Συστηματική μελέτη πυριτικών, πυριτίου-ασβεστίου και φωσφοπυριτικών γυαλιών, με σύσταση 80 SiO2 - (20-x) Na2O - x Me2O (όπου x=0, 10 και Me=Li ή K), 48.7SiO2 - 26.9CaO - (24.4-x) Na2O - x Me2O (όπου x=0, 12.2 και Me=Li ή K) και 46.1 SiO2 - 2.6 P2O5 - 26.9 CaO - (24.4-x) Na2O - x Me2O (όπου x=0, 12.2 και Me=Li ή K), γίνεται με φασματοσκοπικές τεχνικές πυρηνικού μαγνητικού συντονισμού MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance) και MQ–MAS NMR (Multiple Quantum-MAS NMR). Η 29Si MAS NMR ανάλυση του Na2O πυριτικού γυαλιού έδειξε την ύπαρξη δύο κορυφών, οι οποίες αποδίδονται σε Q3 και Q4 πυριτικές δομές. Η υποκατάσταση Na από Κ διατηρεί τις Q3 και Q4 δομές ενώ στο Na2O-Li2O γυαλί, παρατηρήθηκαν τρεις κορυφές, οι οποίες αποδίδονται σε Q3, Q4-3 και Q4-4 πυριτικές δομές. H Q4-4 είναι σχετικά στενή και υποδηλώνει έναρξη κρυστάλλωσης του δικτύου λόγω της μικρής έντασης του σήματος. Στο γυαλί Na2O πυριτίου-ασβεστίου, η ανάλυση οδήγησε σε δυο κορυφές οι οποίες αποδίδονται σε Q1 και Q2 δομές, ενώ στο Na2O-K2O γυαλί, το φάσμα αναλύθηκε μόνο μια κορυφή που αντιπροσωπεύει Q2 πυριτικές δομές. Από την άλλη, στο γυαλί Na2O-Li2O, παρατηρήθηκαν δύο κορυφές οι οποίες αντιστοιχούν σε Q2 και Q3 δομές. Στο Na2O φωσφοπυριτικό γυαλί, η ανάλυση οδήγησε στις κορυφές που αποδίδονται σε Q2 και Q3 δομές. Η 23Na MQ-MAS NMR ανάλυση στο Na2O πυριτικό γυαλί οδήγησε στην παρουσία δύο ιοντικών περιοχών νατρίου (site 1: δiso= 5.1 ppm, CQ= 0.96 MHz, ΔCS= 20 ppm και site 2: δiso= 1.9 ppm, CQ= 3.06 MHz, ΔCS= 20 ppm). Η υποκατάσταση Na από Li ή Κ διατηρεί τις δύο ιοντικές περιοχές στα γυαλιά. Στο γυαλί Na2O πυριτίου-ασβεστίου, η ανάλυση οδήγησε μόνο σε μια ιοντική περιοχή η οποία είναι η site 2 (δiso= 5.4 ppm, CQ= 2.83 MHz, ΔCS= 17 ppm). Στα υπόλοιπα γυαλιά δεν παρατηρούνται διαφορές κατά την υποκατάσταση Na από Li ή Κ. Στο 24.4 Na2O φωσφοπυριτικό γυαλί παρατηρήθηκαν τρεις ιοντικές περιοχές (site 1: δiso= 6.0 ppm, CQ= 1.4 MHz, ΔCS= 20 ppm, site 2: δiso= 6.8 ppm, CQ= 2.6 MHz, ΔCS= 20 ppm, και site 3: δiso= 6.6 ppm, CQ= 1.2 MHz, ΔCS= 1 ppm). Η υποκατάσταση Na από Li ή Κ οδήγησε στην απουσία της τρίτης και πιο ισχυρής ιοντικής περιοχής (site 3). Πιθανολογούμε ότι η απουσία της σχετίζεται με την τροποποίηση του δικτύου που προέρχεται από την εισαγωγή του φωσφόρου στο υαλώδες δίκτυο. Η μελέτη μας επεκτάθηκε και στην μοριακή προσομοίωση των γυαλιών των τριών οικογενειών με την βοήθεια του προγράμματος Gaussian 03W. Πρώτα έγινε η γεωμετρική προσομοίωση του πλέγματος και μετά η προσομοίωση των NMR παραμέτρων με την χρήση της DFT μεθόδου (Density Functional Theory) και με τις βάσεις 6-311++G, 6-31G και 3-21++G. Οι δομές που προέκυψαν έδωσαν μια εικόνα του πυριτικού, πυριτίου-ασβεστίου και φωσφοπυριτικού υαλώδους δικτύου. Οι δομές των αλκαλίων αποτελούνται από τετραεδρικής, εξαεδρικής και οκταεδρικής συμμετρίας κυψελίδες. Μετά από υπολογισμούς διαφόρων πιθανών δομών καταλήξαμε στις δομές για την ερμηνεία των φασμάτων σε εκείνες που υπάρχει καλή συμφωνία μεταξύ των θεωρητικών και πειραματικών 23Na NMR αποτελεσμάτων. Συγκεκριμένα, η site 2 προέρχεται από ένα 23Na σε XXX-εδρικό περιβάλλον. Η site 3 μπορεί να προέρχεται