oils in terms of their geographical origin. The LIBS spectra of these olive oil samples were used to train different machine learning algorithms, namely LDA, ERTC, RFC, XGBoost, and to assess their classification performance. In addition, the variable importance of the spectral features was calculated, for the identification of the most important ones for the classification performance and to reduce their number for the algorithmic training. The algorithmic training was evaluated and tested by means of classification reports, confusion matrices and by external validation procedure as well. The present results demonstrate that machine learning aided LIBS can be a powerful and efficient tool for the rapid authentication of the geographic origin of virgin olive oil.

Classification of Greek Olive Oils from Different Regions by Machine Learning-Aided Laser-Induced Breakdown Spectroscopy and Absorption Spectroscopy.

In the present work, the emission and the absorption spectra of numerous Greek olive oil samples and mixtures of them, obtained by two spectroscopic techniques, namely Laser-Induced Breakdown Spectroscopy (LIBS) and Absorption Spectroscopy, and aided by machine learning algorithms, were employed for the discrimination/classification of olive oils regarding their geographical origin. Both emission and absorption spectra were initially preprocessed by means of Principal Component Analysis (PCA) and were subsequently used for the construction of predictive models, employing Linear Discriminant Analysis (LDA) and Support Vector Machines (SVM). All data analysis methodologies were validated by both "k-fold" cross-validation and external validation methods. In all cases, very high classification accuracies were found, up to 100%. The present results demonstrate the advantages of machine learning implementation for improving the capabilities of these spectroscopic techniques as tools for efficient olive oil quality monitoring and control.

Sulfur Detection in Soil by Laser Induced Breakdown Spectroscopy Assisted by Multivariate Analysis.

Laser-induced breakdown spectroscopy (LIBS) is used for the detection and determination of sulfur content in some organic soil samples. The most suitable sulfur spectral lines for such tasks were found to occur in the vacuum ultraviolet (VUV) spectral region and they were used for the construction of calibration curves. For the analysis, both univariate and multivariate statistical models were employed. The results obtained by the different analysis techniques are evaluated and compared. The present study demonstrates both the applicability and efficiency of LIBS for fast sulfur detection in soil matrices when aided by multivariate analysis methods improving the accuracy and extending the potential use of LIBS in such applications.

Silicon Nanosheets versus Graphene Nanosheets: A Comparison of Their Nonlinear Optical Response.

Silicene, the silicon analogue of graphene, represents a new class of two-dimensional (2D) materials, which shares some of the outstanding physical properties of graphene. Furthermore, it has the advantage of being compatible with the current Si-based technology. However, this 2D material is not stable and is quite prone to oxidation. The hydride-terminated silicene, called silicane, is a more stable form of 2D silicon, if functionalized via, for example, the hydrosilylation reaction. In this work, the third-order nonlinear optical (NLO) properties of two functionalized silicanes, namely hydride-terminated silicon nanosheets (SiNS-H) and 1-dodecene-functionalized silicon nanosheets (SiNS-dodecene), are accessed and compared to those of single-layer graphene, under 35 ps, 532 and 1064 nm excitation. The present results show that the functionalized silicanes exhibit comparable and even higher NLO response than that of single-layer graphene, making them strong competitors of graphene and very interesting candidates for future photonic and optoelectronic applications.

Silicon Nanosheets: An Emerging 2D Photonic Material with a Large Transient Nonlinear Optical Response beyond Graphene.

The present work reports on the transient nonlinear optical (NLO) responses of two different types of 2D silicon nanosheets (SiNSs), namely hydride-terminated silicon nanosheets (SiNS-H) and 1-dodecene-functionalized silicon nanosheets (SiNS-dodecene). The main motivation of this study was to extend the knowledge regarding the NLO properties of these Si-based materials, for which very few published studies exist so far. For that purpose, the NLO responses of SiNS-H and SiNS-dodecene were investigated experimentally in the nanosecond regime at 532 and 1064 nm using the Z-scan technique, while the obtained results were compared to those of certain recently studied graphene nanosheets. SiNS-dodecene was found to exhibit the largest third-order susceptibility χ(3) values at both excitation wavelengths, most probably ascribed to the presence of point defects, indicating the importance of chemical functionalization for the efficient enhancement and tailoring of the NLO properties of these emerging 2D Si-based materials. Most importantly, the results demonstrated that the present silicon nanosheets revealed comparable and even larger NLO responses than graphene nanosheets. Undoubtedly, SiNSs could be strong competitors of graphene for applications in 2D-material-based photonics and optoelectronics.

