Dissertation Submission Process Step 1 Near the time of the final public oral examination shortly before or immediately after the student must complete the online submission of their dissertation via the ProQuest UMI ETD Administrator website www. Students are required to upload a PDF of their dissertation, choose publishing options, enter subject categories and keywords, and make payment to ProQuest if fees apply. This step will take roughly minutes and it must be complete before coming to the Mudd Manuscript Library to deposit the dissertation Step 2 Come to the Mudd Manuscript Library to deposit your dissertation.
Group News Research Program The major thrust of our research program is at the interface of organic, inorganic, and biological chemistry. Many biochemical transformations, as well as important synthetic and industrial processes, are catalyzed by metals.
Thesis site princeton.edu we describe some representative projects of the wide scope of our research in the bioinorganic and bioinspired catalysis fields.
Porphyrin Catalysts for Organic Transformations Biochemistry manifests numerous highly selective transformations of aliphatic C-H bonds into alcohols, halides, and olefins catalyzed by reactive Thesis site princeton.edu intermediates within enzymes.
Using this inspiration, we have worked to develop porphyrin catalytic systems to perform these desired synthetic transformations. Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin. Science, —5. A highly sought after transformation is aliphatic C-H bond fluorination because there is an enormous impetus today to place F at such inaccessible sites in biomolecules and drug candidates.
We have discovered that a manganese porphyrin complex catalyzes alkyl fluorination by fluoride ion under mild conditions in conjunction with stoichiometric oxidation by iodosylbenzene.
Mechanistic analysis suggests that the regioselectivity for C-H bond cleavage is directed by an oxomanganese V catalytic intermediate followed by F delivery via an unusual manganese IV fluoride that has been isolated and structurally characterized.
Given that the source of F in this one-step, one-pot protocol is fluoride ion, we anticipate the potential application of these techniques to the incorporation of 18F into a wide variety of biomolecules and synthetic building blocks. Biomimetic Catalysts and Model Systems The heme prosthetic group is found in a variety of enzymes involved in oxygen metabolism such as the cytochromes P CYP of lung, liver and epithelial tissue.
The characterization of synthetic oxo-metalloporphyrin complexes as models of the heme active site has begun to provide a rational basis for the development of more reactive catalysts. New catalysts have also been developed that expand on the reactivity of the biochemical inspiration, such as the production of chlorine dioxide observed when using a manganese catalytic system as a biomimetic catalyst inspired by the oxygen-producing heme enzyme chlorite dismutase.
We suggest that the high kinetic reactivity observed here experimentally may result from both a low-lying a2u porphyrin HOMO and facilitated spin-state crossing phenomena in the course of the reaction. Chlorine dioxide has emerged as the preferred agent for microbial decontamination, for wood pulp bleaching and for the detoxification of sites contaminated by biological warfare agents such as anthrax.
Recently, we reported the discovery that ClO2 can be produced rapidly and efficiently using a highly electron-deficient, water-soluble manganese porphyrin catalyst.
Key advantages of this system are the mildly acidic to neutral reaction conditions, full conversion of the chlorite starting material, high activity on a solid support, and the fact that ClO2 production occurred within seconds. We have investigated the mechanism of the manganese porphyrin-catalyzed chlorine dioxide production from chlorite ion.
This process involves rate-limiting oxidation of the manganese III catalyst by ClO2— to afford high-valent manganese species.
We argue on kinetic, electrochemical, and thermodynamic grounds that this initial intermediate is the same transdioxoMnVTDMImP species that we have previously observed in reactions of this manganese porphyrin with hypobromite and hydrogen peroxide.
The mechanism of this catalytic process now suggests methods for greatly enhancing the rate of ClO2 generation under mild, neutral conditions. Efforts to address the practical implementation of manganese porphyrin-generated ClO2 are under way.
Mechanisms of Metalloenzymes Our interest in oxidizing enzymes has led us to develop techniques for characterizing and using the oxygenase enzymes found within whole cells. This approach has also enabled us to look directly at the mechanism of action of alkane hydroxylases in new and uncharacterized organisms.
It catalyzes a wide range of H2O2-dependent oxidations including alkane and arene hydroxylations, epoxidations, halogenations, and ether cleavage reactions. AaeAPO functions as a monooxygenase, similar to cytochrome P, and has been shown to produce human metabolites efficiently from drugs.
These aspects are under investigation. Parallel and competitive pathways for substrate desaturation, hydroxylation, and radical rearrangement by the non-heme diiron hydroxylase AlkB J.
The alkane monooxygenase AlkB from Pseudomonas putida is an integral membrane, non-heme iron hydroxylase that initiates the terminal hydroxylation of linear alkanes. We have previously shown that AlkB hydroxylates saturated mechanistic probes such as norcarane and bicyclo[3.
By comparing the product distribution of the deuterated norcarane to that of the non-deuterated norcarane, we were able to determine that the desaturation products from norcarane derive from hydrogen abstraction at C3, while reaction at C2 results in hydroxylation and radical rearrangement of the substrate.Founded in , Princeton in Asia (PiA) has been building bridges between the U.S.
and Asia for over a century. PiA’s original mission is as meaningful and urgent today as it was years ago. concise, (2) contain a clear statement of your thesis, (3) introduce, very succinctly, your topic and explain why it is important, (4) indicate, very briefly, what the main line of argument will be, and (5) map out the overall structure of your paper.
The Department of Chemistry offers a program of study leading to the degree of Doctor of Philosophy (Ph.D.). There are approximately graduate students and postdoctoral researchers, visiting faculty and senior scholars representing diverse backgrounds and experiences pursuing research in all major areas of chemistry.
The senior thesis is a ~ page research paper that you write your senior year. At least, that’s what it looks like in the humanities.
In other fields like math, or lab science, it might look a little shorter. Senior Thesis Awards The GHP Senior Thesis Prize is awarded in recognition of the most outstanding thesis written by a student earning a GHP certificate.
Superlative global health research is also featured in the Princeton Public Health Review, an online student-run publication. The famous "car lab" gives students a chance to apply their skills in a hands-on environment and create small, autonomous vehicles.