Crystallization of water or water-encaged gas molecules occurs when nuclei reach a critical size. Certain antifreeze proteins (AFPs) can inhibit the growth of both of these, with most representations conceiving of an embryonic crystal with AFPs adsorbing to a preferred face, resulting in a higher kinetic barrier for molecule addition. We have examined AFP-mediated inhibition of ice and clathrate hydrate crystallization, and these observations can be both explained and modeled using this mechanism for AFP action. However, the remarkable ability of AFPs to eliminate „memory effect‟ (ME) or the faster reformation of clathrate hydrates after melting, prompted us to examine heterogeneous nucleation. The ubiquitous impurity, silica, served as a model nucleator hydrophilic surface. Quartz crystal microbalance-dissipation (QCM-D) experiments indicated that an active AFP was tightly adsorbed to the silica surface. In contrast, polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap), two commercial hydrate kinetic inhibitors that do not eliminate ME, were not so tightly adsorbed. Significantly, a mutant AFP (with no activity toward ice) inhibited THF hydrate growth, but not ME. QCM-D analysis showed that adsorption of the mutant AFP was more similar to PVCap than the active AFP. Thus, although there is no evidence for „memory‟ in ice reformation, and the structures of ice and clathrate hydrate are distinct, the crystallization of ice and hydrates, and the elimination of the more rapid recrystallization of hydrates, can be mediated by the same proteins.

Certain organisms, including some bugs (both insects and microbes) are able to survive low temperatures by the production of either ice nucleating proteins (INPs) or antifreeze proteins (AFPs). INPs direct crystal growth by inducing rapid ice formation whereas AFPs adsorb to ice embryos and decrease the temperature at which the ice grows. We have also shown that certain AFPs can inhibit the crystallization of clathrate hydrates and eliminate more rapid recrystallization or “memory effect”. Here we examine several bacterial species with iceassociating properties for their effect on tetrahydrofuran (THF) hydrate crystallization. The bacteria Chryseobacterium sp. C14, which shares the ice recrystallization inhibition ability of AFPs, increased induction time to THF hydrate crystallization in isothermal experiments. In an effort to understand the association between AFPs and THF hydrate we have produced bacterially-expressed AFPs as probes for hydrate binding. Although the structure of hydrates is clearly distinct from ice, the apparent potential for these products to perturb clathrate hydrate growth compels us to explore new techniques to uncover “green inhibitors” for hydrate binding.

Ice structuring proteins (ISPs) naturally exist in many foods consumed as part of the human diet including plants or fish. ISPs from winter wheat grass have gained interest in the pharmaceutical and food industries as a non-toxic, natural and cost-effective product, which is easy to prepare as a crude extract. However, they have not been purified reproducibly and studied in detail to elucidate their structures, mechanism of actions and difference(s). ISPs from the apoplast region of cold acclimated winter wheat leaves were extracted through vacuum infiltration and purified using heat and ethanol precipitations, size exclusion and anionic exchange fast protein liquid chromatography techniques. The ISPs showed both significant inhibition of ice growth and thermal hysteresis activities. The non-acclimated apoplastic extracts from winter wheat leaves contained similar proteins without any abovementioned activities. The ISPs contained disulfide bridges, similar to thaumatin-like proteins (TLPs) and partially similar to ISPs from winter rye leaves and carrot. ISPs remained active after thermal treatment (i.e., pasteurization conditions) and over a wide range of pH (3-12). There are very few quantitative assays to measure the activity of antifreeze proteins (AFPs, or Ice Structuring Proteins, ISPs), which often suffer from various inaccuracies and inconsistencies. Some methods rely only on unassisted visual assessment. When microscopy is used to measure ice crystal size, it is critical that standardized procedures be adopted, especially when image analysis software is used to quantify sizes. Differential Scanning Calorimetry (DSC) has been used to measure the thermal hysteresis activity (TH) of AFPs. In this study, DSC was used isothermally to measure enthalpic changes associated with structural rearrangements as a function of time. Differences in slopes of thermograms between winter wheat ISP or AFP type I containing samples, and those without ISP or AFP type I were demonstrated. ISP or AFP type I containing samples had much higher slopes compared to those without ISP or AFP type I. Samples with higher concentration of ISP or AFP type I showed higher slope values. The proteinaceous activity of ISPs or AFP type I was confirmed by demonstrating changes in samples with and without proteases. A proposed mechanism of this method is discussed.

