The present work describes the design and synthesis of a series of dimers [(η5 - ring)MCl]2(μ2 -Cl)2, (where (η5 -ring)MCl = (η5 -Me4C5R)Rh(III)Cl or (η5 -Me4C5R)Ir(III)Cl). Iridium and rhodium dimeric complexes were synthesized via a microwave reaction and directly compared through single-crystal X-ray crystallography. Finally, the dimeric complexes were evaluated as potential oxidation catalysts. The modified HCp*R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, nheptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,5-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (39 - 98%). Reaction of the HCp*R ligands with [M(COD)](μ2 -Cl)2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) gave the dimeric complexes [Cp*RMCl]2(μ2 -Cl)2 in yields ranging from 16 - 96%. The dimers were characterized by nuclear magnetic resonance (NMR)spectroscopy, single-crystal X-ray diffraction (XRD) (supplemented by powder XRD), high-resolution mass spectrometry (HRMS), and elemental analysis. Complexes studied by XRD were analyzed to understand the bond lengths and bond angles throughout each complex. The dimeric complexes synthesized, will facilitate a complete study on how the R group influences catalytic activity. / Master of Science

No / The crystal structure of the I-phase of quinacridone was determined from non-indexed X-ray powder data by means of crystal structure prediction and subsequent Rietveld refinement. This I-phase is another polymorph than the -phase reported by Lincke [G. Lincke and H.-U. Finzel, Cryst. Res. Technol. 1996, 31, 441¿452.]. The crystal structures of the and polymorphs were determined from single crystal data. The knowledge of the crystal structures can be used for crystal engineering, i.e., for targeted syntheses of pigments having desired properties, especially for the syntheses of new red pigments.

No / Three new C-bonded cyclotriphosphazenes, [N3P3(2-thienyl)6], 2, [N3P3(3-thienyl)6], 4, and [N3P3(3,3-bithienyl-2,2-ylene)3], 6, have been prepared by two new synthetic procedures and are the first examples of non-spiro and trispirocyclotriphosphazene derivatives composed of thiophene and 3,3-dithiophene substituents, respectively. Their 1H, 13C and 31P NMR parameters are given. The solid state structures of 2, 4 and 6 have been determined by X-ray crystallography.

No / A macrocycle, 6, has been synthesized in high yield from 2,5-di(pyrazol-1-yl)hydroquinone and 1,1`-fc[B(Me)NMe2]2 {fc = Fe(C5H4)2}. The molecule incorporates two redox-active 1,1`-ferrocenylene units in its backbone and contains four chiral boron centers, each of them possessing the same configuration. It is demonstrated that crystal structures of organometallics of moderate complexity can be solved from high-resolution X-ray powder diffraction patterns, once the connectivity between the functional groups is known.

No / In the 2007 blind test of crystal structure prediction hosted by the Cambridge Crystallographic Data Centre (CCDC), a hybrid DFT/MM method correctly ranked each of the four experimental structures as having the lowest lattice energy of all the crystal structures predicted for each molecule. The work presented here further validates this hybrid method by optimizing the crystal structures (experimental and submitted) of the first three CCDC blind tests held in 1999, 2001, and 2004. Except for the crystal structures of compound IX, all structures were reminimized and ranked according to their lattice energies. The hybrid method computes the lattice energy of a crystal structure as the sum of the DFT total energy and a van der Waals (dispersion) energy correction. Considering all four blind tests, the crystal structure with the lowest lattice energy corresponds to the experimentally observed structure for 12 out of 14 molecules. Moreover, good geometrical agreement is observed between the structures determined by the hybrid method and those measured experimentally. In comparison with the correct submissions made by the blind test participants, all hybrid optimized crystal structures (apart from compound II) have the smallest calculated root mean squared deviations from the experimentally observed structures. It is predicted that a new polymorph of compound V exists under pressure.

No / We report on the organization and outcome of the fourth blind test of crystal structure prediction, an international collaborative project organized to evaluate the present state in computational methods of predicting the crystal structures of small organic molecules. There were 14 research groups which took part, using a variety of methods to generate and rank the most likely crystal structures for four target systems: three single-component crystal structures and a 1:1 cocrystal. Participants were challenged to predict the crystal structures of the four systems, given only their molecular diagrams, while the recently determined but as-yet unpublished crystal structures were withheld by an independent referee. Three predictions were allowed for each system. The results demonstrate a dramatic improvement in rates of success over previous blind tests; in total, there were 13 successful predictions and, for each of the four targets, at least two groups correctly predicted the observed crystal structure. The successes include one participating group who correctly predicted all four crystal structures as their first ranked choice, albeit at a considerable computational expense. The results reflect important improvements in modelling methods and suggest that, at least for the small and fairly rigid types of molecules included in this blind test, such calculations can be constructively applied to help understand crystallization and polymorphism of organic molecules.

