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.

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.

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: 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.

Laser-based classification of olive oils assisted by machine learning.

Olive oil is an essential diet component in all Mediterranean countries having a considerable impact on the local economies, which are producing almost 90% of the world production. Therefore, the quality assessment of olive oil in terms of its acidity and its authentication in terms of PDO (Protected Designation of Origin) and PGI (Protected Geographical Indications) characterizations are nowadays necessary and of great importance for the market of olive oil and the related economic activities. In the present work, Laser Induced Breakdown Spectroscopy (LIBS) is used assisted by machine learning algorithms for retrieving of the information contained in the LIBS spectra to provide a simple, reliable, and ultrafast methodology for olive oils classification in terms of the degree of acidity and geographical origin. The combination of LIBS technique with machine learning statistical analysis approaches constitute a very powerful tool for the fast, in-situ and remote quality control of olive oil.

Thiophenol-Modified Fluorographene Derivatives for Nonlinear Optical Applications.

The synthesis and characterization of two thiophenol-modified fluorographene derivatives, namely methoxythiophenol-and dimethylaminothiophenol-modified fluorographenes, are reported, while their third-order nonlinear optical response were thoroughly investigated under both visible (532 nm) and infrared (1064 nm) with 35 ps and 4 ns laser pulses. The graphene derivatives were obtained by partial nucleophilic substitution/reduction of fluorographene by the corresponding organic thiophenols, and were fully characterized by techniques including infrared/Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force spectroscopy, and high-resolution transmission microscopy. This type of modification resulted in graphenic structures where the attached thiol groups, sp2 domains, and the residual fluorine groups act as donors, π bridges, and acceptors, respectively. Both derivatives exhibited large nonlinear optical response compared to fluorographene, and have potential applications in optical limiting as an alternative to fullerenes.

Experimental Study of the Structural Effect on the Nanosecond Nonlinear Optical Response of O-Doped Polycyclic Aromatic Hydrocarbons.

The nonlinear optical response of some O-doped polycyclic aromatic hydrocarbons (PAHs) is systematically investigated in the present work aiming to understand the influence of structural effects on their nonlinear optical response. In that view, the third-order nonlinear optical properties of these PAHs were measured under 4 ns visible (532 nm) and infrared (1064 nm) laser excitation. The O-doped PAHs were found to exhibit large saturable absorption and negative sign nonlinear refraction under visible excitation, increasing both with the addition of naphthalene units and with the number of O atoms. Their nonlinear optical response was found to be negligible under infrared excitation. Similar measurements performed on thin films of these PAHs have shown that they maintain their large nonlinear optical response even in the solid state, confirming their high potential for optoelectronic and photonic applications.

Tailoring Colors by O Annulation of Polycyclic Aromatic Hydrocarbons.

The synthesis of O-doped polyaromatic hydro- carbons in which two polycyclic aromatic hydrocarbon sub units are bridged through one or two O atoms has been achieved. This includes high-yield ring-closure key steps that, depending on the reaction conditions, result in the formation of furanyl or pyranopyranyl linkages through intramolecular C-O bond formation. Comprehensive photophysical measurements in solution showed that these compounds have exceptionally high emission yields and tunable absorption properties throughout the UV/Vis spectral region. Electrochemical investigations showed that in all cases O annulation increases the electron-donor capabilities by raising the HOMO energy level, whereas the LUMO energy level is less affected. Moreover, third-order nonlinear optical (NLO) measurements on solutions or thin films containing the dyes showed very good values of the second hyperpolarizability. Importantly, poly(methyl methacrylate) films containing the pyranopyranyl derivatives exhibited weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, and thus revealed them to be exceptional organic materials for photonic devices.

Laser-Induced Breakdown Spectroscopy (LIBS) for the Measurement of Spatial Structures and Fuel Distribution in Flames.

Laser-induced breakdown spectroscopy (LIBS) is used for the mapping of local structures (i.e., reactants and products zones) and for the determination of fuel distribution by means of the local equivalence ratio ϕ in laminar, premixed air-hydrocarbon flames. The determination of laser threshold energy to induce breakdown in the different zones of flames is employed for the identification and demarcation of the local structures of a premixed laminar flame, while complementary results about fuel concentration were obtained from measurements of the cyanogen (CN) band Β(2)Σ(+)--Χ(2)Σ(+), (Δυ = 0) at 388.3 nm and the ratio of the atomic lines of hydrogen (Hα) and oxygen (O(I)), Hα/O. The combination of these LIBS-based methods provides a relatively simple to use, rapid, and accurate tool for online and in situ combustion diagnostics, providing valuable information about the fuel distribution and the spatial variations of the local structures of a flame.

The effect of the degree of oxidation on broadband nonlinear absorption and ferromagnetic ordering in graphene oxide.

We report on the effect of the degree of oxidation on the broadband non-linear optical response and magnetic behavior of graphene oxide, as well as on a route for obtaining reduced graphene oxide with enhanced optical properties without sacrificing the high dispersibility of the parent graphene oxide. As more sp(3) states evolved with the rise in oxidation degree, it turned out that the sp(2)/sp(3) fraction and sp(2) clustering are crucial parameters for tuning the broadband non-linear optical absorption over a wide range from ps to ns laser pulses for both visible and infrared laser irradiation. This was clearly confirmed by two different approaches, namely by a synthetic route through the gradual oxidation of graphene oxide from 1 to 3 oxidizing cycles, and reversely by in situ reduction of graphene oxide by UV laser irradiation. Furthermore, as the sp(3) states carry localized magnetic moments, ferromagnetic ordering is observed at low temperatures. The magnetization and temperature at which ferromagnetic ordering evolves are found to increase on increasing the oxidation degree. The tuning of non-linear optical and magnetic properties of graphene oxide by oxidation/reduction thus provides an easy way to endow graphene oxide with tunable physical features highly required in both optoelectronics and spintronics applications.

Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers.

The self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)pyridine termini are reported. Systematic spectroscopic (UV-vis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature.