The main objective of this study was to optimize the processing conditions of breads baked in halogen lamp-microwave combination oven by using response surface methodology. It was also aimed to construct neural network models for the prediction of quality parameters of bread as a function of processing conditions. Different baking time and power combinations were used in order to find the optimum baking conditions of bread in halogen lamp-microwave combination oven. The independent variables were the baking time (4, 4.5, 5, 5.5, and 6 min), power of upper and lower halogen lamps (40, 50, 60, 70, and 80%), and power of the microwave (20, 30, 40, 50, and 60%). As control, breads baked in conventional oven at 200&ordm / C for 13 min were used. The measured quality parameters were the weight loss, color change, specific volume, porosity, and texture profile of the breads. Baking time, upper halogen lamp power, and microwave power were found to be significant on affecting most of the quality parameters. On the other hand, lower halogen lamp power was found to be an insignificant factor for all of the responses. For the optimization process, Response Surface Methodology (RSM) was used. The optimum baking conditions were determined as 5 min of baking time at 70% upper halogen lamp power, 50% lower halogen lamp power, and 20% microwave power. Breads baked at the optimum condition had comparable quality with conventionally baked ones. When halogen lamp-microwave combination oven was used, conventional baking time of breads was reduced by 60%. Artificial neural network models were developed for each of the quality parameters in order to observe the effects of the baking time and different oven conditions on the quality of the breads. High regression coefficients were calculated between the experimental data and predicted values showing that this method is capable in predicting quality parameters of breads during halogen lamp-microwave combination baking. In addition, the results were comparable to the RSM study.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A diversificação das fontes de luz empregadas para fotopolimerização de compósitos e o seu extenso uso nas diversas aplicações odontológicas, torna necessária a investigação da biocompatibilidade das mesmas. A conseqüente exposição dos tecidos durante estes procedimentos, sugere fortemente que mais investigações sobre os efeitos biológicos da luz com comprimentos de onda correspondentes ao da luz azul são necessárias. O efeito positivo provocado pela evolução dos aparelhos fotopolimerizadores desviou a atenção das possíveis alterações fototóxicas sobre o profissional e o paciente. Além disso, o aumento da temperatura causado por estes aparelhos fotopolimerizadores de maiores densidades de potência pode ser prejudicial ao tecido pulpar. Da mesma maneira, a presença de um corante no meio bucal e sua conseqüente exposição à luz azul poderia levar à formação de radicais livres, o que em situações de estresse oxidativo, poderia causar danos aos tecidos adjacentes. Este fenônemo é denominado Ação Fotodinâmica. O objetivo deste estudo foi avaliar em cepas de Escherichia coli (E. coli): (i) o potencial citotóxico de duas fontes de ativação utilizadas em procedimentos odontológicos durante 40 e 80 s de exposição; (ii) o efeito biológico do enxaguatório bucal da marca Plax Classic, contendo corante vermelho; (iii) o efeito biológico da associação das fontes de luz ao enxaguatório bucal da marca Plax Classic, contendo corante vermelho (ação fotodinâmica), durante 40 e 80 s de exposição; (iv) medir a emissão de calor gerada pelas fontes de luz. Foram utilizadas suspensões bacterianas de E.coli AB1157 (proficiente em mecanismos de reparo de lesões no DNA) e de E. coli BW9091 (deficiente no gene xthA-, envolvido no reparo por excisão de bases), irradiadas por um aparelho de luz halógena e um LED, que apresentam comprimentos de onda correspondentes ao da luz azul e densidades de potência de 430 mW/cm2 e 1669 mW/cm2, respectivamente. As medições da potência foram realizadas através de um lediômetro, para o LED, o Hilux LEDMAX, e um radiômetro acoplado ao próprio aparelho de luz halógena, Optilux 501. A partir dos resultados deste estudo, pôde-se constatar que: (i) as fontes de luz nas densidades de potência utilizadas e nos tempos de exposição realizados, não foram capazes de alterar a sobrevivência celular; (ii) o enxaguatório bucal isoladamente reduziu a sobrevivência das cepas de E. coli BW9091 e não causou efeito nas cepas de E. coli AB1157; (iii) quando o enxaguatório bucal foi associado às fontes de luz observamos que não houve diminuição da sobrevivência para as duas cepas bacterianas nos dois períodos de exposição, porém, na cepa mutante, BW9091, houve uma proteção contra o efeito citotóxico do enxaguatório bucal tanto em 40 quanto em 80 s para as duas fontes de luz; (iv) o aumento da temperatura das duas fontes de luz durante a fotoativação não foi capaz de reduzir a sobrevivência das cepas bacterianas. As fontes de luz utilizadas neste trabalho