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English prepositions take only a small proportion of the language but play a substantial role. Although prepositions are of course also frequently used in English textbooks for secondary school, students fail to incidentally acquire them and often show low achievements in using prepositions correctly. The strategy commonly employed by language instructors is teaching the multiple senses of prepositions by rote which fails to help the students to draw links between the different meanings in usage. New findings in Cognitive Linguistics (CL) suggest a different approach to teaching prepositions and thus might have a strong impact on the methodologies of foreign language teaching and learning on the aspects of meaningful learning. Based on the Theory of Domains (Langacker, 1987), the notions of image schemas (Johnson, 1987) as well as the Conceptual Metaphor Theory (Lakoff & Johnson, 1980), the present study developed a CL-inspired approach to teaching prepositions, which was compared to the traditional teaching method by an empirical study conducted in a German school setting. Referring to the participants from the higher track and the medium track, who are at different proficiency levels, the results indicate that the CL-inspired teaching approach improved students" performance significantly more than the traditional approach in all the cases for the higher track and in some cases for the medium track. Thus, these findings open up a new perspective of the CL-inspired meaningful learning approach on language teaching. In addition, the CL-inspired approach demonstrates the unification of the integrated model of text and picture comprehension (the ITPC model) in integrating the new knowledge with related prior knowledge in the cognitive structure. According to the learning procedure of the ITPC model, the image schema as visual image is first perceived through the sensory register, then is processed in the working memory by conceptual metaphor, and finally it is integrated with cognitive schemata in the long term memory. Moreover, deep-seated factors, such as transfer of mother tongue, the difficulty of teaching materials, and the influence of prior knowledge, have strong effects on the acquisition of English prepositions.
Früher wurden in Museen den Besuchern meist gesicherte Wissensbestände präsentiert. Heute ist das vielfach anders: Nicht nur fraglos geltendes Wissen, sondern auch der Prozess dorthin wird aufgezeigt. Die dargebotene Information ist teilweise nicht mehr konsistent und widerspruchsfrei sondern konfligierend. Wie aber reagieren die Besucher auf konfligierende Information? Wie unterstützen ihre persönlichen Vorrausetzungen eine differenziertere Betrachtung? Wie können Museen " obwohl ihre Information doch freiwillig, selbstbestimmt, ohne Zwang und Pression rezipiert wird - die Informationsverarbeitung ihrer Besucher durch eine bestimmte räumliche Informationsanordnung beeinflussen? Diese Fragen wurden mittels vier Feldstudien vor Ort untersucht:
Studie 1 charakterisiert Museumsbesucher durch Persönlichkeitsprofile, die aus den für die Verarbeitung konfligierender Information als relevant betrachteten Personenmerkmalen (epistemologischen Überzeugungen, Ambiguitätstoleranz, Selbstwirksamkeitsannahmen) erstellt sind.
Studie 2 untersucht den Einfluss dieser Personenmerkmale und des situationalen Interesses auf die Tendenz zur Konfliktverarbeitung, ohne Fähigkeiten und Fassungskraft des Besuchers zu berücksichtigen.
Studie 3 überprüft die Effekte von situationalem Interesse, epistemologischen Überzeugungen, Ambiguitätstoleranz und Selbstwirksamkeitsannahmen auf die Konfliktverarbeitungsleistung.
In Studie 4 wird schließlich die Wirkung räumlich naher Informationspräsentation untersucht.