Yes / The sixth blind test of organic crystal-structure prediction (CSP) methods has been held, with five target systems: a small nearly rigid molecule, a polymorphic former drug candidate, a chloride salt hydrate, a co-crystal, and a bulky exible molecule. This blind test has seen substantial growth in the number of submissions, with the broad range of prediction methods giving a unique insight into the state of the art in the field. Significant progress has been seen in treating flexible molecules, usage of hierarchical approaches to ranking structures, the application of density-functional approximations, and the establishment of new workflows and best practices for performing CSP calculations. All of the targets, apart from a single potentially disordered Z0 = 2 polymorph of the drug candidate, were predicted by at least one submission. Despite many remaining challenges, it is clear that CSP methods are becoming more applicable to a wider range of real systems, including salts, hydrates and larger flexible molecules. The results also highlight the potential for CSP calculations to complement and augment experimental studies of organic solid forms. / EPSRC (grants EP/J01110X/1 and EP/K018132/1) and the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC through grant agreements n. 307358 (ERC-stG- 2012-ANGLE) and n. 321156 (ERC-AG-PE5-ROBOT). The Russian Foundation (14-03-01091). GlaxoSmithKline, Merck, and Vertex. VIDI Research Program 700.10.427, which is financed by The Netherlands Organisation for Scientific Research (NWO), and the European Research Council (ERC-2010-StG, grant agreement n. 259510-KISMOL). Foundation for Fundamental Research on Matter (FOM). NSF grant number ACI-1053575. University of Buenos Aires and the Argentinian Research Council. Conflex Corp. and Ministry of Education, Culture, Sports, Science and Technology. Louisiana Board of Regents Award # LEQSF(2014-17)-RD-A-10 “Toward Crystal Engineering from First Principles”, the NSF award # EPS-1003897 “The Louisiana Alliance for Simulation-Guided Materials Applications (LA-SiGMA)”, and by the Tulane Committee on Research Summer Fellowship. Solar Technologies Go Hybrid initiative of the State of Bavaria, Germany. U.S. Department of Energy under contract DE-AC02-06CH11357. EPSRC (EP/J003840/1, EP/J014958/1) and [EP/J017639/1]. Leadership Fellowship Grant [EP/K013688/1]. Robinson College, Cambridge, and the Cambridge Philosophical Society for a Henslow Research Fellowship. Army Research Office under Grant W911NF-13-1- 0387 and by the National Science Foundation Grant CHE-1152899. Polish National Science Centre Grant No. DEC-2012/05/B/ST4/00086. EPSRC, though grant ESPRC EP/K039229/1, and Eli Lilly. The PhD students support: RKH by a joint UCL Max-Planck Society Magdeburg Impact studentship, REW by a UCL Impact studentship; LI by the Cambridge Crystallographic Data Centre and the M3S Centre for Doctoral Training (EPSRC EP/G036675/1). Army Research Office Grant W911NF-13-1-0387 and by the National Science Foundation Grant CHE-1152899. U.S. Army Research Laboratory and the U.S. Army Research Office under contract/grant number W911NF-13-1-0387 (MET and LV) and MRSEC program of the National Science Foundation under Award Number DMR-1420073 (MET and ES). U.S. Army Research Laboratory and the U.S. Army Research Office contract/grant number W911NF-13-1- 0387 and by the National Science Foundation Grant CHE-1152899. National Science Foundation (DMR-1231586), the Government of Russian Federation (Grant No. 14.A12.31.0003), the Foreign Talents Introduction and Academic Exchange Program (No. B08040) and the Russian Science Foundation, project no. 14-43-00052, base organization Photochemistry Center of the Russian Academy of Sciences. Army Research Office Grant W911NF-13-1-0387 and the National Science Foundation Grant CHE-1152899. Deutsche Forschungsgemeinschaft program DFG-SPP 1807. Department of Energy (DOE) Grant Nos. DE-SC0008626. Office of Science of the U.S. Department of Energy Contract No. DE-AC02-06CH11357. Office of Science of the U.S. Department of Energy contract No. DEAC02-05CH11231.

