Study of secondary relaxations of poly(ethylene terephthalate) by photoluminescence technique

The α and β relaxation processes in two types of poly(ethylene terephthalate) with different degrees of crystallinity were studied by means of three methods, differential scanning calorimetry, dynamic-mechanical analysis and fluorescence spectroscopy. Information provided is complementary in the mean that every method sense phenomena that may occur at different times and length scales. Several probes, Coumarin 152 (C152), Coumarin 153 (C153), Coumarin 337 (C337) and 4′-dimethylamino-4-nitrostilbene (DMANS), were adsorbed in polymer films, and their fluorescence analysed over the temperature range from −150 to 150 °C. In general, a decrease in fluorescence intensity of probes as temperature increase was observed. This behaviour has been explained as a consequence of the enhancement of the free volume fraction that favoured the radiationless process of the lowest excited singlet state. Plots of fluorescence intensity versus temperature showed changes around the secondary relaxation temperatures. Therefore, good correlations between fluorescence and dynamic mechanical and calorimetric analysis were established. The obtained results indicated that the fluorescence from the probes incorporated to the material was dependent on the crystallinity of polymer. It would indicate that the fluorescence emission from those probes can be used to analyse annealing processes in semicrystalline polymers.     

Some Statistical-Estimation Methods for Stochastic Finite-State Transducers

Formal translations constitute a suitable framework for dealing with many problems in pattern recognition and computational linguistics. The application of formal transducers to these areas requires a stochastic extension for dealing with noisy, distorted patterns with high variability. In this paper, some estimation criteria are proposed and developed for the parameter estimation of regular syntax-directed translation schemata. These criteria are: maximum likelihood estimation, minimum conditional entropy estimation and conditional maximum likelihood estimation. The last two criteria were proposed in order to deal with situations when training data is sparse. These criteria take into account the possibility of ambiguity in the translations: i.e., there can be different output strings for a single input string. In this case, the final goal of the stochastic framework is to find the highest probability translation of a given input string. These criteria were tested on a translation task which has a high degree of ambiguity.     

Patenting and licensing by Spanish firms: Available survey evidence

This paper presents the results of the OEPM (Spanish Patent and Trademark Office)/OECD (Organisation for Economic Co-operation and Development) survey on the economic and financial uses of patents carried out in 2008 among Spanish business applicants of OEPM patents. It also summarizes evidence from previous surveys. All available information indicates that only a few Spanish firms holding patents license them out. Results from the OEPM/OECD survey also reveal that obtaining public support is the first financial use of patents for Spanish firms. Responses to the same OECD questionnaire by EPO patent applicants from several European countries are quite different: licensing out is an extended practice among EPO patent holders from different countries, including Spain, and convincing venture capitalists and private investors are their two most important financial uses of patents. In our view this suggests that there are significant differences across European countries as regards the development of national technology markets and results from international surveys are driven by responses from the largest and more developed countries. The drivers and actors in markets for patents that only protect inventions nationally may be quite distinct from those in markets for patents that protect inventions regionally, such as EPO patents within Europe.     

Smooth sliding-mode observers for specific growth rate and substrate from biomass measurement

This paper addresses the estimation of specific growth rate and substrate concentration from biomass measurements in fermentation processes. Specifically, sliding-mode observers are proposed, for which finite-time global convergence is demonstrated using Lyapunov stability theory and concepts of variable structure systems. Two observers are developed for specific growth rate estimation, one producing a discontinuous estimation which is used afterwards for substrate estimation, and the other one – based on high-gain observers – that generates a smooth estimation with first-order dynamics and finite-time bounded convergence error. In the case of substrate estimation, an observer that increases the convergence rate to a vicinity of the real substrate concentration while achieving asymptotic convergence despite kinetic model uncertainties in properly excited processes is designed. This observer also exhibits first-order dynamics.     

Multi-source energy systems analysis using a multi-criteria decision aid methodology

In this article, an original multi-criteria approach is applied to multi-source systems used for the design and the choice of the optimal alternative. The high number of alternatives and potential solutions when dealing with multi-source systems require a decision support method to be implemented and easy to use. Information data on the economic variables, energy performance and impact on the environment of the systems are presently data which analysis and quantification is difficult. To deal with this high level of complexity and uncertainty, an evaluation approach is needed. The multi-criteria decision support methodology concept is described (ELECTRE III) and then applied for a case study. The decision support algorithm has its bases on the developed models and makes the outranking of possible solutions. It is also shown that multi-criteria analysis can provide a technical–scientific decision-making support that is capable to justify the clearly rank of the alternatives in the renewable energy sector. The use of multi-criteria decision aid for assessing the multi-source systems showed encouraging results and interesting insights.     