Museumsbesucher können durch die Persönlichkeitsprofile "selbstzweifelnd skeptisch", "selbstbewusst vertrauensvoll" und "stabilitätsgläubig" charakterisiert werden. Eine überwältigende Mehrheit zeigt die Bereitschaft, Konflikte wahrzunehmen und ein großer Teil ist darüber hinaus bereit, konfligierende Informationen auf tieferer Ebene zu verarbeiten. Eine räumlich nahe (thematisch kontinuierliche) Präsentation unterstützt die Tendenz, tief zu verarbeiten. Etwa drei Viertel der Besucher konnten erkennen, wann konfligierende Information logisch widersprüchlich ist und konnten überzufällig gut bei konsistenter und konfligierender Information Kohärenz bilden. Positive Selbstwirksamkeitsannahmen unterstützen vermittelt über hohes situationales Interesse die Tendenz, Information tiefer zu verarbeiten und steigern die Fähigkeit, Kohärenz zu bilden. Reifere epistemologische Überzeugungen der Dimension "Sicherheit" und "Veränderlichkeit" fördern Kohärenzbildung.
The amount of information on the Web is constantly increasing and also there is a wide variety of information available such as news, encyclopedia articles, statistics, survey data, stock information, events, bibliographies etc. The information is characterized by heterogeneity in aspects such as information type, modality, structure, granularity, quality and by its distributed nature. The two primary techniques by which users on the Web are looking for information are (1) using Web search engines and (2) browsing the links between information. The dominant mode of information presentation is mainly static in the form of text, images and graphics. Interactive visualizations offer a number of advantages for the presentation and exploration of heterogeneous information on the Web: (1) They provide different representations for different, very large and complex types of information and (2) large amounts of data can be explored interactively using their attributes and thus can support and expand the cognition process of the user. So far, interactive visualizations are still not an integral part in the search process of the Web. The technical standards and interaction paradigms to make interactive visualization usable by the mass are introduced only slowly through standardatization organizations. This work examines how interactive visualizations can be used for the linking and search process of heterogeneous information on the Web. Based on principles in the areas of information retrieval (IR), information visualization and information processing, a model is created, which extends the existing structural models of information visualization with two new processes: (1) linking of information in visualizations and (2) searching, browsing and filtering based on glyphs. The Vizgr toolkit implements the developed model in a web application. In four different application scenarios, aspects of the model will be instantiated and are evaluated in user tests or examined by examples.
Structure of soil organic matter (SOM) is a hot topic of discussion among scientific community for several decades. The mostly discussed models, among many, are polymer model and supramolecular model. While the former considers SOM as macromolecules consisting of amorphous and crystalline domains, the latter explains SOM as a physicochemical entity dominated by weak hydrophobic and H-bond interactions in the secondary level, which holds individual molecules of primary structure together. The weak forces in secondary level impart characteristic mobility of SOM. Very important consequence of this multidimensional formulation is that physicochemical structure plays a crucial role in most biogeochemical functions of SOM, apart from the chemical composition. Recently introduced concept of cation and water molecule mediated bridges between OM molecular segments (CaB and WaMB, respectively) evolved from physicochemical understanding of SOM structure. Even though several indirect evidences were produced for CaB and WaMB during last years, no clear-cut understanding of these processes has been achieved yet. Experimental difficulty due to overlapping effects of equally important CaB-governing parameters such a pH and competing cations raises huge challenge in investigating CaB-related influences. This thesis, therefore, aims to validate an experimental set-up for inducing CaB within OM structures and assessing it from various chemical and physicochemical aspects.
The method involved removal of omnipresent cations and adjustment of pH before cation addition. This helped to separate pH effects and cation effects. Based on results obtained on two different types of organic matter, it can be deduced that multivalent cations can cross-link SOM, given that functional group density of the SOM material is enough for the functional groups to be arranged in sufficient spatial proximity to each other. Physicochemical structural reorganisation during aging causes formation of more and/or stronger CaB and WaMB. As for inducing CaB directly after cation treatment, cationic size and valency were found determinant also for aging effect. A strongly cross-linked system in the beginning is less vulnerable to structural changes and undergoes aging with lower intensity, than an initially weakly cross-linked system. Responsible for the structural changes is, the inherent mobility of SOM within its physicochemical assemblage. Thus the information on structural requirement of CaB and its consequences on OM matrix rigidity will help to obtain insight into the physicochemical SOM structure. Additionally, organic matter quality (assessed by thermal analysis) and pore structure of SOM formed in a set of artificial soils showed that mineral materials are important for the chemical nature of SOM molecules, but not for the physical structure of organo-mineral associations, at least after several months of SOM development.
