The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Investigation into the determination of arsenic by direct current plasma atomic emission spectrometer

Improvements have been made on the currently available hydride generator system manufactured by SpectraMetrics Incorporated, because the system was found to be unsatisfactory with respect to the following: 1. the drying agent, anhydrous calcium chloride, 2. the special sample tube, 3. the direction of argon flow through the Buchner funnel when it came to dealing with real sample, that is, with reference only to aqueous extracts of soil samples. Changes that were made on the system included the replacement of anhydrous calcium chloride with anhydrous calcium sulphate and the replacement of the special sample tube with a modified one made from silica. Re-directing the flow of argon through the top of the Buchner funnel appeared to make the system compatible with aqueous extracts of soil samples. The interferences from 1000 ~g/mL of nickel(II) , cobalt(II), iron(III), copper(II) have been eliminated with the aid of 1.4 M hydrochloric acid and 1% (weight/volume) L-cystine. Greater than 90% recovery of 0.3 ~g/mL arsenic signal was achieved in each case. Furthermore, 103% of arsenic signal was accomplished in the presence of 1000 ~g/mL cadmium with 5 M Hel. tVhen each of the interferents was present in solution at 1000 ppm, a recovery of 85% was achieved by using 5 M hydrochloric acid and 3% (weight/volume) L-cystine. Without L-cystine and when 1.4 M hydrochloric acid was used, the recoveries were 0% (Ni), 0% (Co), 88% (Fe), 15% (Cu), 18% (Cd). Similarly, a solution containing 1000 ppm of each interferent gave a zero percent recovery of arsenic. The reduction of trivalent and pentavalent arsenic at a pH less than one has also been investigated and shown to be quantitative if peak areas are measured. The reproducibility determination of a 0.3 Vg/mL standard arsenic solution by hydride generation shows a relative standard deviation of 3.4%. The detection limits with and without Porapak Q have been found to be 0.6 ng/mL and 1.0 ng/mL, respectively.

The influence of water on the glucose affinity of hexokinase

In the present thesis, the role of hydration during the glucose induced conformational change of hexokinase is investigated. This is accomplished by applying the osmotic stress technique. The osmotic stress technique is founded on varying of the activity of water in a system in order to determine ifs effects. This is accomplished by adding inert solute molecules that are excluded from the system under study. The solute molecules used within the present investigation are Polyethylene glycols (PEGs). PEGs aid in the removal of water from hexokinase by exerting osmotic pressure. The osmotic pressures of the PEG solutions are also measured with both vapour pressure osmometry and secondary osmometry with phospholipids. An interesting discovery is made in that the osmotic pressures of PEG and co-solute solutions are non-additive. This indicates that PEG concentrates co-solutes in solution by making a certain proportion of the water inaccessible. Glucose binding was measured fluorometrically and the glucose equilibrium dissociation constant (GEDC) of hexokinase is measured in solutions containing the different MW PEGs. Changes in the sensitivity of the glucose affinity with osmotic pressure allows the calculation of the change in the numbers of polymer-inaccessible water molecules upon the binding of glucose to hexokinase ~Nw. It was determined the ~Nw decreases with increases in osmotic pressure in the presence of all MW PEGs. ~Nw decreases from values between 45-290 water molecules at low pressure to approximately 15 at high pressure. There is also a molecular weight dependence observed. There are large decreases in ~Nw with osmotic pressure in the presence of PEGs above MW 1000. However, below MW 1500 changes in ~Nw with osmotic pressure are relatively small. These findings are interpreted with respect to two possible mechanisms involving changes in the conformation of hexokinase u~der osmotic pressure and the access of the PEG molecules to water surrounding hexokinase.

Every man his own guide to the Falls of Niagara : or, The whole story in a few words /

Cover title: Guide to Niagara Falls.

Bowslaugh Family fonds, 1860-1861, 1868, 1876-1877, 1880-1882, 1886-1890, 1892-1893, 1895, 1898-1899, n.d.

