Synthesis of isotope-labelled methoxypyrazine compounds as internal standards and quantitative determination of aroma methoxypyrazines in water and wines by solid-phase extraction with isotope dilution-GC-MS /

An efficient way of synthesizing the deuterium labelled analogues of three methoxypyrazine compounds: 2-d3-methoxy-3-isopropylpyrazine, 2-d3-methoxy-3- isobutylpyrazine, and 2-d3-methoxy-3-secbutylpyrazine, has been developed. To confirm that the deuterium labels had been incorporated into the expected positions in the molecules synthesized, the relevant characterization by NMR, HRMS and GC/MS analysis was conducted. Another part of this work involved quantitative determination of methoxypyrazines in water and wines. Solid-phase extraction (SPE) proved to be a suitable means for the sample separation and concentration prior to GC/MS analysis.Such factors as the presence of ethanol, salt, and acid have been investigated which can influence the recovery by SPE for the pyrazines from the water matrix. Significantly, in this work comparatively simple fractional distillation was attempted to replace the conventional steam distillation for pre-concentrating a sample with a relatively large volume prior to SPE. Finally, a real wine sample spiked with the relevant isotope-labelled methoxypyrazines was quantitatively analyzed, revealing that the wine with 10 beetles per litre contained 138 ppt of 2-methoxy-3-isopropylpyrazine. Interestingly, we have also found that 2-methoxy-3-secbutylpyrazine exhibits an extremely low detection limit in GC/MS analysis compared with the detection limit of the other two methoxypyrazines: 2- methoxy-3-isopropylpyrazine and 2-methoxy-3-isobutylpyrazine.

City of the Falls clippings, 1833, n.d.

The clippings describe the City of the Falls and its attempts by its shareholders to sell lots to this newly developing city. The venture by shareholders W. Allan, James Buchanan, Thomas Clark, J.H. Dunn, Thomas Dixon, General Murray, James Robinson, Samuel Street and William Witla intended to favourably position their city as a destination for “affording an easy approach for the annual assemblage of the Fashionable, the Learned and the Great”. The venture failed due to the building of the Buffalo and Niagara Falls railway.

Custom House Niagara forms, 1833

In 1833 William Clarke, the collector of customs at Niagara, completed and signed four forms for the movement of goods between Niagara and York, and Niagara and Brantford. The forms were issued to the firm of Lewis & Gray, James Armstrong, J.A. Wilks, and William Blackely. The goods being transported included scythes, corn brooms, hide whips, sacks, snuff, shovels, spades and two apple trees.

Gainsborough [Presbyterian] Church records, 1833-1836, 1841-1846, 1855-1857, 1860-1864, 1866 [photocopy]

The Gainsborough Presbyterian Church was organized prior to 1833, but no records were kept until this date. In 1809, the church was lead by Rev. Daniel Ward Eastman. In 1833 the church became part of the Niagara Presbytery of the American Presbyterian Church. The records include transfer of membership, records of marriages, lists of subscribers and session minutes. Photocopies from originals were made in 1977 by E. Phelps, University of Western Ontario, prior to their deposit with the United Church of Canada Archives, Toronto, Ont.

Niagara-Welland Power Company Limited fonds, 1833, 1852, 1904-1906, 1909, n.d.

The Welland Power and Supply Canal Company Limited, established in 1893 and incorporated in 1894 with a capital stock of $500,000. The aim of the company was to harness the natural water supply of the Niagara and Welland Rivers. In 1898 the Canadian Electrical News published a report by Henry Symons, QC outlining the main project of the company. This project involves the construction of a canal from the Welland River to the brow of the mountain at Thorold, a distance of 8 miles; the construction at Thorold of a power house, and from Thorold to Lake Ontario, a raceway by which to carry water into the lake. The estimate for the machinery to generate 100,000 horse power is £125,000; for transmission line to Toronto at a voltage of 10,000….The total estimate therefore amounts to £2,452,162, or roughly speaking, $12,000,000. Source: Canadian Electrical News, August 1898, p. 172. In 1899 the company officers petitioned the federal government desiring a name change to the Niagara-Welland Power Company Limited. Officers of the company were Harry Symons, President; Charles A. Hesson, Vice-President; and M.R. O’Loughlin, James B. Sheehan, James S. Haydon, Frederick K. Foster, directors; John S. Campbell, secretary-treasurer. The company’s head offices were located in St. Catharines, with a New York (City) office on Broad Street. In 1905 and 1909 the company petitioned the federal government for additional time to construct its works, which was granted. The company had until May 16, 1915 to complete construction. John S. Campbell (1860-1950) was a graduate of the University of Toronto and Osgoode Hall. During his university years John began his military career first in "K" Company, Queens Own rifles and then later as Commanding Officer of the 19th Lincoln Regiment, from 1906 to 1910. Upon his return to St. Catharines John Campbell served as secretary in the St. Catharines Garrison Club, a social club for military men begun in 1899. After being called to the Bar, he became a partner in the firm of Campbell and McCarron and was appointed to the bench in 1916, serving until retirement in 1934. Judge Campbell served as an alderman for several terms and was the mayor of St. Catharines in 1908 and 1909. He also served as the first chairman of the St. Catharines Public Utilities in 1914. John S. Campbell was married to Elizabeth Oille, daughter of Jerome B. and Charlotte (St. John) Oille. The family home "Cruachan" was located at 32 Church St.

