In dieser Arbeit wird ein chemisches Abgussverfahren für selbstorganisierte Strukturen in Lösung verwendet, das es ermöglicht definierte poröse Materialien mit Strukturierung auf der Nanometerskala herzustellen. Ähnlich wie beim Gussverfahren von Werkstücken wird die Vorlage durch ein geeignetes Material abgebildet. Durch Entfernen dieser Vorlage erhält man ein poröses (mit Hohlräumen durchsetztes) Negativ derselben. Die auf diese Weise erhaltenen Materialien sind in mehrerer Hinsicht interessant:<br> So lassen sich aus ihrer Morphologie Rückschlüsse über die Natur der selbstorganisierten Strukturen erhalten, da der hier verwendete Abbildungsprozess selbst kleinste strukturelle Details erfasst. Die Hohlräume der synthetisierten porösen Stoffe hingegen können als winzige Reaktionsgefäße, sogenannte &quot;Nano-Reaktoren&quot; verwendet werden. Dies ermöglicht sowohl die Synthese von Nano-Partikeln, die auf anderem Wege nicht zugänglich sind, als auch die Möglichkeit Einflüsse der räumlichen Restriktion auf die Reaktion zu untersuchen. Besonders räumlich ausgedehnte Strukturen sollten hierbei Auffälligkeiten zeigen.<br> Somit ist die Gliederung der Arbeit vorgegeben:<br> - Die Herstellung und Charakterisierung von porösen Stoffen und selbstorganisierten Strukturen<br> - Ihre Verwendung als &quot;Nano-Reaktor&quot; / This work employs a chemical casting technique, which allows the synthesis of mesoporous materials with definite morphology and pore-size distribution. The structure is thereby determined by a self-assembled template on a nanometer length scale. By removing the template, the final mesoporous materials are formed. The materials are interesting from several points of view: <br> First, one can learn about the nature of self-organized structures by casting, since the process is known to map even the smallest details. Second, the porous materials can be used as &quot;nano-reactors&quot;, both for the synthesis of nano-particles, which are not otherwise accessible, and for the investigation of the reaction itself, since reactions in very small volumes often show differences when compared with their bulk counterparts. For the synthesis of geometrically extended structures this confinement could be especially interesting.<br> The work therefore divides into two parts:<br> - The synthesis and characterisation of porous matter and self-organized structures<br> - Their usage as &quot;nano-reactors&quot;

Nanostructured inorganic materials are routinely synthesized by the use of templates. Depending on the synthesis conditions of the product material, either “soft” or “hard” templates can be applied. For sol-gel processes, usually “soft” templating techniques are employed, while “hard” templates are used for high temperature synthesis pathways. In classical templating approaches, the template has the unique role of structure directing agent, in the sense that it is not participating to the chemical formation of the resulting material. This work investigates a new templating pathway to nanostructured materials, where the template is also a reagent in the formation of the final material. This concept is described as “reactive templating” and opens a synthetic path toward materials which cannot be synthesised on a nanometre scale by classical templating approaches. Metal nitrides are such kind of materials. They are usually produced by the conversion of metals or metal oxides in ammonia flow at high temperature (T > 1000°C), which make the application of classical templating techniques difficult. Graphitic carbon nitride, g-C3N4, despite its fundamental and theoretical importance, is probably one of the most promising materials to complement carbon in material science and many efforts are put in the synthesis of this material. A simple polyaddition/elimination reaction path at high temperature (T = 550°C) allows the polymerisation of cyanamide toward graphitic carbon nitride solids. By hard templating, using nanostructured silica or aluminium oxide as nanotemplates, a variety of nanostructured graphitic carbon nitrides such as nanorods, nanotubes, meso- and macroporous powders could be obtained by nanocasting or nanocoating. Due to the special semi-conducting properties of the graphitic carbon nitride matrix, the nanostructured graphitic carbon nitrides show unexpected catalytic activity for the activation of benzene