Asymptotic analysis of plane-strain mode I steady-state crack growth in transformation toughening ceramics (II)

Based on a constitutive law which includes the shear components of transformation plasticity, the asymptotic solutions to near-tip fields of plane-strain mode I steadity propagating cracks in transformed ceramics are obtained for the case of linear isotropic hardening. The stress singularity, the distributions of stresses and velocities at the crack tip are determined for various material parameters. The factors influencing the near-tip fields are discussed in detail.

O processo decisório legislativo na criação e reforma do Bacen e do CMN em 1964 e 1994 : incerteza, cooperação e resultados legislativos

Analisa o processo decisório legislativo nos casos da criação e reforma do Bacen e do CMN em 1964 e 1994, ocorridos no âmbito de planos exitosos de combate à inflação (PAEG e Plano Real, respectivamente). A definição de um formato institucional para a autoridade monetária é uma escolha dos legisladores em termos da produção da política pública de responsabilidade daqueles órgãos, que em ambos os casos foi importante na busca da estabilidade de preços. A partir da Teoria Política Formal utilizaram-se dados primários e fontes secundárias para construir modelo e hipóteses que consideraram as dimensões de interesse geral (combate à inflação) e de políticas particularistas/distributivistas (crédito rural e representação privada no CMN). Concluiu-se que em ambos os processos a iniciativa do Poder Executivo foi fundamental para o resultado final, contudo, em ambas as situações, mesmo durante o ano de 1964 (período militar), o Legislativo teve papel relevante na definição do formato final de ambas as decisões. No primeiro caso houve uma barganha entre os Poderes Executivo e Legislativo para aprovação da proposta, que envolveu concessões no sentido de garantir representação privada no CMN e a institucionalização do crédito rural. No segundo caso o uso da Medida Provisória caracterizou uma forma diferente de coordenação entre os poderes, em que a MP atuou para diminuir a incerteza em relação aos resultados do plano e às alterações na composição do CMN e assim permitir a aprovação da matéria. Os resultados da tese, favorecidos pela comparação de dois períodos diversos do sistema político brasileiro, colaboram com a análise das relações Executivo-Legislativo, sobretudo ao valorizar os instrumentos legislativos do Presidente da República e a forma de equacionamento da incerteza nos processos decisórios. Ainda, permite-se um maior conhecimento da realidade legislativa durante o ano de 1964, quando, ao menos para a Reforma Bancária, não se pode falar de solapamento dos poderes e prerrogativas do Congresso Nacional pelo governo militar.

Florida's West Coast inlets: shoreline effects and recommended action

This report responds to the 1986 Beaches Bill which, in recognition of the potential deleterious impact on Florida's beaches of inlets modified for navigation, mandated a study of those inlets with identification of recommended action to reduce the impacts. This report addresses west Coast inlets; East Coast inlets are the subject of a companion report. There are 37 inlets along that portion of Florida's West Coast commencing from Pensacola Bay Entrance to Caxambas Pass at the south end of Marco Island. Compared to those on the East Coast, most West Coast inlets have not had the deleterious effects on the adjacent beaches, yet all modified inlets without proper management have the potential of impacting unfavorably on the adjacent shorelines. Moreover, at present there is interest in opening three West Coast entrances which either have been open in the past (Midnight Pass) or which have opened occasionally (Navarre Pass and Entrance to Phillips Lake). A review of inlets in their natural condition demonstrates the presence of a shallow broad outer bar across which the longshore transport Occurs. These shallow and shifting bar features were unsuitable for navigation which in many cases has led to the deepening of the channels and fixing with one or two jetty structures. Inlets in this modified state along with inappropriate maintenance practices have the potential of placing great ero$ional stress along the adjacent beaches. Moreover. channel dredging can reduce wave sheltering of the shoreline by ebb tidal shoals and alter the equilibrium of the affected shoreline segments. The ultimate in poor sand management practice is the placement of good quality beach sand in water depths too great for the sand to reenter the longshore system under natural forces; depths of 12 ft. or less are considered appropriate for Florida in order to maintain the sand in the system. With the interference of the nearshore sediment transport processes by inlets modified for navigation, if the adjacent beaches are to be stabilized there must be an active monitoring program with commitment to placement of dredged material of beach quality on shoreline segments of documented need. Several East Coast inlets have such transfer facilities; however. the quantities of sand transferred should be increased. Although an evolution and improvement in the technical capability to manage sand resources in the vicinity of inlets is expected, an adequate capability exists today and a concerted program should be made to commence a scheduled implementation of this capability at those entrances causing greatest erosional stress on the adjacent shorelines. A brief summary review for each of the 37 West Coast inlets is presented including: a scaled aerial photograph, brief historical information, several items related to sediment losses at each inlet and special characteristics relevant to State responsibilities. For each inlet, where appropriate, the above infor~tion is utilized to develop a recommenced action. (PDF has 101 pages.)

