Rheo-optical characterization of liquid crystalline acetoxypropylcellulose melt undergoing large shear flow and relaxation after flow cessation

The rheological and structural characteristics of acetoxypropylcellulose (APC) nematic melt are studied at shear rates ranging from 10 s(-1) to 1000 s(-1) which are relevant to extrusion based processes. APC shows a monotonic shear thinning behavior over the range of shear rates tested. The negative extrudate-swell shows a minimum when a critical shear rate (gamma) over dot(c) is reached. For shear rates smaller than (gamma) over dot(c), the flow-induced texture consists of two set of bands aligned parallel and normal to the flow direction. At shear rates larger than (gamma) over dot(c), the flow induced texture is reminiscent of a 2 fluids structure. Close to the shearing walls, domains elongated along the flow direction and stacked along the vorticity are imaged with POM, whereas SALS patterns indicate that the bulk of the sheared APC is made of elliptical domains oriented along the vorticity. No full nematic alignment is achieved at the largest shear rate tested. Below (gamma) over dot(c), the stress relaxation is described by a stretched exponential. Above (gamma) over dot(c), the stress relaxation is described by a fast and a slow process. The latter coincides with the growth of normal bands thicknesses, as the APC texture after flow cessation consists of two types of bands with parallel and normal orientations relative to the flow direction. Both bands thicknesses do not depend on the applied shear rate, in contrast to their orientation. (C) 2015 Elsevier Ltd. All rights reserved.

The optical and scopic urges viewed from a phenomenological perspective

Taking as starting points the books The Address of the Eye: A Phenomenology of Film Experience, by Vivian Sobchak, and Les quatre concepts fondamentaux de la psychanalyse, by Jacques Lacan, this article proposes to look at two well renowned film objects – Rear Window (Alfred Hitchcock, 1954, USA) and Peeping Tom (Michael Powell, 1960, UK) – in order to equate two forms of perception that, all things considered, come together as one: the perception of the mechanical apparatuses that record and project film and the optical and mental apparatuses that operate on the human filmmakers as well as their intradiegetic protagonists. In fact, these two films not only explore the characteristics and limits of vision and affection in their diegetic world, that is part of the filmmaker’s world itself, but reveals just how much the human lives through the eye and the expression of the machine itself. Film ontology is foremost a matter of (re)production rather than creation.

Visible range plasmonic effect produced by aluminium nanoparticles embedded in amorphous silicon

We present results, obtained by means of an analytic study and a numerical simulation, about the resonant condition necessary to produce a Localized Surface Plasmonic Resonance (LSPR) effect at the surface of metal nanospheres embedded in an amorphous silicon matrix. The study is based on a Lorentz dispersive model for a-Si:H permittivity and a Drude model for the metals. Considering the absorption spectra of a-Si:H, the best choice for the metal nanoparticles appears to be aluminium, indium or magnesium. No difference has been observed when considering a-SiC:H. Finite-difference time-domain (FDTD) simulation of an Al nanosphere embedded into an amorphous silicon matrix shows an increased scattering radius and the presence of LSPR induced by the metal/semiconductor interaction under green light (560 nm) illumination. Further results include the effect of the nanoparticles shape (nano-ellipsoids) in controlling the wavelength suitable to produce LSPR. It has been shown that is possible to produce LSPR in the red part of the visible spectrum (the most critical for a-Si:H solar cells applications in terms of light absorption enhancement) with aluminium nano-ellipsoids. As an additional results we may conclude that the double Lorentz-Lorenz model for the optical functions of a-Si:H is numerically stable in 3D simulations and can be used safely in the FDTD algorithm. A further simulation study is directed to determine an optimal spatial distribution of Al nanoparticles, with variable shapes, capable to enhance light absorption in the red part of the visible spectrum, exploiting light trapping and plasmonic effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of method, standard and sample components on the total antioxidant capacity of commercial waters assessed by optical conventional assays