in Friedel-Crafts type reactions, making this material an interesting metal free catalyst. Furthermore, due to the chemical composition of g-C3N4 and the fact that it is totally decomposed at temperatures between 600°C and 800°C even under inert atmosphere, g-C3N4 was shown to be a good nitrogen donor for the synthesis of early transition metal nitrides at high temperatures. Thus using the nanostructured carbon nitrides as “reactive templates” or “nanoreactors”, various metal nitride nanostructures, such as nanoparticles and porous frameworks could be obtained at high temperature. In this approach the carbon nitride nanostructure played both the role of the nitrogen source and of the exotemplate, imprinting its size and shape to the resulting metal nitride nanostructure. / Die Nanostrukturierung anorganischer Materialien, d.h. die Kontrolle ihrer Form und Größe auf der Nanometerebene durch unterschiedliche Herstellungsverfahren, ist ein sich immer noch erweiterndes Forschungsgebiet. Eine solche Nanostrukturierung wird oft über sogenannte Templatierungsverfahren erreicht: Hier werden Formgeber (Template) mit definierter Morphologie und Größe verwendet und deren Struktur in ein neues Material abgebildet. Templatierungsverfahren können, je nach der Beschaffenheit des Templats, zwischen „weich“ und „hart“ unterschieden werden. Die Begriffe beziehen sich dabei vor allem auf die mechanische und thermische Stabilität der Template, d.h. weiche Template sind vornehmlich organischer, harte Template anorganischer Natur. Wo weiche Template in milden chemischen Verfahren eingesetzt werden, werden harte Template zur Herstellung von Materialien bei Hochtemperaturverfahren verwendet (z. B. poröse Kohlenstoffe). Allgemein dienen Template ausschließlich als Strukturgeber und gehen in keiner Weise in Form einer chemischen Reaktion in die Synthese des gewünschten Materials mit ein. Gegenstand dieser Arbeit ist ein neues Templatierungsverfahren: Die „reaktive Templatierung“. Hierbei wird das Templat - neben seiner Funktion als Strukturgeber – auch als Reagenz für die Synthese des Produktes verwendet. Dieser Synthese-Ansatz öffnet damit neue Wege für die Synthese von nanostrukturierten Materialien, die durch klassische Templatierungsansätze schwer zugänglich sind. Hierzu zählen zum Beispiel die Metallnitride. Üblicherweise werden Metallnitride über die Umsetzung von Metallen oder Metalloxiden in einem Ammoniakstrom bei Mindesttemperaturen von 1000°C gewonnen, was die Anwendung klassischer Templatierungsverfahren beinahe unmöglich macht. Darüber hinaus sind konzentrierte Lauge oder Flusssäure, welche zur Entfernung klassischer harter Template benötigt werden auch Aufschlussmittel für Metallnitride. Graphitisches Kohlenstoffnitrid, g-C3N4, ist wohl eines der meistversprechendsten Materialien um Kohlenstoff in der Materialwissenschaft zu ergänzen. Es wurden bereits viele potentielle Syntheseansätze beschrieben. Eine durch Groenewolt M. erstellte Route ist die thermisch induzierte Polykondensation von Cyanamid (NCNH2) bei 550°C. Da g-C3N4 sich zwischen 600°C und 800°C vollständig in NH3 und CxNyH-Gase zersetzt, ist es eine geeignete Festkörper-Stickstoffquelle für die Herstellung von Metalnitriden. Daher boten sich nanostrukturierte graphitische Kohlenstoffnitride als geeignete reaktive Template oder Nanoreaktoren zur Herstellung von nano-strukturierten Metalnitriden an. Die Templatierung der g-C3N4-Matrix wurde über klassische Harttemplatierungsverfahren erreicht. So konnte eine Vielzahl nano-strukturierter g-C3N4 Materialien synthetisiert werden wie zum Beispiel Nanostäbchen, Nanoröhren, mesoporöse oder makroporöse graphitische Kohlenstoffnitride. Diese haben sich interessanterweise, als metalfreie Katalysatoren für die Aktivierung von Benzol in Friedel-Crafts-Acylierung und -Alkylierung erwiesen. Durch die Infiltrierung der nano-strukturierten g-C3N4-Materialien mit diversen Metal-Präkursoren und nachfolgendem Tempern bei 800°C unter Schutzgas, konnten entsprechende nano-strukturierte Metalnitride, als Nanoabdrücke der vorgegebenen Kohlenstoffnitrid Nanostrukturen hergestellt werden. So konnten TiN, VN, GaN, AlGaN und TiVN Nanopartikel synthetisiert werden, macroporöse TiN/Kohlenstoff Komposite sowie TiN Hohlkugeln. Die so hergestellten Materialien erwiesen sich als effektive basische Katalysatoren für Aldol-Kondensations Reaktionen.

