Influence of stationary phase and eluent properties on chromatographic separation of carbohydrates

In this thesis, the sorption and elastic properties of the cation-exchange resins were studied to explain the liquid chromatographic separation of carbohydrates. Na+, Ca2+ and La3+ form strong poly(styrene-co-divinylbenzene) (SCE) as well as Na+ and Ca2+ form weak acrylic (WCE) cation-exchange resins at different cross-link densities were treated within this work. The focus was on the effects of water-alcohol mixtures, mostly aqueous ethanol, and that of the carbohydrates. The carbohydrates examined were rhamnose, xylose, glucose, fructose, arabinose, sucrose, xylitol and sorbitol. In addition to linear chromatographic conditions, non-linear conditions more typical for industrial applications were studied. Both experimental and modeling aspectswere covered. The aqueous alcohol sorption on the cation-exchangers were experimentally determined and theoretically calculated. The sorption model includes elastic parameters, which were obtained from sorption data combined with elasticity measurements. As hydrophilic materials cation-exchangers are water selective and shrink when an organic solvent is added. At a certain deswelling degree the elastic resins go through glass transition and become as glass-like material. Theincreasing cross-link level and the valence of the counterion decrease the sorption of solvent components in the water-rich solutions. The cross-linkage or thecounterions have less effect on the water selectivity than the resin type or the used alcohol. The amount of water sorbed is higher in the WCE resin and, moreover, the WCE resin is more water selective than the corresponding SCE resin. Theincreased aliphatic part of lower alcohols tend to increase the water selectivity, i.e. the resins are more water selective in 2-propanol than in ethanol solutions. Both the sorption behavior of carbohydrates and the sorption differences between carbohydrates are considerably affected by the eluent composition and theresin characteristics. The carbohydrate sorption was experimentally examined and modeled. In all cases, sorption and moreover the separation of carbohydrates are dominated by three phenomena: partition, ligand exchange and size exclusion. The sorption of hydrophilic carbohydrates increases when alcohol is added into the eluent or when carbohydrate is able to form coordination complexes with the counterions, especially with multivalent counterions. Decreasing polarity of the eluent enhances the complex stability. Size exclusion effect is more prominent when the resin becomes tighter or carbohydrate size increases. On the other hand,the elution volumes between different sized carbohydrates decreases with the decreasing polarity of the eluent. The chromatographic separation of carbohydrateswas modeled, using rhamnose and xylose as target molecules. The thermodynamic sorption model was successfully implemented in the rate-based column model. The experimental chromatographic data were fitted by using only one adjustable parameter. In addition to the fitted data also simulated data were generated and utilized in explaining the effect of the eluent composition and of the resin characteristics on the carbohydrate separation.

"In vitro" comparative experimental study of antimicrobial action of mouth washing products

Regular use of mouth rinses modifies the oral habitat, since bacterial populations are submitted to a high selective pressure during the treatment exercised by the active presence of the disinfectant. Mostly mouth rinses are based on the antibacterial effect of Chlorhexidine, Triclosan, essential oils and other antibacterials although other pharmaceutical characteristics can also affect their effectiveness. In this paper we compare"in vitro" the antibacterial effect of different oral rinsing solutions. Minimal Inhibitory Concentrations (MIC) and Minimal Bactericidal Concentrations (MBC) were determined as well as the kinetics of bacterial death in the presence of letal concentrations of the mouth rinses. MIC values expressed as Maximal Inhibitory Dilution (MID) of the mouth rinse ranged from 1 to 1/2048 depending on the microorganism and product, whereas Minimal Biocidal Concentration (MBC), expressed as Maximal Biocidal Dilution (MBD) ranged from 1 to 1/1024, being in general one dilution less than MIC. Maximal Biocidal Dilution is a good tool to measure the actual efficiency of mouth washing solutions. However, kinetics of death seems to be better in our work killing curves demonstrate that bacterial populations are mostly eliminated during the first minute after the contact of bacterial suspension and the mouth-washing solution. In all tested bacterial species mouth-washing solutions tested were able to reduce until suspension treated except 1 and 5

The Impact of ICTs on Lecturer and Student Interaction in University Education Processes

