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.

Production of fungal volatile organic compounds in bedding materials

Selostus: Haihtuvien orgaanisten yhdisteiden muodostuminen kuivikkeissa

Variation in soil organic carbon and thickness of soil horizons within a boreal forest stand - effect of trees and implications for sampling

Summary

Dietary preferences of weaned piglets offered diets containing organic acids

Selostus: Orgaanisten happojen vaikutus porsasrehun maittavuuteen

Export of dissolved organic carbon, nitrogen and phosphorus following clear-cutting of three Norway spruce forest growing on drained peatlands in southern Finland

Abstract

Inorganic and organic phosphorus fractions in peat from drained mires in northern Finland

Abstract

Separation mechanisms in nanofiltration and retention changes of organic compounds

Orgaanisten yhdisteiden negatiivinen retentio nanosuodatuksessa on ilmiö, jota eiole kovin paljon tutkittu. Negatiivisen retentioon vaikuttavat syyt tai tekijäteivät ole kovin hyvin tiedossa. Erotusmenetelmänä negatiivinen retentio voi olla käyttökelpoinen tietyissä sovelluksissa. Työn kirjallisuusosa käsittelee nanosuodatuksen erotusmekanismeja ja retentioon vaikuttavia tekijöitä. Myös joitakin malleja on esitetty. Nanosuodatus on monimutkainen prosessi, josta ei voida löytää vain yhtä erotusmekanismia tai retentioon vaikuttavaa tekijää. Prosessit ovat kokonaisuuksia, joissa erottumiseen vaikuttavat syöttöliuoksen, erotettavan komponentin ja kalvon ominaisuudet, ja niiden väliset vuorovaikutukset. Työn kokeellisessa osassa koottiin mahdollisimman paljon esimerkkejä, joissa monosakkaridien negatiivinen retentio ilmenee. Muita orgaanisia ja epäorgaanisia yhdisteitä käytettiin 'häiriöyhdisteinä' syöttöliuoksessa monosakkaridien kanssa. Kokeet suoritettiin kahdella laboratoriomittakaavan suodatuslaitteella käyttäen kahta kaupallista nanosuodatuskalvoa. Negatiivinen retentio ilmeni useissa tapauksissa. Permeaattivuon ja 'häiriöyhdisteiden' pitoisuuksien havaittiin vaikuttavan voimakkaasti negatiivisen retention ilmenemiseen.

Choice of Optimal MembraneProcesses for Economical Treatment of Paper Machine Clear Filtrate

In this thesis membrane filtration of paper machnie clear filtrate was studied. The aim of the study was to find membrane processes which are able to produce economically water of sufficient purity from paper machine white water or its saveall clarified fractions for reuse in the paper machnie short circulation. Factors affecting membrane fouling in this application were also studied. The thesis gives an overview af experiments done on a laboratory and a pilot scale with several different membranes and membrane modules. The results were judged by the obtained flux, the fouling tendency and the permeate quality assessed with various chemical analyses. It was shown that membrane modules which used a turbulence promotor of some kind gave the highest fluexes. However, the results showed that the greater the reduction in the concentration polarisation layer caused by increased turbulence in the module, the smaller the reductions in measured substances. Out of the micro-, ultra- and nanofiltration membranes tested, only nanofiltration memebranes produced permeate whose quality was very close to that of the chemically treated raw water used as fresh water in most paper mills today and which should thus be well suited for reuse as shower water both in the wire and press section. It was also shown that a one stage nanofiltration process was more effective than processes in which micro- or ultrafiltration was used as pretreatment for nanofiltration. It was generally observed that acidic pH, high organic matter content, the presence of multivalent ions, hydrophobic membrane material and high membrane cutoff increased the fouling tendency of the membranes.

Contents of trichothecenes in oats during official variety, organic cultivation and nitrogen fertilization trials in Finland

Selostus: Kauran trikotekeenipitoisuus virallisissa lajikekokeissa sekä typpilannoitus- ja luomulajikekokeissa

Annual and seasonal changes in production and composition of grazed clover-grass mixtures in organic farming

Selostus: Alsike-, puna- ja valkoapilan vaikutus laitumen tuottoon luonnonmukaisessa tuotannossa