Studies show that dynamical properties of ultra-thin polymer films deviate from those of bulk materials. Despite some controversial issues, there is growing evidence indicating that the interfacial properties play a key role for observed dynamical anomalies. However, how and how much the interfacial properties affect the average dynamics of the nanometer scale systems are still elusive. In this work, we developed several novel techniques to investigate near-free-surface dynamics of thin polymer films. We studied surface dynamics of glassy i-PMMA films using a nano surface hole relaxation technique: a strong substrate property dependence and an unexpected molecular weight dependence were observed; we found that a local Tg of ~40K below bulk Tg could be assigned to the surface region. We used nano gold particle embedding to study PS surface dynamics: enhanced surface dynamics and weak temperature dependence were observed for the surface region; a depth profile with the nm resolution was observed; viscous liquid-like and soft solid-like properties were observed in the first 5.5nm and next 3.3 nm regions in PS films; no molecualr weight dependence was found in glassy PS films. We built a low level noise measurement system to study the thermal polarization noise in PVAc films: cooperative rearranging dynamics were evidenced; the noise power spectral density (PSD) is found to fluctuate around a certain average level without discernable peak shift; we observed some relatively big jumps or fluctuations in successive integrated PSD’s, which indicate some energy exchange between different microscopic domains in glassy polymer systems. We developed a novel nano rheology AFM technique to study the near-free-surface dynamics of thin polymer films: enhanced near-free-surface dynamics with weak temperature dependence are observed for PVAc films, which is similar with the PS case.

Studies show that dynamical properties of ultra-thin polymer films deviate from those of bulk materials. Despite some controversial issues, there is growing evidence indicating that the interfacial properties play a key role for observed dynamical anomalies. However, how and how much the interfacial properties affect the average dynamics of the nanometer scale systems are still elusive. In this work, we developed several novel techniques to investigate near-free-surface dynamics of thin polymer films. We studied surface dynamics of glassy i-PMMA films using a nano surface hole relaxation technique: a strong substrate property dependence and an unexpected molecular weight dependence were observed; we found that a local Tg of ~40K below bulk Tg could be assigned to the surface region. We used nano gold particle embedding to study PS surface dynamics: enhanced surface dynamics and weak temperature dependence were observed for the surface region; a depth profile with the nm resolution was observed; viscous liquid-like and soft solid-like properties were observed in the first 5.5nm and next 3.3 nm regions in PS films; no molecualr weight dependence was found in glassy PS films. We built a low level noise measurement system to study the thermal polarization noise in PVAc films: cooperative rearranging dynamics were evidenced; the noise power spectral density (PSD) is found to fluctuate around a certain average level without discernable peak shift; we observed some relatively big jumps or fluctuations in successive integrated PSD’s, which indicate some energy exchange between different microscopic domains in glassy polymer systems. We developed a novel nano rheology AFM technique to study the near-free-surface dynamics of thin polymer films: enhanced near-free-surface dynamics with weak temperature dependence are observed for PVAc films, which is similar with the PS case.

