Abstract

A series of hydrophobic and hydrophilic self-assembled monolayers (SAMs) were deposited by the adsorption of 1- dodecanethiol (SAM I), 11-mercapto-1-undecanol (SAM II), 16- mercaptohexadecanoic acid (SAM III), 5-(10-mercaptodecyloxy) benzene-1,3-dioic acid (SAM IV) and 4-(10-mercaptodecyloxy)- pyridine-2,6-dicarboxylic acid (SAM V) on gold substrates. Crystallization experiments were carried out on SAMs I-V, on control surfaces (bulk gold, glass and PDMS (polydimethlysiloxane)) and in microfluidic devices to screen the polymorphs of two well known drugs, acetaminophen and barbital. Microfluidic devices consist of PDMS (polydimethlysiloxane) patterned with microchannels and then bonded to self-assembled monolayers (SAMs) of organic molecules on gold substrates. The crystallization of acetaminophen was carried out under thermodynamic conditions from solutions at room temperature and under kinetic conditions by rapid cooling. The results of crystallization experiments and the influence of self-assembled monolayers (SAMs) in controlling polymorphism by acting as nucleation sites, or templates, are discussed.

<p> A high temperature polymorph of α-Cu2P2O7 was found above 70°C. The lattice parameters and space groups of both phases were determined from X-ray photographs. The crystal structures of α and β-Cu2P2O7 were refined by crystallographic least squares analysis and the molecular geometry obtained was compared with that of other closely related compounds of the transition metal ion pyrophosphate series. The central oxygen atom was found to have enhanced thermal motion or disorder in agreement with I.R. spectroscopic studies of Lazarev. The bond lengths obtained for the P2O7^4- ion were discussed in reference to values predicted by Cruickshank. Evidence of a Jahn-Teller effect was found in the case of the Cu++ ion. A description is given of a relatively efficient method of measuring intensities of Bragg reflections, using a single crystal diffractometer.</p> / Thesis / Master of Science (MSc)

No

Resultados de medidas de ponto de fusão, análise por raios-x e de espectroscopia infravermelho são apresentados para a identificação de dois polimorfos do ácido 5-etil-5-sec-butil barbitúrico (butabarbital).A estrutura do polimorfo II foi refinada simultaneamente com dois conjuntos de dados de origens diversas. Os dados cristalográficos são: a= 10,280 &#197, b= 20,091, c= 11,920, d= 110&#176 30\' monoclínico, grupo espacial I2/c, com oito moléculas por cela unitária.Os resultados obtidos com os dois conjuntos de dados concordam a menos do erro experimental. É comprovada a existência de desordem na estrutura e é feita uma análise dos problemas do refinamento. / Results of measures of melting point, X-ray analysis and infrared spectroscopy are presented for the identification of two polymorphs of acid 5-ethyl-5-sec-butyl barbiturate (butabarbital).The structure of polymorph II was refined simultaneously with two sets of data of different origins. The crystallographic data is a= 10,280 &#197, b= 20,091, c= 11,920, d= 110&#176 30\' monoclinic system, space group I2 / c with eight molecules per unit cell.The results obtained with the two data sets agree nothing experimental error. It neas proved the existence of disorder in the structure and on analyses done about the problems of refinement.

Resultados de medidas de ponto de fusão, análise por raios-x e de espectroscopia infravermelho são apresentados para a identificação de dois polimorfos do ácido 5-etil-5-sec-butil barbitúrico (butabarbital).A estrutura do polimorfo II foi refinada simultaneamente com dois conjuntos de dados de origens diversas. Os dados cristalográficos são: a= 10,280 &#197, b= 20,091, c= 11,920, d= 110&#176 30\' monoclínico, grupo espacial I2/c, com oito moléculas por cela unitária.Os resultados obtidos com os dois conjuntos de dados concordam a menos do erro experimental. É comprovada a existência de desordem na estrutura e é feita uma análise dos problemas do refinamento. / Results of measures of melting point, X-ray analysis and infrared spectroscopy are presented for the identification of two polymorphs of acid 5-ethyl-5-sec-butyl barbiturate (butabarbital).The structure of polymorph II was refined simultaneously with two sets of data of different origins. The crystallographic data is a= 10,280 &#197, b= 20,091, c= 11,920, d= 110&#176 30\' monoclinic system, space group I2 / c with eight molecules per unit cell.The results obtained with the two data sets agree nothing experimental error. It neas proved the existence of disorder in the structure and on analyses done about the problems of refinement.