από οκταεδρικούς σχηματισμούς υψηλής συμμετρίας των ιόντων Na γιατί αυτές οι περιοχές οδηγούν με βάση τους υπολογισμούς μας σε περιβάλλον με αυξημένη ιοντική ισχύ και συμμετρία. / Silicate, calcium-silicate and phosphosilicate glasses of the composition 80 SiO2 - (20-x) Na2O - x Me2O (where x=0, 10 and Me=Li or K), 48.7SiO2 - 26.9CaO - (24.4-x) Na2O - xMe2O (where x=0, 12.2 and Me=Li or K) and 46.1 SiO2 - 2.6 P2O5 - 26.9 CaO - (24.4-x) Na2O - x Me2O (where x=0, 12.2 and Me=Li or K), have been investigated using the advanced NMR methods of MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance) and MQ-MAS NMR (Multiple Quantum-MAS NMR). The 29Si MAS NMR analysis of the sodium silicate glass revealed two lines attributed to Q3 and Q4 silicate species. Substitution of Na with K conserves the Q3 and Q4 species while in the Na2O-Li2O glass, three lines were obtained attributed to Q3, Q4-3 and Q4-4 species. The Q4-4 signal is attributed to initial stage of crystallization due to the narrow size distribution and low intensity. In the sodium calcium-silicate glass, two lines were resolved assigned to Q1 and Q2, while in the Na2O-K2O glass, only one line was resolved attributed to Q2 species. For the Na2O-Li2O glass, two lines were revealed assigned to Q2 and Q3. In the sodium phosphosilicate glass, the analysis revealed two lines ascribed to Q2 and Q3. The 23Na MQ-MAS NMR analysis in the sodium silicate glass exhibits two Na ionic sites (site 1: δiso= 5.1 ppm, CQ= 0.96 MHz, ΔCS= 20 ppm and site 2: δiso= 1.9 ppm, CQ= 3.06 MHz, ΔCS= 20 ppm). Substitution of Na with Li or K conserves the two sites in the glasses. For the sodium calcium-silicate glass, the analysis revealed only one site (site 2: δiso= 5.4 ppm, CQ= 2.83 MHz, ΔCS= 17 ppm). No difference was observed by the substitution of Na with Li or K in the glasses. In the 24.4 Na2O phosphosilicate glass three sites were obtained with: site 1 (δiso= 6.0 ppm, CQ= 1.4 MHz, ΔCS= 20 ppm), site 2 (δiso= 6.8 ppm, CQ= 2.6 MHz, ΔCS= 20 ppm), site 3 (δiso= 6.6 ppm, CQ= 1.2 MHz, ΔCS= 1 ppm). The substitution of Na with Li or K resulted in the absence of the third and most ionic site, which is probably associated with the presence of phosphorus in the glassy network. Our study was completed by the molecular simulation of the three types of glasses, for which the Gaussian 03W program was used. For the geometrical optimization and the optimization of the NMR parameters was used the DFT (Density Functional Theory) method and the 6-311++G, 6-31G, and 3-21++G basis sets. The resulting structures gave an insight into the silicate, calcium-silicate and phosphosilicate glassy network. These structures consist of tetrahedral, hexahedral, and octahedral symmetry shells which enclose the alkali ions. The good agreement between the theoretical and experimental 23Na NMR results leads to the depiction of the Na ionic sites and especially of site 2. This site was attributed to sodium in XXX-coordination. Concerning site 3, was observed that the increased ionic strength of the site could possible be ascribed to high symmetry octahedral configurations of Na ions.