The total antioxidant capacity (TAC) of 28 flavoured water samples was assessed by ferric reducing antioxidant potential (FRAP), oxygen radical absorbance capacity (ORAC), trolox equivalent antioxidant capacity (TEAC) and total reactive antioxidant potential (TRAP) methods. It was observed that flavoured waters had higher antioxidant activity than the corresponding natural ones. The observed differences were attributed to flavours, juice and vitamins. Generally, higher TAC contents were obtained on lemon waters and lower values on guava and raspberry flavoured waters. Lower and higher TACs were obtained by TRAP and ORAC method, respectively. Statistical analysis suggested that vitamins and flavours increased the antioxidant content of the commercial waters.

Novel optical PVC probes for on-site detection/determination of fluoroquinolones in a solid/liquid interface: Application to the determination of Norfloxacin in aquaculture water

A novel optical disposable probe for screening fluoroquinolones in fish farming waters is presented, having Norfloxacin (NFX) as target compound. The colorimetric reaction takes place in the solid/liquid interface consisting of a plasticized PVC layer carrying the colorimetric reagent and the sample solution. NFX solutions dropped on top of this solid-sensory surface provided a colour change from light yellow to dark orange. Several metals were tested as colorimetric reagents and Fe(III) was selected. The main parameters affecting the obtained colour were assessed and optimised in both liquid and solid phases. The corresponding studies were conducted by visible spectrophotometry and digital image acquisition. The three coordinates of the HSL model system of the collected image (Hue, Saturation and Lightness) were obtained by simple image management (enabled in any computer). The analytical response of the optimised solid-state optical probe against concentration was tested for several mathematical transformations of the colour coordinates. Linear behaviour was observed for logarithm NFX concentration against Hue+Lightness. Under this condition, the sensor exhibited a limit of detection below 50 μM (corresponding to about 16 mg/mL). Visual inspection also enabled semi-quantitative information. The selectivity was ensured against drugs from other chemical groups than fluoroquinolones. Finally, similar procedure was used to prepare an array of sensors for NFX, consisting on different metal species. Cu(II), Mn(II) and aluminon were selected for this purpose. The sensor array was used to detect NFX in aquaculture water, without any prior sample manipulation.

Microcystin-LR detection in water by the Fabry–Pérot interferometer using an optical fibre coated with a sol–gel imprinted sensing membrane

Cyanobacteria deteriorate the water quality and are responsible for emerging outbreaks and epidemics causing harmful diseases in Humans and animals because of their toxins. Microcystin-LR (MCT) is one of the most relevant cyanotoxin, being the most widely studied hepatotoxin. For safety purposes, the World Health Organization recommends a maximum value of 1 μg L−1 of MCT in drinking water. Therefore, there is a great demand for remote and real-time sensing techniques to detect and quantify MCT. In this work a Fabry–Pérot sensing probe based on an optical fibre tip coated with a MCT selective thin film is presented. The membranes were developed by imprinting MCT in a sol–gel matrix that was applied over the tip of the fibre by dip coating. The imprinting effect was obtained by curing the sol–gel membrane, prepared with (3-aminopropyl) trimethoxysilane (APTMS), diphenyl-dimethoxysilane (DPDMS), tetraethoxysilane (TEOS), in the presence of MCT. The imprinting effect was tested by preparing a similar membrane without template. In general, the fibre Fabry–Pérot with a Molecular Imprinted Polymer (MIP) sensor showed low thermal effect, thus avoiding the need of temperature control in field applications. It presented a linear response to MCT concentration within 0.3–1.4 μg L−1 with a sensitivity of −12.4 ± 0.7 nm L μg−1. The corresponding Non-Imprinted Polymer (NIP) displayed linear behaviour for the same MCT concentration range, but with much less sensitivity, of −5.9 ± 0.2 nm L μg−1. The method shows excellent selectivity for MCT against other species co-existing with the analyte in environmental waters. It was successfully applied to the determination of MCT in contaminated samples. The main advantages of the proposed optical sensor include high sensitivity and specificity, low-cost, robustness, easy preparation and preservation.

