The application of the structural correlation method to determine the reaction coordinate for a putative ring closure reaction

The cr ystal structure of the compound 2-benzoylethylidene-3-(2,4- dibromophenyl)-2,3-dihydro-5-phenyl-l,3,4-thiadiazole* C23H16Br2NZOS (BRMEO) has been determined by using three dimensiona l x-ray diffraction data. The crys tal form is monoclinic, space group P21/c, a = 17.492(4), o -.t' 0 R 0 b =: 16.979(1), c = 14.962(1) A, "X. =o= 90 ',= 106.46(1) , z = 8, graphite-monochromatized Mo~ rad iation, Jl= 0.710J3~, D = 1.62g/cc and o D = 1.65g/cc. The data were col lected on ~ Nonius CAD-4 c diffractometer. The following atoms were made anisotropic: Br, S, N, 0, C7, and C14-C16 for each i ndependent molecu le ; the rest were left isotropic. For 3112 independent refl ec tions with F > 6G\F), R == 0.057. The compound has two independent molecules within the asymmetric unit. Two different conformers were observed which pack well together. /l The S---O interaction distances of 2.493(6) and 2 . 478(7) A were observed for molecules A and B respectively. These values are consistent with earlier findings for 2-benzoylmethylene-3-(2,4-dibromophenyl)- ~~ 2,3-dihydro-5-phenyl-l,3,4-thiadiazole C22H14Br2N20S (BRPHO) and 2-benzoylpropylidene-3-(2,4-dibromophenyl)-2,3-dihydroiii ,'r 5-phenyl-l,3,4-thiadiazole C24H18Br2N20S (BRPETO ) where S---O distances are l ess than the van der Waals (3.251\) but greater than those expected for () a single bond (1.50A). From the results and the literature it appears obvious that the energy/reaction coordinate pathway has a minimum between the end structures (the mono- and bicyclic compounds). * See reference (21) for nomenclature.

Chemoenzymatic Total Synthesis of Morphine alkaloids: Synthesis of Dihydrocodeine and Hydrocodone via a Double Claisen Strategy and ent-Hydromorphone via an Oxidative Dearomatization/intramolecular [4+2] Cycloaddition

This thesis describes the chemoenzymatic synthesis of three morphine alkaloids. The total synthesis of dihydrocodeine and hydrocodone was accomplished starting from bromobenzene in 16 and 17 steps, respectively. The key steps included a microbial oxidation of bromobenzene by E. coli JM109 (pDTG601A), a Kazmaier-Claisen rearrangement of glycinate ester to generate C-9 and C-14 stereo centers, a Johnson-Claisen rearrangement to set the C-13 quaternary center, and a C-10/C-11 ring closure via a Friedel-Crafts reaction. In addition, the total synthesis of ent-hydromorphone starting from β-bromoethylbenzene in 12 steps is also described. The key reactions included the enzymatic dihydroxylation of β-bromoethylbenzene to the corresponding cis-cyclohexadienediol, a Mitsunobu reaction, and an oxidative dearomatization followed by an intramolecular [4+2] cycloaddition.

Letter - E.C. Schmon to Arthur A. Schmon, 14 February 1918

The letter discusses Valentine's Day and she has drawn hearts in red ink. She also describes the events of the previous day: Red Cross work, lunch at YWCA, Club meeting. The letter also includes a list of items in a package she has sent to Arthur. The letter is labelled number 56.

Letter - E.C. Schmon to Arthur A. Schmon, 14 June 1918

Eleanore Celeste has been to visit Arthur Schmon's parents. His father has not been feeling well and takes a week vacation per month. His mother worries because the checks Arthur sends do not come when they should. Eleanore Celeste requests that Arthur write to Washington to have it straightened out. She also mentions her family and who they are visiting over the next week. This letter is labelled number 114.

Letter - E.C. Schmon to Arthur A. Schmon, 14 February 1920

This letter is decorated for Valentine's Day. There is a red cut out hard included that reads "To my Valentine from your Valentine xxxxxx". The second part of the letter talks about how to get to Shelter Bay and Eleanore Celeste remarks "So you do not think it advisable for me to make the trip to Shelter Bay by dog team! Let me tell you dearest, that I wouldn't mind if I had to walk there." These letters are labelled number 126 and 127.

Letter - E.C. Schmon to Arthur A. Schmon, 14 & 15 May 1919

Eleanore Celeste mentions that Arthur is to return in July. She discusses the way the troops are returning to New York and New Jersey and the discharge process. These letters are labelled number 279 and 280.