não apresentaram letalidade às cepas de E. coli. O enxaguatório bucal apresentou efeito biológico para a cultura de E. coli BW9091, possivelmente pela sua natureza antimicrobiana. A associação dos agentes físico e químico neste estudo não pareceu causar um estresse oxidativo nas células a ponto de reduzir a sobrevivência das culturas bacterianas, contrariamente, pareceu ativar mecanismos de proteção celular na cepa de E. coli BW9091 e mantê-la mais resistente à ação antimicrobiana do enxaguatório bucal. A variação da temperatura, apesar de elevada, parece ter sido dissipada pelo meio aquoso que continha a cultura bacteriana. / The diversity of light curing units (LCUs), its large use on variety dental applications, and its function as an activator of dental composites polymerization make necessary a study of its biocompatibility. The consequent exposure of tissues during photo activation, strongly suggests that more investigations about the biological effects of blue light are needed. The positive effect promoted by the LCUs evolution biased the attention of possible phototoxic effects on professionals and patients. In addition, the temperature rise caused by these LCUs with higher power densities may be harmful to the pulp tissue. On the same way, the presence of a photosensitizer upon oral environment and its consequent exposure to blue light could lead the formation of free radicals, in which oxidative stress outcome could damage the adjacent tissues. This phenomenon is called Photodynamic Action. The aim of this study was to evaluate in Escherichia coli (E. coli) strains: (i) the cytotoxic effect of two LCUs used in dental procedures during 40 and 80 seconds of irradiation times; (ii) the biological effect of a mouth rinse with a red photosensitizer, Plax Classic; (iii) the biological effect of the association of the LCUs to a mouth rinse, with a red photosensitizer, Plax Classic, during 40 and 80 seconds of irradiation times; (iv) measurement of the LCUs thermal emission. Suspensions of E. coli AB1157 (proficient in all DNA repair mechanisms) and E. coli BW9091 (gene xthA- deficient, related to DNA damage repair), were irradiated by a halogen light and a LED (light emitting diode), that presents intervals of wavelength correspondents with blue light and power densities of 430 mW/cm2 and 1669 mW/cm2, respectively. The power density for the LED LCU was measured on a Hilux LEDMAX power meter, and for the halogen LCU, on the Optilux 501 power meter. The results indicated that: (i) the LCUs used with these power densities and these irradiation times, were not capable in altering the cellular survival rate; (ii) the mouth rinse itself reduced the survival rate of E. coli strain BW9091 and did not caused effect in E. coli strain AB1157; (iii) when the mouth rinse was associated to the LCUs, we observed that there was no reduction of the survival rate to both E. coli strains in both irradiation times; however, in the mutant strain, BW9091, a protection against the citotoxic effect of the mouth rinse was observed in 40 and 80 seconds of irradiation times to both LCUs; (iv) the temperature rise of both LCUs during photo activation, despite being elevated, was not capable in reducing the bacterial strains survival rate. The LCUs used in this study did not present lethal effect to the E. coli strains. The mouth rinse presented a biological effect to the E. coli strain BW9091, possibly because its antimicrobial nature. Although the association of the physical and chemical agents did not seem to cause an oxidative stress that could reduce the bacterial survival rate of E. coli strains, it seemed to activate mechanisms of cellular protection in E. coli BW9091 that kept them more resistants to the antimicrobial nature of the chemical agent. The temperature rise seemed to be dissipated by the aquous solution that contained the bacterial culture.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A diversificação das fontes de luz empregadas para fotopolimerização de compósitos e o seu extenso uso nas diversas aplicações odontológicas, torna necessária a investigação da biocompatibilidade das mesmas. A conseqüente exposição dos tecidos durante estes procedimentos, sugere fortemente que mais investigações sobre os efeitos biológicos da luz com comprimentos de onda correspondentes ao da luz azul são necessárias. O efeito positivo provocado pela evolução dos aparelhos fotopolimerizadores desviou a atenção das possíveis alterações fototóxicas sobre o profissional e o paciente. Além disso, o aumento da temperatura causado por estes aparelhos fotopolimerizadores de maiores densidades de potência pode ser prejudicial ao tecido pulpar. Da mesma maneira, a presença de um corante no meio bucal e sua conseqüente exposição à luz azul poderia levar à formação de radicais livres, o que em situações de estresse oxidativo, poderia causar danos aos tecidos adjacentes. Este fenônemo é denominado Ação Fotodinâmica. O objetivo deste estudo foi avaliar em cepas de Escherichia coli (E. coli): (i) o potencial citotóxico de duas