Thermal, optical, electrochemical properties and conductivity of trans- and cis-poly(1-ethynylpyrene): a comparative investigation

The thermal, optical and electrochemical properties of trans-poly(1-ethynylpyrene) (trans-PEP) and cis-poly(1-ethynylpyrene) (cis-PEP) have been studied as a function of polymer backbone configuration and internal stacking. Absorption spectra of the polymers showed that trans-PEP possesses a higher degree of conjugation than its homologue, cis-PEP. Intramolecular interactions occur between adjacent pendant pyrene units (associated pyrenes) present in each polymer, giving rise to static excimer emissions, strongest in cis-PEP because of the shorter distances between aromatic rings. Data resulting from excitation spectra and fluorescence decay profiles proved that such interactions take place in the ground state. Cyclic voltammetry of trans- and cis-PEP exhibited irreversible behaviors with different oxidation potentials as a result of their dissimilar geometry.     

Structural relaxation in the amorphous and liquid-crystalline phases of a thermotropic polymer

Summary The analysis of the structural relaxation in specimens of a thermotropic polymer that are either in the glassy amorphous or in the liquid crystalline state (or in a mixture of them) has been carried out. The results indicate that the two phases behave independently, exhibiting two independent (and well different) glass transitions and with their own structural relaxations. Moreover, the physical aging has a profound influence on the ability to develop the liquid-crystalline phase. It seems that the changes in local order associated with a densification of the liquid-like packing lead to the development of some kind or local alignment, which favors the subsequent liquid-crystallization.     

Analysis of paraffin precipitation from petroleum mixtures by means of DSC: Iterative procedure considering solid-liquid equilibrium equations

Wax deposition is a well known flow assurance risk in crude oil production due to temperature decrease which depends mainly on the crude oil nature and the type and content of paraffin. The prevention of this problem requires a detailed characterization of the crude oil and the availability of reliable predictive models.The experimental determination and quantification of the precipitation process is quite complex and time consuming and simpler techniques are of interest to carry out such study. Among them, differential scanning calorimetry (DSC) technique is appropriate to develop routine essays and has been extensively applied to determine wax appearance temperature in crude oil and fractions because the simplicity and fast response of the technique.However, the determination of wax precipitation curve from a quantitative DSC interpretation is usually based on pure n-alkane properties and involves some difficulties. In this work, a new procedure has been developed including the effect of the fluid composition on the precipitation temperature and the melting heat. Solid-liquid equilibrium equations were introduced through a simplified thermodynamic model in the integration procedure resulting in an iterative method combining experimental and calculated values. The final method yields the wax appearance temperature (WAT), the full wax precipitation curve and the estimated wax composition.In order to validate the procedure, several crude oil fractions were used as standards due to the advantage of a narrow n-alkane distribution. Experimental characterization for the cloud point temperature, the n-alkane distribution (determined by gas chromatography with mass detector, GCMS) and DSC was carried out. The agreement between experimental results and those obtained from the DSC interpretation is a good check for the proposed procedure.     

Structural performance of alkali/acid-ultrasound modified Agave fibers during the melt mixing process with polyvinyl alcohol

This study aims to investigate changes in the structural properties of alkali/acid-ultrasound modified Agave fibers and their performance immersed on a polyvinyl alcohol (PVA) matrix with plasticizer during melt mixing processing. Structural analysis revealed that ultrasound enhances the effectiveness of the conventional alkaline/acid treatments to modify fibers since the simultaneous treatment increased the partial removal of lignocellulosic components, water molecules, and amorphous regions which improved their processability on a PVA matrix. Specific energy consumption values indicated that during melt mixing the modified fibers required more energy to expose the chains of cellulose fraction to function as an interaction site for PVA chains. Once the mixture was homogenized, the fiber-matrix interactions promoted high viscosity, friction, and mechanical stress in the chamber. Therefore, the modified fibers restricted the interaction between plasticizer and PVA in the obtained films, resulting in a highly structured, and reinforced network, increasing the storage modulus as dynamic mechanical analysis indicated. These findings highlight a feasible way to valorize Agave fibers and allow the understanding of the matrix-fiber interactions during melt mixing processing, useful to predict the structural and mechanical properties of the films.     

