Multiway partial least-squares coupled to residual trilinearization: a genuine multidimensional tool for the study of third-order data. Simultaneous analysis of procaine and its metabolite p-aminobenzoic acid in equine serum

A new third-order multivariate calibration approach, based on the combination of multiway-partial least-squares with a separate procedure called residual trilinearization (N-PLS/RTL), is presented and applied to multicomponent analysis using third-order data. The proposed chemometric algorithm is able to predict analyte concentrations in the presence of unexpected sample components, which require strict adherence to the second-order advantage. Results for the determination of procaine and its metabolite p-aminobenzoic acid in equine serum are discussed, based on kinetic fluorescence excitation-emission four-way measurements and application of the newly developed multiway methodology. Since the analytes are also the reagent and product of the hydrolysis reaction followed by fast-scanning fluorescence spectroscopy, the classical approach based on parallel factor analysis is challenged by strong linear dependencies and multilinearity losses. In comparison, N-PLS/RTL appears an appealing genuine multiway alternative that avoids the latter complications, yielding analytical results that are statistically comparable to those rendered by related unfolded algorithms, which are also able to process four-way data. Prediction was made on validation samples with a qualitative composition similar to the calibration set and also on test samples containing unexpected equine serum components.     

Amplified spontaneous emission in polymer films doped with a perylenediimide derivative

The presence of amplified spontaneous emission (ASE) by optical pump in polystyrene films doped with N,N'-di(10-nonadecyl)perylene-3,4:9,10-tetracarboxylic diimide (PDI-N) in a range of PDI-N concentrations between 0.25 and 5 wt. % is reported. Gain coefficients up to 10 cm(-1), at a pump intensity of 74 kW/cm2, were obtained. The lowest thresholds (approximately 15 kW/cm2) and largest photostabilities measured at 50% (approximately 50 min, i.e., 30,000 pump pulses) were obtained for concentrations up to 1 wt. %. The observation of an increase in the ASE threshold and a decrease in the photostability for larger concentrations is attributed to the presence of aggregated species.     

Application of the differential neural network observer to the kinetic parameters identification of the anthracene degradation in contaminated model soil

In this work a new technique dealing with differential neural network observer (DNNO), which is related with differential neural networks (DNN) approach, is applied to estimate the anthracene dynamics decomposition and to identify the kinetic parameters in a contaminated model soil treatment by simple ozonation. To obtain the experimental data set, the model soil (sand) is combined with an initial anthracene concentration of 3.24mg/g and treated by ozone (with the ozone initial concentration 16mg/L) during 90min in a reactor by the "fluid bed" principle. The anthracene degradation degree was controlled by UV-vis spectrophotometry and HPLC techniques. Based on the HPLC data, the obtained results confirm that anthracene may be decomposed completely in the solid phase by simple ozonation during 20min and by-products of ozonation are started to be destroyed after 30min of treatment. In the ozonation process the ozone concentration in the gas phase at the reactor outlet is registered by an ozone detector. The variation of this parameter is used to obtain the summary characteristic curve of the anthracene ozonation (ozonogram). Then, using the experimental decomposition dynamics of anthracene and the ozonogram, the proposed DNNO is trained to reconstruct the anthracene decomposition and to estimate the anthracene ozonation constant using the DNN technique and a modified Least Square method.     