fontes de ativação utilizadas em procedimentos odontológicos durante 40 e 80 s de exposição; (ii) o efeito biológico do enxaguatório bucal da marca Plax Classic, contendo corante vermelho; (iii) o efeito biológico da associação das fontes de luz ao enxaguatório bucal da marca Plax Classic, contendo corante vermelho (ação fotodinâmica), durante 40 e 80 s de exposição; (iv) medir a emissão de calor gerada pelas fontes de luz. Foram utilizadas suspensões bacterianas de E.coli AB1157 (proficiente em mecanismos de reparo de lesões no DNA) e de E. coli BW9091 (deficiente no gene xthA-, envolvido no reparo por excisão de bases), irradiadas por um aparelho de luz halógena e um LED, que apresentam comprimentos de onda correspondentes ao da luz azul e densidades de potência de 430 mW/cm2 e 1669 mW/cm2, respectivamente. As medições da potência foram realizadas através de um lediômetro, para o LED, o Hilux LEDMAX, e um radiômetro acoplado ao próprio aparelho de luz halógena, Optilux 501. A partir dos resultados deste estudo, pôde-se constatar que: (i) as fontes de luz nas densidades de potência utilizadas e nos tempos de exposição realizados, não foram capazes de alterar a sobrevivência celular; (ii) o enxaguatório bucal isoladamente reduziu a sobrevivência das cepas de E. coli BW9091 e não causou efeito nas cepas de E. coli AB1157; (iii) quando o enxaguatório bucal foi associado às fontes de luz observamos que não houve diminuição da sobrevivência para as duas cepas bacterianas nos dois períodos de exposição, porém, na cepa mutante, BW9091, houve uma proteção contra o efeito citotóxico do enxaguatório bucal tanto em 40 quanto em 80 s para as duas fontes de luz; (iv) o aumento da temperatura das duas fontes de luz durante a fotoativação não foi capaz de reduzir a sobrevivência das cepas bacterianas. As fontes de luz utilizadas neste trabalho não apresentaram letalidade às cepas de E. coli. O enxaguatório bucal apresentou efeito biológico para a cultura de E. coli BW9091, possivelmente pela sua natureza antimicrobiana. A associação dos agentes físico e químico neste estudo não pareceu causar um estresse oxidativo nas células a ponto de reduzir a sobrevivência das culturas bacterianas, contrariamente, pareceu ativar mecanismos de proteção celular na cepa de E. coli BW9091 e mantê-la mais resistente à ação antimicrobiana do enxaguatório bucal. A variação da temperatura, apesar de elevada, parece ter sido dissipada pelo meio aquoso que continha a cultura bacteriana. / The diversity of light curing units (LCUs), its large use on variety dental applications, and its function as an activator of dental composites polymerization make necessary a study of its biocompatibility. The consequent exposure of tissues during photo activation, strongly suggests that more investigations about the biological effects of blue light are needed. The positive effect promoted by the LCUs evolution biased the attention of possible phototoxic effects on professionals and patients. In addition, the temperature rise caused by these LCUs with higher power densities may be harmful to the pulp tissue. On the same way, the presence of a photosensitizer upon oral environment and its consequent exposure to blue light could lead the formation of free radicals, in which oxidative stress outcome could damage the adjacent tissues. This phenomenon is called Photodynamic Action. The aim of this study was to evaluate in Escherichia coli (E. coli) strains: (i) the cytotoxic effect of two LCUs used in dental procedures during 40 and 80 seconds of irradiation times; (ii) the biological effect of a mouth rinse with a red photosensitizer, Plax Classic; (iii) the biological effect of the association of the LCUs to a mouth rinse, with a red photosensitizer, Plax Classic, during 40 and 80 seconds of irradiation times; (iv) measurement of the LCUs thermal emission. Suspensions of E. coli AB1157 (proficient in all DNA repair mechanisms) and E. coli BW9091 (gene xthA- deficient, related to DNA damage repair), were irradiated by a halogen light and a LED (light emitting diode), that presents intervals of wavelength correspondents with blue light and power densities of 430 mW/cm2 and 1669 mW/cm2, respectively. The power density for the LED LCU was measured on a Hilux LEDMAX power meter, and for the halogen LCU, on the Optilux 501 power meter. The results indicated that: (i) the LCUs used with these power densities and these irradiation times, were not capable in altering the cellular survival rate; (ii) the mouth rinse itself reduced the survival rate of E. coli strain BW9091 and did not caused effect in E. coli strain AB1157; (iii) when the mouth rinse was associated to the LCUs, we observed that there was no reduction of the survival rate to both E. coli strains in both irradiation times; however, in the mutant strain, BW9091, a protection against the citotoxic effect of the mouth rinse was observed in 40 and 80 seconds of irradiation times to both LCUs; (iv) the temperature rise of both LCUs during photo activation, despite being elevated, was not capable in reducing the bacterial strains survival rate. The LCUs used in this study did not present lethal effect to the E. coli strains. The mouth rinse presented a biological effect to the E. coli strain BW9091, possibly because its antimicrobial nature. Although the association of the physical and chemical agents did not seem to cause an oxidative stress that could reduce the bacterial survival rate of E. coli strains, it seemed to activate mechanisms of cellular protection in E. coli BW9091 that kept them more resistants to the antimicrobial nature of the chemical agent. The temperature rise seemed to be dissipated by the aquous solution that contained the bacterial culture.

