Dr. Richard Caulfield: antiquarian, scholar and academic librarian

The history of higher learning in Cork can be traced from its late eighteenth-century origins to its present standing within the extended confines of the Neo-Gothic architecture of University College, Cork. This institution, founded in 1845 was the successor and ultimate achievement of its forerunner, the Royal Cork Institution. The opening in 1849 of the college, then known as Queen's College, Cork, brought about a change in the role of the Royal Cork Institution as a centre of education. Its ambition of being the 'Munster College' was subsumed by the Queen's College even though it continued to function as a centre of learning up to the 1805. At this time its co-habitant, the School of Design, received a new wing under the benevolent patronage of William Crawford, and the Royal Cork Institution ceased to exist as the centre for cultural, technical and scientific learning it had set out to be. The building it occupied is today known as the Crawford Municipal Art Gallery.

Assessment of the origin and stability of Nifedipine polymorph IV by differential scanning calorimetry (DSC)

Purpose. To examine the thermal transition(s) between different polymorphic forms of Nifedipine and to define experimental conditions that lead to the generation of polymorph IV. Methods. Experiments were performed using a DSC 823e (Mettler Toledo). Nifedipine exists in four polymorphic forms, as well as an amorphous state. Examination of Nifedipine was conducted using the following method(s): cycle 1: 25ºC to 190ºC, 190ºC to 25ºC (formation of amorphous Nifedipine); cycle 2: 25ºC to X (60,70,80...150ºC), X to 25ºC; cycle 3: 25ºC to 190ºC and holding isothermally for 5 min between cycles (heating/cooling rate of 10ºC/min). Results. The amorphous state Nifedipine can sustain heating up to 90ºC without significant changes in its composition. Cycle 2 of amorphous material heated up to 90ºC shows only the glass transition at ~44ºC. In cycle 3 of the same material, a glass transition has been recorded at ~44ºC, followed by two exotherms (~100 and ~115ºC (crystallisation of polymorph III and II, respectively) and an endotherm (169ºC (melting of polymorphs I/II)). Samples that have been heated to temperatures between 100ºC and 120ºC in the second cycle showed a glass transition at ~44ºC and an additional exotherm at ~95ºC (crystallisation of polymorph III) on cooling a exotherm was observed at ~40ºC (crystallisation of polymorph IV). The same material showed no glass transition in cycle 3 but an endotherm at around 62ºC (melting of polymorph IV) an exotherm (~98ºC) and an endotherm (169ºC) melting of polymorph I/II. Heating the sample to a temperatures greater than 130ºC in cycle two results in a glass transition at ~44ºC, and two exotherms at ~102 and 125ºC (crystallisation of polymorphs III and I, respectively). Conclusions. DSC data suggests that polymorph IV can only be produced from amorphous or polymorph III samples. The presence of polymorph I or II drives the conversion of the less stable polymorphic form IV into the most stable form, I. Although form IV of Nifedipine can easily be created, following defined experimental conditions, it may only coexist with amorphous or polymorph III states. When polymorphs I and II are present in the sample polymorph IV cannot be etected.

Synthesis, Kinetic Evaluation and Utilization of a Biotinylated Dipeptide Proline Diphenyl Phosphonate for the Disclosure of Dipeptidyl Peptidase IV-like Serine Proteases

In this study, we report on the synthesis, kinetic characterisation, and application of a novel biotinylated and active site-directed inactivator of dipeptidyl peptidase IV (DPP-IV). Thus, the dipeptide-derived proline diphenyl phosphonate NH(2)-Glu(biotinyl-PEG)-Pro(P)(OPh)(2) has been prepared by a combination of classical solution- and solid-phase methodologies and has been shown to be an irreversible inhibitor of porcine DPP-IV, exhibiting an over all second-order rate constant (k(i)/K(i)) for inhibition of 1.57 x 10(3) M(-1) min(-1). This value compares favourably with previously reported rates of inactivation of DPP-IV by dipeptides containing a P(1) proline diphenyl phosphonate grouping [B. Boduszek, J. Oleksyszyn, C.M. Kam, J. Selzler, R.E. Smith, J.C. Powers, Dipeptide phophonates as inhibitors of dipeptidyl peptidase IV, J. Med. Chem. 37 (1994) 3969-3976; B.F. Gilmore, J.F. Lynas, C.J. Scott, C. McGoohan, L. Martin, B. Walker, Dipeptide proline diphenyl phosphonates are potent, irreversible inhibitors of seprase (FAPalpha), Biochem, Biophys. Res. Commun. 346 (2006) 436-446.], thus demonstrating that the incorporation of the side-chain modified (N-biotinyl-3-(2-(2-(3-aminopropyloxy)-ethoxy)-ethoxy)-propyl) glutamic acid residue at the P(2) position is compatible with inhibitor efficacy. The utilisation of this probe for the detection of both purified dipeptidyl peptidase IV and the disclosure of a dipeptidyl peptidase IV-like activity from a clinical isolate of Porphyromonas gingivalis, using established electrophoretic and Western blotting techniques previously developed by our group, is also demonstrated.