Disposable solid state probe for optical screening of chlorpromazine

We are presenting a simple, low-cost and rapid solid-state optical probe for screening chlorpromazine (CPZ) in aquacultures. The method exploits the colourimetric reaction between CPZ and Fe(III) ion that occurs at a solid/liquid interface, the solid layer consisting of ferric iron entrapped in a layer of plasticized PVC. If solutions containing CPZ are dropped onto such a layer, a colour change occurs from light yellow to dark pink or even light blue, depending on the concentration of CPZ. Visual inspection enables the concentration of CPZ to be estimated. The resulting colouration was also monitored by digital image collection for a more accurate quantification. The three coordinates of the hue, saturation and lightness system were obtained by standard image processing along with mathematical data treatment. The parameters affecting colour were assessed and optimized. Studies were conducted by visible spectrophotometry and digital image acquisition, respectively. The response of the optimized probe towards the concentration of CPZ was tested for several mathematical transformations of the colour coordinates, and a linear relation was found for the sum of hue and luminosity. The limit of detection is 50 μM (corresponding to about 16 μg per mL). The probe enables quick screening for CPZ in real water samples with prior sample treatment.

Adhesive thickness effects of a ductile adhesive by optical measurement techniques

Adhesive bonding is an excellent alternative to traditional joining techniques such as welding, mechanical fastening or riveting. However, there are many factors that have to be accounted for during joint design to accurately predict the joint strength. One of these is the adhesive layer thickness (tA). Most of the results are for epoxy structural adhesives, tailored to perform best with small values of tA, and these show that the lap joint strength decreases with increase of tA (the optimum joint strength is usually obtained with tA values between 0.1 and 0.2 mm). Recently, polyurethane adhesives were made available in the market, designed to perform with larger tA values, and whose fracture behaviour is still not studied. In this work, the effect of tA on the tensile fracture toughness (View the MathML source) of a bonded joint is studied, considering a novel high strength and ductile polyurethane adhesive for the automotive industry. This work consists on the fracture characterization of the bond by a conventional and the J-integral techniques, which accurately account for root rotation effects. An optical measurement method is used for the evaluation of crack tip opening (δn) and adherends rotation at the crack tip (θo) during the test, supported by a Matlab® sub-routine for the automated extraction of these parameters. As output of this work, fracture data is provided in traction for the selected adhesive, enabling the subsequent strength prediction of bonded joints.

Tensile fracture characterization of adhesive joints by standard and optical techniques

The use of adhesive joints has increased in recent decades due to its competitive features compared with traditional methods. This work aims to estimate the tensile critical strain energy release rate (GIC) of adhesive joints by the Double-Cantilever Beam (DCB) test. The J-integral is used since it enables obtaining the tensile Cohesive Zone Model (CZM) law. An optical measuring method was developed for assessing the crack tip opening (δn) and adherends rotation (θo). The proposed CZM laws were best approximated by a triangular shape for the brittle adhesive and a trapezoidal shape for the two ductile adhesives.

Optical measurements of rat muscle samples under treatment with ethylene glycol and glucose

With the objective to study the variation of optical properties of rat muscle during optical clearing, we have performed a set of optical measurements from that kind of tissue. The measurements performed were total transmittance, collimated transmittance, specular reflectance and total reflectance. This set of measurements is sufficient to determine diffuse reflectance and absorbance of the sample, also necessary to estimate the optical properties. All the performed measurements and calculated quantities will be used later in inverse Monte Carlo (IMC) simulations to determine the evolution of the optical properties of muscle during treatments with ethylene glycol and glucose. The results obtained with the measurements already provide some information about the optical clearing treatments applied to the muscle and translate the mechanisms of turning the tissue more transparent and sequence of regimes of optical clearing.