Furthermore, nanothermal analysis using atomic force microscopy (AFM-nTA) was implemented in soils for the first time to reveal nanoscale thermal properties and their spatial distribution in nano- and micrometer scales. This helped to identify physicochemical processes, such as disruption of WaMB, in low-organic soils, in which bulk methods fail due to their low sensitivity. Further, various types of materials constituting in soils were distinguished with high resolution by advanced application of the method, in combination with other AFM parameters. Attempts were done to identify various materials, with the usage of defined test materials. Above all, the method is potent to reveal microspatial heterogeneity on sample surfaces, which could help understanding process-relevant hotspots, for example.
This thesis thus contributes to the scientific understanding on physicochemical structural dynamics via cross-linking by cations and via nanoscale thermal properties. Direct investigation on CaB demonstrated here will potentially help making a big leap in knowledge about the interaction. The observed aging effects add well to the understanding of supramolecular consideration of SOM. By introducing nanothermal analysis to the field of soil science, it is made possible to face the problem of heterogeneity and spatial distribution of thermal characteristics. Another important achievement of AFM-nTA is that it can be used to detect physicochemical processes, which are of low intensity.
Studies on the toxicity of chemical mixtures find that components at levels below no-observed-effect concentrations (NOECs) may cause toxicity resulting from the combined effects of mixed chemicals. However, chemical risk assessment frequently focuses on individual chemical substances, although most living organisms are substantially exposed to chemical mixtures rather than single substances. The concepts of additive toxicity, concentration addition (CA), and independent action (IA) models are often applied to predict the mixture toxicity of similarly and dissimilarly acting chemicals, respectively. However, living organisms and the environment may be exposed to both types of chemicals at the same time and location. In addition, experimental acquisition of toxicity data for every conceivable mixture is unfeasible since the number of chemical combinations is extremely large. Therefore, an integrated model to predict mixture toxicity on the basis of single mixture components having various modes of toxic action (MoAs) needs to be developed. The objectives of the present study were to analyze the challenges in predicting mixture toxicity in the environment, and to develop integrated models that overcome the limitations of the existing prediction models for estimating the toxicity of non-interactive mixtures through computational models. For these goals, four sub-topics were generated in this study. Firstly, applicable domains and limitations of existing integrated models were analyzed and grouped into three kinds of categories in this study. There are current approaches used to assess mixture toxicity; however, there is a need for a new research concept to overcome challenges associated with such approaches, which recent studies have addressed. These approaches are discussed with particular emphasis on those studies involved in computational approaches to predict the toxicity of chemical mixtures based on the toxicological data of individual chemicals. Secondly, through a case study and a computational simulation, it was found that the Key Critical Component (KCC) and Composite Reciprocal (CR) methods (as described in the European Union (EU) draft technical guidance notes for calculating the Predicted No Effect Concentration (PNEC) and Derived No Effect Level (DNEL) of mixtures) could derive significantly different results. As the third and fourth sub-topics of this study, the following two integrated addition models were developed and successfully applied to overcome the inherent limitations of the CA and IA models, which could be theoretically used for either similarly or dissimilarly acting chemicals: i) a Partial Least Squares-Based Integrated Addition Model (PLS-IAM), and, ii) a Quantitative Structure-Activity Relationship-Based Two-Stage Prediction (QSAR-TSP) model. In this study, it was shown that the PLS-IAM might be useful to estimate mixture toxicity when the toxicity data of similar mixtures having the same compositions were available. In the case of the QSAR-TSP model, it showed the potential to overcome the critical limitation of the conventional TSP model, which requires knowledge of the MoAs for all chemicals. Therefore, this study presented good potential for the advanced integrated models (e.g., PLS-IAM and QSAR-TSP), while considering various non-interactive constituents that have different MoAs in order to increase the reliance of conventional models and simplify the procedure for risk assessment of mixtures.