Magnetic nanoscale devices have shown great promise in both research and industry. Magnetic nanostructures have potential for non-volatile data storage applications, reconfigurable logic devices, biomedical devices and many more. The S-state magnetic element is one of the promising structures for non-volatile data storage applications and reconfigurable logic devices. It is a single-layer logic element that can be integrated in magnetoresistive structures. We present a detailed micromagnetic analysis of the geometrical parameter space in which the logic operation is carried out. The influence of imperfections, such as sidewall roughness and roundness of the edge is investigated. Magnetic nanowires are highly attractive materials that has potential for applications in ultrahigh magnetic recording, logic operation devices, and micromagnetic and spintronic sensors. To utilize applications, manipulation and assembly of nanowires into ordered structures is needed. Magnetic self-alignment is a facile technique for assembling nanowires into hierarchical structures. In my thesis, I focus on synthesizing and assembling nickel nanowires. The magnetic behaviour of a single nickel nanowire with 200~nm diameter is investigated in micromagnetic simulations. Nickel nanowires with Au caps at the ends were synthesized by electrochemical deposition into nanopores in alumina templates. One-dimensional alignment, which forms chains and two-dimensional alignment, which forms T-junctions as well as cross-junctions are demonstrated. Attempts to achieve three-dimensional alignment were not successful yet. I will discuss strategies to improve the alignment process.

In order to obtain sustainable engineering systems, this research investigates surface and interface properties of metals and active nanostructured coatings. The goal is to develop new approaches in order to improve the corrosion resistance and obtain knowledge in reconstruction of worn and/or corroded surfaces. The research will focus on high carbon steels as the substrate. These materials are used in most of industries and vehicles like aircrafts and automobiles. For anti-corrosion and self-healing applications, the layer-by-layered (LBL) coatings consisting photo-catalytic materials, the corrosion inhibitor, and the polyelectrolyte will be studied. Potential dynamic tests will be carried out in order to characterize the corrosion potential and current. For wear study, we will develop a metallic composite that has several functions, such as corrosion and wear protection, refresh or reverse worn or corroded surface. Characterization techniques used include optical microscope, surface interferometer, tribometer and the hardness tester. The ultimate goal of this research is to understand several types of problems on metal surface, such as corrosion and wear, and explore the possible ways to reduce those by using active nano-structured composite coating on metal surface.

Magistrantūros studijų baigiamajame darbe pateikiami cukrinių runkelių augimo intensyvumo, lapų ploto formavimosi, sausų medžiagų kaupimosi, fotosintetinių parametrų, derlingumo bei cukringumo tyrimo duomenys ir kokią įtaką turėjo bioorganinių nano trąšų NAGRO panaudojimas cukrinių runkelių pasėlyje. Darbo objektas – ‘Ernestina‘ veislės cukrinių runkelių pasėliai, papildomai apipurkšti bioorganiniu universalių nano trąšų NAGRO tirpalu. Darbo metodai: 2013 m. ASU Bandymų stotyje atlikti cukrinių runkelių (Beta vulgaris L. var. saccharifera) pasėlio formavimo naudojant NAGRO trąšas tyrimai. Tirta cukrinių runkelių veislė ‘Ernestina‘. Cukrinių runkelių daigai keturių porų tikrųjų lapelių tarpsnyje apipurkšti NAGRO trąšų tirpalu. Cukriniams runkeliams esant 5 – 6 porų tikrųjų lapelių tarpsnyje 3 ir 5 bandymo variantuose augantys augalai dar kartą pagal schemą apipurkšti bioorganinių nano trąšų tirpalu. Kitos agrotechninės priemonės buvo atliktos pagal Bandymo stotyje taikomą cukrinių runkelių auginimo technologiją. Darbo rezultatai: Papildomas cukrinių runkelių apipurškimas NAGRO trąšomis turėjo teigiamos įtakos cukrinių runkelių augimo ir vystymosi procesams. Didžiausias lapų skaičius, šakniavaisio diametras ir didžiausia biomasė gauta augalus apipurškus du kartu 1 l ha-1 norma. Lapų plotas (14,75 %) buvo patikimai didesnis cukrinius runkelius apipurškus du kartus 1 l ha-1 norma. Cukriniai runkeliai daugiausiai sausųjų medžiagų lapuose (21,23 g.), šakniavaisiuose (20,76 g.)... [toliau žr. visą tekstą] / Master´s thesis presents the research data on sugar beet growth intensity, the formation of leaf area, dry matter accumulation, photosynthetic parameters, yield and sugar content as well as reveals the effect the application of the bio-organic nano fertilizer “NAGRO” had on sugar beet crop. Object of the research: 'Ernestina' variety of sugar beet crop applied by the solution of the universal bio-organic nano fertilizer “NAGRO”. Research methods: The research on crop formation of sugar beet (Beta vulgaris L. var. saccharifera) sprayed by “NAGRO” fertilizer was carried out at the Experimental Station of Aleksandras Stulginskis University in 2013. 