Edward W. Bowslaugh (1843-1923) was the son of Jacob and Anna (Beamer) Bowslaugh. Edward Bowslaugh married Mary Southward, and the couple had six children, Edgar Morley, Edward Freeman, twins Alfred Malcolm and Alice Mary, Annie Olivia, John Jacob and Mabel Florence. Edward W. Bowslaugh was a farmer, contractor and owner of the Grimsby Planing Mills in Grimsby, Ont. and Bowslaugh’s Planing Mill in Kingsville, Ont. The mills manufactured door and sash trim and other wood related products. Some customers contracted the firm to provide wood products for cottages being built at Grimsby Park, the Methodist camp ground. Some time before 1885 Edward Bowslaugh and his family moved to Kingsville, Ont. to open up a new planing mill and door and sash manufactory. He later sold the Grimsby Planing Mills to Daniel Marsh. The diaries and account books include many names of workers as well as friends and family members residing in the Grimsby and Kingsville areas. James M. Bowslaugh (1841-1882) was the son of Jacob and Anna (Beamer) Bowslaugh. James married first Anna Catharine Merritt and after her death in 1875 he married Mary Gee in 1877. James and Anna had three children, Eliza, James Herbert, George Hiram, all died very young. James and Mary Gee had one son, Charles Leopold Kenneth Frederich Bowslaugh, b. 1881. James Bowslaugh was a farmer and lumberman, much like his younger brother Edward. James’ early diaries often note the activities of himself and his brother Edward. Both Edward and James were heavily involved in the Methodist church, teaching or leading Sunday school and attending prayer meetings. Alfred M. Bowslaugh b. 1873 was the son of Edward W. Bowslaugh and his wife Mary Southward. The school notebook is from his days as a student in Kingsville, Ont.

Rick Bell Family fonds, 1874-1875, 1879, 1884, 1886, 1888-1889, 1896, 1898, 1909-1910, 1939, 1945, n.d.

Lewis Tyrell married Jane Gains on August 31, 1849 in Culpeper Court House, Virginia. Jane Gains was a spinster. Lewis Tyrell died September 25, 1908 at his late residence, Vine St. and Welland Ave., St. Catharines, Ont. at the age of 81 years, 5 months. Jane Tyrell died March 1, 1886, age 64 years. Their son? William C. Tyrell died January 15, 1898, by accident in Albany, NY, age 33 years, 3 months. John William Taylor married Susan Jones were married in St. Catharines, Ont. on August 10, 1851 by William Wilkinson, a Baptist minister. On August 9, 1894 Charles Henry Bell (1871-1916), son of Stephen (1835?-1876) and Susan Bell, married Mary E. Tyrell (b. 1869?) daughter of Lewis and Alice Tyrell, in St. Catharines Ontario. By 1895 the Bell’s were living in Erie, Pennsylvania where children Delbert Otto (b. 1895) and Edna Beatrice (b. 1897) were born. By 1897 the family was back in St. Catharines where children Lewis Tyrell (b. 1899), Gertrude Cora (b. 1901), Bessie Jane (b. 1902), Charles Henry (b. 1906), Richard Nelson (b. 1911) and William Willoughby (b. 1912) were born. Charles Henry Bell operated a coal and ice business on Geneva Street. In the 1901 Census for St. Catharines, the Bell family includes the lodger Charles Henry Hall. Charles Henry Hall was born ca. 1824 in Maryland, he died in St. Catharines on November 11, 1916 at the age of 92. On October 24, 1889 Charles Hall married Susan Bell (1829-1898). The 1911 Census of Canada records Charles Henry Hall residing in the same household as Charles Henry and Mary Bell. The relationship to the householder is step-father. It is likely that after Stephen Bell’s death in 1876, his widow, Susan Bell married Hall. In 1939, Richard Nelson Bell, son of Charles Henry and Mary Tyrell Bell, married Iris Sloman. Iris (b. 22 May 1912 in Biddulph Township, Middlesex, Ontario) was the daughter of Albert (son of Joseph b. 1870 and Elizabeth Sloman, b. 1872) and Josie (Josephine Ellen) Butler Sloman of London, Ont. Josie (b. 1891) was the daughter of Everett Richard and Elizabeth McCarthy (or McCarty) Butler, of Lucan Village, Middlesex North. According to the 1911 Census of Canada, Albert, a Methodist, was a porter on the railroad. His wife, Josephine, was a Roman Catholic. Residing with Albert and Josie were Sanford and Sadie Butler and Sidney Sloman, likely siblings of Albert and Josephine. The Butler family is descended from Peter Butler, a former slave, who had settled in the Wilberforce Colony in the 1830s. Rick Bell b. 1949 in Niagara Falls, Ont. is the son of Richard Nelson Bell. In 1979, after working seven years as an orderly at the St. Catharines General Hospital while also attending night school at Niagara College, Rick Bell was hired by the Thorold Fire Dept. He became the first Black professional firefighter in Niagara. He is a founding member of the St. Catharines Junior Symphony; attended the Banff School of Fine Arts in 1966 and also performed with the Lincoln & Welland Regimental Band and several other popular local groups. Upon the discovery of this rich archive in his mothers’ attic he became passionate about sharing his Black ancestry and the contributions of fugitive slaves to the heritage Niagara with local school children. He currently resides in London, Ont.