Chemical plant protection is an essential element in integrated pest management and hence, in current crop production. The use of Plant Protection Products (PPPs) potentially involves ecological risk. This risk has to be characterised, assessed and managed.
For the coming years, an increasing need for agricultural products is expected. At the same time, preserving our natural resources and biodiversity per se is of equally fundamental importance. The relationship of our economic success and cultural progress to protecting the environment has been made plain in the Ecosystem Service concept. These distinct 'services' provide the foundation for defining ecological protection goals (Specific Protection Goals, SPGs) which can serve in the development of methods for ecological risk characterisation, assessment and management.
Ecological risk management (RM) of PPPs is a comprehensive process that includes different aspects and levels. RM is an implicit part of tiered risk assessment (RA) schemes and scenarios, yet RM also explicitly occurs as risk mitigation measures. At higher decision levels, RM takes further risks, besides ecological risk, into account (e.g., economic). Therefore, ecological risk characterisation can include RM (mitigation measures) and can be part of higher level RM decision-making in a broader Ecosystem Service context.
The aim of this thesis is to contribute to improved quantification of ecological risk as a basis for RA and RM. The initial general objective had been entitled as "… to estimate the spatial and temporal extent of exposure and effects…" and was found to be closely related to forthcoming SPGs with their defined 'Risk Dimension'.
An initial exploration of the regulatory framework of ecological RA and RM of PPPs and their use, carried out in the present thesis, emphasised the value of risk characterisation at landscape-scale. The landscape-scale provides the necessary and sufficient context, including abiotic and biotic processes, their interaction at different scales, as well as human activities. In particular, spatially (and temporally) explicit landscape-scale risk characterisation and RA can provide a direct basis for PPP-specific or generic RM. From the general need for tiered landscape-scale context in risk characterisation, specific requirements relevant to a landscape-scale model were developed in the present thesis, guided by the key objective of improved ecological risk quantification. In principle, for an adverse effect (Impact) to happen requires a sensitive species and life stage to co-occur with a significant exposure extent in space and time. Therefore, the quantification of the Probability of an Impact occurring is the basic requirement of the model. In a landscape-scale context, this means assessing the spatiotemporal distribution of species sensitivity and their potential exposure to the chemical.
The core functionality of the model should reflect the main problem structures in ecological risk characterisation, RA and RM, with particular relationship to SPGs, while being adaptable to specific RA problems. This resulted in the development of a modelling framework (Xplicit-Framework), realised in the present thesis. The Xplicit-Framework provides the core functionality for spatiotemporally explicit and probabilistic risk characterisation, together with interfaces to external models and services which are linked to the framework using specific adaptors (Associated-Models, e.g., exposure, eFate and effect models, or geodata services). From the Xplicit-Framework, and using Associated-Models, specific models are derived, adapted to RA problems (Xplicit-Models).
Xplicit-Models are capable of propagating variability (and uncertainty) of real-world agricultural and environmental conditions to exposure and effects using Monte Carlo methods and, hence, to introduce landscape-scale context to risk characterisation. Scale-dependencies play a key role in landscape-scale processes and were taken into account, e.g., in defining and sampling Probability Density Functions (PDFs). Likewise, evaluation of model outcome for risk characterisation is done at ecologically meaningful scales.
Xplicit-Models can be designed to explicitly address risk dimensions of SPGs. Their definition depends on the RA problem and tier. Thus, the Xplicit approach allows for stepwise introduction of landscape-scale context (factors and processes), e.g., starting at the definitions of current standard RA (lower-tier) levels by centring on a specific PPP use, while introducing real-world landscape factors driving risk. With its generic and modular design, the Xplicit-Framework can also be employed by taking an ecological entity-centric perspective. As the predictive power of landscape-scale risk characterisation increases, it is possible that Xplicit-Models become part of an explicit Ecosystem Services-oriented RM (e.g., cost/benefit level).