New Oncogenic Drivers in Hepatocellular Carcinoma: Role of the RNA Binding Protein Hu antigen R

156 p. : graf.

Distribution of skipjack in the Pacific Ocean, based on records of incidental catches of the Japanese longline tuna fishery

ENGLISH: All available longline data on skipjack captured in the Pacific Ocean by Japanese research vessels (1949-1965) and from incidental skipjack catches by Japanese commercial vessels (1956-1964) were analyzed. As skipjack are not specifically sought by longline vessels, the data are limited. Considering this it was found that: longline gear captures skipjack of wider size-range and is more selective for larger skipjack than conventional fishing methods, i.e. pole-and-line and purse-seine; skipjack are widely and almost continuously distributed across the Pacific; throughout the year average hook-rates are greater in the southeastern Pacific than in the northwestern Pacific; areas of high hook-rate shift south during the second and third quarters and north during the first and fourth quarters; in the western Pacific the north-south range of the catch distribution was greatest in the first and fourth quarters; skipjack hook-rates are relatively high in the northwestern Pacific east of Japan only during the first and fourth quarters; the highest hook-rates were recorded in extensive areas along the equator (from lO°N to 20°8 between approximately 155°W-100°W); generally more skipjack were captured by research longline gear in water temperature ranges approaching both the upper and lower temperature limits of skipjack distribution (18-21C and 26-28C), than is the case in surface skipjack fisheries; tentative comparisons of longline skipjack catch distributions with Pacific current systems, suggests low skipjack abundance in both North Pacific Central and North Pacific Equatorial water; the sex ratio was 95 males : 63 females in a small sample of skipjack examined; longlines capture skipjack of three, and possibly more, age groups; in skipjack size-composition samples studied, the smaller modal group (65 cm) observed in January-March in the northwestern Pacific (1600E-180oE and 20oN-45°N) corresponds in size to the larger modal group appearing in the late-summer surface fishery off the Izu-Bonin Islands southeast of Japan, and also compares in modal size to the skipjack taken in the Hawaiian fishery in spring time; the analysis of skipjack catches by hook position on the longline and by death-rate studies, indicates that part of the catch is made while the gear is in motion near the surface, and a lesser part of the catch is made when the gear is stabilized at a depth of 70 to 140 m. A brief discussion is given, in the light of new information presented, on several hypotheses by other authors concerning the population structure and migration of skipjack in the Pacific Ocean. SPANISH: Se analizaron todos los datos disponibles de la pesca con palangre de barriletes capturados en el Océano Pacífico por barcos japoneses de investigación (1949-1965) y por las capturas incidentales de los barcos comerciales japoneses (1956-1964). Como los barcos palangreros específicamente, no persiguen al barrilete, los datos son limitados. Considerando ésto, se encontró: que el arte palangrero obtiene barriletes con una distribución más amplia de tallas, y es más selectivo en cuanto a los barriletes de mayor talla, que los métodos convencionales de pesca, Le. cañas de pescar y redes de cerco; el barrilete se encuentra amplia y casi continuamente distribuido a través del Pacífico; en todo el año, las tasas promedio de captura por anzuelo son superiores en el Pacífico sudoriental que las del Pacífico noroeste; las áreas con una tasa alta de captura por anzuelo, se cambian hacia el sur durante los trimestres segundo y tercero, y durante los trimestres primero y cuarto hacia el norte; en el Pacífico occidental la amplitud de la distribución de captura norte-sur, fue superior en los trimestres primero y cuarto; las tasas de captura por anzuelo de barrilete, son relativamente altas en el Pacífico noroeste al este del Japón, únicamente durante los trimestres primero y cuarto; las tasas de captura por anzuelo más altas fueron registradas en extensas áreas a lo largo del ecuador (desde los 10°N hasta los 20°S, aproximadamente entre los 155°W-100°W) ; generalmente las artes palangreras de investigación capturaron más barrilete en aguas en las que la temperatura se aproximaba a los límites más altos o bajos de la temperatura en la distribución del barrilete (18-21 C y 26-28 C), que en el caso de la pesca superficial de barrilete; las comparaciones tentativas de la captura de barrilete con palangre, con el sistema de las corrientes del Pacífico, sugieren una abundancia inferior de barrilete tanto en las aguas del Pacífico central del norte como en las del Pacífico ecuatorial del norte; la proporcíon sexual examinada en una pequeña muestra de barriletes, fue de 95 machos y 63 hembras; los palangreros capturan barriletes de tres grupos de edad y posiblemente de más; en las muestras estudiadas de la composición de las tallas de barrilete, el grupo modal más pequeño (65 cm), observado en enero-marzo en el Pacífico noroeste (160 0E-180° y 20 oN-45°N), corresponde en talla al grupo modal más grande que aparece en la pesca de superficie a fines del verano frente a las Islas Izu-Bonín al sudeste del Japón, y se compara también con la talla modal del barrilete obtenido en la pesca hawaiana en la época de primavera; el análisis de las capturas de barrilete por medio del estudio de la posición de los anzuelos en el palangre y por la tasa de mortalidad, indica que parte de la captura se efectúa cuando el equipo está en movimiento cerca a la superficie y una parte inferior de la captura se realiza, cuando las artes se estabilizan a una profundidad de 70 a 140 m. Se ofrece una breve discusión sobre varias hipótesis de otros autores, en vista de la nueva información presentada referente a la estructura poblacional y a la migración del barrilete en el Océano Pacífico. (PDF contains 100 pages.)