Bright’s Wines Limited fonds, 1983-1989

One of the oldest wineries in Ontario, Bright’s Wines is now a part of Vincor International Inc. and still producing wines today. In the year 1874 Thomas G. Bright and Francis A. Shirriff came together in a partnership and formed a wine company in Toronto, Ontario. As the company began to prosper the gentlemen decided to move the location to Niagara, Ontario. Sixteen years later the Niagara Falls Wine Company opened on Dorchester Road. In 1911, Bright bought out all of Shirriff’s shares in the company and the name became the T. G. Bright and Co. Limited. A few years later in 1933 Harry C. Hatch bought the wine company from the Bright family and began changing how Bright’s operated through greater, more diverse wine production, as well as research and development. Bright’s leadership in wine research and development in Canada helped bring Canadian wines to their position of respect around the world. In 1934 Bright’s began a viticultural and vinicultural program, changing the way the Canadian wine industry worked. They put more money into research and development than any other winery in all of Canada. Soon, gold medals and “best of class” international designations were being awarded to Bright’s wines. As a result of their success, the founders soon discovered that they needed additional money to develop their business. So they borrowed money from a local bank and other lenders, or creditors, and used the funds to expand the business. Subsequent acquisition of other companies and consolidations in the wine industry led to the creation of Vincor International in 1993. Today, Vincor has established itself as a major participant in the North American super-premium wine market. By acquiring other companies, Vincor has fuelled growth in its sales from $114 million in 1995 to $654 million in 2005. The company’s success attracted the attention of its competitors. On September 27, 2005, Constellation Brands, Inc. announced its intention to buy Vincor and subsequently acquired the company in June 2006.

Welland Canal Survey of Lands Village Lot in Allanburgh, 1833

Survey map and description of a village lot in Allanburgh. Created by The Welland Canal Company. Included is a written description of the land along with a drawing of the lot. Noteable features include; Holland road, grave land, Niagara street. The land totals 3/4 of an acre. Surveyor notes are seen in pencil on the map.

Welland Canal Survey of Lands Village of Allanburgh, 1833

Survey map and description of the Village of Allanburgh, created by The Welland Canal Company. Included is a drawing of the land. Noteable features include; lot divisions, Welland Canal, Niagara street, Holland road, lock 36 and 37, foundry, Canal street, mill, Canby street, Dover street, Rose street, Helen street, Water street, Falls street, Centre street, Welland street, Hall street, Clifton street, James street, Mary street, Catherine street, J.G. Stockley's land, reservoir, graveyard. Surveyor notes are seen in pencil on the map.

Barnes Wines: Canada’s Oldest Winery flyer. n.d.

In 1873 George Barnes, Andrew Skinner, James Skinner, John Young Reid, Charles Robert Murray, George Magan, Thomas Barnes and Robert Duncan applied for, and received a charter for a commercial winery which would be called The Ontario Grape Growing and Wine Manufacturing Company Limited. It opened in 1894 and became known as Barnes Wines Limited. In 1973 the company completed a merger with Reckitt and Coleman (Canada) Limited. The winery operated until 1988 and was located on the banks of the old Welland Canal in St. Catharines, Ontario. The company produced a complete line of table wines, dessert wines, sherries, ports, and both crackling and sparkling wines. Barnes Wines called itself “Canada’s oldest winery” at the time of the printing of this flyer.