No description available.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24002号 / エネ博第438号 / 新制||エネ||83(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)准教授 高井 茂臣, 教授 萩原 理加, 教授 佐川 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Organic crystals are found in everyday goods such as foods, drugs, dyes, and agricultural products. To better understand the solid-state behaviour of organic crystals, the study of their surfaces is crucial, as several reactions occur at the interface between the crystal surface and its immediate environment. While atomic force microscopy (AFM) is a useful tool for studying surfaces, it is not a common technique for studying organic crystals. The rst part of this report aims to address problems of imaging organic crystals by AFM which arise from the nature of the imaging technique and the material property of organic crystals. Methods of detecting and predicting the likelihood of the problems encountered in imaging organic crystals are suggested in order for a more accurate interpretation of the information obtained by this technique. The e ect of humidity on aspirin crystal surfaces is then investigated by AFM. The growth of new features on the surface is believed to be a result of the hydrolysis of aspirin molecules. Mechanisms are suggested based on the observed surface response of aspirin, where surface defects and the mobility of surface molecules are believed to be important factors a ecting reactivity. The last section investigates the solid-state photochemical reaction of anthracene, which is a reaction that should not occur according to the topochemical postulate. The surface response of anthracene crystals to UV light was studied, and the results indicate strong reactivity at sites of surface defects, which is likely due to photodimerisation. A similar mechanism that described the behaviour of aspirin surfaces was suggested for this reaction. In summary, both reactions that were studied provided a better insight towards understanding the solid-state reactivity of organic crystals. The proposed surface mechanisms imply that surface defects and the presence of humidity or solvent vapour are very likely to play a role in determining reactivity. Further studies on the origin of defects are suggested in order to better control the behaviour of organic crystals in the solid-state.

Les matériaux multiferroïques, dans lesquels magnétisme et ferroélectricité coexistent, sont un intérêt majeur dans le domaine du stockage de l'information. Un couplage magnétoélectrique robuste, ainsi qu'une polarisation électrique importante, sont les conditions requises à température ambiante pour ces matériaux multifonctionnels. Ce manuscrit rend compte de travaux théoriques visant à principalement caractériser les propriétés magnétiques d'oxydes à majorité cuivrés, susceptibles de répondre à ces exigences. Une première partie vise à une présentation succincte des cuprates, et de concepts fondamentaux concernant le magnétisme et la multiferroïcité. La seconde partie expose les méthodes de modélisation employées. Le chapitre trois donne à un aperçu de techniques expérimentales, tels que le magnétomètre à SQUID ou la RPE. Ensuite, les composés AFeO₃ (A = Sc, In et Bi) et un complexe à base de chrome servent de terrain de jeu, à la mise en place de l'approche calculatoire. La complémentarité entre les méthodes ab initio et les techniques de type Monte-Carlo ou Diagonalisation Exacte, permet une description complète du diagramme de phases magnétiques, alimentée d'une discussion permanente avec l'expérience. Une stratégie similaire est utilisée dans le chapitre suivant, avec l'étude du composé SeCuO₃ et de ses fluctuations quantiques. La dernière partie consiste en la caractérisation de l'effet d'une pression physique (hydrostatique ou uniaxiale) ou chimique sur les propriétés magnétiques des composés CuO, Cu₂OX₂ et CuX₂ (X=F, Cl, Br et I). / Multiferroic materials, in which magnetism and ferroelectricity coexist, have a great interest for memory devices. A robust magnetoelectric coupling, and a high electric polarization, are required at ambient temperature for these multifunctional materials. This thesis reports theoretical works mainly devoted to characterize magnetic properties of cuprates and other oxide compounds, which could develop such skills. A first part aims at briefly discussing cuprates and fundamental concepts of magnetism and multiferroicity. The second chapter is devoted to the theoretical methods used during these works. The third chapter corresponds to a brief overview of experimental techniques, like SQUID magnetometry or EPR. In the fourth chapter, AFeO₃ (A = Sc, In and Bi) multiferroic hexaferrites and a complex based on chromium centers are considered as a "testing ground" to the establishment of the computational approach. Thanks to the complementarity between ab initio methods, using Density Functional Theory, and simulation techniques as Monte-Carlo or Exact Diagonalization procedures, the entire magnetic phase diagram can be fully described. In chapter 5, a similar strategy is considered for studying the SeCuO₃ compound, which exhibits two decoupled magnetic sub-networks and quantum fluctuations. The last chapter of this thesis focuses on the tuning of the magnetic phases diagrams of CuO, Cu₂OX₂ and CuX₂ compounds (X = F, Cl, Br, I) applying physical (hydrostatic and uniaxial) and chemical pressures.