Meine Arbeit umfasst zwei Teile: (1) die Erstellung von knock-out Mäusen für Erp28, ein Gen, welches für ein Chaperone des Endoplasmatischen Reticulums kodiert, (2) die strukturelle und funktionelle Analyse von Wind, das ERp28-Homolog von Drosophila. Um eine ERp28 Knock-out Maus zu erstellen, musste zuerst die Genstruktur (Exonverteilung) von ERp28 etabliert werden. Danach wurde eine genomische Bibliothek von Mäusen mit 32P-markierten cDNA-Fragmenten gescreent, und zwei positive Klone, die den Genlokus von ERp28 enthalten, isoliert. Eine Restriktions karte vom Genlokus wurde erstellt. Das Gen für ERp28 hat eine einfache Struktur mit nur drei Exons. Das erste Exon enthält das Start codon ATG und das dritte das Stopcodon TGA. Fast die gesamte D-Domäne, die einzigartig für die Unterfamilie von PDI-D Proteinen ist, wird vom dritten Exon kodiert. Bei der RT-PCR für die Klonierung der cDNA von ERp78, habe ich möglicherweise eine alternative splice form von ERp28 entdeckt, in welcher das zweite Exon ausgeschnitten ist. Diese cDNA konnte auch bei Mensch und Ratte gefunden werden, nicht aber bei Drosophila, was auf eine limitierte Verbreitung bei verschiedenen Species hindeutet. Weitere Studien müssen aber gemacht werden, um die Existenz dieser alternativen splice Form zu bestätigen und zu charakterisieren. Auf der Basis der Genstruktur und des Restriktionsverdaus des ERp28- Locus, wurde ein knock-out (KO) Vektor erstellt und in ES-Zellen transfiziert. Drei positive Rekombinanten wurden durch Selektion mit Antibiotika und PCR-Screening erhalten. Chimere Mäuse wurden nach Microinjektion von zwei dieser 3 Klone in Mausblastocysten generiert. Heterozygote Mäuse wurden dann durch Paarung von männliche Chimeren und weiblichen C57BL6N Wildtypmäusen erstellt.Homozygoten wurden dann durch erneute Kreuzung von Heterozygoten erstellt. Durch Genotypiserung in PCR-Analysen und/oder Southern Blot wurden Chimeren, Heterozygoten und Homozygoten charakterisiert. Zur Zeit habe ich auch keinen auffälligen Phenotyp von -/- Homozygoten entdeckt. Deswegen werden, um die Funktion von ERp28 zu klären, detailierte Analysen gemacht. Immunologische Studien zeigen, dass obwohl ERp28 in verschieden Geweben und Organen exprimiert wird, es in E12 embryos in einigen spezifischen Geweben und Zellen relativ stärkes exprimiert wird, zum Beispiel in Glialzellen im Gehirn, im plexüs choreoideüs der weiterer Ventrikel und im Heren. Diese Beobachtungen stellen wichtige Informationen für eine genaüere phänotypische Analyse dar.Im 2. Teil meiner Arbeit sollte das PDI-Dß-Protein Wind kristallisiert werden. Da eine Kristallisation von Erp28 bisher nicht möglich war, konzentrierte ich mich auf sein Homolog Wind. Wind spielt eine wichtige Rolle in der Dorsoventral-Entwicklung in Drosophila Embryonen. Kürzlich wurde gezeigt, dass es für die richtige Lokalisation von Pipe, einem Schlüsselfaktor in der Dorsoventral-Entwicklung, essentiell ist. Die Kristallisation dieses Proteins wurde in Zusammenarbeit mit der Abteilung für Strukturchemie der Universität Göttingen ( Prof. Dr. Sheldrick) durchgeführt. Das Wind-Protein konnte bei einer Auflösung von 1,9 Ả kristallisiert werden. Wie sich zeigte, liegt es als Homodimer vor. Jedes Monomer besteht aus 2 unterschiedlichen Domänen: einer N-terminalen Domäne mit Ähnlichkeit zu Thioredoxin und einer C-terminal gelegenen D-Domäne. Das Dimer wird allein durch die Beteiligung der Thioredoxin-ähnlichen Domäne gebildet. In der N-terminalen Domäne liegt ein charakteristisches Strukturelement vor bestehend aus ßaßaßaßßa, welches dem Thioredoxinfold zugeordnet wird. Die D-Domäne hingegen besteht nur aus 5 a-Helices. Durch die Homodimerisierung entsteht ein tiefer, negativ geladener Dimerspalt, in welchem kleiner Peptide gebunden werden könnten. Auf der Oberfläche von Wind gibt es konservierte Aminosäuren. Ergebnisse aus Strukturanalyse, biochemischen Experimenten sowie Mutagenesestudien lassen auf eine mögliche Substrat-Bindestelle um Y55 in der Thioredoxin-Domäne herum schliessen, (Ma et al., 2003).Durch Insulin Reduktionsexperimente und Mutagenese konnten wir zeigen, dass das vorhandene CTGC-Motiv in der N-terminalen Domäne von Wind redox-inaktiv und nicht für den Transport von Pipe vom ER zum Golgi erforderlich ist. Daraus kann man folgern, dass es sich bei Wind um ein redox-unabhängiges Chaperon/ Escortprotein handelt. Weiterhin konnten wir zeigen, dass obwohl die b- und die D-Domäne für die Funktion von Wind wichtig sind die D-Domäne von Wind durch die seines Maus-Homologs Erp28 ersetzt werden konnte, ohne den Transport von Pipe zu beeinflussen. Dieses lässt auf eine ähnliche oder sogar gleiche Funktion der D-Domäne schliessen.Die Ergebnisse aus den Wind-Studien gaben wichtige Informationen zur Funktion von Erp28. Weiterhin sei betont, dass es sich bei der Kristallisierung von Wind um die erste Kristallstruktur eines PDI-verwandten Proteins im ER handelt. Die Struktur und die mögliche Substrat-Bindestelle, die in dieser Arbeit aufgeklärt wurden, können wichtige Hinweise geben für die Funktionen anderer PDI-Proteine.

