Dynamic reflective color pixels based on molybdenum oxide.

Active materials which show phase transitions, usually known as Phase Change Materials (PCM), have paved the way to a new generation of reconfigurable plasmonic platforms. Tunable color devices have experienced a great development in the recent years. In particular, reflective color filters can take advantage from sunlight to select and reflect a specific resonant wavelength in the visible spectrum range. Reflective displays are usually structural color filters based on asymmetric Fabry-Perot cavities (AFPCs). For a fixed geometry, most of AFPCs filters generate static color, limiting their potential as tunable color devices. Dynamic color is achieved by introducing an active layer whose optical properties can be modulated by an external stimuli. In this paper, we propose AFPCs based on molybdenum oxide (MoOx, 2

Physically meaningful Monte Carlo approach to the four-flux solution of a dense multilayered system.

Due to the complexity of the radiative transfer equation, light transport problems are commonly solved using either models under restrictive assumptions, e.g., N-flux models where infinite lateral extension is assumed, or numerical methods. While the latter can be applied to more general cases, it is difficult to relate their parameters to the physical properties of the systems under study. Hence in this contribution we present, first, a review of a four-flux formalism to study the light transport problem in a plane-parallel system together with a derivation of equations to evaluate the different contributions to the total absorptance and, second, as a complementary tool, a Monte Carlo algorithm with a direct correspondence between its inputs and the properties of the system. The combination of the four-flux model and the Monte Carlo approach provides (i) all convergence warranties since the formalism has been established as a limit and (ii) new added capabilities, i.e., both temporal (transient states) and spatial (arbitrarily inhomogeneous media) resolution. The support between the theoretical model and the numerical tool is reciprocal since the model is utilized to set a Monte Carlo discretization criterion, while the Monte Carlo approach is used to validate the aforementioned model. This reinforces the parallel approach used in this work. Furthermore, we provide some examples to show its capabilities and potential, e.g., the study of the temporal distribution of a delta-like pulse of light.

Extension of the Kubelka-Munk theory to an arbitrary substrate: a Monte Carlo approach.

In this work we review and-to some extent-upgrade one of the main theories of light flux through homogeneous isotropic media, namely, the Kubelka-Munk (K-M) theory, and in particular the later expansion made by Kubelka to obtain the reflectance of a specimen when a substrate lies underneath. We have completed this solution by calculating the transverse energy density in the specimen and the transmission of the whole. We show that this last result-compatible with Kubelka's upgrade for layered media-also allows for the calculation of the specimen/substrate absorption split. In order to validate these expressions, the results were reproduced by means of a Monte Carlo simulation working on a layered medium under the same assumptions as the K-M theory. Interestingly, the numerical procedure introduces new capabilities in the model regarding the history of any absorbed or outgoing elemental light beam, such as the recording of its time-of-flight through a given system.

Enhanced Magneto-Optical Edge Excitation in Nanoscale Magnetic Disks.

We report unexpected enhancements of the magneto-optical effect in ferromagnetic Permalloy disks of diameter D<400 nm. The effect becomes increasingly pronounced for smaller D, reaching more than a 100% enhancement for D=100 nm samples. By means of experiments and simulations, the origin of this effect is identified as a nanoscale ring-shaped region at the disk edges, in which the magneto-optically induced electric polarization is enhanced. This leads to a modification of the electromagnetic near fields and causes the enhanced magneto-optical excitation, independent from any optical resonance.

Influence of pollutants in the magneto-dielectric response of silicon nanoparticles.

The influence of the degree of purity of a silicon nanoparticle on its resonances, either electric or magnetic, is assessed by using Mie theory as well as finite-element simulations. In particular, it is shown that the main effect of the increase of absorption due to the pollutants is observed in the magnetic resonances. Concerning Kerker's conditions for the directionality of the scattering [J. Opt. Soc. Am.73, 765 (1983)], it is found that both are strongly shifted when the material's purity is varied. Resistive losses confirm the quenching of magnetic resonances, showing that the region of influence in the magnetic dipole resonance is much larger than in the electric one, although it has been found that losses are not critical for silicon content over 99.50%.

Comprehensive polarimetric analysis of Spectralon white reflectance standard in a wide visible range.