Crowland Municipality : an act for regulating and governing auctioneers, and other persons putting up for sale, goods, wares, and merchandise to the highest or best bidder., 1854

On February 1st, 1854 an act was passed in order to regulate the sale of goods, wares and merchandise. Section I pertained to the fact that any merchant would first obtain a license. Section II deemed that no merchant should sell any wine or spirituous liquors, beer or ale within the municipality of Crowland in any less quantity than 5 gallons or less than 12 bottles in any place other than a House of Public Entertainment without having obtained a license. Section III was in regard to licensing any person who would use a billiard table which was set up for hire or gain. Section IV stated that all sums of money paid by the keepers of Houses of Public Entertainment plus the imperial duty of 2 pound would be payable to the Treasurer of the Municipality of Crowland. Section V was written regarding the continuance of the act to regulate inns, taverns, temperance houses and other Houses of Public Entertainment. Section VI specified that all recesses (not authorized to sell liquor) would pay the sum of 2 pounds. Section VII declared that Peter Benedict was appointed Revenue Inspector of the township and section VIII stated that recess-keepers who took out liquor licenses would be required to pay 6 pounds 5 shillings and for violating this they would pay a penalty. This document was written by Leonard M. Matthews, Township reeve and Alex Reid, clerk.

Charles Larned letter, April 3, 1813.