Mémoire (M.Eng.)-- Université du Québec à Chicoutimi, 1993. / Document électronique également accessible en format PDF. CaQCU

Mémoire (M.Sc.A.)-- Université du Québec à Chicoutimi, 1993. / Document électronique également accessible en format PDF. CaQCU

This thesis develops composition of heat transfer fluids with antifreeze properties next to traditional one component glycols produced from propene and ethene. Based on assessment of physical properties it considers application of progressive antifreeze compounds of glycerine and propan-1,3-diole and their mixtures with classic glycols, which do not have negative influence on the environment and which are produced in last years from renewable sources. Due to the necessity of selection of certain compromise between their heat transfer properties, price, solubility and other factors physical properties of selected mixtures are determined together with synergy of each compound, including formulas with glycols: ethan 1,2 diol and propan 1,2 diol Another evaluated factor of studied formulations in addition to their heat transfer properties was anticorrosive protection of common corrosion inhibitors mixtures. The result of whole work is the proposal of several most perspective formulations based on mixtures of polyhydric alcohols in terms of their features enabling them heat transfer, reasonable costs, and the restrictions of impact of their use, particularly in heat transfer systems, to human health and the environment. The knowledge of physical properties of water solutions of polyhydric alcohols mixtures also helps to better using of recycled materials from planning recycling plant for glycols.

No / This paper reports on the growth of benzamide crystals in the presence of 2'-aminoacetophenone. The resulting self-replicating intergrowth of benzamide crystals gives rise to ordered crystal aggregates in which individuals share a common c*. This behavior is interpreted using the concept of a motif capper additive which is able to halt the extension of structural motifs at the surface of a growing crystal. In this case the additive was selected to terminate the hydrogen-bonding ribbons, which extend along the b axis of the benzamide structure.

Volvo Cars är ett välkänt företag som säljer bilar över hela världen. Idag skickar Volvo Cars sin kylvätska till leverantörer för analys. Processen är komplicerad och tar mycket tid. Det finns ett intresse hos Volvo Cars att själva kunna analysera kylvätskan. För att kunna göra detta krävs det att en metod som de kan använda för att analysera kylvätskan utvecklas. Examensarbetet syftar till att utveckla en metod som gör det möjligt att analysera koncentrationen av organiska syror i Volvos kylvätska. Analysen ska göras med hjälp av en High Performance Liquid Chromatography - HPLC. De organiska syrorna är inhibitorer som skyddar material i motorn från korrosion när det kommer i kontakt med kylvätskan. Metoden utvecklas i flera steg, det är viktigt att veta hur olika organiska syror kan analyseras med en HPLC. HPLC-analyser är mycket beroende av de intrumentella inställningarna. Inställningarna som ändrar när metoden utvecklas är pH, typ av kolonn, våglängd på detektorn, flödeshastighet i kolonnen, injektionsvolymen, sammansättning av eluent (lösningsmedel) och analystid. Kalibreringskurvor konstrueras för att sedan kunna användas i fortsatta studier. Tre av fem organiska syror som skulle analyseras var möjliga att analysera med två olika metoder. Den enda skillnaden mellan metoderna var våglängden på detektorn. En av de organiska syrorna hade en mer linjär kalibreringskurva vid en högre våglängd. / Volvo Cars is a well-known company and they are selling their cars all over the world. Today, Volvo Cars send their engine coolant to the supplier of engine coolant for analysis. This process is complicated and takes a lot of time. It is in the interest of Volvo Cars to be able to analyze the engine coolant themselves. In order to do that, a method where they can analyze the engine coolant must be developed. This exam work aim to develop a method where it is possible to analyze the concentration of organic acids in Volvo´s engine coolant with a High Performance Liquid Chromatography - HPLC. The organic acids are inhibitors that protect the materials in the engine from corrosion when in contact with the engine coolant. The method is developed in several steps. First it is important to know how different organic acids could be analyzed with an HPLC. HPLC-analysis is very dependent of the instrumental parameters. The parameters you change when developing a method are pH, kind of column, wavelength of the detector, kind of detector, flow rate in the column, injections volume, composition of the eluent (solvent) and, analysis time. Calibration curves are created and could be used as a reference in further analysis. Three of the five organic acids that were supposed to be analyzed were possible to analyze. Three organic acids were analyzed with one method and the two remaining organic acids with another method. The only difference between the methods is the wavelengths of the detector.