<div><div><div><p>To prolong their long-term stability, protein molecules are commonly dispensed as lyophilized powders to be reconstituted before use. Evaluating the stability of these biomolecules in the solid state is routinely done by using various analytical techniques such as glass transition temperature, residual moisture content and other spectroscopic techniques. However, these techniques often show poor correlation with long term storage stability studies. As a result, time intensive long term storage stability studies are still the golden standard for evaluating protein formulations in the solid state. Over the past few years, our lab has developed solid-state hydrogen deuterium exchange- mass spectrometry (ssHDX-MS) as an analytical tool that probes the backbone of a protein molecule in the solid state. ssHDX-MS gives a snapshot of protein-matrix interactions in the solid state and has a quick turnaround of a few weeks as opposed to a few months for accelerated stability testing. Additionally, various studies in the past have demonstrated that ssHDX-MS can be used for a wide range of biomolecules and shows strong correlation to long term stability studies routinely employed.</p><p>The main aim of this dissertation is to provide an initial understanding of the mechanism behind ssHDX-MS in structured protein formulations. Specifically, this dissertation is an attempt at studying the effects of various experimental variables on the ssHDX-MS of myoglobin formulations as well as demonstrating the utility of this analytical technique. Firstly, the effects of varying temperature and relative humidity on ssHDX-MS of myoglobin formulations is studied with the help of statistical modeling. Secondly, the effects of pressure on ssHDX-MS of myoglobin formulations are evaluated at an intact and peptide digest levels. Finally, ssHDX-MS is used as a characterization tool to evaluate the effects of two different lyophilization methods on the structure and stability of myoglobin formulations. The results of studies described in this dissertation show ssHDX-MS to be sensitive to changes in experimental parameters, namely temperature, relative humidity, pressure, and excipients. Additionally, ssHDX-MS results were in good agreement with other routinely employed analytical and stability testing techniques when used to compare the effects of two lyophilization methods on myoglobin formulations.</p></div></div></div>

<p>Solid-state (SS) luminescent materials are an important class of materials in a myriad of technological applications including light-emitting devices (LEDs) and displays, SS lasers, sensors, imaging agents, etc. Unfortunately, the design of efficient SS emitters is often plagued by sensitivity to environment/matrix (e.g. aggregation-induced quenching, AIQ), competing non-radiative relaxation pathways, and complicated emission mechanisms that are difficult to systematically study and tune. Copper-based systems have been proven to be good candidates for SS emissive materials due to their low-cost, high synthetic variation and well-defined features. Examples of copper-cluster systems, specifically, have been shown to be highly stable, exhibit high photoluminescent quantum yields (ΦPL), and are often relatively insensitive to environmental changes. However, many of these systems are complicated in nature, and often evoke additional relaxation pathways. To mitigate these issues, tetranuclear Cu(I)-pyrazolate complexes have been made which exhibit high ΦPL, matrix insensitivity and proceed through one major radiative emission pathway: cluster-centered based phosphorescence (3CC). The pyrazoles are highly tunable, and by increasing the size of the ligand substituents (H, F, Cl/Me/Br), a rigidochromic effect is observed, causing a significant blue-shift in their photoluminescence, making these viable materials for organic LEDs (OLEDs), especially in the deep-blue region. Furthermore, by increasing the chain length of the ligand substituent (e.g., Me → Et), another material which exhibits stimuli-responsive luminochromism in response to solvent vapor or heat can be achieved. This material exhibits blue ↔ green rigidochromic luminescence in response to stimuli via isomerization of the ethyl units from exo ↔ endo resulting in additional steric effects that effectively prevent rigidification of the Cu4 cluster. This additional phenomenon opens the door for further exploration of Cu(I)-pyrazolate complexes for stimuli-responsive luminescent materials (SRLMs) applications.</p>