'Ernestina' variety of sugar beet crop was researched. At the stage of 4 pairs of true leaves the application of “NAGRO” fertilizer solution was made to sugar beet seedlings whereas at the growth stage of 5–6 pairs of leaves the plants of the 3rd and 5th test versions were additionaly applied by the solution of “NAGRO” fertilizer. Other agro measures were carried out in accordance with the growing technology for sugar beet applicable in the Experimental Station. Research results: Additional application of “NAGRO” fertilizer on sugar beet had a positive impact on the sugar beet growth and development processes. The leaf area (14,75%) of sugar beet was significantly higher after twofold application in 1 l ha-1 rate. Dry matter accumulation in the leaves (21,23 g) and roots (20,76 g) of sugar beet was the highest after the application of... [to full text]

Magnetic nanoscale devices have shown great promise in both research and industry. Magnetic nanostructures have potential for non-volatile data storage applications, reconfigurable logic devices, biomedical devices and many more. The S-state magnetic element is one of the promising structures for non-volatile data storage applications and reconfigurable logic devices. It is a single-layer logic element that can be integrated in magnetoresistive structures. We present a detailed micromagnetic analysis of the geometrical parameter space in which the logic operation is carried out. The influence of imperfections, such as sidewall roughness and roundness of the edge is investigated. Magnetic nanowires are highly attractive materials that has potential for applications in ultrahigh magnetic recording, logic operation devices, and micromagnetic and spintronic sensors. To utilize applications, manipulation and assembly of nanowires into ordered structures is needed. Magnetic self-alignment is a facile technique for assembling nanowires into hierarchical structures. In my thesis, I focus on synthesizing and assembling nickel nanowires. The magnetic behaviour of a single nickel nanowire with 200~nm diameter is investigated in micromagnetic simulations. Nickel nanowires with Au caps at the ends were synthesized by electrochemical deposition into nanopores in alumina templates. One-dimensional alignment, which forms chains and two-dimensional alignment, which forms T-junctions as well as cross-junctions are demonstrated. Attempts to achieve three-dimensional alignment were not successful yet. I will discuss strategies to improve the alignment process.

Le microenvironnement apporte une multitude d'informations aux cellules régulant ainsi leurs fonctions et leur organisation. L'objectif de cette thèse a été de contrôler différents paramètres du microenvironnement cellulaire in vitro afin de moduler l'autorenouvellement et la destinée des cellules souches embryonnaires (CSE).Cette thèse comporte 3 parties. Premièrement, des films de polyélectrolytes multicouches à base de poly(L-lysine) et de hyaluronane ont été utilisés comme substrats modulables. Les propriétés mécaniques ainsi que la chimie des films régulent la proportion de sous-populations de CSE qui reflètent soit le stade masse cellulaire interne, soit le stade épiblaste.Dans un deuxième temps, un équilibre entre l'expression des marqueurs embryonnaires de l'axe proximodistal a été mis en évidence dans la culture de CSE. L'emploi de micro-patrons adhésifs permettant de contrôler la géométrie des colonies a révélé l'importance des contraintes topologiques sur la distribution des cellules exprimant le marqueur proximal Brachyury. Enfin, l'action combinée de BMP2 et de wnt3a mimant l'environnement biochimique du stade tardif de la ligne primitive a permis d'isoler une population pure et très précoce de progéniteurs cardiaques SSEA1+ multipotents. / The microenvironment provides stem cells with numerous pieces of information. Biochemical and mechanical cues synergize to regulate cell function and organization. The aim of this PhD thesis was to control specific microenvironmental parameters to modulate embryonic stem cell (ESC) self-renewal and fate.First, poly(L-lysine) and hyaluronan based polyelectrolyte multilayer films were used as tunable substrates. Both mechanical and chemical properties of the films influenced the balance between ESC subpopulations reflecting different embryonic stages (inner cell mass versus epiblast)Second, a dynamic equilibrium was found between the expression of embryonic proximal and distal markers within ESC culture. The uses of micropatterned substrates to control colony shape uncovered a key role for geometrical constraints in the distribution of Brachyury expression.Last, BMP2 was used together with secreted wnt3a to mimic the late streak stage of the embryo and to trigger the differentiation of pluripotent cells towards the cardiogenic mesoderm. Responsive cells could be sorted out based on SSEA1 expression. This purified population represents the earliest ESC derived multipotent cardiac progenitor population identified to date.

