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.

Dictionary of the Zeta Psi Fraternity of North America

A hardcover Dictionary of the Zeta Psi Fraternity, edited by Arthur H. Motley and Harry B. Carpenter. An excerpt from the forward reads: "Having the sincere purpose of placing in the hands of all Brothers of the Fraternity a Directory of the full membership of our order, with addresses as perfectly correct as time and equipment would permit, supplemented with such alphabetical and geographical indices as will make the volume a handy and accurate cross-reference to our membership...". Included with this book is a typewritten letter from Gordon Waldie, treasurer of the Toronto Chapter of the Zeta Psi Fraternity thanking Mrs. Percy Band for the gift of the original initiation certificate of the late Hamilton K. Woodruff. Mr. Woodruff was one of the Charter members of the Fraternity and he was the 7th man initiated into this, the first Canadian chapter of any fraternity. The letter is dated Nov. 21, 1949. The full text is available in the Brock University Special Collections and Archives.

City of Hamilton land abstracts (lots 93-203), 1865

An abstract of title for multiple lots in Peter H. Hamilton’s survey, south of Hunter Street, in the City of Hamilton. The lots involved range from lots 93-203 (non-inclusive). The document is dated November 10, 1865. The entries are dated from 1798 to 1865 and include the grantor, grantee, lands and instrument. The name Geo. S. Papps, Esq. appears centred at the top of the page. The document is signed at the bottom by John H. Greer, Registrar. A note on the reverse side of the document reads “Re Angus Abstract”.

Gilbert McMicken document, n.d.

Gilbert McMicken emigrated to Upper Canada in 1832 and settled in Chippawa. In 1835 he was married to Ann Theresa Duff. In 1837 the family moved to Queenston where he was directly involved in the Kingston-Queenston trade endeavours begun by Robert Hamilton. He had a variety of interests, including a partnership with James Hamilton, son of Robert Hamilton. He was also a collector of customs in Queenston and operated the Niagara Suspension Bridge Bank for a time. He entered politics and represented Niagara as well as becoming mayor of Clifton, now part of Niagara Falls, Ont., in 1856. McMicken went on to have an illustrious career, serving as land agent and leader of Canada’s first undercover agency. McMicken moved to Manitoba and was active in business and politics. He died in Winnipeg in 1891. Source: Dictionary of Canadian Biography – Gilbert McMicken website (March 22, 2010)

The Welland Canals Foundation, Honourable William Hamilton Merritt and the St. Catharines Historical Society and Museum, 1971-1990, n.d.

‘The Father of Canadian Transportation’ is a term commonly associated with William Hamilton Merritt. Although he is most known for being one of the driving forces behind the building of the first Welland Canal, he was many things throughout his life; a soldier, merchant, promoter, entrepreneur and politician to name a few. Born on July 3, 1793 at Bedford, Westchester County, N.Y. to Thomas Merritt and Mary Hamilton, Merritt’s family relocated to Canada shortly after in 1796. The move came after Merritt’s father petitioned John Graves Simcoe for land in Upper Canada after serving under him in the Queen’s Rangers during the American Revolution. The family quickly settled into their life at Twelve Mile Creek in St. Catharines. Merritt’s father became sheriff of Lincoln County in 1803 while Merritt began his education in mathematics and surveying. After some brief travel and further education Merritt returned to Lincoln County, in 1809 to help farm his father’s land and open a general store. While a farmer and merchant, Merritt turned his attention to military endeavours. A short time after being commissioned as a Lieutenant in the Lincoln militia, the War of 1812 broke out. Fulfilling his duty, Merritt fought in the Battle of Queenston Heights in October of 1812, and numerous small battles until the Battle of Lundy’s Lane in July 1814. It was here that Merritt was captured and held in Cheshire, Massachusetts until the war ended. Arriving back in the St. Catharines area upon his release, Merritt returned to being a merchant, as well as becoming a surveyor and mill owner. Some historians hypothesize that the need to draw water to his mill was how the idea of the Welland Canals was born. Beginning with a plan to connect the Welland River with the Twelve mile creek quickly developed into a connection between the Lakes Erie and Ontario. Its main purpose was to improve the St. Lawrence transportation system and provide a convenient way to transport goods without having to go through the Niagara Falls portage. The plan was set in motion in 1818, but most living in Queenston and Niagara were not happy with it as it would drive business away from them. Along with the opposition came financial and political restraints. Despite these factors Merritt pushed on and the Welland Canal Company was chartered by the Upper Canadian Assembly on January 19, 1824. The first sod was turned on November 30, 1824 almost a year after the initial chartering. Many difficulties arose during the building of the canal including financial, physical, and geographic restrictions. Despite the difficulties two schooners passed through the canal on November 30, 1829. Throughout the next four years continual work was done on the canal as it expended and was modified to better accommodate large ships. After his canal was underway Merritt took a more active role in the political arena, where he served in various positions throughout Upper Canada. In 1851, Merritt withdrew from the Executive Council for numerous reasons, one of which being that pubic interest had diverted from the canals to railways. Merritt tried his hand at other public works outside transportation and trade. He looked into building a lunatic asylum, worked on behalf of War of 1812 veterans, aided in building Brock’s monument, established schools, aided refugee slaves from the U.S. and tried to establish a National Archives among many other feats. He was described by some as having “policy too liberal – conceptions too vast – views too comprehensive to be comprehensible by all”, but he still made a great difference in the society in which he lived. After his great contributions, Merritt died aboard a ship in the Cornwall canal on July 5, 1862. Dictionary of Canadian Biography Online http://www.biographi.ca/EN/ShowBio.asp?BioId=38719 retrieved October 2006 Today numerous groups carry on the legacy of Merritt and the canals both in the past and present. One such group is the Welland Canals Foundation. They describe themselves as: “. . . a volunteer organization which strives to promote the importance of the present and past Welland Canals, and to preserve their history and heritage. The Foundation began in 1980 and carries on events like William Hamilton Merritt Day. The group has strongly supported the Welland Canals Parkway initiative and numerous other activities”. The Welland Canals Foundation does not work alone. They have help from other local groups such as the St. Catharines Historical Society. The Society’s main objective is to increase knowledge and appreciation of the historical aspects of St. Catharines and vicinity, such as the Welland Canals. http://www.niagara.com/~dmdorey/hssc/dec2000.html - retrieved Oct. 2006 http://www.niagara.com/~dmdorey/hssc/feb2000.html - retrieved Oct. 2006