This thesis reports the investigation of molecular materials for hydrogen storage applications with a particular emphasis on alkali-metal amidoboranes. I have developed new routes for the synthesis of $alpha$-LiNH$_{2}$BH$_{3}$ and NaNH$_{2}$BH$_{3}$, and have studied their hydrogen storage properties by thermogravimetric analysis, variable temperature X-ray and neutron diffraction and inelastic neutron scattering. I report the synthesis and full structural characterization of two new materials, KNH$_{2}$BH$_{3}$ and $beta$-LiNH$_{2}$BH$_{3}$, and have performed initial studies on a tetragonal phase of a variant of LiNH$_{2}$BH$_{3}$ with a preliminary structure solution. I have also performed variable temperature neutron diffraction on ammonium borodeuteride, ND$_{4}$BD$_{4}$, and report the full structural characterisation of the three phases identified as a result of these measurements. Furthermore, variable temperature inelastic neutron scatting (INS) measurements were performed on ammonia borane, NH$_{3}$BH$_{3}$, and the results are discussed in terms of crystallographic phase changes.

Dissolution of hydrogen into intermetallic compounds characteristically occurs at interstitial sites, causing little alteration to the base metal substructure but often bringing about substantial electronic and magnetic changes to the material. These hydrogen-induced alterations in the intermetallic hydrides are of interest both on a fundamental research level and in terms of technological applications; however, there exists no general theory as to how and why these alterations arise. The objective of this research is to elucidate to general effect of hydrogen on intermetallic compounds through the study of crystallographic, magnetic and electronic properties. An investigation has been carried out on the properties of three intermetallic compound - hydrogen systems of general formula ZrM₂, where M = V, Cr, Mn. All three compounds reversibly absorbed hydrogen with no change in crystal symmetry: powder diffraction studies showed that hydrogen was accommodated in interstitial sites of the existing metal sublattice via lattice expansion. The measurement of the magnetic properties of these systems was combined with the determination of conductivity and dielectric properties in order to describe the electronic e¤ects of hydrogen absorption. Despite the lack of signi…cant structural alteration in these systems, electron transfer between the metal sublattice and hydrogen may occur, as manifested in the appearance/disappearance of magnetic phenomena and the increase/decrease of electrical conductivity. Whilst the hydrogen addition in ZrM₂-H occurs simply via an expansion of the crystal structure, hydrogen does not act purely as null dilutant - there exist subtle electronic changes connected with the hydriding process as well.

This thesis investigates the structure and thermal behaviour of LiBH4, NaBH4, KBH4, LiK(BH4)2, Ca(BH4)2 and Sr(BH4)2. LiK(BH4)2 is the first mixed alkali metal borohydride and was synthesised and characterised during this work. The crystal structures of these borohydrides were studied using variable temperature neutron and synchrotron X-ray diffraction. The synthesis of isotopically enriched samples of 7Li11BD4, Li11BD4, Na11BD4 and K11BD4 allowed high quality neutron diffraction data to be collected. Particular attention was paid to the exact geometry of the borohydride ions which were generally found to be perfect tetrahedra but with orientational disorder. New structures of Ca(BH4)2 were identified and the first crystal structure of Sr(BH4)2 was determined from synchrotron X-ray diffraction data. Solid state 11B NMR and Raman spectroscopy provided further information about the structure of these borohydrides. The thermal behaviour of the borohydrides was investigated using thermogravimetric analysis with mass spectrometry of the decomposition gas products. Hydrogen is the main decomposition gas product from all of these compounds but small amounts of B2H6 and BH3 were also detected during decomposition. Thermogravimetic analyses of Na11BD4 and K11BD4 were completed whilst collecting in-situ neutron diffraction data allowing information about structural changes and mass losses to be combined in order to better understand the decomposition process.