Le cadre de cette étude est le coût énergétique lié à la production des Microfibrilles de Cellulose (MFC) qui est aujourd’hui un facteur limitant à son développement à l’échelle industrielle. Le but de cette étude est de caractériser les interactions cellulose/hémicellulose au sein de ces systèmes.Des MFC provenant de différentes pâtes à papier chimiques ont été caractérisées par RMN du solide afin d’obtenir des informations à l’échelle moléculaire. Suite à l’optimisation d’un protocole expérimental, les hémicelluloses contenues dans les MFC issues de pâte kraft de bouleau ont ensuite été extraites avec un rendement de 60% et sont composés uniquement d’un homopolymère de xylan de DP 75.La turbidimétrie a été utilisée pour qualifier la qualité des suspensions, dont il a été montré qu’elle dépend fortement du procédé de mise en pâte et du séchage. Des corrélations positives ont été établies entre l’état de dispersion et les propriétés mécaniques de feuilles de papier additionnées de microfibrilles. L’analyse RMN de modèles biomimétiques reconstitués a confirmé le changement de conformation du xylan lorsqu’il est adsorbé sur la cellulose et les mesures de surface spécifique ont montré que seule la couche de xylan en contact avec la cellulose était concernée par ce changement.Les interactions cellulose/xylane ont été étudiées par RMN du solide et par dynamique moléculaire atomistique (MD). Les simulations MD ont montré que le xylan s’adsorbe parallèlement aux chaines de cellulose. Des mesures d'interaction sur ce système ont conduit à une mesure d'énergie de 9kJ/résidu de xylose.Des tests de mesure d’adhésion ont également été réalisés à partir d’un modèle trois couches constitué de xylan entre deux films de cellulose et une forte adhésion a pu être observée.L’utilisation de xylanase comme prétraitement est proposé pour améliorer la production des MFC. / The study was motivated by the necessity to reduce the high energy costs of Micro-Fibrillated Cellulose (MFC) production, which is a limiting factor for its industrial development and aimed at understanding the cellulose/hemicelluloses interaction within this system. MFC resulting from different chemical pulps were characterized by solid-state NMR spectroscopy to get information on the hemicelluloses content and molecular conformation. By optimizing an extraction protocol, more than 60% of the residual hemicelluloses were extracted from birch kraft MFC and characterized as a high purity homopolymer of β-1,4 linked xylan of DP 75.Turbidimetry was used to qualify the quality of the suspensions, which strongly depended on the pulping and drying history. Positive correlations between the state of dispersion, specific surface and mechanical properties of MFC-reinforced handsheets were evidenced.Cellulose/xylan interactions were investigated using solid-state NMR and atomistic molecular dynamics (MD) simulation. NMR spectra confirmed that xylan in contact with cellulose altered its conformation, from the three-fold helix to a presumable cellulose-like two-fold one. In combination with specific surface area measurements, the conformational change was shown to happen only for the first layer of xylan adsorbed in direct interaction with the cellulose surface. MD simulations showed that adsorbed xylan tends to align parallel to the cellulose chain direction fully extended. Interaction energy between xylan chain and cellulose surface estimated with MD was 9kJ/xylose. Then a three-layers system made of xylan between two cellulose films were built to perform adhesion tests that showed strong adhesion between xylan and cellulose surfaces. Xylanase was proposed as a pulp pretreatment for MFC production.