The nature of interactions within a molecule, i.e. chemical bonding, is well understood today. However, our understanding about intermolecular interactions, which has great relevance in nature, is still evolving. Historically there are two types of intermolecular interactions, van der Waals interaction and hydrogen bonding. However, there has been an upsurge of interest in the halogen bonding and lithium bonding during the last decade. The main emphasis of our research is to understand these interactions in detail, in particular non-conventional hydrogen bond acceptors. In this work, weakly bound complexes are studied using Pulsed Nozzle Fourier Transform Microwave Spectrometer, which has been fabricated in our laboratory and various theoretical methods. FTMW spectroscopy in the supersonic beam provides accurate structural information about the near-equilibrium geometry of small dimers and trimers in isolation. The home-built Pulsed Nozzle Microwave spectrometer, having a spectral range of 2-26.5 GHz has been used to record the microwave spectrum of these complexes. The spectrometer consists of a Fabry-Perot cavity, electronic circuit and pumps. Fabry-Perot cavity is the interaction zone of the molecules and radiation. The electronic circuit is used for the polarization and detection of the signal. Mechanical and diffusion pumps are used to maintain the vacuum inside the cavity. The gas molecules of interest are then mixed with a carrier gas and pulsed supersonically inside the cavity through a nozzle of 0.8 mm diameter. The emission from the complexes formed during the expansion is detected by super-heterodyne detection technique and then Fourier transformed. The first chapter of the thesis gives a brief introduction to intermolecular interactions, hydrogen bonding, halogen bonding, lithium bonding and molecular 2 of clusters. The chapter also includes a brief introduction to rotational spectroscopy. The second chapter of the thesis discusses the experimental and theoretical methods. It includes a detailed discussion of the mechanical and electrical parts of the spectrometer and the software used, which is developed in Labview 7.1. The various theoretical methods (ab initio and DFT) and the basis sets are discussed along with Atoms In Molecules Theory and the criteria used to characterize hydrogen bond. In the third chapter, to understand the ability of saturated hydrocarbons to act as hydrogen bond donor and acceptor, interaction of CH4 with H2S is studied using rotational spectroscopy as well as theoretical methods such as ab initio and Atoms In Molecules theory. Three progressions were obtained for the CH4•••H2S complex using microwave spectroscopy. The progressions were independently fitted to a linear top Hamiltonian. Absence of J10 transition in Progression II confirms the presence of higher internal angular momentum state, m=1. This also confirms the internal rotation of the monomers in the complex. Progressions II and III have negative centrifugal distortion constants. Hence both the states are from some excited internal rotation/torsional motion with strong vibrational-rotational coupling. The moment of inertia obtained from the experimental rotational constant confirms the structure in which sulphur of H2S is close to CH4. This also supports the structure in which CH4 is the hydrogen bond donor, if such an interaction is present. AIM analysis and the potential energy barrier for internal rotation show orientational preference and hence hydrogen bonding. The ab initio results show that CH4•••HSH interaction is more favorable than CH3H•••SH2. Ab initio and AIM studies also gave a structure where there is direct interaction between C and S. This is interesting since the electronegativities of C and S are comparable. Experimentally obtained negative distortion constants for the other two states, confirm excited state rotational-vibrational coupling. The experimental data give a floppy structure having internal rotation. In the fourth chapter the complex chosen for investigation is benzene-ethylene. Experiments in condensed phase and theoretical works show evidence of - stacking in benzene dimer, but there is no gas phase spectroscopic evidence available for the same. The lack of permanent dipole moment in the -stacked geometry of benzene dimer is the hindrance in the experimental observation of the same using