Iridium and rhodium analogues of the Shilov cycle catalyst; and the investigation and applications of the Reduction-Coupled Oxo Activation (ROA) mechanistic motif towards alkane upgrading

This dissertation will cover several disparate topics, with the overarching theme centering on the investigation of organometallic C-H activation and hydrocarbon transformation and upgrading. Chapters 2 and 3 discuss iridium and rhodium analogues of the Shilov cycle catalyst for methane to methanol oxidation, and Chapter 4 on the recently discovered ROA mechanistic motif in catalysts for various alkane partial oxidation reactions. In addition, Chapter 5 discusses the mechanism of nickel pyridine bisoxazoline Negishi catalysts for asymmetric and stereoconvergent C-C coupling, and the appendices discuss smaller projects on rhodium H/D exchange catalysts and DFT method benchmarking.

Climate change and its risk reduction by mangrove ecosystem of Bangladesh

Climate change is amongst the most dreaded problems of the new millennium. Bangladesh is a coastal country bounded by Bay of Bengal on its southern part and here natural disasters are an ongoing part of human life. This paper discusses about the possible impact of climate change through tropical cyclones, storm surges, coastal erosion and sea level rise in the coastal community of Bangladesh and how they cope with these extreme events by the help of mangrove ecosystem. Both qualitative and quantitative discussions are made by collected data from different research work those are conducted in Bangladesh. Mangrove ecosystem provides both goods and services for coastal community, helps to improve livelihood options and protect them from natural disaster by providing variety of environmental support

The influence of freestream turbulence, freestream nuclei populations and a drag-reducing polymer on cavitation inception on two axisymmetric bodies

The influence upon the basic viscous flow about two axisymmetric bodies of (i) freestream turbulence level and (ii) the injection of small amounts of a drag-reducing polymer (Polyox WSR 301) into the test model boundary layer was investigated by the schlieren flow visualization technique. The changes in the type and occurrence of cavitation inception caused by the subsequent modifications in the viscous flow were studied. A nuclei counter using the holographic technique was built to monitor freestream nuclei populations and a few preliminary tests investigating the consequences of different populations on cavitation inception were carried out.

Both test models were observed to have a laminar separation over their respective test Reynolds number ranges. The separation on one test model was found to be insensitive to freestream turbulence levels of up to 3.75 percent. The second model was found to be very susceptible having its critical velocity reduced from 30 feet per second at a 0.04 percent turbulence level to 10 feet per second at a 3.75 percent turbulence level. Cavitation tests on both models at the lowest turbulence level showed the value of the incipient cavitation number and the type of cavitation were controlled by the presence of the laminar separation. Cavitation tests on the second model at 0.65 percent turbulence level showed no change in the inception index, but the appearance of the developed cavitation was altered.

The presence of Polyox in the boundary layer resulted in a cavitation suppression comparable to that found by other investigators. The elimination of the normally occurring laminar separation on these bodies by a polymer-induced instability in the laminar boundary layer was found to be responsible for the suppression of inception.

Freestream nuclei populations at test conditions were measured and it was found that if there were many freestream gas bubbles the normally present laminar separation was elminated and travelling bubble type cavitation occurred - the value of the inception index then depended upon the nuclei population. In cases where the laminar separation was present it was found that the value of the inception index was insensitive to the free stream nuclei populations.

Development of Metalloenzyme Dioxygen Reduction Cathodes

The prime thrust of this dissertation is to advance the development of fuel cell dioxygen reduction cathodes that employ some variant of multicopper oxidase enzymes as the catalyst. The low earth-abundance of platinum metal and its correspondingly high market cost has prompted a general search amongst chemists and materials scientists for reasonable alternatives to this metal for facilitating catalytic dioxygen reduction chemistry. The multicopper oxidases (MCOs), which constitute a class of enzyme that naturally catalyze the reaction O₂ + 4H⁺ + 4e^- → 2H₂O, provide a promising set of biochemical contenders for fuel cell cathode catalysts. In MCOs, a substrate reduces a copper atom at the type 1 site, where charge is then transferred to a trinuclear copper cluster consisting of a mononuclear type 2 or “normal copper” site and a binuclear type 3 copper site. Following the reduction of all four copper atoms in the enzyme, dioxygen is then reduced to water in two two-electron steps, upon binding to the trinuclear copper cluster. We identified an MCO, a laccase from the hyperthermophilic bacterium Thermus thermophilus strain HB27, as a promising candidate for cathodic fuel cell catalysis. This protein demonstrates resilience at high temperatures, exhibiting no denaturing transition at temperatures high as 95°C, conditions relevant to typical polymer electrolyte fuel cell operation.

In Chapter I of this thesis, we discuss initial efforts to physically characterize the enzyme when operating as a heterogeneous cathode catalyst. Following this, in Chapter II we then outline the development of a model capable of describing the observed electrochemical behavior of this enzyme when operating on porous carbon electrodes. Developing a rigorous mathematical framework with which to describe this system had the potential to improve our understanding of MCO electrokinetics, while also providing a level of predictive power that might guide any future efforts to fabricate MCO cathodes with optimized electrochemical performance. In Chapter III we detail efforts to reduce electrode overpotentials through site-directed mutagenesis of the inner and outer-sphere ligands of the Cu sites in laccase, using electrochemical methods and electronic spectroscopy to try and understand the resultant behavior of our mutant constructs. Finally, in Chapter IV, we examine future work concerning the fabrication of enhanced MCO cathodes, exploring the possibility of new cathode materials and advanced enzyme deposition techniques.

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

Physiology of nitrate reduction in Pseudomonas aeruginosa. [Translation from: Z.allg.Mikrobiol. 13, 83-94, 1973.]