No description available.

No / We demonstrate that nanofiltration of aqueous glycine solutions has a pronounced effect on laser-induced nucleation. Two nucleation regimes were observed in nonfiltered, irradiated solutions under isothermal conditions: a rapid initial regime associated with laser-induced nucleation and a second much slower spontaneous nucleation regime. Filtration of the solutions prior to irradiation greatly suppressed the rapid regime, while the slow regime was similar regardless of filtration or irradiation, for all supersaturations studied. A clear effect of filtration on crystal polymorphism was also observed. Nonfiltered irradiated solutions at a lower supersaturation almost exclusively yielded the α-polymorph, while at higher supersaturations there was significant presence (∼40%) of the γ-polymorph. On the other hand, filtered solutions almost exclusively yielded the α-polymorph of glycine at all supersaturations studied. These surprising results challenge some established ideas about laser-induced nucleation, showing that previously reported laser-induced nucleation phenomena in glycine aqueous solutions can be effectively suppressed by filtration, so that the underlying mechanism is unlikely to be based on molecular scale interactions involving just the solute and the solvent alone. Instead, laser-induced nucleation in this system appears to be related to either colloidal scale solution clusters or foreign solid or molecular impurities that can be removed by nanofiltration.

"Porous materials have been a focus of researchers for their applications as molecular storage, molecular sensing, catalysis, asymmetric synthesis and host materials. Metal-organic frameworks (MOFs) represent a promising new class of porous crystalline solids because they exhibit large pore volumes, high surface areas, permanent porosity, high thermal stability, and feature open channels with tunable dimensions and topology. We are currently investigating the design, synthesis, and structures of a new family of MOFs derived from transition metals complexes of 4-(imidazole-1-yl)benzoic acids. Here we present our effort in continuing design and synthesis MOFs composed of 4-(imidazole-1-yl)benzoic acids to expand our knowledge about 4-(imidazole-1-yl)benzoic acid MOF family. A series of ligands are synthesized and Cu MOF-3N, 4, 5 and Cd MOF-3 were synthesized, structure determination found out metal-ligand complex follows our proposal, while Cu MOF-4,5 exhibit porous framework structure via absolute structure determination. Sorption behavior is a key focus in MOF application because the great potential applications MOF bears. Here we carry out a fundamental study about MOF texture and selectivity on MOF-5 and Cd MOF-2. Non-polar polyaromatic hydrocarbons such as naphthalene, phenanthrene, and pyrene, polar molecules such as 2-naphthol, ibuprofen were selected to test our hypothesis that sorption is influenced by the degree of tight fitting, and guest-host interaction such as van der waals and hydrogen bonding. By determining Langmuir isotherms of selected guest molecules, we are able to demonstrate our hypothesis that tighter the fit of the guest molecule and the pores, the higher the amount it would sorb. The sorption difference of non-polar and polar molecules suggest hydrogen bonding is not involved in guest sorption and the dominating force of sorption is hydrophobic interaction. Polymorphism is an interesting phenomenon that bears great value in pharmaceutical industry. Here we report the first case for MOF to serve as a heterogeneous surface that induced nucleation of indomethacin. It is also a first report of this polymorph form of indomethacin. PXRD, DSC, TGA, NMR are conducted as our initial investigation effort. This polymorph exhibits exceptionally thermal stability and low solubility, indicating an unusual tight binding between indomethacin and ethanol solvate. "

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.