Interaction is a basic element in any educational process, and it is something that needs to be reconsidered in the light of technology. In order to examine the methodological changes that ICTs bring to teaching from an interaction perspective, a study was carried out at the University of Lleida to observe interaction processes in various face-to-face, blended learning and e-learning subjects. The methodological design was based on three data collection techniques: documentary analysis of subject curricula, lecturer and student questionnaires, and lecturer interviews. The data showed that, as the online component of subjects increased, the lecturers and students used more technological tools to communicate (e-mail, forums, chats, social networks, etc.). Furthermore, we found that the lecturers and students basically communicated for academic purposes. While they hardly ever communicated for personal reasons (guidance, support, etc.), they claimed that closer contact with a non-academic focus would be preferable. We also observed that the students’ work was more individual in e-learning subjects. Although there is still a considerable way to go in ICT-mediated lecturer-student interaction, both the lecturers and students recognise the potential of such technologies, even though they still do not use them as they feel they should.

Epäpuhtaudet sinkin uutossa

Työssä tutkittiin metalli- ja anioniepäpuhtauksien myötäuuttautumista sinkin mukana di(2-etyyliheksyyli)fosforihappoalla (D2EHPA). Laboratoriokokeissa selvitettiin pH:n vaikutusta metalliepäpuhtauksien uuttautumiseen pH-alueella -O, l... 3 sekä pesujen vaikutusta sinkillä ladatun orgaanisen faasin metallipitoisuuksiin. Kokeita tehtiin sekä synteettisillä että autenttisilla prosessiliuoksilla. Anionikokeissa tutkittiin raudan ja sinkin vaikutusta kloridin ja fluoridin uuttautumiseen. Synteettisillä liuoksilla tehdyissä kokeissa tutkittiin kadmiumin, koboltin, nikkelin, kuparin sekä antimonin uuttautumista sinkkisulfaattiliuoksesta. Kokeissa havaittiin D2EHPA:n uuttavan sinkkiä selvästi em. metalleja paremmin. Sinkki uuttautui sulfaattiliuoksesta lähes täydellisesti tasapaino-pH:n ollessa yli 2,3. Sinkin jälkeen muista metalleista uuttautui eniten kadmium ja järjestyksessä sitten kupari, koboltti ja nikkeli. Epäpuhtausmetallien myötäuuttautumista lisääntyi uuton tasapaino-pH:n kasvaessa ja väheni sinkkilatauksen kasvaessa. Kahdella peräkkäisellä pesuaskeleella, joissa ensimmäinen pesuliuos sisälsi 5 g/L rikkihappoa ja toinen sekä 15 g/L rikkihappoa että 5 g/L sinkkiä saatiin kaikkien epäpuhtausmetallien pitoisuudet jäämään alle 3 mg/L. Antimonin uuttokokeissa huomattiin antimonin uuttautuvan täydellisesti D2EHPA:lla pH:sta riippumatta pH-alueella0...3. Prosessiliuoksilla tehdyissä kokeissa todettiin D2EHPA:n pystyvän tehokkaasti erottamaan sinkin magnesiumista ßzn,Mg ˜107 ja kadmiumista ßzn,cd ˜106. Havaittiin myös, että mitä suurempi sinkki- ja rautalataus orgaanisessa faasissa on sitä vähemmän magnesiumia ja kadmiumia uuttautuu. Ensimmäisessä pesussa saatiin sekä kadmiumin että magnesiumin pitoisuudet putoamaan keskimäärin 0,1 mg/L eli 30 alkuperäisestä pitoisuudesta. Toisella pesuaskeleella ei enää ollut vaikutusta kadmiumin ja magnesiumin pitoisuuksiin orgaanisessa faasissa. Kokeissa havaittiin myös, että D2EHPA:n latausasteen ylittäessä 0,7 alkaa sinkki-D2EHPA-kompleksit polymeroitua ja faasit eivät enää selkeytyneet helposti. Anionikokeissa huomattiin, ettei D2EHPA uuttanut kloridi tai fluoridi sinkin tai raudan mukana. D2EHPA:n havaittiin myös itsessään sisältävän hieman kloridia.

A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form) in non-aqueous media. The anion loading of the AER (OH− form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.