Funktionalisierte Poly(2-oxazoline) als neue Materialien stellen sowohl unter strukturellen Gesichtspunkten als auch im Hinblick auf potentielle Anwendungen eine interessante Polymerklasse dar. Die Ausbildung von hierarchischen Strukturen mit Poly(2-oxazolinen) über intermolekulare Wasserstoffbrückenbindungen ist hierbei ein bisher nicht beachteter Aspekt. Über einen bioinspirierten Ansatz sollten gezielt funktionelle Gruppen, die für einen hierarchischen Aufbau, z.B. in Proteinen, verantwortlich sind, in vereinfachter Weise auf die synthetische Substanzklasse der Poly(2-oxazoline) übertragen werden. Die vorliegende Arbeit beschäftigt sich mit der modularen Synthese neuer, funktionalisierter Poly(2-oxazolin) Homo- und Copolymere. Ausgehend von der Synthese von 2-(3-Butenyl)-2-oxazolin wurden definierte Präpolymere in einer kationischen Isomerisierungspolymerisation unter kontrolliert/„lebenden“ Bedingungen hergestellt. In einer anschließenden „Thio-Click“ (Thiol-En-Reaktion) Modifizierungsreaktion wurden die gewünschten funktionellen Gruppen quantitativ eingeführt. Hydroxylierte Poly(2-oxazoline) wurden hinsichtlich ihres Aggregationsverhaltens in Wasser untersucht. Bereits die jeweiligen Homopolymere bildeten aufgrund von intermolekularen Wasserstoffbrückenbindungen supramolekulare tubuläre Nanofasern aus. Durch Einsatz verschiedener analytischer Methoden konnte die innere Struktur der Nanoröhren beschrieben und ein entsprechendes Modell aufgestellt werden. Die dargestellten funktionellen Poly(2-oxazoline) wurden hinsichtlich ihrer Anwendung als potentielle, synthetische „antifreeze additives“ untersucht. Alle Polymere besitzen eine ausgeprägte Tendenz zur Nukleierung von Wasser und führen daher zu signifikanten Änderungen der Eismorphologie. Des weiteren wurde ein carboxyliertes Derivat zur biomimetischen Mineralisation von Kalziumcarbonat eingesetzt und nach phänomenologischen Gesichtspunkten untersucht. / Functionalized poly(2-oxazoline)s are a promising class of materials concerning their self-assembly behavior as well as for future applications. Hierarchical structure formation based on hydrogen bonding interactions has not been investigated yet. Applying a bioinspired approach, functional groups promoting hierarchical structure formation are introduced to poly(2-oxazoline)s. This work is focused on the modular synthesis of new functionalized poly(2-oxazoline) homo and copolymers. Starting from the synthesis of the new monomer 2-(3-butenyl)-2-oxazolin, well-defined precursor materials were prepared via cationic isomerization polymerization. Next, the polymers were quantitatively modified with the aimed functional groups using a “thio-click” (thiol-ene) reaction. The aggregation behaviour of hydroxylated poly(2-oxazolines) in water was investigated. Homo- as well as block copolymers can form supramolecular hollow nanofibers via intermolecular hydrogen bonding. Using a variety of different analytical methods, the structure of the nanotubes was determined and a formation model was proposed. Furthermore, the functionalized poly(2-oxazoline)s were investigated as synthetic mimics of natural anti-freeze additives. It was found, that these polymers show the tendency to nucleate water, thus influencing the morphology of ice. Finally, a carboxylated derivative was applied as an additive for the mineralization of calcium carbonate.

Mémoire (M.Eng.)--Université du Québec à Chicoutimi, 1996. / Document électronique également accessible en format PDF. CaQCU