Der Krill im Südatlantik. Entwicklung der Bestände, der Fischerei und des Bestandsmanagements

Since 1976 the Institute of Sea Fisheries of the Federal Research Center for Fisheries, Hamburg, has been conducting long-term monitoring research on Antarctic krill in order to manage the stocks according to the precautionary approach. The krill stocks of the South Atlantic fluctuate seasonally as well as inter-annually in biomass and recruitment success. Following high densities in the late 1970s, the stocks are recently declining. Shortly after the onset of a commercial fishery the catches reached a maximum of around 500 000 t annually, but stabilized around 100 000 t during recent years. Actual survey results indicate mean krill densities in the South Atlantic of 21.4 g/m2, corresponding to 44 Mio. t. The potential yield and maximum catch rate was set at 4.0 Mio. t per year subdivided for the various CCAMLR Subareas. CCAMLR is expected to introduce further conservation measures to control the fishery in the convention area in the near future, however, there is still room for developing a krill fishery in the Antarctic.

Structure-function studies of serine hydrolases: synthesis of a gene for ∝-lytic protease and the purification and characterization of a mutant β-lactamase

The author has constructed a synthetic gene for ∝-lytic protease. Since the DNA sequence of the protein is not known, the gene was designed by using the reverse translation of ∝-lytic protease's amino acid sequence. Unique restriction sites are carefully sought in the degenerate DNA sequence to aid in future mutagenesis studies. The unique restriction sites are designed approximately 50 base pairs apart and their appropriate codons used in the DNA sequence. The codons used to construct the DNA sequence of ∝-lytic protease are preferred codons in E-coli or used in the production of β-lactamase. Codon usage is also distributed evenly to ensure that one particular codon is not heavily used. The gene is essentially constructed from the outside in. The gene is built in a stepwise fashion using plasmids as the vehicles for the ∝-lytic oligomers. The use of plasmids allows the replication and isolation of large quantities of the intermediates during gene synthesis. The ∝-lytic DNA is a double-stranded oligomer that has sufficient overhang and sticky ends to anneal correctly in the vector. After six steps of incorporating ∝-lytic DNA, the gene is completed and sequenced to ensure that the correct DNA sequence is present and that no mutations occurred in the structural gene.

β-lactamase is the other serine hydrolase studied in this thesis. The author used the class A RTEM-1 β- lactamase encoded on the plasmid pBR322 to investigate the roll of the conserved threonine residue at position 71. Cassette mutagenesis was previously used to generate all possible amino acid substitutions at position 71. The work presented here describes the purification and kinetic characterization of a T71H mutant previously constructed by S. Schultz. The mutated gene was transferred into plasmid pJN for expression and induced with IPTG. The enzyme is purified by column chromatography and FPLC to homogeneity. Kinetic studies reveal that the mutant has lower k_(cat) values on benzylpenicillin, cephalothin and 6-aminopenicillanic acid but no changes in k_m except for cephalothin which is approximately 4 times higher. The mutant did not change siginificantly in its pH profile compared to the wild-type enzyme. Also, the mutant is more sensitive to thermal denaturation as compared to the wild-type enzyme. However, experimental evidence indicates that the probable generation of a positive charge at position 71 thermally stabilized the mutant.