Die Wirbelsäule als tragende Säule des menschlichen Körpers ist bei vielen Bewegungsabläufen hohen Belastungen ausgesetzt. Fehl- und Überbelastungen rufen dabei oft dauerhafte Schädigungen hervor. Daher ist es von Interesse, die innerhalb der Wirbelsäule auftretenden Belastungen zu bestimmen. Eine moderne und zuverlässige Methode zur Belastungsbestimmung ist der Aufbau eines Berechnungsmodells.
In der vorliegenden Arbeit wurde ein Mehr-Körper-System (MKS) Modell der Lendenwirbelsäule erstellt. Mit Hilfe des Modells können sowohl die übertragenen Kräfte und Momente in allen inneren Strukturen berechnet als auch die Kinematik des Bewegungsablaufs simuliert werden. Die Grundstruktur des Modells bilden die als Starrkörper angenommenen knöchernen Strukturen der fünf Lendenwirbel L1 bis L5, des Os Sacrums und des Os iliums, die über die Segmentierung eines CT-Datensatzes des Abgusses der Wirbeloberflächen eines durchschnittlich großen Europäers gewonnen wurden. Die elastischen Elemente der Wirbelsäule wurden unter Berücksichtigung ihrer physikalischen Eigenschaften in das Modell implementiert. Grundlage für die Modellierung der Zwischenwirbelscheiben waren dabei eigens durchgeführte experimentelle Messungen. Das charakteristische Kraft-Deformations-Verhalten der Ligamente wurde der Literatur entnommen.
Die Umsetzung im Computermodell berücksichtigt neben dem physikalischen Verhalten eines einzelnen Ligamentes zusätzlich durch einen Gewichtungsfaktor das Zusammenspiel aller Ligamente im komplex aufgebauten Ligamentapparat. Die Facettengelenke wurden durch Kontaktmodellierung in den Knorpelschichten realisiert. Daneben wurde ein Modell eines Implantatsystems entwickelt, das zur dynamischen Stabilisierung der Lendenwirbelsäule genutzt wird. Die Validierung der erstellten Modelle erfolgte über den Vergleich mit In-Vitro erhobenen Daten. Betrachtet wurden neben der intakten Wirbelsäule zudem degenerative Schädigungen der Zwischenwirbelscheibe und deren operative Versorgung durch Nukleotomie und dynamische Stabilisierung. Die Ergebnisse der Simulationen zeigen dabei eine sehr gute Näherung an die experimentell ermittelten Messwerte. Durch Anwendung der Computermodelle konnten die Auswirkungen verschiedener operativer Eingriffe, wie Interlaminotomie, Hemilaminektomie und Laminektomie auf die unterschiedlichen Strukturen der Lendenwirbelsäule berechnet werden. Ein weiteres Anwendungsgebiet lag in der Untersuchung des momentanen Drehzentrums. Neben der Bestimmung der Drehpunktbahn bei intakter Wirbelsäule konnten die Effekte einer degenerativ geschädigten und operativ versorgten Zwischenwirbelscheibe auf den Verlauf des momentanen Drehzentrums berechnet und simuliert werden.
Die vorliegende Arbeit wurde verfasst, um Einflüsse und Zusammenhänge von Mitarbeiterzufriedenheit auf Burnout zu erforschen. Zudem wurde der Frage nachgegangen, inwieweit organisationsbedingte Variablen beim Zusammenhang von Mitarbeiterzufriedenheit und Burnout bei Flugbegleitern eine Rolle spielen. Hierfür wurde die Airline-Branche, genau genommen das Kabinenpersonal als Repräsentant, verwendet und eine umfangreiche Arbeitsplatzanalyse durchgeführt.