Charles Larned (1791-1834) was a lawyer and American military officer who served during the War of 1812. He was the son of Simon Larned (1753-1817), who served as a captain in the Revolutionary War and was a member of the United States Congress from Massachusetts from 1804-1805. Charles studied law in the office of Henry Clay in Kentucky, and was dining with a group of prominent citizens when word was received that General William Henry Harrison could soon be overpowered by General Henry Proctor. Colonel Owen, a member of the group, organized a regiment to reinforce Harrison’s troops. Larned became a member and subsequently survived the River Raisin Massacre and was later present at the Battle of the Thames. He was also part of a group of men who learned of General William Hull’s plan to surrender Detroit to the British and planned to overtake him should this occur. However, the plan failed, Hull did surrender and the men became prisoners of the British. After the war, Larned became a lawyer, and served as Attorney General of Michigan Territory during the Black Hawk War. During the cholera epidemic of 1834, he worked tirelessly to assist others, but was stricken with the disease and died. Letter Transcription: Pittsfield, April 8, 1813 I think that by this time my dear Charles you will allow I have some reason to give you a gentle reprimand for breach of duty—but I will not censure you upon suspicion maybe you have substantial reasons—at any rate one cannot very graciously reproach the other for negligence I for one am healthy as ham & that we have so seldom exchanged letters during your absence & on my honor promise to be a better girl in future—but the truth is my Dear Charles I am secretary for the Family—Mama you know never writes & James but seldom & they are all dispersed in different directions, consequently I have many calls upon my time—this to be sure is a pleasant duty & I urge it only as a slight palliation for my remissness if you should consider it as such—now I have finished my preface—I will try to be more interesting & doubtless I succeed. Our dear Father we hope & trust is now in Green Bush, where he will probably remain a month perhaps & from thence he expects to go to Sacket’s harbor—at which place you know our troops are fast collecting-- We shall hope to see him either here or there before he goes. Brother George I believe is [still] at Plattsburgh but expects soon to be removed to some other military part perhaps with Papa (I hope so at least). We have just got letters from Brothers Sylvester & Joseph at Middlebury—they are in good health. Mama has for some weeks been afflicted with an inflammation in her eyes but seems now to be convalescing. Sister Martha has been somewhat unwell for a few weeks but is now tolerably recovered. James & myself are both in our usual good health & at this time seated by the same stand, one reading, the other writing. Thus my Dear Charles have I given you an abstract history of our Family—but here indeed is a wonderful omission; not a word about Miss Harriet Hunt, who in truth ought to have been noted first but the last she’s not the least in my memory. She is much grown since you saw her, but does not speak as fluently as we could wish—a few word she can say. Probably before this you have been informed of the great loss your friend Sherrill has sustained in the death of his mother—also of the revolution that has taken place in Hackbridge as it respects the religion & morality of the place that more than one hundred on the plain have become religious converts & c—indeed I am at a loss what to say that will afford your pleasure—a narrative at this time must be gloomy indeed. The distressing situation of our country at this time would make almost any recital melancholy. The prevailing epidemic has swept off many of your acquaintance no doubt. Mrs. Dewey of Williamstown, the sister of Mrs. Danforth, has left a Husband, Children & many Friends sincerely to lament her loss—some few have died in our village, but we have escaped astonishingly –it has raged in every town about us--If we are unwilling to acknowledge a God in his mercies. I fear she shall be compelled to do it in the awfulness of his judgments.--------I am much [pleased] with our new neighbors the Parsons Wife & a Miss Woodward her cousin is a fine girl, I think, Mrs. Allen has not a handsome face but something in her manner that interests one her person I think the handsomest I ever saw & the Parson seems well pleased with his selection—Mrs. Ripley is with them this winter & will probably remain thro the summer—Her husband at [Sackett’s Harbor] little or no alteration is apparent since her marriage—she seems as gay & fond of company as ever.-------Mrs. [McKnight] it is expected will commence housekeeping in about three weeks in the house formerly occupied by Mr…. [Report] says that Mr. Goodman & Clarissa Weller are soon to be married & many other things that I must omit to mention for Mama wants a… PS reserved--now my Dear Charles remember you are considerably… & I am confident you have as much leisure as I have –… be ceremonious but write whenever I find time not & I beg… the same – I tell James I shall not send his love for he must write himself. I shall anxiously expect you to write & do not disappoint your affectionate, sister--H One word my Dear Charles from your affectionate Mother who longs to see Her Dear son Charles—but being deprived of that rich blessing at present—begs Him so to conduct that she may hope for it ere long—do you search the Scriptures and keep the Sabbath holy unto the Lord—and all the sacred Commandments of God—it is my ardent desire…He would protect, support and provide for your soul and body and believe me your affectionate friend and Mother. R Larned.

Reflected rays of light upon Freemasonry, or, the Freemason's pocket compendium (1874)

"With an emblematical frontespiece." Inscribed on front free endpaper: A. Graham Barrie 30th Sep 1881.