Since polarimetry has extended its use for the study of scattering from surfaces and tissues, Spectralon, a white reflectance standard, is acquiring the role of a polarimetric standard. Both the behavior of Spectralon as a Lambertian surface and its performance as a perfect depolarizer are analyzed in detail. The accuracy of our dynamic polarimeter, together with the polar decomposition to describe the Mueller matrix (MM) depolarizing action, combine to produce a powerful tool for the proper analysis of this scattering surface. Results allowed us to revisit, for confirmation or revision, the role of some MM elements, as described in the bibliography. The conditions under which it can be considered a good Lambertian surface are specified in terms of incidence and scattering angle and verified over a large wavelength range.

Quantum optical response of metallic nanoparticles and dimers.

The optical properties of metallic nanoparticles (NPs) can be described with analytical models based on fundamental quantum mechanical principles, of which the Drude model constitutes the classical limit. Here, we examine the plasmonic properties of silver and gold nanospheres and dimers, with radii ranging from 10 to 1 nm, extending from the classically described regime to the quantum size regime. We have studied the spectral extinction cross section by using the T-matrix method. The results indicate an increasingly substantial change in NP permittivity as the radius is reduced below 5 nm, showing a clear blueshift and weakening of the plasmon resonances for both silver and gold. As a consequence, we observe a dramatic change in the interaction of dimers, especially in the case of gold, where the introduction of quantum mechanically corrected optical properties quenches the plasmonic resonance and predicts an absence of the expected associated redshift.

Directionality in scattering by nanoparticles: Kerker's null-scattering conditions revisited.

Since the first studies made by Kerker in the 1970s stating the conditions for null light scattering in certain directions by particles, such conditions have remained unquestioned. The increasing interest in scattering directionality by tuning the optical properties of materials demands a new analysis of this problem. In addition, as has been shown recently, one of Kerker's statements does not comply with the optical theorem. We propose corrected expressions for the null-scattering conditions that satisfy the optical theorem.

Prediction of total and volatile acidity in red wines by Fourier-transform mid-infrared spectroscopy and iterative predictor weighting.

Fourier-transform mid-infrared (FT-MIR) spectroscopy, combined with partial least-squares (PLS) regression and IPW as feature selection method, was used to develop reduced-spectrum calibration models based on a few IR bands to provide near-real-time predictions of two key parameters for the characterization of finished red wines, which are essential from a quality assurance standpoint: total and volatile acidity. Separate PLS calibration models, correlating IR data (only considering those regions showing a high signal to noise ratio) with each response studied, were developed. Wavenumber selection was also performed applying IPW-PLS to take into account only significant predictors, in an attempt to improve the quality of the final models constructed. Using both PLS and IPW-PLS regression, prediction of the two responses modelled was performed with very high reliability, with RMSECV and RMSEP values on the order of 1% (comparable in terms of accuracy to the results provided by the respective reference analysis methods). An important advantage derived from the application of the IPW-PLS method had to do with the low number of original variables needed for modelling both total acidity (22 significant wavenumbers) and volatile acidity (only 11 selected predictor variables), in such a way that variable selection contributed to enhance the stability and parsimony properties of the final calibration models. The high quality of the calibration models proposed encourages the feasibility of implementing them as a fast and reliable tool in routine analysis for the determination of critical parameters for wine quality.

Polar decomposition of the Mueller matrix: a polarimetric rule of thumb for square-profile surface structure recognition.

In this research, the polar decomposition (PD) method is applied to experimental Mueller matrices (MMs) measured on two-dimensional microstructured surfaces. Polarization information is expressed through a set of parameters of easier physical interpretation. It is shown that evaluating the first derivative of the retardation parameter, δ, a clear indication of the presence of defects either built on or dug in the scattering flat surface (a silicon wafer in our case) can be obtained. Although the rule of thumb thus obtained is established through PD, it can be easily implemented on conventional surface polarimetry. These results constitute an example of the capabilities of the PD approach to MM analysis, and show a direct application in surface characterization.

Extended discrete dipole approximation and its application to bianisotropic media.

In this research we introduce the formalism of the extension of the discrete dipole approximation to a more general range of tensorial relative permittivity and permeability. Its performance is tested in the domain of applicability of other methods for the case of composite materials (nanoshells). Then, some early results on bianisotropic nanoparticles are presented, to show the potential of the Extended Discrete Dipole Approximation (E-DDA) as a new tool for calculating the interaction of light with bianisotropic scatterers.

Interaction of nanoparticles with substrates: effects on the dipolar behaviour of the particles.

In this work, we present a numerical analysis of the surface electric field of a metallic nanoparticle (either 2D or 3D) interacting with a flat substrate underneath. The influence of the distance to the substrate, particle size, the surrounding media and the substrate optical properties is analyzed as a function of the incident wavelength. We show that these are crucial factors that change the field distribution associated to the dipolar behavior of the particle. A useful parameter for illustrating the changes in the angular distribution is theta(max), the angle at which the maximum of the surface electric field is located.