Zur Erfassung der vielfältigen Dimensionen der Mitarbeiterzufriedenheit diente der Fragebogen zur Erfassung der Mitarbeiterzufriedenheit (FEMAZU), sowie für die Facetten von Burnout die Burnout-Screening-Skalen (BOSS) "Beruf" und "körperliche Beschwerden". Die organisationsbedingten Variablen wurden im Zuge einer Gruppendiskussion erhoben und zu entsprechenden Statements ausformuliert, um für den Fragebogen verwendet werden zu können. Dieser wurde im nach der Erstellung durch einen Pretest praktisch validiert. Die Online-Erhebung erfolgte anhand 420 Flugbegleitern im deutschsprachigen Raum.rnZu der quantitativen Erhebung wurde eine qualitative Methode angewandt, um detaillierter Informationen bezüglich der Komplexität in Entstehung und Verlauf der Krankheitsgeschichte von Burnout zu bekommen und Hinweise für die Einwirkung organisationsbedingter Variablen zu erhalten.
Entsprechend der repräsentativen Stichprobe in der vorliegenden Arbeit konnte ein starker Zusammenhang von Mitarbeiterzufriedenheit auf die verschiedenen Facetten von Burnout erwiesen sowie überwiegend signifikante Ergebnisse verzeichnet werden. Als wesentliche Einflussvariablen konnten individuelle Ziele, Arbeitsbedingungen, Aufgabenfeld, Empowerment, Commitment, Emotionsregulation und Work-Life-Balance identifiziert werden. Bedingt durch die ohnehin sehr speziellen Arbeitsbedingungen im Berufsleben der Flugbegleiter sollten die Airlines bei ihren Mitarbeitern auf eine ausgeglichene Work-Life-Balance achten. Die Ergebnisse zeigten hierfür deutliche Zusammenhänge mit Mitarbeiterzufriedenheit und Burnout. Um entsprechende ausfallsbedingten Kosten vorzubeugen, wurde in der vorliegenden Arbeit eine Handlungsempfehlung gegeben. Durch die hohe Flexibilitätsanforderung in der Tätigkeit des Kabinenpersonals sowie den zahlreichen physiologischen Einflüssen wie beispielsweise Lärm, Jetlag, Schichtdienst oder Zeitverschiebungen ist es für Unternehmen, die auf langfristige Mitarbeiter setzen besonders wichtig, an dieser Stelle häufigen und langen krankheitsbedingten Fehlzeiten vorzubeugen. Eine höhere Planstabilität, ein größerer Einfluss auf die Plangestaltung und ausreichend Ruhezeit würde beispielsweise der Vereinbarkeit von Beruf und Privat entgegen kommen.
Andere in der Literatur als bedeutend eruierten Variablen, wie bspw. die Arbeitsplatzsicherheit und der Zivilstand, zeigten keine oder nur eine sehr geringe Signifikanz. Abschließend wurden Faktoren, welche einen Einfluss auf das Ergebnis haben könnten, ausführlich erläutert und diskutiert sowie eine Empfehlung für die Praxis und zukünftige wissenschaftliche Untersuchungen abgeleitet. Insbesondere der Forschungsausblick zeigt, dass der Zusammenhang der Dimensionen Mitarbeiterzufriedenheit und Burnout, welche anhand der Stichprobe der Flugbegleiter in dieser Arbeit erhoben wurde, noch umfassende Erforschungen erfordert, um hier vor allem für die Wirtschaft Verbesserungen und entsprechende Kostenreduktion bewirken zu können. Sowohl für die Wirtschaft als auch die Wissenschaft wäre eine engere Zusammenarbeit wünschenswert und gewinnbringend.