Barnes Wines Fonds

4 Minute Books dated: 1880, 1892, 1901, 1934, 1948-1950, 1952-1953, 1955, 1958, 1962 – 1975, 1981, 1984, 1986; 3 Common stock books dated: 1934-1935, 1937-1941, 1946, 1948-1950, 1955-1956, 1958, 1961-1974, 1981 and 2 Class A stock books dated:1948 - 1951

METHOXYPYRAZINES AND LADYBUG TAINT IN WINES

Methoxypyrazines are aroma active compounds found in many wine varietals. These compounds can be of either grape-derived nature or can be introduced into wines via Coccinellidae beetles. Regardless of their origin, methoxypyrazines can have either a beneficial role for wine quality, contributing to the specificity of certain wine varietals (Cabernet sauvignon, Cabernet franc, Sauvignon blanc) or a detrimental role, particularly at higher concentrations, resulting in overpowering green, unripe and herbaceous notes. When methoxypyrazines of exogenous nature are responsible for these unpleasant characteristics, wines are considered to be affected by what is generally known as Ladybug taint (LBT). This is work is a collection of studies seeking to create a sensitive analytical method for the detection and quantification of methoxypyrazines in wines; to investigate the role of different Coccinellidae species in the tainting of wines with LBT and identify the main compounds in ladybug tainted wines responsible for the typical green herbaceous characteristics; to determine the human detection threshold of 2,5-dimethyl-3-methoxypyrazine in wines as well as investigate its contribution to the aroma of wines; and finally to survey methoxypyrazine concentrations in a large set of wines from around the world. In the first study, an analytical method for the detection and quantitation of methoxypyrazines in wines was created and validated. The method employs multidimensional Gas Chromatography coupled with Mass Spectrometry to detect four different methoxypyrazines (2,5-dimethyl-3-methoxypyrazine, isobutyl methoxypyrazine, secbutyl methoxypyrazine and isopropyl methoxypyrazines) in wine. The low limits of detection for the compounds of interest, improved separation and isolation capabilities, good validation data, as well as the ease of use recommend this method as a good alternative to the existing analytical methods for methoxypyrazine detection in wine. In the second study the capacity of two Coccinellidae species, found in many wine regions – Harmonia axyridis and Coccinella septempunctata - to taint wines is evaluated. Coccinella septempunctata is shown to be as capable as causing LBT in wines as Harmonia axyridis. Dimethyl methoxypyrazine, previously thought to be of exogenous nature only (from Coccinellidae haemolymph), is also detected in control (untainted) wines. The main odor active compounds in LBT wines are investigated through Aroma Extract Dilution Assay. These compounds are identified as isopropyl methoxypyrazine, sec- and iso- butyl methoxypyrazine. In the third study, the human detection threshold for dimethyl methoxypyrazine in wine is established to be 31 ng/L in the orthonasal modality and 70 ng/L retronasally. After wines spiked with various amounts of dimethyl methoxypyrazine are evaluated sensorally, dimethyl methoxypyrazine causes significant detrimental effects to wine aroma at a concentration of 120 ng/L. The final study examines methoxypyrazine (dimethyl methoxypyrazine, isopropyl methoxypyrazine, secbutyl methoxypyrazine and isobutyl methoxypyrazine) concentrations in 187 wines from around the world. Dimethyl methoxypyrazine is detected in the majority of the red wines tested. Data are interpreted through statistical analyses. A new measure for predicting greenness/herbaceousness in wines - methoxypyrazine “total impact factor” is proposed.

The Vintners Quality Alliance - VQA Officially Launches its "Appellation of Origin" System for Ontario Wines, June 27 1989

An official launch for the '"Appellation of Origin" System for Ontario Wines'. The VQA announces the labeling system which will identify "Ontario wines based on the origin of the grapes from which they are produced". The system relies on Provincial and Geographic Designations which are outlined in the announcement.

Inniskillin Award Winning Wines - '98-'02

A list of awards for Inniskillin wines for the years 1998-2002.

Inniskillin Wines at Macy's New York for Ontario Fine Foods Promotion

A letter from Export Development Officer, Kenneth M. Mueller which is part of a large photo album, dated May 9, 1986. The letter indicates that Mueller put together the album showing the reception at the Trillium Room and the Macy's Marketplace presentations. The promotion was for Ontario fine products and included Inniskillin. The photograph featured from the album shows Donald Ziraldo at his Inniskillin table in the Trillium room talking to patrons of the event.

Plan of part of the lands of the Six Nations Indians, January 26, 1833

A plan of part of the lands of the Six Nations Indians, dated January 26, 1833. A note on the plan reads “Part of the lands of the Six Nations Indians as surveyed by order of their Superintendent, John Brant, Esq. Dated at the Mohawk Village, the 29th day of April, 1831. Part of which was returned to the office of the Honourable, the Commissior of Crown Lands, on the 31st Oct. 1831, and now rendered more complete by a continuation of the survey under the same order in 1832, and by information obtained from private practice not connected with my official instructions all of which is most respectfully submitted to the inspection and for the information of His Majesty’s Government by Lewis Burwell, Surveyor”. The map shows the early loyalist land holdings in the Brantford area.