Hysteresis of a biomaterial: Influence of sutures and biological adhesives

We studied the changes in energy consumption of samples of calf pericardium, when joined or not joined by sutures and adhesives, by means of hysteretic cycles. Sixty-four samples were subsequently subjected to tensile stress until rupture. An overlapping suture sewn in the form of a rectangle presented an acceptable mean resistance to rupture of over 10 MPa, although lower than the mean values in an unsutured control series where the mean resistance surpassed 15 MPa. The contribution of an acrylic adhesive to the resistance to rupture was negligible. The sutured samples that were reinforced with adhesives and had not been subjected to hysteretic cycles prior to rupture showed an anisotropic behavior. This behavior appeared to be lost in all the samples that underwent hysteretic cycles. We found an inflection point in the stress/strain curve following the stepwise increase in the load, with a value greater than and proximate to the final load applied. This inflection should be analyzed by means of microscopy. Finally, the mathematical relationship between the energy consumed and the stress applied, the strain or deformation produced and the number of cycles of hysteresis to which the samples were subjected was established as the ultimate objective of this study. The bonding systems provoked a greater consumption of energy, with the greatest consumption corresponding to the first cycle in all the series assayed. An equation relating the energy consumption in a sample to the number of hysteretic cycles to which it was subjected was obtained. Its asymptote on the x-axis indicates the energy consumption for a theoretical number of cycles, making it possible to estimate the durability of the sample.     

Transversal superresolution with noncontact axial movement of periodic structures

We present an innovative approach that allows superresolved images to be obtained by axial moving of two gratings and time integrating in the detector plane. The two gratings do not have to be in contact with either the object or the detector, and both are positioned between the object and the image planes. One of the main applications for the proposed approach in contrast to previously discussed time multiplexing superresolving methods is that it may fit well to superresolved imaging of remote objects, since both gratings are not in contact with either the object or the detector planes.     

Dynamic in situ observation of rapid size and shape change of supported Pd nanoparticles during CO/NO cycling

Understanding and improving the behaviour of supported precious-metal catalysts for a vast array of environmentally and economically important processes is a central area of research in catalysis. The removal of toxic gases such as CO and NO, without forming others (such as N(2)O), is particularly important. By combining energy-dispersive extended X-ray absorption fine-structure spectroscopy with a vibrational spectroscopy (infrared) and mass spectrometry, at high time resolution, in a single in situ experiment, we dynamically observe and quantify CO-, and subsequent NO-, induced size and shape changes of Pd nanoparticles during CO/NO cycling. In doing so we demonstrate a novel, non-oxidative redispersion (for example, an increase in metal surface area) mechanism, and suggest a model to bridge the structural and reactive functions of supported Pd catalysts.     

Mimicking cellular environments by nanostructured soft interfaces

We present herein an innovative technique for decorating soft polymer surfaces with metallic nanostructures fabricated by diblock copolymer micelle nanolithography. Thus far, such nanolithography has been limited to plasma-resistant inorganic substrates such as glass. Our new development is based on the transfer of nanopatterns from glass to soft substrates. Special emphasis is given to hydrogel surfaces with respect to their properties for tailoring cell adhesion. Besides planar surfaces, periodic gold nanopatterns on curved surfaces have been fabricated, as demonstrated on the interior surface of a tubelike hydrogel, which potentially mimic situations of vessels in vivo.     

Formation and rupture of Schottky nanocontacts on ZnO nanocolumns

In this paper, the electrical transport and mechanical properties of Pt/ZnO Schottky nanocontacts have been studied simultaneously during the formation and rupture of the nanocontacts. By combining multidimensional conducting scanning force spectroscopy with appropriated data processing, the physical relevant parameters (the ideality factor, the Schottky barrier height, and the rupture voltage) are obtained. It has been found that the transport curves strongly depend on the loading force. For loading forces higher than a threshold value, the transport characteristics are similar to those of large-area Schottky contact, while below this threshold deviations from strictly thermionic emission are detected. Above the threshold, stable and reproducible Pt/ZnO nanocontacts with ideality factors of about 2 and Schottky barrier heights of around 0.45 eV have been obtained.     

Nanoparticles as nonviral gene delivery vectors

Gene therapy, as therapeutic treatment to genetic or acquired diseases, is attracting much interest in the research community, leading to noteworthy developments over the past two decades. Although this field is still dominated by viral vectors, nonviral vectors have recently received an ever increasing attention in order to overcome the safety problems of their viral counterpart. This review presents the biological aspects involved in the gene delivery process and explores the recent developments and achievements of nonviral gene carriers.