Surface inspection by monitoring spectral shifts of localized plasmon resonances.

We present a numerical study of the spectral variations of localized surface plasmon resonances (LSPR) in a 3D-probe metallic nanoparticle scanned over an inhomoegeneous dielectric surface. The possibilities for both, index monitoring and lateral resolution at nanoscale level are explored, with special attention paid to the shape of the probe and the profile of the near field underneath.

Robustness test of a headspace solid-phase microextraction method for the determination of chloroanisoles and chlorophenols related to cork taint in wine using experimental design.

A robustness test of a solid-phase microextraction-based method optimised for the simultaneous determination of chloroanisoles and acetyl-chlorophenols implicated in the presence of corky taste in wine has been carried out using a hybrid experimental design. The influence of small changes around the nominal level of four factors (Vs/Vt ratio, extraction temperature, exposure time and sample incubation time) on the measured response were evaluated in order to indicate if the method is robust for the experimental range considered. Moreover, it was also necessary to identify the critical parameters in the validated model in order to keep them under strict control. Experimental design provides an effective approach for robustness testing as a part of the analytical method validation.

Monitoring of substrate and product concentrations in acetic fermentation processes for onion vinegar production by NIR spectroscopy: value addition to worthless onions.

Wastes and by-products of the onion-processing industry pose an increasing disposal and environmental problem and represent a loss of valuable sources of nutrients. The present study focused on the production of vinegar from worthless onions as a potential valorisation route which could provide a viable solution to multiple disposal and environmental problems, simultaneously offering the possibility of converting waste materials into a useful food-grade product and of exploiting the unique properties and health benefits of onions. This study deals specifically with the second and definitive step of the onion vinegar production process: the efficient production of vinegar from onion waste by transforming onion ethanol, previously produced by alcoholic fermentation, into acetic acid via acetic fermentation. Near-infrared spectroscopy (NIRS), coupled with multivariate calibration methods, has been used to monitor the concentrations of both substrates and products in acetic fermentation. Separate partial least squares (PLS) regression models, correlating NIR spectral data of fermentation samples with each kinetic parameter studied, were developed. Wavelength selection was also performed applying the iterative predictor weighting-PLS (IPW-PLS) method in order to only consider significant spectral features in each model development to improve the quality of the final models constructed. Biomass, substrate (ethanol) and product (acetic acid) concentration were predicted in the acetic fermentation of onion alcohol with high accuracy using IPW-PLS models with a root-mean-square error of the residuals in external prediction (RMSEP) lower than 2.5% for both ethanol and acetic acid, and an RMSEP of 6.1% for total biomass concentration (a very satisfactory result considering the relatively low precision and accuracy associated with the reference method used for determining the latter). Thus, the simple and reliable calibration models proposed in this study suggest that they could be implemented in routine applications to monitor and predict the key species involved in the acetic fermentation of onion alcohol, allowing the onion vinegar production process to be controlled in real time.

Raman spectroscopy for wine analyses: A comparison with near and mid infrared spectroscopy.

Routine wine analysis are commonly employed to ensure the quality and safety standards, and to meet consumers' demands and legal requirements. In the last decades, efforts have been done in order to replace the traditional analytical techniques by vibrational spectroscopic techniques such as near infrared (NIR) and mid infrared (MIR) spectroscopy. The potential of these techniques has already been proved by several studies that revealed their ability for the determination of several wine parameters with high levels of precision and accuracy. Raman spectroscopy, (which is also a vibrational technique), was much less explored in the wine industry. In this work, the ability of Raman spectroscopy for routine wine analysis was evaluated and compared to NIR and MIR spectroscopy. Several calibration models were developed aiming the quantitative assessment of alcoholic strength, density, total acidity, volatile acidity, total sugars and pH in white wines. For this purpose, partial least squares (PLS) regression was employed, enabling the correlation between reference results and spectral information obtained by NIR, MIR and Raman spectroscopy. Results revealed the better performance of MIR spectroscopy for the measurement of alcoholic strength (R2P = 0.99, RMSEP=1.77%, and RER=56.41), and total acidity (R2P = 0.98, RMSEP=2.02%, and RER=49.46). Raman spectroscopy was pointed out as the most suitable for the determination of total sugars (R2P = 0.97, RMSEP=5.12%, RER=19.52), and pH (R2P = 0.90, RMSEP=4.92%, RER=20.34). The three techniques presented similar results in what referred the assessment of density (R2P = 0.96, 0.98, and 0.97, RMSEP=4.72%, 3.90%, and 3.80%, for Raman, MIR, and NIR respectively). None of the three techniques seemed to be suitable for the accurate determination of volatile acidity (R2P <0.78, RMSEP>14.32%, and RER<6.98).