On the relationship between C and N fixation in nodulated alfalfa (Medicago sativa)

Legumes such as alfalfa (Medicago sativa L.) are vital N2-fixing crops accounting for a global N2 fixation of ~35 MtNyear-1. Although enzymatic and molecular mechanisms of nodule N2 fixation are now well documented, some uncertainty remains as to whether N2 fixation is strictly coupled with photosynthetic carbon fixation. That is, the metabolic origin and redistribution of carbon skeletons used to incorporate nitrogen are still relatively undefined. Here, we conducted isotopic labelling with both 15N2 and 13C-depleted CO2 on alfalfa plants grown under controlled conditions and took advantage of isotope ratio mass spectrometry to investigate the relationship between carbon and nitrogen turn-over in respired CO2, total organic matter and amino acids. Our results indicate that CO2 evolved by respiration had an isotopic composition similar to that in organic matter regardless of the organ considered, suggesting that the turn-over of respiratory pools strictly followed photosynthetic input. However, carbon turn-over was nearly three times greater than N turn-over in total organic matter, suggesting that new organic material synthesised was less N-rich than pre-existing organic material (due to progressive nitrogen elemental dilution) or that N remobilisation occurred to sustain growth. This pattern was not consistent with the total commitment into free amino acids where the input of new C and N appeared to be stoichiometric. The labelling pattern in Asn was complex, with contrasted C and N commitments in different organs, suggesting that neosynthesis and redistribution of new Asn molecules required metabolic remobilisation. We conclude that the production of new organic material during alfalfa growth depends on both C and N remobilisation in different organs. At the plant level, this remobilisation is complicated by allocation and metabolism in the different organs. Additional keywords: carbon exchange, carbon isotopes, nitrogen fixation, nitrogen 15 isotope

Apple biological and physiological disorders in the orchard and in postharvest according to production system

The study aimed to evaluate the incidence of biological and physiological disorders in the field and postharvested apples cvs. Gala, Fuji and Catarina grown in four production systems: conventional, organic transition, integrated and organic. Apples were evaluated for damages related to biological and physiological disorders in the orchard and after harvest. The greatest damages were attributed to pests, especially Anastrepha fraterculus in the organic system and Grapholita molesta in the organic transition. Apples produced in organic orchards had higher damage levels caused by postharvest physiological disorders than those grown in other production systems. For apples becoming from organic orchards most of the damage was due to lenticels breakdown and degeneration ('Gala'), and bitter pit ('Fuji' and 'Catarina'). The incidence of postharvest rot was not influenced by apple production system.

Automatic Brain Extraction in Fetal MRI using Multi-Atlas-based Segmentation

In fetal brain MRI, most of the high-resolution reconstruction algorithms rely on brain segmentation as a preprocessing step. Manual brain segmentation is however highly time-consuming and therefore not a realistic solution. In this work, we assess on a large dataset the performance of Multiple Atlas Fusion (MAF) strategies to automatically address this problem. Firstly, we show that MAF significantly increase the accuracy of brain segmentation as regards single-atlas strategy. Secondly, we show that MAF compares favorably with the most recent approach (Dice above 0.90). Finally, we show that MAF could in turn provide an enhancement in terms of reconstruction quality.

Mentoring in the acquisition of professional skills through practices in companies by degree students

Abstract This work has had as objective to analyze the skills acquired through internships in business companies by students of the Faculty of Economics and Business at the University Pompeu Fabra. The internship is a basic item in order to obtain a hard connection between the University and social-economic world where University and Enterprises develop their activity. In this study we want to know about two aspects. The first one, we want to know the profit that is obtained from the Student as a consequence of internship and mentoring. Also, we want to study about the importance of mentoring as a principal element that establishes the relationship between the Student and the Company. Moreover, it has sought to analyze if certain factors such as the size of the company where the practices has been performed, the study rank level that was achieved or the fact of being a man or a woman, were among the determining factors at the time of acquiring the skills. The results presented here indicate that the size of the company that have been making the practices and the gender of the student are related to the acquisition of certain skills. There was not a statistically significant relationship related to the rank level have by the students in the practice. In the future we are going to study if the labor market Integration is easier if the Student has performed work placement. Keywords Skills; employability; internship; meatoring.