microwave spectroscopy. Substitution of one of the benzene with ethylene in the -stacked structure will result in a complex having permanent dipole moment. C6H6 C2H4 complex can have, in addition to -stacking, C-H/interaction. There could be a competition between C6H6 and C2H4, either of which can act as H-bond donor. Experiments show the evidence of C-H/interaction, where C2H4 is the hydrogen bond donor. To ascertain hydrogen bond interaction AIM analysis has been carried out. The results show C-H/interaction, where one of the C2H4 hydrogen interacts with the benzene. Even though the aim was to get the -stacked geometry, it could not be obtained. However theory and AIM supports the formation of -stacked complex. In the fifth chapter using theoretical methods the ability of radicals as acceptor of hydrogen, lithium and chlorine bonds are examined with CF3 radical as the model system. As hydrogen bonds are highly sensitive to the environment, the effect of substitution of hydrogen by fluorine is also analyzed. It is found that, even though CH3 and CF3 radicals are topologically different, they interact in a similar fashion. AIM analysis of CF3HY satisfies all the eight criteria proposed by Koch and Popelier for hydrogen bonding. Here the hydrogen bond formed is charge transfer assisted. The interaction energies of the complexes are inversely proportional to the dipole moment of hydrogen bond donors and are proportional to the charge transfer occurring in the complex. Interaction energies from ab initio calculations confirm complexation of CF3 radical with LiY(Y=F, Cl, Br) and ClF. AIM analysis of CF3LiY and CF3ClF complexes show a bond critical point between Li/Cl and the C of CF3 and the condition of mutual penetration is also met. In CF3LiY complexes the interaction energies and charge transferred are directly proportional to the dipole moment of the Li bond donor. In the sixth chapter in order to extend the concept of non-conventional hydrogen bond acceptors to transition metals, complexes of Fe (Fe(CO)5) with HX (X=F,Cl,Br) have been studied theoretically. DFT calculations show that the structure in which the hydrogen of HX interacting with Fe through the sixth co-ordination site is a stable geometry. AIM analysis shows the presence of a bond critical point between the iron and the hydrogen of HX and hence bond formation. Q obtained from NBO analysis shows that there is charge transfer from the organometallic system to the hydrogen bond donor. However the interaction energies of the complexes are proportional to the dipole moment of hydrogen bond donors and are inversely proportional to the charge transfer for these complexes. H-bonding leads to the stabilization of square pyramidal geometry. ‘Hydrogen bond radius’ of iron has also been defined. Studies on the interaction of Fe(CO)5 with ClF and ClH showed that Fe can also act as a chlorine bond acceptor. Seventh chapter provides the overall conclusion and also discusses future direction.

Solid-state nuclear magnetic resonance (SSNMR) has proven to be a useful tool in the characterization of non-covalent interactions such as hydrogen bonding and cation-π interactions. In recent years, the scientific community has manifested a renewed interest towards an important class of non-covalent interaction, halogen bonding (XB), as it has applications in various fields such as crystal engineering and biological processes. This dissertation demonstrates that NMR parameters measured in the solid state are sensitive to changes in electronic structure, which are caused by halogen bonds. A series of halogen bonded compounds exhibiting interactions between different diiodoperfluorobenzenes (p- C6F4I2, o- C6F4I2, sym- C6F3I3, p- C6H4I2) and various halogen bond acceptors have been synthesized as part of this work. These new halogen bonded compounds were characterized with a combined theoretical and experimental SSNMR, X-ray diffraction (XRD) methods. The complete multinuclear magnetic resonance spectroscopy of the nuclei involved directly in the halogen bond (13C, 14/15N, 31P, 77Se, 35/37Cl and 79/81Br) were recorded at multiple magnetic fields (4.7, 9.4, 11.75 and 21.1 T). The specialized SSNMR experiments provided high-resolution spectra of quadrupolar nuclei, which were WURST-QCPMG or solid-echo type experiments combined with the variable offset cumulative spectral (VOCS) method, as for spin 1/2 nuclei cross polarization magic angle spinning (CPMAS) experiments were usually appropriate. This dissertation will discuss successful applications of SSNMR spectroscopy to characterize halogen bonds, it will demonstrate the significant changes in NMR observables in the presence of XB interaction and thus establish that NMR parameters are very sensitive to halogen bonding interaction. Furthermore, this work explains why the NMR parameters are correlated with the halogen bonding interaction. The different trends observed between the NMR observables and the halogen bonding were further understood with a ZORA-DFT natural localized molecular orbital (NLMO) study.