British Methodist Episcopal Church Tithing Ticket, 1874

A quarterly tithing ticket from the British Methodist Episcopal Church, signed by Walter Hawkins, Minister, issued on August 16, 1874. This ticket was in the possession of the Richard Bell Family of St. Catharines.Minister Walter Hawkins was Superintendent of the Conference for the British Methodist Episcopal Church (Brant Co.) This excerpt from the Dictionary of Canadian Biography Online describes his role in reestablishing the BMEC in Canada following a period of reunion with the African Methodist Episcopal Church, an initiative spearheaded by Richard Randolph Disney, a free-born black American Methodist preacher. "By the end of the 1870s the BMEC had 56 congregations with about 3,100 members, the bulk of the latter being in the Danish West Indies and British Guiana. Because mission work outside Canada had overtaxed the church's financial resources, in 1880 Disney began negotiations towards reunion with the AMEC. The reunion was effected that year, and it was overwhelmingly ratified at a BMEC convention held at Hamilton in June 1881. A referendum showed that although a majority in Ontario was opposed, 86 per cent of the membership was in favour. Disney was accepted as an AMEC bishop and was assigned to its Tenth Episcopal District, a region embracing his former territory as well as some of the AMEC churches in Canada which had not joined the BMEC. Reunification appeared to have been a triumph for Disney, but trouble soon occurred. A majority of the Ontario churches and preachers, led by the Reverend Walter Hawkins of Chatham, sought to re-establish the BMEC, fearing the loss of their distinctive identity and perhaps feeling that the Caribbean groups had exercised too much influence on the reunification question. In 1886 this group held an ecclesiastical council at Chatham, at which it was claimed that Disney had defected to the AMEC. At a subsequent general conference that year the BMEC was reconstituted. The conference deposed Disney, agreeing to "erase his name and ignore his authority, and cancel his official relationship as bishop." The conference minutes also refer to a court case instigated by Disney which reached the High Court of Chancery in Britain, but records of this case have not been located. The reconstituted BMEC elected Hawkins as its general superintendent, avoiding the title of bishop for several years." Source: Dictionary of Canadian Biography Online. Government of Canada.

Contract between John Cronyn and Nelson Forsyth, December 16, 1854.

John Cronyn (1827-1898) emigrated to Canada from Ireland in 1837. He studied medicine at the University of Toronto, but was not granted his degree upon completion of the requirements. He refused to take the test oaths meant to exclude Catholics from the profession and was not granted his degree until several years later, when the discriminatory laws were rescinded. In 1850, he married Elizabeth Willoughby of Toronto. They settled in Fort Erie and he established a successful medical practice there. He was active in the community, serving as Superintendent of schools and one term as Reeve. In 1859 he relocated to Buffalo and continued to practice medicine there. Cronyn was instrumental in the establishment of a medical department at Niagara University, where he was a professor and president of faculty. Nelson Forsyth was the son of William Forsyth (1771-1841), a prominent businessman in Niagara who owned and operated the Pavilion Hotel (later known as Forsyth’s Inn). Nelson was also a businessman and lived in Fort Erie with his wife Archange Warren.

Plymouth Gin Advertisement

An advertisement for Plymouth Gin, it reads "Plymouth Gin. Double distilled, unsweetened; a delicious compromise between Holland and Old Tom. Unsurpassed for Cocktail, Phiz, Silver Phiz, or John Collins. Combines well with Soda and Lemon Peel. Adopted in the principal Clubs and Restaurants, with steadily increasing popularity. Recognized as invaluable medicinally. DuVivier & Co., Sole Agents. 22 Warren Street, New York. 7 Sibley Warehouses, Chicago." The image on the reverse is of a friar holding a glass surrounded by barrels and crates all labelled with company names.