Aspects of the hemes and modulation of hydrogen donors in catalases from bovine liver, yeast, and escherichia coli

Catalase is the enzyme which decomposes hydrogen peroxide to water and oxygen. Escherichia coli contains two catalases. Hydroperoxidase I (HPI) is a bifunctional catalase-peroxidase. Hydroperoxidase II (HPII) is only catalytically active toward H202. Expression of the genes encoding these proteins is controlled by different regimes. HPJI is thought to be a hexamer, having one heme d cis group per enzymatic subunit. HPII wild type protein and heme containing mutant proteins were obtained from the laboratory of P. Loewen (Univ. of Manitoba). Mutants constructed by oligonucleotidedirected mutagenesis were targeted for replacement of either the His128 residue or the Asn201 residue in the vicinity of the HPII heme crevice. His128 is the residue thought to be analogous to the His74 distal axial ligand of the heme in the bovine liver enzyme, and Asn201 is believed to be a residue critical to the function of the enzyme because of its role in orienting and interacting with the substrate molecule. Investigation of the nature of the hemes via absorption spectroscopy of the unmodified catalase proteins and their derived pyridine hemochromes showed that while the bovine and Saccharomyces cerevisiae catalase enzymes are protoheme-containing, the HPII wild type protein contains heme d, and the mutant proteins contain either solely protoheme, or heme d-protoheme mixtures. Cyanide binding studies supported this, as ligand binding was monophasic for the bovine, Saccharomyces cerevisiae, and wild type HPII enzymes, but biphasic for several of the HPII mutant proteins. Several mammalian catalases, and at least two prokaryotic catalases, are known to be NADPH binding. The function of this cofactor appears to be the prevention of inactivation of the enzyme, which occurs via formation of the inactive secondary catalase peroxide compound (compound II). No physiologically plausible scheme has yet been proposed for the NADPH mediation of catalase activity. This study has shown, via fluorescence and affinity chromatography techniques, that NADPH binds to the T (Typical) and A (Atypical) catalases of Saccharomyces cerevisiae, and that wild type HPII apparently does not bind NADPH. This study has also shown that NADPH is unlike any other hydrogen donor to catalase, and addresses its features as a unique donor by proposing a mechanism whereby NADPH is oxidized and catalase is protected from inactivation via the formation of protein radical species. Migration of this radical to a position close to the NADPH is also proposed as an adjunct hypothesis, based on similar electron migrations that are known to occur within metmyoglobin and cytochrome c peroxidase when reacted with H202. Validation of these hypotheses may be obtained in appropriate future experiments.

NMR studies of the exchange reactions of CH3CN.BX3 with excess CH3CN /|nJoseph Fogelman. -- 260 St. Catharines, Ont. : [s. n.],

Exchange reactions between molecular complexes and excess acid or base are well known and have been extensively surveyed in the literature(l). Since the exchange mechanism will, in some way involve the breaking of the labile donor-acceptor bond, it follows that a discussion of the factors relating to bonding in molecular complexes will be relevant. In general, a strong Lewis base and a strong Lewis acid form a stable adduct provided that certain stereochemical requirements are met. A strong Lewis base has the following characteristics (1),(2) (i) high electron density at the donor site. (ii) a non-bonded electron pair which has a low ionization potential (iii) electron donating substituents at the donor atom site. (iv) facile approach of the site of the Lewis base to the acceptor site as dictated by the steric hindrance of the substituents. Examples of typical Lewis bases are ethers, nitriles, ketones, alcohols, amines and phosphines. For a strong Lewis acid, the following properties are important:( i) low electron density at the acceptor site. (ii) electron withdrawing substituents. (iii) substituents which do not interfere with the close approach of the Lewis base. (iv) availability of a vacant orbital capable of accepting the lone electron pair of the donor atom. Examples of Lewis acids are the group III and IV halides such (M=B, AI, Ga, In) and MX4 - (M=Si, Ge, Sn, Pb). The relative bond strengths of molecular complexes have been investigated by:- (i) (ii) (iii) (iv) (v] (vi) dipole moment measurements (3). shifts of the carbonyl peaks in the IIIR. (4) ,(5), (6) .. NMR chemical shift data (4),(7),(8),(9). D.V. and visible spectrophotometric shifts (10),(11). equilibrium constant data (12), (13). heats of dissociation and heats of reactions (l~), (16), (17), (18), (19). Many experiments have bben carried out on boron trihalides in order to determine their relative acid strengths. Using pyridine, nitrobenzene, acetonitrile and trimethylamine as reference Lewis bases, it was found that the acid strength varied in order:RBx3 > BC1 3 >BF 3 • For the acetonitrile-boron trihalide and trimethylamine boron trihalide complexes in nitrobenzene, an-NMR study (7) showed that the shift to lower field was. greatest for the BB~3 adduct ~n~ smallest for the BF 3 which is in agreement with the acid strengths. If electronegativities of the substituents were the only important effect, and since c~ Br ,one would expect the electron density at the boron nucleus to vary as BF3

