Towards reverse engineering of Photosystem II: Synergistic Computational and Experimental Approaches

ABSTRACT Photosystem II (PSII) of oxygenic photosynthesis has the unique ability to photochemically oxidize water, extracting electrons from water to result in the evolution of oxygen gas while depositing these electrons to the rest of the photosynthetic machinery which in turn reduces CO2 to carbohydrate molecules acting as fuel for the cell. Unfortunately, native PSII is unstable and not suitable to be used in industrial applications. Consequently, there is a need to reverse-engineer the water oxidation photochemical reactions of PSII using solution-stable proteins. But what does it take to reverse-engineer PSII’s reactions? PSII has the pigment with the highest oxidation potential in nature known as P680. The high oxidation of P680 is in fact the driving force for water oxidation. P680 is made up of a chlorophyll a dimer embedded inside the relatively hydrophobic transmembrane environment of PSII. In this thesis, the electrostatic factors contributing to the high oxidation potential of P680 are described. PSII oxidizes water in a specialized metal cluster known as the Oxygen Evolving Complex (OEC). The pathways that water can take to enter the relatively hydrophobic region of PSII are described as well. A previous attempt to reverse engineer PSII’s reactions using the protein scaffold of E. coli’s Bacterioferritin (BFR) existed. The oxidation potential of the pigment used for the BFR ‘reaction centre’ was measured and the protein effects calculated in a similar fashion to how P680 potentials were calculated in PSII. The BFR-RC’s pigment oxidation potential was found to be 0.57 V, too low to oxidize water or tyrosine like PSII. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of iii tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. The results were used to develop a second generation of BFR-RC using a high oxidation pigment. The hypervalent phosphorous porphyrin forms a radical pair that can be observed using Transient Electron Paramagnetic Resonance (TR-EPR). Finally, the results from this thesis are discussed in light of the development of solar fuel producing systems.

Photograph - Train Station, Military Men

A photograph of a train with a large crowd gathered. There appears to be a large number of military men departing on the train.

Canadian Military Institute: Officers of the British Forces in Canada during the War of 1812-1815

There is a note in the front cover written to Mary from B. Johnston on April 22, 1942. He refers to page 73 of the book in which William Woodruff is listed as a Lieutenant and Richard Woodruff is listed as an Ensign in the Niagara District. A full text version is available at the following link: http://www.archive.org/details/officersbritish00instgoog

Engineering school notebook which belonged to S.D. Woodruff

Engineering school notebook which belonged to S.D. Woodruff. This book contains logarithm notes, plane trigonometry, surveying and content of land. The outer page is torn and the notebook is quite discoloured. This does not affect the text. It has no covers, n.d.

Engineering school notebook which belonged to S.D. Woodruf

Engineering school notebook which belonged to S.D. Woodruff. This book contains questions for exercise as well as other mathematical topics. It also contains a page which has the title “The Cataract of Niagara in North America” and quite a few pages of repetitive lines as in “writing lines”. Some of the pages are loose or torn and the notebook is discoloured. This does not affect the text. This book has no covers, n.d.

Estimate from the County of Welland to S.D. Woodruff for engineering services in marsh lands drainage for 1 year

Estimate from the County of Welland to S.D. Woodruff for engineering services in marsh lands drainage for 1 year, Dec. 1857.

Engineering services in marsh lands drainage for the months of October, November and December

Engineering services in marsh lands drainage for the months of October, November and December. This is signed by S.D. Woodruff, Dec. 31, 1856.

Engineering services in marsh lands drainage for the months of January, February, March and April for Fred Holmes, Joseph Simpson, D. Davidson, Rose Osborne, Henry Wilson and William Baird

Engineering services in marsh lands drainage for the months of January, February, March and April for Fred Holmes, Joseph Simpson, D. Davidson, Rose Osborne, Henry Wilson and William Baird. This is signed by S.D. Woodruff, May 1, 1857.

Engineering services in marsh lands drainage for the months of May, June, July and August 1857 for Fred Holmes, Joseph Simpson and William Baird

Engineering services in marsh lands drainage for the months of May, June, July and August 1857 for Fred Holmes, Joseph Simpson and William Baird. This is signed by S.D. Woodruff, Aug. 31, 1857.

Letter to Henry Nelles from Michael Harris of the Perth Military Settlement

Letter to Henry Nelles from Michael Harris of the Perth Military Settlement (3 pages, handwritten). He is married to Mary Fanning, sister of Henry Nelles but is having marital troubles as he says he “may have to be on the lookout for another wife”. He thinks that his wife Mary may have departed for the United States, Apr. 6, 1821.

Letter to Colonel Nelles of the 4th Lincoln Militia in Grimsby from Apt. Military Secrets, Quebec

Letter to Colonel Nelles of the 4th Lincoln Militia in Grimsby from Apt. Military Secrets, Quebec. When this envelope is unfolded it contains the printed words “On his Majesty’s service” “The Ordnance Storekeeper” and “Military Secretary”. This item is badly stained and torn but text is not affected, Jan. 9, 1839.

The Rough and Ready annual ; or military souvenir

UANL

Notes of a military reconnoissme, from fort Leavenworth in Missouri to San Diego, in California : including part of the Arkansas, del Norte, and Gila Bivers

UANL

Report of the Secretary of War, communicating; in compliance witha resolution of the Senate, a map showing the operations of the army of the United States in Texas and the adjacent Mexican Stateson the Rio Grande, accompanied by astronomical observations, and descriptive and military memoirs of the country.

UANL

Mexico and her military chieftains, from the revolution of Hidalgo to the present time : Comprising sketches of the lives of Hidalgo, Morelos, Iturbide, Santa Anna, Gomez, Farias, Bustamente, Paredes, Almonte, Arista, Alaman, Ampudia, Herrera, and De la Vega. by Fay. Robinson. Illustratd by twelve portraits and engravings.

UANL