Pseudomonas aeruginosa has for some time been known as a denitrifier. Pseudomonas aeruginosa was chosen for further studies, because P. aeruginosa occurs abundantly in Plusssee and moreover there are contradictory assertions on the gas products of denitrification by this bacteria. In experimental research the pattern of growth and gas production of Pseudomonas aeruginosa on nutrient broth was studied.

For the determination of iron (II) and total iron with 2,2'-dipyridyl in mineral waters. Reduction of iron (III) with ascorbic acid [Translation from: Zeitschrift fur Analytische Chemie 209 340-341, 1965]

The determination of bi- and trivalent iron in proximity, in mineral waters has gained in significance, on biological and technical grounds. This short paper describes the procedure of the determination of bivalent iron and total iron in a water sample.

Electrocatalytic reduction of dioxygen at chemically modified electrodes

The kinetics of the reduction of O₂ by Ru(NH₃)₆⁺² as catalyzed by cobalt(II) tetrakis(4-N-methylpyridyl)porphyrin are described both in homogeneous solution and when the reactants are confined to Nafion coatings on graphite electrodes. The catalytic mechanism is determined and the factors that can control the total reduction currents at Nafion-coated electrodes are specified. A kinetic zone diagram for analyzing the behavior of catalyst-mediator-substrate systems at polymer coated electrodes is presented and utilized in identifying the current-limiting processes. Good agreement is demonstrated between calculated and measured reduction currents at rotating disk electrodes. The experimental conditions that will yield the optimum performance of coated electrodes are discussed, and a relationship is derived for the optimal coating thickness.

The relation between the reduction potentials of adsorbed and unadsorbed cobalt(III) tetrakis(4-N-methylpyridyl)porphyrin and those where it catalyzes the electroreduction of dioxygen is described. There is an unusually large change in the formal potential of the Co(III) couple upon the adsorption of the porphyrin on the graphite electrode surface. The mechanism in which the (inevitably) adsorbed porphyrin catalyzes the reduction of O₂ is in accord with a general mechanistic scheme proposed for most monomeric cobalt porphyrins.

Four new dimeric metalloporphyrins (prepared in the laboratory of Professor C. K. Chang) have the two porphyrin rings linked by an anthracene bridge attached to meso positions. The electrocatalytic behavior of the diporphyrins towards the reduction of O₂ at graphite electrodes has been examined for the following combination of metal centers: Co-Cu, Co-Fe, Fe-Fe, Fe-H₂. The Co-Cu diporphyrin catalyzes the reduction of O₂ to H₂O₂ but no further. The other three catalysts all exhibit mixed reduction pathways leading to both H₂O₂ and H₂O. However, the pathways that lead to H₂O do not involve H₂O₂ as an intermediate. A possible mechanistic scheme is offered to account for the observed behavior.

Coulomb drag and tunneling studies in quantum Hall bilayers

The bilayer quantum Hall state at total filling factor ν_T=1, where the total electron density matches the degeneracy of the lowest Landau level, is a prominent example of Bose-Einstein condensation of excitons. A macroscopically ordered state is realized where an electron in one layer is tightly bound to a "hole" in the other layer. If exciton transport were the only bulk transportmechanism, a current driven in one layer would spontaneously generate a current of equal magnitude and opposite sign in the other layer. The Corbino Coulomb drag measurements presented in this thesis demonstrate precisely this phenomenon.

Excitonic superfluidity has been long sought in the ν_T=1 state. The tunneling between the two electron gas layers exihibit a dc Josephson-like effect. A simple model of an overdamped voltage biased Josephson junction is in reasonable agreement with the observed tunneling I-V. At small tunneling biases, it exhibits a tunneling "supercurrent". The dissipation is carefully studied in this tunneling "supercurrent" and found to remain small but finite.

Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes

The activation of Fe-coordinated N₂ via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N₂ to NH₃. To understand these reactions, the N₂ reactivity of a series of molecular Fe(N₂) platforms is investigated. A trigonal pyramidal, carbon-ligated Fe^I complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N₂, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(N_xH_y) species during N₂ conversion to NH₃. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH₃. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N₂) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH₂)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH₃ production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N₂) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH₂) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH₂NH₂)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N₂ activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH₄ and NH₃ are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNH_x) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N₂-derived Fe(NNH_x) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H₂. As a whole, these works both establish and provide a means to understand Fe-mediated N₂ activation via the addition of hydrogen atom equivalents.

Minimum drag profiles in infinite cavity flows

The problem considered is that of minimizing the drag of a symmetric plate in infinite cavity flow under the constraints of fixed arclength and fixed chord. The flow is assumed to be steady, irrotational, and incompressible. The effects of gravity and viscosity are ignored.

Using complex variables, expressions for the drag, arclength, and chord, are derived in terms of two hodograph variables, Γ (the logarithm of the speed) and β (the flow angle), and two real parameters, a magnification factor and a parameter which determines how much of the plate is a free-streamline.

Two methods are employed for optimization:

(1) The parameter method. Γ and β are expanded in finite orthogonal series of N terms. Optimization is performed with respect to the N coefficients in these series and the magnification and free-streamline parameters. This method is carried out for the case N = 1 and minimum drag profiles and drag coefficients are found for all values of the ratio of arclength to chord.

(2) The variational method. A variational calculus method for minimizing integral functionals of a function and its finite Hilbert transform is introduced, This method is applied to functionals of quadratic form and a necessary condition for the existence of a minimum solution is derived. The variational method is applied to the minimum drag problem and a nonlinear integral equation is derived but not solved.