Self-presentational motives in eating disorders : a known groups difference approach

Self-presentation reflects the processes by which individuals attempt to monitor and control the impressions others form of them (Schlenker & Leary, 1982). Concerns over impressions conveyed have been linked to numerous health behaviors (Crawford & Eklund, 1994; Martin, Leary, & O'Brien, 2001). The present study investigated the role of cognitive manifestations of dispositional and situational self presentational motivation (SPM) in 131 females with known groups differences on a measure of eating disorders. Participants were classified as in-treatment (IN = 39); at risk (AT = 46); and not at risk (NOT = 46) for eating disordered behaviour. Each participant completed The Brief Fear of Negative Evaluation Scale (FNE; Leary, 1983), the Public Self-Consciousness Scale (PSC; Fenigstein, Sheier, & Buss, 1975), and the Social Physique Anxiety Scale (SPA; Hart, Leary, & Rejeski, 1989), as measures of dispositional SPM. Situational SPM was assessed through Self-Presentational Efficacy (SPE; Gammage, Hall, & Martin, 2004), and the Exercise Motivation Inventory-2 (Markland & Ingeldew, 1997). Significant differences emerged on the measure of eating disorder behaviour between AT and NOT. To determine if group differences existed on measures of trait SPM an ANOVA was conducted. Results indicated that the NOT group experienced less FNE, PSC and SPA than the IN and AT groups, and the AT group experienced less FNE and PSC than the IN group. Pearson bivariate correlations were conducted on measures of trait SPM and EMI-2 subscales theoretically linked to SPM. It was found that FNE, PSC and SPA were all positively correlated with weight management for the NOT group. To determine if group differences existed on selfpresentational exercise motives independent samples I-tests were conducted. Results revealed that the AT group was more motivated to exercise for weight management, and appearance, and social recognition than the NOT group. To determine if group differences existed on the state measure of self-presentational efficacy a series of ANOVA's were conducted. Results revealed that the NOT group experienced significantly greater self-presentational efficacy expectancy and self-presentational outcome value than the AT group. Finally, a discriminant function analysis was conducted to determine if trait SPM would predict group membership. Results revealed that 63.4% of participants were correctly classified, with SPA, PSC, and FNE differentiating the NOT group from the AT and IN groups and FNE and PSC differentiating the AT group from the IN group. Thus self-presentation motivation appears to have an influence on females who have an eating disorder and those at risk for an eating disorder. Potential applications of the influence of self-presentational motives on eating disorders and future research directions are discussed.

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

Note that John Brown has done grading in the section between Geneva Street and Slabtown [known as Merritton prior to amalgamation with St. Catharines in 1961]

Note that John Brown has done grading in the section between Geneva Street and Slabtown [known as Merritton prior to amalgamation with St. Catharines in 1961]. This document is badly stained and faded. It is signed by S.D. Woodruff, 1855.

Letter of agreement to Welland D. Woodruff to pay Hamilton K. Woodruff $27, 500 for the property known as DeVeaux Hall

Letter of agreement to Welland D. Woodruff to pay Hamilton K. Woodruff $27, 500 for the property known as DeVeaux Hall.