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Surface, Aggregation, and Phase Characterization of Microbially-Produced & Chemically-Synthesized MonorhamnolipidsEismin, Ryan J., Eismin, Ryan J. January 2017 (has links)
The purpose of this research has been to explore the native monorhamnolipid (mRL) mixture produced by Pseudomonas aeruginosa ATCC 9027, as well as newly- synthesized monorhamnolipid diastereomers (R,R)-Rha-C10-C10, (R,S)-Rha-C10-C10, (S,S)-Rha-C10-C10 and (S,R)-Rha-C10-C10, to understand their aggregation and phase behavior in aqueous solution. This work is in response to the consideration that biosurfactants offer a "greener" alternative to conventional surfactants. Relationships between chemical structure of the diastereomers and surface activity were studied using surface tension measurements. It was found that the critical aggregation concentration (CAC) values are lower for deprotonated (R,S)-Rha-C10-C10 and higher for protonated (R,S)-Rha-C10-C10 compared to the other diastereomers or the native mRL mixture. Furthermore, the 1:1:1:1 diastereomeric mixture has the overall lowest cross-sectional area for deprotonated rhamnolipids. Dynamic light scattering (DLS) was used to study the hydrodynamic radii (Rh) of the mRL aggregates and the four diastereomers in aqueous solution. In all five surfactants studied, each observed at pH 8.0 and 4.0, three aggregate populations were observed. For all deprotonated rhamnolipids the micelle, at a hydrodynamic radius of ~2 nm, was found to be in the highest abundance where the two lower abundant other population take on a lamellar aggregate structure. Data to support this were collected using fluorescence probing techniques. For the surfactants in the protonated state, pH 4.0, it was found that all form primarily lamellar structures, also confirmed using fluorescence probing. The average aggregation numbers (Nagg) of the micelles for the deprotonated native mRL mixture and the four diastereomers were studied using steady-state and time-resolved fluorescence quenching measurements. Somewhat unexpectedly, the Nagg values were observed to be a strong function of the rhamnolipid concentration for all systems. At low concentrations, pre-micellar aggregates with aggregation numbers too small for micelles were observed. A critical concentration is identified at which a critical aggregation number is defined; this is proposed to be the smallest fully-formed micelle in solution with values of ~25-30 molecules/micelle for the native mRL mixture and all four diastereomers. Thus, the aggregation properties of the native mRL mixture and the four diastereomers are generally similar at this critical concentration. However, the increase in aggregation number above this critical point varies for all the surfactants, where the (R,R)-Rha-C10-C10 diastereomer has the greatest increase in monomers with concentration and the (S,S) and (R,S) diastereomers have the lowest. The increased observed aggregation number is consistent with the computational work showing increased growth with concentration for the deprotonated rhamnolipid micelles. Furthermore, these computations have confirmed the ability of protonated rhamnolipids to form lamellar structures in solution. Fluorescence probing work was also used to study rhamnolipid phase behavior as a function of varying solution conditions, such as ionic strength, solution pH, surfactant concentration, and temperature. Steady-state fluorescence methods are utilized to probe the surfactant microenvironment using the polarity-sensitive dyes prodan and laurdan. By dissolving the dye within the rhamnolipid aggregates and observing their solvatochromic behavior, all surfactants studied are known to form more micellar aggregates at high pH and low surfactant concentration, whereas elongation of the micelle is observed at low pH and moderate to high surfactant concentration.
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CO₂-balance in the athmosphere and CO₂-utilisation:an engineering approachTurunen, H. (Helka) 09 August 2011 (has links)
Abstract
The subject of the thesis was to analyze by an engineering approach the global CO₂ balance and CO₂ utilisation. The aim was to apply methods and knowledge used in engineering sciences to describe the global CO₂ balance and the role of CO₂ in anthropogenic utilisation applications. Moreover barriers restricting commercialisation of new applications are discussed. These subjects were studied by literature reviews and calculations based on thermodynamics models.
Engineering methods have shown to be applicable to describe the global balance of CO₂ and to define by a numerical way the Earth’s system carrying capacity. Direct and indirect actions, which mitigate the overload situation, were derived from the results. To screen out the attractive CO₂ properties in utilisation applications a mapping analysis was carried out. Properties, which enhance mass and heat transfer, are one of the most meaningful characteristics from the chemical engineering point of view. Attractive properties are often achieved at the supercritical state.