Issues in fortification and analysis of omega‐3 fatty acids in foods

It is extensively documented that omega‐3 fatty acids play important roles in many bioactive processes. Omega‐3 can also influence the onset, prevention, and control of many illnesses, including prevention of cardiovascular disease. The main sources of omega‐3 fatty acids are currently from vegetable oils and cold water fish. New sources such as from microalgae and krill oils are quickly increasing their share in the supplement market. Challenges for the incorporation of omega‐3 into foods and supplements have been gradually overcome by the introduction of new, more effective, antioxidants and by the use of various types of encapsulation technologies. Also, the smaller, micronutrient level, amounts of omega‐3 fatty acids normally added to fortified foods and supplements present several challenges of sample extraction, preparation and analysis of bioactive omega‐3 ingredients.     

Enzymatic changes in pectic polysaccharides related to the beneficial effect of soaking on bean cooking time

BACKGROUND: Cooking time decreases when beans are soaked first. However, the molecular basis of this decrease remains unclear. To determine the mechanisms involved, changes in both pectic polysaccharides and cell wall enzymes were monitored during soaking. Two cultivars and one breeding line were studied. RESULTS: Soaking increased the activity of the cell wall enzymes rhamnogalacturonase, galactanase and polygalacturonase. Their activity in the cell wall was detected as changes in chemical composition of pectic polysaccharides. Rhamnose content decreased but galactose and uronic acid contents increased in the polysaccharides of soaked beans. A decrease in the average molecular weight of the pectin fraction was induced during soaking. The decrease in rhamnose and the polygalacturonase activity were associated (r = 0.933, P = 0.01, and r = 0.725, P = 0.01, respectively) with shorter cooking time after soaking. CONCLUSION: Pectic cell wall enzymes are responsible for the changes in rhamnogalacturonan I and polygalacturonan induced during soaking and constitute the biochemical factors that give bean cell walls new polysaccharide arrangements. Rhamnogalacturonan I is dispersed throughout the entire cell wall and interacts with cellulose and hemicellulose fibres, resulting in a higher rate of pectic polysaccharide thermosolubility and, therefore, a shorter cooking time. Copyright © 2011 Society of Chemical Industry     

Optimization of high-resolution continuous flow analysis for transient climate signals in ice cores

Over the past two decades, continuous flow analysis (CFA) systems have been refined and widely used to measure aerosol constituents in polar and alpine ice cores in very high-depth resolution. Here we present a newly designed system consisting of sodium, ammonium, dust particles, and electrolytic meltwater conductivity detection modules. The system is optimized for high-resolution determination of transient signals in thin layers of deep polar ice cores. Based on standard measurements and by comparing sections of early Holocene and glacial ice from Greenland, we find that the new system features a depth resolution in the ice of a few millimeters which is considerably better than other CFA systems. Thus, the new system can resolve ice strata down to 10 mm thickness and has the potential of identifying annual layers in both Greenland and Antarctic ice cores throughout the last glacial cycle.     

Comparison of four test methods to measure damping properties of materials by using piezoelectric transducers

This article presents the experimental results of damping loss factor and Young’s modulus obtained for stiff and flexible materials through the use of four different methodologies: the Central Impedance Method, the Modified Oberst Method, the Seismic Response Method, and the simply supported beam method. The first three methods are based on the ASTM standard but using different experimental setting and different Frequency Response Functions. The fourth method corresponds to a non-resonant technique used in the characterization of materials at very low frequencies. In this work, the results of damping loss factor and Young’s modulus obtained through these four methods are compared, the variability of results is studied and the sensitivity of each technique when facing controlled temperature variations is verified.     

A new spontaneous pupillary oscillation-based verification system

A novel pupillary-based verification system is introduced, along with the early identity authentication results and analysis, based on the spatio-temporal features computed from the spontaneous pupillary oscillations. The authors demonstrate that this biometric trait has the capability to provide enough discriminative information to authenticate the identity of a subject. A new methodology to compute the spatio-temporal biometric template recordings of the pupil area changes, in a video-oculography sequence under constant luminance level, is also introduced in this paper. According to the authors’ knowledge, there is no evidence that other attempts were made, addressing this methodology to distinguish individuals based on the spatio-temporal representations, computed from the normal dilation-contraction behavior of the pupil. In this work, liveness will be detected by using the information obtained from the spontaneous pupillary oscillation mechanism. Preliminary experiments were conducted by using a particular own collected database, resulting in a (Equal Error Rate) in the order of 0.2338%.