Backscattering of metallic microstructures with small defects located on flat substrates.

Micron-sized structures on flat substrates supporting submicron defects are analyzed by means of a parameter based on integrated backscattering calculations. This analysis is performed for different particle and defect sizes, optical properties and for two different configurations (defect on the microstructure or on the substrate). Calculations in the far field are complemented by some near field results. It is shown that information about the defect presence, size and optical properties) can be obtained from the proposed backscattering parameter.

Optimisation of a microwave-assisted extraction method for the simultaneous determination of haloanisoles and halophenols in cork stoppers.

This study presents a method based on the use of microwave-assisted extraction (MAE) for the quantitative analysis of 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole (TeCA), pentachloroanisole (PCA), 2,4,6-tribromoanisole (TBA), 2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol (TeCP), pentachlorophenol (PCP) and 2,4,6-tribromophenol (TBP) in cork stoppers. The influential parameters of the MAE procedure (extraction time, temperature and solvent volume) were optimised using a central composite experimental design combined with desirability functions. The optimal conditions identified were temperature 170 degrees C, solvent volume 35 mL and extraction time 90 min. MAE extracts were concentrated and derivatised prior to separation and quantification by gas chromatography with electron capture detection. To evaluate the applicability of the proposed MAE method, recovery results were compared with those obtained with the Soxhlet extraction method; the results were similar with both extraction methods. The new method was also satisfactorily applied to real cork stopper samples.

Determination of Brett character responsible compounds in wines by using multiple headspace solid-phase microextraction.

This study presents a method based on the use of multiple headspace solid-phase microextraction (MHS-SPME) for the quantitative analysis of 4-ethylphenol, 4-ethylguaiacol, 4-vinylphenol and 4-vinylguaiacol. MHS-SPME is a modification of SPME that implies several consecutive extractions from the same sample and avoids possible matrix effects. This study demonstrates the existence of a matrix effect in the analysis of compounds responsible for Brett character in wine when an HS-SPME based method is used with a carbowax/divinylbenzene (CW/DVB) fibre. For this reason, MHS-SPME is proposed as an alternative technique with respect to HS-SPME. The method proposed was validated and the detection limits obtained were 0.06 microg/l for 4-ethylguaiacol and 4-ethylphenol and, 0.20 microg/l for 4-vinylguaiacol and 0.12 microg/l for 4-vinylphenol. These detection limits are below the odour detection thresholds of the compounds in wine matrices. The repeatability obtained, in terms of relative standard deviation (RSD), was considered acceptable, ranging from 1 to 12%. To evaluate the applicability of the proposed MHS-SPME method, concentration results were compared with those obtained with the standard addition method, and the results were similar with both methods. Furthermore, the new method was satisfactorily applied to a number of commercial red, white and rosé wines. Therefore, MHS-SPME can be considered as an alternative to avoid the matrix effect in wine samples.

Optimisation of a headspace solid-phase microextraction with on-fiber derivatisation method for the direct determination of haloanisoles and halophenols in wine.

A solid-phase microextraction (SPME) procedure for the determination of four haloanisoles (2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, pentachloroanisole and 2,4,6-tribromoanisole), as well as their precursor halophenols (2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol and 2,4,6-tribromophenol), involved in the presence of cork taint in wine, was developed. Firstly, analytes were concentrated on a SPME fiber, and then halophenols were derivatised using N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA). The compounds were desorbed for 5 min in the gas chromatography injector port and then determined with an electron capture detector. The influence of different parameters on the efficiency of extraction (volume of sample, type of fibre coating and time) and derivatisation (time, temperature and volume of MSTFA) steps was evaluated. Polyacrylate (PA) was selected as the extraction fiber, optimised parameters for SPME were 10 ml of wine, temperature 70 degrees C and extraction time 60 min. The optimal conditions identified for the derivatisation step were temperature 25 degrees C, reagent volume 50 microl and extraction time 25 min. Under optimal conditions, the proposed method showed satisfactory linearity, precision and detection limits. The method was applied successfully to the analysis of red wine samples. To our knowledge, this is the first time that headspace (HS) SPME combined with on-fiber derivatisation has been applied to determine cork taint responsible compounds in wine.