Annealing Effect on the Properties of Electrochromic V2O5 Thin Films Grown by Spray Deposition Technique.

Nanostructured electrochromic V2O5 thin films were prepared using spray pyrolysis technique growth at a temperature of 250 °C using air-carrier spray deposition, starting from ammonium metavanadate precursor in water, followed by annealing at 400 °C in O2 atmosphere for 2 h. The V2O5 films were characterized by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy, and their electrochromic behavior was studied using optical spectroscopy and cyclic voltammetry in both the as-deposited and postannealing case. The studies showed that the simple, cost -effective, suitable for large area deposition method used can lead to an interesting surface structuring with large active surface properties suitable for electrochromic applications. Further studies for growth optimization and improvements of films properties and stability are to be performed.

Enhancing and Tuning the Nonlinear Optical Response and Wavelength-Agile Strong Optical Limiting Action of N-octylamine Modified Fluorographenes.

Fluorographene has been recently shown to be a suitable platform for synthesizing numerous graphene derivatives with desired properties. In that respect, N-octylamine-modified fluorographenes with variable degrees of functionalization are studied and their nonlinear optical properties are assessed using 4 ns pulses. A very strong enhancement of the nonlinear optical response and a very efficient optical limiting action are observed, being strongly dependent on the degree of functionalization of fluorographene. The observed enhanced response is attributed to the increasing number of defects because of the incorporation of N-heteroatoms in the graphitic network upon functionalization with N-octylamine. The present work paves the way for the controlled covalent functionalization of graphene enabling a scalable access to a wide portfolio of graphene derivatives with custom-tailored properties.

Outstanding Broadband (532 nm to 2.2 µm) and Very Efficient Optical Limiting Performance of Some Defect-Engineered Graphenes.

Graphene derivatives and defect-engineered graphenes have attracted the interest of researchers owing to the excellent and tunable properties they exhibit. In this work the optical limiting performance of two defect-engineered boron- and nitrogen-doped reduced graphene oxides is investigated. Both graphenes are found to exhibit exceptional and broadband optical limiting action ranging from 532 to 2200 nm. Their optical limiting efficiency was found to be superior to that of all the other graphene derivatives studied to date, exhibiting a gradually decreasing optical limiting onset, reaching the record low value of ∼0.002 J cm-2 at 2200 nm. The results demonstrate the potential of engineering the defects of such reduced graphene oxides, resulting in very broadband and efficient optical limiting graphene derivatives, showing a promising method to further tailor their optical and optoelectronic properties.

Electrochromic Performance of V2O5 Thin Films Grown by Spray Pyrolysis.

A new approach regarding the development of nanostructured V2O5 electrochromic thin films at low temperature (250 °C), using air-carrier spray deposition and ammonium metavanadate in water as precursor is presented. The obtained V2O5 films were characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy, while their electrochromic response was studied using UV-vis absorption spectroscopy and cyclic voltammetry. The study showed that this simple, cost effective, suitable for large area deposition method can lead to V2O5 films with large active surface for electrochromic applications.

On the measurement of the nonlinear optical response of graphene dispersions using fs lasers.

In this work, the nonlinear optical (NLO) response of some graphene dispersions is investigated under low (i.e., 10 Hz) and high (i.e., 80 MHz) repetition rate femtosecond (fs) laser excitation conditions, using ${Z}$Z-scan, optical Kerr effect (OKE), and a combination of ${Z}$Z-scan and thermal lensing techniques. It is shown, that the NLO response of graphene dispersions is negligible under low repetition rate fs laser excitation, while it becomes very large under high repetition rate laser excitation. In the latter case, it is shown that the observed very large NLO response arises entirely from thermal cumulative effects.