5 resultados para MOLECULAR-SIZE DISTRIBUTION

em Universidad de Alicante


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The cell concentration and size distribution of the microalgae Nannochloropsis gaditana were studied over the whole growth process. Various samples were taken during the light and dark periods the algae were exposed to. The distributions obtained exhibited positive skew, and no change in the type of distribution was observed during the growth process. The size distribution shifted to lower diameters in dark periods while in light periods the opposite occurred. The overall trend during the growth process was one where the size distribution shifted to larger cell diameters, with differences between initial and final distributions of individual cycles becoming smaller. A model based on the Logistic model for cell concentration as a function of time in the dark period that also takes into account cell respiration and growth processes during dark and light periods, respectively, was proposed and successfully applied. This model provides a picture that is closer to the real growth and evolution of cultures, and reveals a clear effect of light and dark periods on the different ways in which cell concentration and diameter evolve with time.

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Conformational changes of a humic acid (HA) and a fulvic acid (FA) induced by iron complexation were followed by high-performance size exclusion chromatography (HPSEC) with both UV–vis and refractive index (RI) detectors. Molecular size distribution was reduced for HA and increased for FA with progressive iron complexation. Since interactions of Fe with humic components are electrostatic, it is likely that the triple-charged Fe ions formed stronger complexes with the more acidic hydrophilic and hydrated FA than with the less acidic and more hydrophobic HA. The large content of ionized carboxyl groups in FA, thus favored the formation of intra- or intermolecular bridges between the negatively charged fulvic acid molecules, and led to more compact and larger size network than for HA. Conversely, iron complexation with HA disrupted the humic conformational arrangements stabilized by only weak hydrophobic bonds into smaller-size aggregates of greater conformational stability due to formation of strong metal complexes. These results confirmed that humic molecules in solution were organized in supramolecular associations of relatively small molecules loosely bound together by dispersive interactions and hydrogen bonds, and they specifically responded to chemical changes brought about by metal additions. The present study revealed the molecular changes occurring in superstructures of natural organic matter when in metal complexes and contributed to understand and predict the environmental behavior in waters and soil of metal complexes with natural organic matter.

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Development of new silica membranes properties, e.g., molecular sieving properties, has been increasingly gaining importance in the last few years. A novel unsupported silica membrane, referred to as hydrophobic metal-doped silica, was developed by cobalt-doping within the organic templated silica matrix. The novel material was prepared by the acid-catalyzed hydrolysis and condensation process of tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES), which is the precursor for methyl ligand covalently bounded to the silica matrix. The synthesis and surface properties of the novel unsupported silica membrane as well as the unsupported blank silica and modified silica membranes were revealed by surface and microstructural techniques, such as water contact angle measurement, FTIR, X-ray, Solid-state 29Si MAS NMR, TGA and N2 and CO2 adsorption measurements. The results showed that the thermal stability of the organic templated silica matrix was enhanced by cobalt-doping process. A hydrophobic microporous silica membrane material with high thermal stability up to ∼560 °C in oxidizing atmosphere and a narrow pore size distribution centered at 1.1 nm was obtained. Therefore, a novel precursor material for molecular sieve silica membranes applications has been achieved and developed.

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Carbon molecular sieve membranes have been analyzed in supported and unsupported configurations in this experimental study. The membranes were used to adsorb CO2, N2 and CH4, and their adsorption data were analyzed to establish differences in rate and capacity of adsorption between the two types of samples (supported and unsupported). Experimental results show an important effect of the support, which can be considered as an additional parameter to tailor pore size on these carbon membranes. Immersion calorimetry values were measured by immersing the membranes into liquids of different molecular dimensions (dichloromethane, benzene, n-hexane, 2,2-dimethylbutane). Similarities were found between adsorption and calorimetric analysis. The pore volume of the samples analyzed ranged from 0.016 to 0.263 cm3/g. The effect of the pyrolysis temperature, either 550 or 700 °C, under N2 atmosphere was also analyzed. Quantification of the pore-size distribution of the support was done by liquid-liquid displacement porosimetry. The composite membrane was used for CO2/CH4 separation before and after pore plugging was done. The ideal selectivity factors value (4.47) was over the Knudsen theoretical factor (0.60) for membrane pyrolyzed at 600 °C, which indicates the potential application of these membranes for the separation of low-molecular weight gases.

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We compare the pore size distribution of a well-characterized activated carbon derived from model-dependent, adsorption integral equation (AIE) methods with those from model-independent, immersion calorimetry and isosteric heat analyses. The AIE approach applied to nitrogen gave a mean pore width of 0.57 nm; the CO2 distribution exhibited wider dispersion. Spherical model application to CO2 and diffusion limitations for nitrogen and argon were proposed as primary reasons for inconsistency. Immersion enthalpy revealed a sharp decrease in available area equivalent to a cut-off due to molecular exclusion when the accessible surface was assessed against probe kinetic diameter. Mean pore width was identified as 0.58 ± 0.02 nm, endorsing the underlying assumptions for the nitrogen-based AIE approach. A comparison of the zero-coverage isosteric heat of adsorption for various non-polar adsorptives by the porous test sample was compared with the same adsorptives in contact with a non-porous reference adsorbent, leading to an energy ratio or adsorption enhancement factor. A linear relationship between the energy ratio and probe kinetic diameter indicated a primary pore size at 0.59 nm. The advantage of this enthalpy, model-independent methods over AIE were due to no assumptions regarding probe molecular shape, and no assumptions for pore shape and/or connectivity.