Letter - E.C. Schmon to Arthur A. Schmon, 14 March 1917

The letter is a thank you for a book Arthur has sent to Eleanore Celeste. The title of the book is not mentioned.

Incidence of resistance to benzimidazole fungicides in a field population of Venturia inaequalis /

The allele-specific polymerase chain reaction (PCR) was used to screen for the presence of benomyl resistance, and to characterize their levels and frequencies in field populations of Venturia inaequalis during two seasons. Three hundred isolates of V. inaequalis were collected each season from infected leaves of MalusX domestica. Borkh c.v. Mcintosh. The trees used were sprayed in the year prior to collection with five applications of benomyl, its homologue Azindoyle, or water. Monoconidial isolates of V. inaequalis were grown on 2% potato dextrose agar (PDA) for four weeks. Each isolate was taken from a single lesion from a single leaf. Total genomic DNA was extracted from the four week old colonies of V. inaequalis, prepared and used as a template in PCR reactions. PCR reactions were achieved by utilizing allele-specific primers. Each primer was designed to amplify fragments from a specific allele. Primer Vin was specific for mutations conferring the ben^^"^ phenotype. It was expected to amplify a 171 bp. DNA fragment from the ben^"^ alleles only. Primers BenHR and BenMR were specific for mutations conferring the ben"" and ben'^'' phenotypes, respectively. They were expected to amplify 172 bp. and 165 bp. DNA fragments from the ben"" and ben"^" alleles, respectively. Of the 953 isolates tested, 414 (69.9%) were benomyl sensitive (ben^) and 179 (30.1%) were benomyl resistant. All the benomyl resistant alleles were ben^"", since neither the ben"" nor the ben"" alleles were detected. Frequencies of benomyl resistance were 23%, 24%, and 23% for the 1997 collections, and were 46%, 26% and 38% for the 1998 collections for benomyl, Azindoyle and water treatments, respectively. Growth assay was performed to evaluate the applicability of using PCR in monitoring benomyl resistance in fungal field populations. Tests were performed on 14 isolates representing the two phenotypes (ben^ and ben^"'' alleles) characterized by PCR. Results of those tests were in agreement with PCR results. Enzyme digestion was also used to evaluate the accuracy and reliability of PCR products. The mutation associated with the ben^"'' phenotype creates a unique site for the endonuclease enzyme Bsh^236^ allowing the use of enzyme digestion. Isolates characterized by PCR as ben^'^'^ alleles had this restriction site for the SsA7l2361 enzyme. The most time consuming aspect of this study was growing fungal isolates on culture media for DNA extraction. In addition, the risk of contamination or losing the fungus during growth processes was relatively high. A technique for extracting DNA directly from lesions on leaves has been used (Luck and Gillings 1 995). In order to apply this technique in experiments designed to monitor fungicide resistance, a lesion has to be homogeneous for fungicide sensitivity. For this purpose, PCR protocol was used to determine lesion homogeneity. One hundred monoconidial isolates of V. inaequalis from 10 lesions (10-conidia/ lesion) were tested for their phenotypes with respect to benomyl sensitivity. Conidia of six lesions were homogeneous, while conidia of the remaining lesions were mixtures of ben^ and ben^ phenotypes. Neither the ben" nor the ben' phenotype was detected.

Isolation and analysis of a corprinus cinereus DNA fragment showing homology to a fimbrial cDNA from ustilago violacea