This thesis focuses on a number of aspects governing the transformation of gibbsite, via intermediate phases, to a-alumina. These aspects include the size and morphology of the gibbsite grains, the influence of additions of foreign elements, the effect of a mechanical treatment of the gibbsite prior to calcination, and combinations of these factors. The materials were characterisedb y scanninge lectron microscopy, X-ray diffraction and surfacea rea measurementsF. or someo f the calcined materials an attempt was made to sinter the powders to a dense body to investigate if any of the treatments during calcination had an effect on this process. The literature review covers the current state of understanding of the production of bulk alumina powder by the Bayer process and the phase changes seen on calcination of precursors to the stable a-alumina phase. A detailed description of the phase changes is given and the various routes and conditions necessary for the transformations to occur are considered. The transformations are examined in relation to the morphology of the crystals and the variables controlling the phase transformation route are discussed. Calcination in air showed that the size of the gibbsite grain governs the calcination route taken to reach a-alumina. The standard gibbsites used in this work show a mixed calcination sequence transforming both via the boehmite phase, followed by the y, 8 and 0 phases, and via the x and K phases. The formation of boehmite is attributed to retention of water vapour within the grainDifferences in morphology of the starting materials showed that for the range of materials seen, the morphology of the grain is less important than its size. The super fine material confirmed that a small grain size transforms via the non-boehmite route only, with the other gibbsites taking intermediate routes as for the standard gibbsites. Of the additions made prior to calcination, aluminium fluoride was found to reduce the transformation temperature to a-alumina by approximately 300°C. Other additions had little effect on the transformation temperature although a reduction in grain size was seen with aluminium chloride. It was found that good mixing of the alumina fluoride was essential to obtain reliable and reproducible results. This is due to the small amounts of additive that are needed and the sensitivity of the process to concentration variations. Mineralisation of a range of gibbsites showed that the presence of sodium in the starting material was crucial in reducing the calcination temperature. This led to the conclusion that the sodium and fluoride react to form a liquid phase. The presence of a liquid phase increases the mobility of the aluminium and oxygen atoms resulting in a reduction of the transformation temperature. Fluoride additions to the gibbsites with different morphologies showed that the presence of sodium was the governing factor in reduction of the transformation temperature. Milling of the starting materials showed that there was a small reduction in the transformation temperature between some of the phases. The energy involved in milling leads to activation of the gibbsite. This activation takes the form of a reduction in the grain size and in a reduction of the crystallinity seen in the XRD patternFluoride additions during the calcination of sapphire with a standard gibbsite powder showed preferential grain growth. It was possible to initiate growth of small plate-like crystals on the polished surface of a piece of sapphire parallel to the basal plane. Crystal growth was also seen in scratches on a polished surface perpendicular to the basal plane

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