Engineering thermodynamic methods were used in fluid phase determination of the case studies. Even simple methods are sufficient to advice experimental research work. The thermodynamic knowledge is the basement in creation of industrial scale chemical processes. If detailed information on system properties is needed, a model development due to the special requirements of high pressure systems and CO₂ features is required. This knowledge covers property information from all the components involved in chemical reactions. In addition to engineering knowledge successful technology transfer requires positive social structure as well. Finally, if the humankind is willing to mimic Nature and use light of the Sun as an energy source in engineering systems, development of thermodynamic methods is required also in this area. Especially the work terms, originally defined in classical mechanical thermodynamics and afterwards formulised also in other parts of the engineering fields, play a key role. If this development work is successful, we may see the shift from thermodynamics approach to ‘photodynamics’.
Mitigation of global warming is a problem, which needs several kinds of activities. As a result of this study, there are listed a few engineering actions, which have a possibility to contribute to the work towards the carbon neutral society. / Tiivistelmä
Väitöskirjatyössä sovelletaan insinööritieteissä käytettyjä metodeja ja tietämystä määriteltäessä ilmakehän CO₂-tase sekä antropogeenisten hyötykäyttökohteiden merkitys teollisissa prosesseissa ja globaaleissa CO₂-virroissa. Lisäksi pohditaan uusien CO₂-hyötykäyttösovellusten kaupallistamiseen liittyviä rajoitteita. Näitä aiheita on tutkittu käymällä läpi tieteellistä kirjallisuutta ja tekemällä laskelmia.
Insinööritieteistä tutun taselaskennan avulla tarkastellaan ilmakehän CO₂-virtoja. Sen pohjalta määritetään numeerisesti maapallon CO₂-kantokyky. Tuloksista johdetaan suoria ja epäsuoria toimenpide-ehdotuksia, joiden avulla voidaan lieventää ilmakehän CO₂-ylikuormaa. Kartoitusmenetelmän avulla selvitetään hyötykäytön kannalta edulliset CO₂:n aineominaisuudet. Kemiantekniikan näkökulmasta ominaisuudet, jotka parantavat aineen- ja lämmönsiirtoa, ovat kiinnostavimpia. Nämä ominaisuudet tulevat esille silloin, kun fluidi on ylikriittisessä olomuodossa.
Termodynaamisia laskentamenetelmiä sovelletaan esimerkkiseosten olomuodon eli faasin määrityksessä. Tulokset osoittavat, että jopa verraten yksinkertaiset menetelmät antavat tietoja, jotka auttavat ymmärtämään laboratoriokokeiden faasikäyttäytymistä. Teollisen mittakaavan kemiallisten prosessien kehityksessä ja suunnittelussa termodynamiikan hallitseminen on keskeinen edellytys. Jos CO₂:n kiinnostavia ominaisuuksia toivotaan hyödynnettävän teollisesti, korkeapaineisten systeemien termodynaamisen teorian hallinta sekä aineominaisuuksien määrittäminen kaikille systeemiin osallistuville komponenteille ja niiden seoksille nousee merkittävään asemaan. Läpikotainen teorian ja teknisten perusteiden hallitseminen ei vielä takaa menestyksellistä teknologiansiirtoa pienestä suureen mittakaavaan. Lisäksi tarvitaan myönteinen ja kannustava yhteiskuntajärjestelmä.
Mikäli tavoitellaan vielä rohkeampaa kehitysnäkymää, tilannetta, jossa luonnon tavoin CO₂-prosessien energianlähteenä käytettäisiin auringonvaloa, havaitaan, että tämäkin askel edellyttäisi termodynaamista menetelmäkehitystä. Keskeinen termodynaaminen konsepti on työ. Työ siirtää energiaa ympäristön ja systeemin välillä. Tämä on määritelty jo klassisessa mekaniikassa; kappaleen siirto tietystä paikasta toiseen. Kemiantekniikassa työlle on kehitetty käyttökelpoisia kaavoja paine–tilavuus–lämpötila-systeemeihin. Mikäli työn elementit kyettäisiin määrittelemään auringonvalon fotoenergialle, avaisi se uusia näkymiä reaktiokemiaan. Silloin termodynamiikan sijaan voitaisiin ehkä mieluummin puhua 'photodynamiikasta'.
Ilmaston lämpeneminen on ongelma, jonka lieventämiseen tarvitaan useanlaisia toimia. Etsittäessä tietä kohti hiilineutraalia yhteiskuntaa, insinöörit voivat avustaa suunnan löytämisessä hyödyntämällä tieteenalallaan käytettyjä metodeja ja teorioita sekä tarpeen vaatiessa kehittää niitä edelleen uusille alueille.
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