Surface proteinaceous fibrils, termed fimbriae, were first identified on gram negative bacteria in the 1940s. Fungal fimbriae, discovered some 25 years later, are found on members of all fungal classes. In the present study, polyclonal antiserum raised against the fimbrial proteins of U. vio/acea were used in order to identify antigenically related proteins from Coprinus cinereus and Schizophy//um commune. Two polypeptides with molecular masses of 37 and 39 kDa from C. cinereus were observed and confirm earlier results. A single previously unidentified 50 kDa polypeptide in S. commune crossreacted with the antiserum. The 50 kDa protein was found to consist of 3 isoforms with isoelectric points ranging from 5.6 to 5.8. A fimbrial cDNA derived from U. vio/acea was used to identify DNA restriction fragments from C. cinereus and S. commune showing homology to the fimbrial transcript of U. vio/acea. Heterologous hybridization with this cDNA was used in order to screen a C. cinereus genomic DNA library. A single clone, A2-3A, with a 14 kbp insert showed strong homology to the pfim3-1 cDNA. The region of homology, a 700 bp Xba I fragment, was subcloned into pUG19. This plasmid was refered to as pXX8. DNA sequence determinations of pXX8 and adjacent fragments from A2-3A suggested that the cloned DNA was a portion of the rONA repeat encoding the small subunit rRNA. DNA sequence analysis of pfim3-1 yielded an incomplete open reading frame. The predicted amino acid sequence codes for a 206 amino acid, 22 kDa polypeptide which contains a domain similar to a transmembrane domain from rat leukocyte antigen, GDS3. As well, an untranslated 576 nucleotide domain showed 81 % homology to pXX8 and 830/0 homology to the 188 rRNA sequence of Ustilago maydis. This sequence was found adjacent to a region of adenine-thymine base pairs presumed to represent the polyadenylation sequence of the fimbrial transcript. The size and extent of homology is sufficient to account for the hybridization of pfim3-1 to rDNA. It is suggested that this domain represents a completely novel regulatory domain within eukaryotes that may enable the observed rapid regeneration of fimbriae in U. violacea.

Second Welland Canal - Book 2, Survey Map 14 - Lock 26 and Allanburgh

Survey map of the Second Welland Canal created by the Welland Canal Company showing the canal as it passes through the Village of Allanburgh. Identified structures and features associated with the Canal include Lock 26, a Guard Lock, Lock Tender's House, the New Cut, waste wear, and the towing path. Parts of the old canal are indentified and include Old Lock 36 and 37, and the Old Cut. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads (ex. Holland Road, Centre Street, Falls Street, Canal Street, and Clifton Street), Allanburgh Hotel, Rannies Store, Wright and Duncan Grist Mill, A. Vanderburgh Saw Mill, W. Pennock Shingle Factory, John Harper Tavern, a very delapitated Grist and Saw Mill, store house, a shanty, and a number of other structures - some of which are identified by their owners: A. Vanderburgh, W. Wright, C. Brent, and H. Mussen. Properties and property owners of note are: Lots 118 and 119, Captain Creighton, and William H. Merritt Jr. A number of small properties labeled 1 through 39 are present and of these 6 - 15 are reserved for a Mill Site and are outlined in red. Several other pieces of land are outlined in blue and belong to: W. B. Hendershot, P. Finlay, W. Wright, and L. Leslie. There is also a piece of land reserved for hydraulic purposes.

Second Welland Canal - Book 3, Survey Map 14 - Village of Junction and Crowland

Survey map of the Second Welland Canal created by the Welland Canal Company showing the border area of the townships of Crowland and Humberstone, as well as the Village of Junction. Identified structures associated with the Canal include ditches, guard lock, old canal, new towing path, bridge, feeder to Dunnville, covered drain. Surveyor measurements and notes can be seen in red and black ink and pencil. Local area landmarks include James Turf Tavern and possible marshland. Roads parallel to Canal include western Road Allowance, the new towing road, road to Welland and road to Junction. Roads perpendicular to Canal include Road Allowance between the 5th and 6th Concession. Properties and property owners are noted as Thomas. C. Street, James Tuft, and John Hellems. Lots noted are: Lots Number 26, 27, 6th Concession.

Two leaves from a Medieval breviary (prayer-book), c.1350-1400

The actual scripture quotations begin with blue and gold illuminated letters. Towards the end of each passage, there is a small red “R” that marks the “Response”. At the conclusion of the Response, the next lesson is announced. There are three lessons on these leaves. The first leaf begins with the word “Requiem” with the initial letter illuminated. The third lesson begins with the illuminated letter “M” on the word “Manus”. This passage is from the Book of Job, Chapter 10, verses 8-11 which reads: Your hands have formed me and fashioned me; will you then turn and destroy me? Oh, remember that you fashioned me from clay. Will you then bring me down to dust again? Did you not pour me out as milk, and thicken me like cheese? With skin and flesh you clothed me, with bones and sinews knit me together.

Letter - E.C. Schmon to Arthur A. Schmon, 6 August 1918

The letter mentions some men that may be returning the United States and some that have returned. This letter is labelled number 138.

Bill C-373 - First Reading, 24 January 1975

"An Act to provide for the recognition of the Beaver (Castor canadensis) as a symbol of the sovereignty of the Dominion of Canada." Mr. Sean O'Sullivan worked to have this Bill passed, recognizing the Beaver as a symbol of Canadian sovereignty.