The characteristic time of glucose diffusion measured for muscle tissue at optical clearing

The study of agent diffusion in biological tissues is very important to understand and characterize the optical clearing effects and mechanisms involved: tissue dehydration and refractive index matching. From measurements made to study the optical clearing, it is obvious that light scattering is reduced and that the optical properties of the tissue are controlled in the process. On the other hand, optical measurements do not allow direct determination of the diffusion properties of the agent in the tissue and some calculations are necessary to estimate those properties. This fact is imposed by the occurrence of two fluxes at optical clearing: water typically directed out of and agent directed into the tissue. When the water content in the immersion solution is approximately the same as the free water content of the tissue, a balance is established for water and the agent flux dominates. To prove this concept experimentally, we have measured the collimated transmittance of skeletal muscle samples under treatment with aqueous solutions containing different concentrations of glucose. After estimating the mean diffusion time values for each of the treatments we have represented those values as a function of glucose concentration in solution. Such a representation presents a maximum diffusion time for a water content in solution equal to the tissue free water content. Such a maximum represents the real diffusion time of glucose in the muscle and with this value we could calculate the corresponding diffusion coefficient.

Software development for estimation of optical clearing agent’s diffusion coefficients in biological tissues

The study of chemical diffusion in biological tissues is a research field of high importance and with application in many clinical, research and industrial areas. The evaluation of diffusion and viscosity properties of chemicals in tissues is necessary to characterize treatments or inclusion of preservatives in tissues or organs for low temperature conservation. Recently, we have demonstrated experimentally that the diffusion properties and dynamic viscosity of sugars and alcohols can be evaluated from optical measurements. Our studies were performed in skeletal muscle, but our results have revealed that the same methodology can be used with other tissues and different chemicals. Considering the significant number of studies that can be made with this method, it becomes necessary to turn data processing and calculation easier. With this objective, we have developed a software application that integrates all processing and calculations, turning the researcher work easier and faster. Using the same experimental data that previously was used to estimate the diffusion and viscosity of glucose in skeletal muscle, we have repeated the calculations with the new application. Comparing between the results obtained with the new application and with previous independent routines we have demonstrated great similarity and consequently validated the application. This new tool is now available to be used in similar research to obtain the diffusion properties of other chemicals in different tissues or organs.

Ligand K-edge X-ray absorption spectroscopy and DFT calculations on [Fe3S4]0,+ clusters: delocalization, redox, and effect of the protein environment

Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the í2Ssulfide, í3Ssulfide, and Sthiolate ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe3+ and Fe2.5+ components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm-1 vs -360 cm-1, respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter ì2/k-, leads to an S ) 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe3+ center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.

Optical clearing mechanisms characterization in muscle

Optical immersion clearing is a technique that has been widely studied for more than two decades and that is used to originate a temporary transparency effect in biological tissues. If applied in cooperation with clinical methods it provides optimization of diagnosis and treatment procedures. This technique turns biological tissues more transparent through two main mechanisms — tissue dehydration and refractive index (RI) matching between tissue components. Such matching is obtained by partial replacement of interstitial water by a biocompatible agent that presents higher RI and it can be completely reversible by natural rehydration in vivo or by assisted rehydration in ex vivo tissues. Experimental data to characterize and discriminate between the two mechanisms and to find new ones are necessary. Using a simple method, based on collimated transmittance and thickness measurements made from muscle samples under treatment, we have estimated the diffusion properties of glucose, ethylene glycol (EG) and water that were used to perform such characterization and discrimination. Comparing these properties with data from literature that characterize their diffusion in water we have observed that muscle cell membrane permeability limits agent and water diffusion in the muscle. The same experimental data has allowed to calculate the optical clearing (OC) efficiency and make an interpretation of the internal changes that occurred in muscle during the treatments. The same methodology can now be used to perform similar studies with other agents and in other tissues in order to solve engineering problems at design of inexpensive and robust technologies for a considerable improvement of optical tomographic techniques with better contrast and in-depth imaging.