The influence of cardiac frequency on the hemodynamic consequences of mitral stenosis (author's transl)

In eleven patients with isolated mitral stenosis and regular sinus rhythm a right cardiac catheterization was performed and the wedged pulmonary capillary pressure recorded at rest and during electrical pacing of the right atrium at successive frequencies of 100, 120, 140, and, occasionally, 160 and 180 beats/min, while cardiac output was estimated by the Fick's principle. In all cases a significant elevation of pulmonary capillary pressure with a simultaneous reduction in cardiac output was obtained. The rise of wedged pulmonary pressure was proportional to the increment in cardiac frequency and related also to the calculated area of the mitral valve. The influence of active atrial contraction upon pulmonary pressure and cardiac output is discussed and comparisons with other studies are made. Emphasis is made on the value of atrial pacing as a diagnostic method in mitral stenosis, especially in cases in whom classical effort manoeuvres can not be applied or are insufficient to rise cardiac frequency.     

Determination of linear alkylbenzenesulfonates and their degradation products in soils by liquid chromatography-electrospray-ion trap multiple-stage mass spectrometry

Linear alkylbenzenesulfonates (LAS) (C(10)-C(13)) and their degradation products, sulfophenyl carboxylate compounds (SPCs) (C(2)-C(6), C(8), C(11)), have been extracted from soil samples with methanol, isolated, concentrated by solid-phase extraction, and determined by liquid chromatography/negative ion electrospray quadrupole ion-trap tandem mass spectrometry (MS(n)). The ion fragmentation processes and pathways were studied in detail by MS, MS(2), and MS(3). Upon collision-induced dissociation, the deprotonated molecules of LASs render the ethylene-substituted benzenesulfonate ion (m/z 183), the fragmentation of which gave the intense signal at m/z 119, corresponding to the ethylene-substituted phenoxide ion formed by the loss of sulfur dioxide. The fragmentation pattern of SPCs shows that, for the analytes of large carbon atom chains (>5C), the neutral loss of water is favored whereas for those of short carbon atoms chain, the loss of carbon dioxide is more frequent. Multiple reaction monitoring using isolation only for MS and using isolation and fragmentation for MS(2) and MS(3) were used to identify and quantify each compound. The three MS modes have been validated in terms of sensitivity, selectivity, and precision, showing that each MS stage used reduces sensitivity 10 times. Recoveries from soil were higher than 65% at LOQ level for all the analytes tested, except for C(2)-C(4) SPCs by any MS mode, with relative standard deviation lower than 19%. The utility of the method is demonstrated by successfully quantifying real samples treated with these products. Quantification limits for the methodology developed in this work ranged from 0.5 to 50 microg kg(-1) by MS, from 2 to 400 microg kg(-1) by MS(2), and from 20 to 4000 microg kg(-1) by MS(3). Concentration levels of LASs and SPCs-ranging from 0.1 to 15 mg kg(-1)-were found in soil samples amended with sludges, thus indicating their input and persistence in the soil compartment.     

Solid-phase microextraction liquid chromatography/tandem mass spectrometry to determine postharvest fungicides in fruits

A method to determine five postharvest fungicides (dichloran, flutriafol, o-phenylphenol, prochloraz, tolclofos methyl) in fruits (cherries, lemons, oranges, peaches) has been developed using solid-phase microextraction (SPME) coupled to liquid chromatography (LC) with photodiode array (DAD), mass spectrometry (MS), or tandem mass spectrometry (MS/MS) with ion trap detection. Extraction involved sample homogenization with an acetone/water solution (5:1), filtration, and acetone evaporation prior to fiber extraction. The pesticides were isolated with a fused-silica fiber coated with 50-microm Carbowax/template resin. The effects of pH, ion strength, sample volume, and extraction time were investigated, and their impact on the SPME-LC/MS was studied. Dynamic and static modes of desorption were compared and the variables affecting desorption processes in SPME-LC optimized. Static desorption provided the best recoveries and peak shapes. Recoveries at the limit of quantification (LOQ) levels were between 10% for prochloraz and 60% for o-phenylphenol, with relative standard deviations from 13.6% for prochloraz to 3.1% for o-phenylphenol. The versatility of the method was also exhibited by its excellent linearity in the concentration intervals between 0.0005 and 5 mg kg(-1) for dichloran and 0.01-10 mg kg(-1) for tolclofos methyl and prochloraz. LOQs ranged from 0.25 to 1 microg g(-1) using DAD, from 0.002 to 0.01 microg g(-1) using LC/MS, and from 0.0005 to 0.01 to microg g(-1) using LC/MS/MS. LOQs obtained in the present study using LC/MS and LC/MS/MS are lower than maximum residue limits established for all the fungicides in any matrix studied. The method enables to determine polar pesticides at low-microgram per gram levels in fruits.