Charles Larned letter - April 3, 1813

Letter Transcription: Pittsfield, April 8, 1813 I think that by this time my dear Charles you will allow I have some reason to give you a gentle reprimand for breach of duty—but I will not censure you upon suspicion maybe you have substantial reasons—at any rate one cannot very graciously reproach the other for negligence I for one am healthy as ham & that we have so seldom exchanged letters during your absence & on my honor promise to be a better girl in future—but the truth is my Dear Charles I am secretary for the Family—Mama you know never writes & James but seldom & they are all dispersed in different directions, consequently I have many calls upon my time—this to be sure is a pleasant duty & I urge it only as a slight palliation for my remissness if you should consider it as such—now I have finished my preface—I will try to be more interesting & doubtless I succeed. Our dear Father we hope & trust is now in Green Bush, where he will probably remain a month perhaps & from thence he expects to go to Sacket’s harbor—at which place you know our troops are fast collecting-- We shall hope to see him either here or there before he goes. Brother George I believe is [still] at Plattsburgh but expects soon to be removed to some other military part perhaps with Papa (I hope so at least). We have just got letters from Brothers Sylvester & Joseph at Middlebury—they are in good health. Mama has for some weeks been afflicted with an inflammation in her eyes but seems now to be convalescing. Sister Martha has been somewhat unwell for a few weeks but is now tolerably recovered. James & myself are both in our usual good health & at this time seated by the same stand, one reading, the other writing. Thus my Dear Charles have I given you an abstract history of our Family—but here indeed is a wonderful omission; not a word about Miss Harriet Hunt, who in truth ought to have been noted first but the last she’s not the least in my memory. She is much grown since you saw her, but does not speak as fluently as we could wish—a few word she can say. Probably before this you have been informed of the great loss your friend Sherrill has sustained in the death of his mother—also of the revolution that has taken place in Hackbridge as it respects the religion & morality of the place that more than one hundred on the plain have become religious converts & c—indeed I am at a loss what to say that will afford your pleasure—a narrative at this time must be gloomy indeed. The distressing situation of our country at this time would make almost any recital melancholy. The prevailing epidemic has swept off many of your acquaintance no doubt. Mrs. Dewey of Williamstown, the sister of Mrs. Danforth, has left a Husband, Children & many Friends sincerely to lament her loss—some few have died in our village, but we have escaped astonishingly –it has raged in every town about us--If we are unwilling to acknowledge a God in his mercies. I fear she shall be compelled to do it in the awfulness of his judgments.--------I am much [pleased] with our new neighbors the Parsons Wife & a Miss Woodward her cousin is a fine girl, I think, Mrs. Allen has not a handsome face but something in her manner that interests one her person I think the handsomest I ever saw & the Parson seems well pleased with his selection—Mrs. Ripley is with them this winter & will probably remain thro the summer—Her husband at [Sackett’s Harbor] little or no alteration is apparent since her marriage—she seems as gay & fond of company as ever.-------Mrs. [McKnight] it is expected will commence housekeeping in about three weeks in the house formerly occupied by Mr…. [Report] says that Mr. Goodman & Clarissa Weller are soon to be married & many other things that I must omit to mention for Mama wants a… PS reserved--now my Dear Charles remember you are considerably… & I am confident you have as much leisure as I have –… be ceremonious but write whenever I find time not & I beg… the same – I tell James I shall not send his love for he must write himself. I shall anxiously expect you to write & do not disappoint your affectionate, sister--H One word my Dear Charles from your affectionate Mother who longs to see Her Dear son Charles—but being deprived of that rich blessing at present— begs Him so to conduct that she may hope for it ere long—do you search the Scriptures and keep the Sabbath holy unto the Lord—and all the sacred Commandments of God—it is my ardent desire…He would protect, support and provide for your soul and body and believe me your affectionate friend and Mother. R Larned.

Indenture between Owen Clifford and Margaret Clifford to John Charles Rykert and William B. Gilleland

Indenture of mortgage deed between Owen Clifford and Margaret Clifford of the Township of Grantham to John Charles Rykert and William B. Gilleland of St. Catharines regarding parts of Lots no. 10 and 11 in the 9th Concession of the Township of Grantham. Registered in the Township of Grantham Register on September 15, 1870 - instrument no. 804 and registered in the Township of Grantham Register of February 8, 1872 - instrument no. 1104, September 15, 1870.