Galerucinae, Latreille 1802 is the second largest subgroup of chrysomelidae. 1837 Chervrolat described the taxon Ootheca, which has originally only one listed species. Nearly 200 years all galerucinae with a "compact" bodyshape, a broad pronotum, a convex dorsum , short antennae and short legs were assigned to Ootheca. When I started a revision of Ootheca, this taxon included 38 species. Comparing morphological characters of the exoskeleton combined with the depiction/description of characteristic structures of the male genitalia allowed a detailed description of the genus Ootheca and its species. After the revision 9 valid species remained in Ootheca, 4 are described to be new, 13 species were transferred to other valid described genera and 10 species remained, because of a lack of unambiguous assignment. The examination of the median lobe additionally enables me to describe three sister taxa: Oothecoides (6 species), Ootibia (5 species ) und Oosagitta (6 species).
The polysaccharide hydration phenomenon is nowadays the subject of intense research. The interaction of native and modified polysaccharides and polysaccharides-based bioconjugates with water has an important influence on their functional behaviour. Notwithstanding that the hydration phenomenon has been studied for decades, there is still a lack of awareness about the influence of hydration water on the polysaccharide´s structure and consequences for industrial or medicinal applications. The hydration of polysaccharides is often described by the existence of water layers differing in their physical properties depending on the distance from the polysaccharide. Using the differential scanning calorimetry (DSC) such water layers were categorized according their properties upon cooling in hyaluronan (HYA, sodium salt of ß-1,4-linked units of ß-1,3-linked D-glucuronic acid and N-acetyl-D-glucosamine), a model polysaccharide in the present work. The amount of non-freezing water, i.e. water in close proximity of HYA chain which does not freeze et all, was determined around 0.74gH2O/gHYA for HYA with molecular weight from 100 to 740kDa and 0.84gH2O/gHYA for molecular weight of 1390kDa. The amount of freezing-bound water, the water pool which is affected by presence of HYA but freezes, was determined in the range from 0.74 to 2gH2O/gHYA. Above this value only non-freezing and bulk water are present since melting enthalpy measured above this concentration reached the same value as for pure water. Since this approach suffers from several experimental problems, a new approach, based on the evaporation enthalpy determination, was suggested. The analysis of the evaporation enthalpies revealed an additional process associated with apparent energy release taking part below the water content of 0.34gH2O/gHYA. Existence of this phenomenon was observed also for protonated form of HYA. The existence of energy compensating process was confirmed with the Kissinger-Akahira-Sunose method which allowed determination of actual water evaporation/desorption enthalpies in all stages of the evaporation process. In fact, the apparent evaporation enthalpy value increased until water content of 0.34gH2O/gHYA, and then dropped down to lower values which were, still higher than the value of the pure water evaporation enthalpy. By the use of time domain nuclear magnetic resonance (TD-NMR) technique it was revealed that this phenomenon is the plasticisation of HYA.
Further, it was revealed that the non-freezing water determined by the use of DSC consists of two water fractions, i.e. 15% of water structurally integrated, interacting directly with polar sites, and 85% of water structurally restricted, embedded in-between the HYA chains. The occurrence of plasticisation concentration close to equilibrium moisture content provided the possibility to influence the HYA physical structure during the drying. In this way three samples of native HYA, dried under various conditions were prepared and their physical properties were analyzed. The samples differed in kinetics of rehydration, plasticisation concentration, glass transitions, and morphology. The properties of water pool were studied in solutions of 10"25mg HYA/mL as well. The fast filed cycling (FFC) NMR relaxometry showed the existence of three water fractions which correlation times spanned from 10"6 to 10"10 seconds, progressively decreasing in dependency on its distance from HYA chain. The formation of a weak and transient intramolecular water bridge between HYA chains was observed. It was shown that, unlike the inorganic electrolytes, polyelectrolytes hydration is a dynamic process which reflects not only the technique used for the analysis, experimental conditions but also the conformation of the polysaccharide and its "thermal" and "hydration" history.
It was demonstrated that some native polysaccharide structures can be easily modified by manipulation of preparation conditions, giving fractions with specific physicochemical properties without necessity of any chemical modification.