An evaluation of the pelagic primary productivity and potential fish yield of Kainji Lake, Nigeria

The environmental conditions of Kainji Lake from 1971/72 to date appear to have stabilized to a large extent, judging from the similarity of physico-chemical parameters investigated in this study over the period. Solar radiation (as reflected in variation in temperature) and pH have remained largely constant over the years, while conductivity (index of nutrient enrichment), though significantly higher in 1995/96, could be described as sporadic and needs further monitoring to ascertain its trend in the lake. While water transparency and dissolved oxygen were higher in 1971/72 compared to the other years, these increases cannot be said to be overwhelming. The lower transparency in 1995/96 was due to the exceptional flood of that year and may have also accounted for the poorer dissolved oxygen concentration compared to the other years due to its impact on photosynthesis. There is no evidence from this study to indicate that primary productivity has increased over the years. Consequently, the observed increase in fish yield by the KLFPP from CAS, which is corroborated by estimates from the MEI, cannot be supported on the basis of improved photosynthetic production. The phenomenal high levels of conductivity recorded during certain periods in 1995 (600 mu mhos cm super(-1)) are hitherto unknown in the lake and may indicate a trend towards nutrient enrichment. However, it is premature at this stage to conclude on its long-term impact on primary production and consequently, on fish yield. Secondly, the notion of overfishing in the 80s (Ita, 1993), may need to be further examined as low or dwindling catches could be due to a number of factors among which are the level of fishing effort, the type and efficiency of gears and the intensity of sampling. It would appear that with the intervention of KLFPP, the better management of the lake's fisheries would increase the current level of catch. It also needs to be examined how much of the clupeid fisheries, which is now known to account for a substantial proportion of the total fish yield in Kainji Lake, was included in the sampling of the 80s. (PDF contains 43 pages)

Recognition of double helical DNA by purine oligonucleotides via triple helix formation

Oligonucleotide-directed triple helix formation is one of the most versatile methods for the sequence specific recognition of double helical DNA. Chapter 2 describes affinity cleaving experiments carried out to assess the recognition potential for purine-rich oligonucleotides via the formation of triple helices. Purine-rich oligodeoxyribonucleotides were shown to bind specifically to purine tracts of double helical DNA in the major groove antiparallel to the purine strand of the duplex. Specificity was derived from the formation of reverse Hoogsteen G•GC, A•AT and T•AT triplets and binding was limited to mostly purine tracts. This triple helical structure was stabilized by multivalent cations, destabilized by high concentrations of monovalent cations and was insensitive to pH. A single mismatched base triplet was shown to destabilize a 15 mer triple helix by 1.0 kcal/mole at 25°C. In addition, stability appeared to be correlated to the number of G•GC triplets formed in the triple helix. This structure provides an additional framework as a basis for the design of new sequence specific DNA binding molecules.

In work described in Chapter 3, the triplet specificities and required strand orientations of two classes of DNA triple helices were combined to target double helical sequences containing all four base pairs by alternate strand triple helix formation. This allowed for the use of oligonucleotides containing only natural 3'-5' phosphodiester linkages to simultaneously bind both strands of double helical DNA in the major groove. The stabilities and structures of these alternate strand triple helices depended on whether the binding site sequence was 5'-(purine)_m (pyrimidine)_n-3' or 5'- (pyrimidine)_m (purine)_n-3'.

In Chapter 4, the ability of oligonucleotide-cerium(III) chelates to direct the transesterfication of RNA was investigated. Procedures were developed for the modification of DNA and RNA oligonucleotides with a hexadentate Schiff-base macrocyclic cerium(III) complex. In addition, oligoribonucleotides modified by covalent attachment of the metal complex through two different linker structures were prepared. The ability of these structures to direct transesterification to specific RNA phosphodiesters was assessed by gel electrophoresis. No reproducible cleavage of the RNA strand consistent with transesterification could be detected in any of these experiments.

Fracture of materials undergoing solid-solid phase transformation

A large number of technologically important materials undergo solid-solid phase transformations. Examples range from ferroelectrics (transducers and memory devices), zirconia (Thermal Barrier Coatings) to nickel superalloys and (lithium) iron phosphate (Li-ion batteries). These transformations involve a change in the crystal structure either through diffusion of species or local rearrangement of atoms. This change of crystal structure leads to a macroscopic change of shape or volume or both and results in internal stresses during the transformation. In certain situations this stress field gives rise to cracks (tin, iron phosphate etc.) which continue to propagate as the transformation front traverses the material. In other materials the transformation modifies the stress field around cracks and effects crack growth behavior (zirconia, ferroelectrics). These observations serve as our motivation to study cracks in solids undergoing phase transformations. Understanding these effects will help in improving the mechanical reliability of the devices employing these materials.