Supramolecular Gold Metallogelators: The Key Role of Metallophilic Interactions

Gold metallogelators is an emerging area of research. The number of results published in the literature is still scarce. The majority of these gels is observed in organic solvents, and the potential applications are still to be explored. In this work, we present an overview about gold metallogelators divided in two different groups depending on the type of solvent used in the gelation process (organogelators and hydrogelators). A careful analysis of the data shows that aurophilic interactions are a common motif directly involved in gelation involving Au(I) complexes. There are also some Au(III) derivatives able to produce gels but in this case the organic ligands determine the aggregation process. A last section is included about the potential applications that have been reported until now with this new and amazing class of supramolecular assemblies.

Nuclear magnetic resonance investigation of structure and dynamics of some electrolyte solutions

Electrolyte solutions are of importance in a wide range of scientific contexts and as such have attracted considerable theoretical and experimental effort over many years. Nuclear Magnetic resonance provides a precise and versatile tool for investigation of electrolyte solutions, both in water and in organic solvents. Many structural and dynamic properties can be obtained through NMR experiments. The solution of aluminum chloride in water was studied. Different concentrations were taken for investigation. Independence of maximum line shift from concentration and acidity was shown. Six-coordinated structure of solvation shell was confirmed by experiments on 'H and 27A1 nuclei. Diffusion coefficients were studied. The solution of nickel chloride in methanol was studied. Lines, corresponding to coordinated and bulk methanol were found. Four-, five- and six-coordinated structures were found in different temperatures. The line for coordinated -OD group of deuterated methanol was observed on 2H spectrum for the first time. Partial deuteration of CH3 group was detected. Inability to observe coordinated -OH group was explained.

Organo-gel de heptano: diagrama de fases e aplicações sintéticas

The phase diagram formation of microemulsion-based gels composed of an anionic surfactant aerosol-OT sodium bis (2-ethylhexyl)-sulphosuccinate), water, gelatin and an organic solvent is presented for heptane. The stability of this organo- gel, when an enzyme is immobilized is discussed in terms of its reutilization in various esters synthesis.

Redução seletiva aplicada à especiação de mercúrio em peixes: uma adaptação do método de Magos

In the selective reduction procedure proposed by Magos SnCl2 was used as reductant for inorganic mercury while total mercury was determined after reduction with a mixture of SnCl2 and CdCl2. The difference between total mercury and inorganic mercury determines the content of organic mercury. The procedure of the present work differs of Magos in that the mercury vapour is carried to the absorption cell after magnetic stirring of the solution in the reaction flask; in the Magos procedure, mercury vapour is carried by bubbling the gas in to the solution. In contrast to the Magos procedure this slight modification overcame the necessity of at calibration by analyte addition, saving time and gainning accuracy.

O emprego de lipases como agentes de resolução cinética de enantiômeros em síntese orgânica: aspectos gerais sobre a influência do solvente

In organic synthesis, lipases are the most frequently used biocatalysts. They are efficient stereoselective catalysts in the kinetic resolution of a wide variety of chiral compounds. The discovery that enzymes possess catalytic activity in organic solvents has made it possible to address the question of reaction medium influence on enzymatic specificity. Perhaps the most exciting and significant development in this emerging area is the discovery that enzyme specificity, in particular enantioselectivity, can be affected by changing from one organic solvent to another. This article discusses the scope and possible mechanistic models of this phenomenon in hydrolases, specially lipases, as well as directions of future research in the area.

Síntese do butirato de n-butila empregando lipase microbiana imobilizada em copolímero de estireno-divinilbenzeno

This work investigates the reaction parameters of an immobilized lipase in the esterification reaction of n-butanol and butyric acid. Microbial lipase from Candida rugosa was immobilized onto styrene-divinylbenzene copolymer (STY-DVB) and subsequently introduced in an organic medium containing substrates in appropriate concentrations. Heptane was selected as solvent on the basis of its compatibility with the resin and the enzyme. The influence of molar ratio of acid to alcohol, amount of immobilized lipase and temperature on the butyl butyrate formation was determined. The results were compared with those achieved with free lipase and Lipozyme (commercially immobilized lipase) under the same operational conditions.