The goal of this thesis was to process theoretical basis required for better understanding the matters of thermal simulations, to perform particular simulation and its debugging according to the measurement on actual sample. Theoretical part focuses on the variety of the automotive light sources, then kinds of heat transfer, thermal simulations and possibilities of measurement and results verifying. Practical approach was consisted of reverse engineering of particular light source and building its 3D model. In consequence, the characterization of the material properties was made. At the end the thermal simulation of designed 3D model was performed and the optimalization according to realized measurement was implemented.

No description available.

Electrostatic interactions such as halogen bonding and pnictogen bonding interactions have gained a lot of interest in the field of crystal engineering and pharmaceutical science. In the first part of this thesis, we expand our knowledge on anion coordinated halogen bonded cocrystals by looking at a series of cocrystals made from 3-iodoethynyl pyridine and 3-iodoethynylbenzoic acid. We utilize the power of mechanochemistry to create the new cocrystals made with phosphonium salts and use multinuclear solid-state nuclear magnetic resonance spectroscopy and X-ray diffraction and characterize them. We found that mechanochemistry is a fast and powerful tool to explore and synthesize new halogen bonded cocrystals and ³¹P solid-state NMR is a rapid way to identify the formation of a cocrystal. In the second part, we look at the versatility of the pnictogen atom, specifically antimony, as a pnictogen bond donor and a halogen bond acceptor. We evaluate these electrostatic interactions with nuclear quadrupolar resonance and found that nuclear quadrupole resonance is a strong spectroscopy tool to probe these types of electrostatic interactions.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24872号 / 理博第4982号 / 新制||理||1711(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 有賀 哲也, 教授 堀毛 悟史 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Stereochemistry is important aspect of chemistry that customarily includes the study of the relative spatial arrangement of atoms within molecules (static stereochemistry), and the study of the stereochemical requirements and outcomes of chemical reactions (dynamic stereochemistry). These two branches complement each other in modern stereochemistry. Chiral organometallics feature prominently in organic synthesis as reactive intermediates. The possibility of exploring their stereochemistry in synthesis is associated with the configurational stability of the metal-bearing stereogenic center. We were interested in the configurational stability of lithiated and magnesiated nitriles. We developed a new series of lithio-cyclopropylnitriles bearing chelating groups for intramolecular coordination, as a possible strategy to impart configurational stability. Although this strategy has not yet been successful, using density functional theory (DFT) method, we addressed the effect of chelating groups on racemization via the "conducted tour" mechanism. We then explored metal-bromine exchange on enantiopure bromonitrile as alternative route to metalated nitriles. In this way, we demonstrated that magnesiated 2,2-diphenyl cyclopropylnitrile is configurationally stable on the macroscopic timescale. No other metallated nitrile has ever demonstrated configurational stability on this timescale. In contrast, bromine-lithium exchange of 1-bromo-2,2-diphenyl-cyclopropylnitrile demonstrated fast racemization under the same conditions. Another major project focused on conformational control of acyclic molecules. Using X-ray crystallography and NMR spectroscopy, we found that the 2,6-disubstituted aryl group eclipses its geminal hydrogen, and induces an antiperiplanar relationship of the geminal and vicinal hydrogens. Interestingly, anti-nitrile aldols or syn-ketone aldols bearing 2,6-disubstituted aryl groups demonstrate unanticipated remote effects on acyclic conformation: the 2,6-disubstituted aryl group prefers to be in a gauche position to the largest vicinal group. The minimization of allylic 1,3-strain and syn-pentane-like interaction works together in establishing this conformational preference. / Ph. D.