In this thesis we present work on two problems concerning the interplay between cracks and phase transformations. First, we consider the directional growth of a set of parallel edge cracks due to a solid-solid transformation. We conclude from our analysis that phase transformations can lead to formation of parallel edge cracks when the transformation strain satisfies certain conditions and the resulting cracks grow all the way till their tips cross over the phase boundary. Moreover the cracks continue to grow as the phase boundary traverses into the interior of the body at a uniform spacing without any instabilities. There exists an optimal value for the spacing between the cracks. We ascertain these conclusion by performing numerical simulations using finite elements.

Second, we model the effect of the semiconducting nature and dopants on cracks in ferroelectric perovskite materials, particularly barium titanate. Traditional approaches to model fracture in these materials have treated them as insulators. In reality, they are wide bandgap semiconductors with oxygen vacancies and trace impurities acting as dopants. We incorporate the space charge arising due the semiconducting effect and dopant ionization in a phase field model for the ferroelectric. We derive the governing equations by invoking the dissipation inequality over a ferroelectric domain containing a crack. This approach also yields the driving force acting on the crack. Our phase field simulations of polarization domain evolution around a crack show the accumulation of electronic charge on the crack surface making it more permeable than was previously believed so, as seen in recent experiments. We also discuss the effect the space charge has on domain formation and the crack driving force.

Interplay of martensitic phase transformation and plastic slip in polycrystals

Inspired by key experimental and analytical results regarding Shape Memory Alloys (SMAs), we propose a modelling framework to explore the interplay between martensitic phase transformations and plastic slip in polycrystalline materials, with an eye towards computational efficiency. The resulting framework uses a convexified potential for the internal energy density to capture the stored energy associated with transformation at the meso-scale, and introduces kinetic potentials to govern the evolution of transformation and plastic slip. The framework is novel in the way it treats plasticity on par with transformation.

We implement the framework in the setting of anti-plane shear, using a staggered implicit/explict update: we first use a Fast-Fourier Transform (FFT) solver based on an Augmented Lagrangian formulation to implicitly solve for the full-field displacements of a simulated polycrystal, then explicitly update the volume fraction of martensite and plastic slip using their respective stick-slip type kinetic laws. We observe that, even in this simple setting with an idealized material comprising four martensitic variants and four slip systems, the model recovers a rich variety of SMA type behaviors. We use this model to gain insight into the isothermal behavior of stress-stabilized martensite, looking at the effects of the relative plastic yield strength, the memory of deformation history under non-proportional loading, and several others.

We extend the framework to the generalized 3-D setting, for which the convexified potential is a lower bound on the actual internal energy, and show that the fully implicit discrete time formulation of the framework is governed by a variational principle for mechanical equilibrium. We further propose an extension of the method to finite deformations via an exponential mapping. We implement the generalized framework using an existing Optimal Transport Mesh-free (OTM) solver. We then model the $\alpha$--$\gamma$ and $\alpha$--$\varepsilon$ transformations in pure iron, with an initial attempt in the latter to account for twinning in the parent phase. We demonstrate the scalability of the framework to large scale computing by simulating Taylor impact experiments, observing nearly linear (ideal) speed-up through 256 MPI tasks. Finally, we present preliminary results of a simulated Split-Hopkinson Pressure Bar (SHPB) experiment using the $\alpha$--$\varepsilon$ model.

Flight dynamics in Drosophila through a dynamically-scaled robotic approach

Flies are particularly adept at balancing the competing demands of delay tolerance, performance, and robustness during flight, which invites thoughtful examination of their multimodal feedback architecture. This dissertation examines stabilization requirements for inner-loop feedback strategies in the flapping flight of Drosophila, the fruit fly, against the backdrop of sensorimotor transformations present in the animal. Flies have evolved multiple specializations to reduce sensorimotor latency, but sensory delay during flight is still significant on the timescale of body dynamics. I explored the effect of sensor delay on flight stability and performance for yaw turns using a dynamically-scaled robot equipped with a real-time feedback system that performed active turns in response to measured yaw torque. The results show a fundamental tradeoff between sensor delay and permissible feedback gain, and suggest that fast mechanosensory feedback provides a source of active damping that compliments that contributed by passive effects. Presented in the context of these findings, a control architecture whereby a haltere-mediated inner-loop proportional controller provides damping for slower visually-mediated feedback is consistent with tethered-flight measurements, free-flight observations, and engineering design principles. Additionally, I investigated how flies adjust stroke features to regulate and stabilize level forward flight. The results suggest that few changes to hovering kinematics are actually required to meet steady-state lift and thrust requirements at different flight speeds, and the primary driver of equilibrium velocity is the aerodynamic pitch moment. This finding is consistent with prior hypotheses and observations regarding the relationship between body pitch and flight speed in fruit flies. The results also show that the dynamics may be stabilized with additional pitch damping, but the magnitude of required damping increases with flight speed. I posit that differences in stroke deviation between the upstroke and downstroke might play a critical role in this stabilization. Fast mechanosensory feedback of the pitch rate could enable active damping, which would inherently exhibit gain scheduling with flight speed if pitch torque is regulated by adjusting stroke deviation. Such a control scheme would provide an elegant solution for flight stabilization across a wide range of flight speeds.

A genetic and biochemical analysis of pre-mRNA splicing in Saccharomyces cerevisiae

Pre-mRNA splicing requires interaction of cis- acting intron sequences with trans -acting factors: proteins and small nuclear ribonucleoproteins (snRNPs). The assembly of these factors into a large complex, the spliceosome, is essential for the subsequent two step splicing reaction. First, the 5' splice site is cleaved and free exon 1 and a lariat intermediate (intron- exon2) form. In the second reaction the 3' splice site is cleaved the exons ligated and lariat intron released. A combination of genetic and biochemical techniques have been used here to study pre-mRNA splicing in yeast.

Yeast introns have three highly conserved elements. We made point mutations within these elements and found that most of them affect splicing efficiency in vivo and in vitro, usually by inhibiting spliceosome assembly.

To study trans -acting splicing factors we generated and screened a bank of temperature- sensitive (ts) mutants. Eleven new complementation groups (prp17 to prp27) were isolated. The four phenotypic classes obtained affect different steps in splicing and accumulate either: 1) pre-mRNA, 2) lariat intermediate, 3) excised intron or 4) both pre-mRNA and intron. The latter three classes represent novel phenotypes. The excised intron observed in one mutant: prp26 is stabilized due to protection in a snRNP containing particle. Extracts from another mutant: prpl8 are heat labile and accumulate lariat intermediate and exon 1. This is especially interesting as it allows analysis of the second splicing reaction. In vitro complementation of inactivated prp18 extracts does not require intact snRNPs. These studies have also shown the mutation to be in a previously unknown splicing protein. A specific requirement for A TP is also observed for the second step of splicing. The PRP 18 gene has been cloned and its polyadenylated transcript identified.

Physical characterization of the rack effect and hydrogen bond networks in blue copper proteins

A summary of previous research is presented that indicates that the purpose of a blue copper protein's fold and hydrogen bond network, aka, the rack effect, enforce a copper(II) geometry around the copper(I) ion in the metal site. In several blue copper proteins, the C-terminal histidine ligand becomes protonated and detaches from the copper in the reduced forms. Mutants of amicyanin from Paracoccus denitrificans were made to alter the hydrogen bond network and quantify the rack effect by pK_a shifts.

The pK_a's of mutant amicyanins have been measured by pH-dependent electrochemistry. P94F and P94A mutations loosen the Northern loop, allowing the reduced copper to adopt a relaxed conformation: the ability to relax drives the reduction potentials up. The measured potentials are 265 (wild type), 380 (P94A), and 415 (P94F) mV vs. NHE. The measured pK_a's are 7.0 (wild type), 6.3 (P94A), and 5.0 (P94F). The additional hydrogen bond to the thiolate in the mutants is indicated by a red-shift in the blue copper absorption and an increase in the parallel hyperfine splitting in the EPR spectrum. This hydrogen bond is invoked as the cause for the increased stability of the C-terminal imidazole.

Melting curves give a measure of the thermal stability of the protein. A thermodynamic intermediate with pH-dependent reversibility is revealed. Comparisons with the electrochemistry and apoamicyanin suggest that the intermediate involves the region of the protein near the metal site. This region is destabilized in the P94F mutant; coupled with the evidence that the imidazole is stabilized under the same conditions confirms an original concept of the rack effect: a high energy configuration is stabilized at a cost to the rest of the protein.

Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.