(Un)settling the Irish emigrant identity: representation and construction of an Irish emigrant/exile identity in the travel narratives of Kathleen Nevin and William Bulfin

Through an examination of the travel works of William Bulfin, Tales of the Pampas (1900) and Kathleen Nevin's You'll Never Go Back this paper considers the representation of the Irish in Argentina and the contribution of these narratives in the construction of identity and the reconstruction of the emigrant identity into an exilic one. Escaping one colonial framework (Britain/Ireland), travelling to and writing from within another postcolonial construct (Argentina and the Spanish Empire), this paper analyses how Bulfin and Nevin use language as a tool to construct, and even invent, an Irish identity. This identity is inextricably linked to home and the desire to return there. Despite this desire, Argentina becomes internalised to some extent, which in Bulfin can be seen in the mix of the Spanish, English and Irish languages in his stories, highlighting that the Irish were doing with language what they had already done with their lives; trying to adapt it to their new situation. In Nevin, the contrast between us and them (Irish and 'Native') demonstrates her attempts to shape an exilic rather than emigrant mentality. Through these texts I analyse how Argentina never quite becomes a new home, but a place where Irish identity is played out and acquires form.

ESI-MS[n] of anticancer pt[iv] organoamido complexes and their interactions with DNA-model compounds /

The general solution behaviour and" the major fragmentation pathways of the anticanceractive PtIV coordination complexes, trans, trans, cis, cis-[PtCIOH{N(pFC6F4) CH2h(pY)2] (1), trans, cis, cis-[Pt(OH)2{N(p-FC6F4)CH2h(Py)2] (2), trans, cis, cis-[Pt(OH)2{N(p-HC6F4)CH2h(Py)2] (3), trans, trans, cis, cis-[PtCIOH{N(pHC6F4) CH2h(Py)2] (4), and trans, trans, cis, cis-[PtOH(OCH3){N(p-HC6F4)CH2h(PY)2] (5) (Py = pyridine) have been deduced by positive-ion tandem-in-time ESI-MS. Overall, the acquired full-scan, positive-ion ESI-MS spectra of 2, 3, and 5 were characterized by the presence of relatively low-intensity [M+Nar and [M+Kt mass spectral peaks, whereas those of 1 and 4 were dominated by extremely intense [M+Hr peaks. Complexes 2 and 3 were also noted to form [2M+Ht and [2M+Nat dilneric cations. The source of Na + and K+ ions is believed to be the sample, the solvent systems used or the transport line carrying the sample solutions into the ES ion source. Further, the fragmentation pathway of all complexes studied was found to be almost identical with concurrent loss of py and H20 molecules, loss of a {N(p-YC6F4)CH2} (Y = F, H) group and/or concomitant release of the latter group and a py ligand being the most conunon. The photochemical degradation behaviour of 1 and 2 was also investigated using either fluorescent or ultraviolet light and some products of that degradation were positively identified. Altogether, light irradiation of solutions of both complexes resulted in cation cationisation, reductive-elimination, ligand-release, ligand-exchange and ligand-addition reactions. Finally, positive- and negative-ion ESI-MSn spectra of 5' -GMP, guanosine, inosine and products of their reactions with 1, 2,3, and 4 were also recorded. On the whole, full-scan ESI-MS spectra of the pure nucleobases revealed the presence of cationic and anionic species that are highly reflective of both their solution ionic composition and their propensity t9 form polymeric clusters. Analyses of mass spectra acquired from their reaction solutions with the aforementioned platinum complexes indicated very slow kinetics. However, all complexes investigated formed, to various degrees, Pt-nucleobase adducts with guanosine and inosine, but not with 5'-GMP. The products included species having coordination numbers of III, IV, V, and VI, among which the first-time· observed, coordinatively saturated, jive-coordinate PtlI-nucleobase complexes were of most interest. The latter complexes are presumably stabilized by 7tback- donation involving the filled d orbitals of the PtII centre and the empty pz· orbital of MeCN. All products, whose peaks appeared inlull-scan ESI-MS spectra, are believed to represent solution species rather than artifacts of gas-phase processes. Finally, negativeion ESI-MSn spectra recorded in reaction solutions of 1 and 4 with guanosine and of the latter complex with inosine revealed the negative-ion-ESI-MS first-time observed, noncovalent, nucleoside-chloride adducts, with the source of chloride anion being complexes 1 and 4 theillselves. In contrast, no such adducts were observed to form with Na25'-GMP or its protonated fonn. Few suggestions are offered for the possible cause(s) behind the absence of such adduct ions.

Welland Canal Survey of Lands William May Jr., 1826

Survey map and description of William May Jr.'s land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. The land is described as having 2 good acres and the rest being swamp. The property borders 12 mile creek in Grantham township. Noteable features include; a large pond, division line between lots 20 and 21 as well as 21 and 22, concession line. Surveyor notes are seen in pencil on the map. Click on 'detail' to see Map

Welland Canal Survey of Lands William Hamilton Merritt Esquire 1826

Survey map and description of William Hamilton Merritt's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. The drawing also includes John Hainer's Land. Noteable features include; saw mill, salt works, line between Hainer's and Merritt's land,line between John Clendennan's and Merritt's land, road, bridge, tow path, 12 mile creek and canal. Surveyor notes are seen in pencil on the map. The survey was signed and submitted on August 23rd, 1826. The land is 17 acres, 3 roads and 20 perches.

Welland Canal Survey of Lands William Chisholm 1836

Survey map and description of William Chisholm's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; line between Elias Adams and Chisholm's land, line between Chisholm and Shipman's land, canal. The land is a total of 1 acre and 2 perches. The deed for the land is dated August 23, 1836. Surveyor notes are seen in pencil on the map.

Welland Canal Survey of Lands William C. Chace 1826

Survey map and description of William C. Chace's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; concession line. The land totals 1/4 of an acre. The survey was signed and submitted on August 23, 1826. Surveyor notes are seen in pencil on the map.

Welland Canal Survey of Lands Isabella Steward and William Sanderson, 1826

The first survey map and description is of Isabella Steward's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; high water mark. The survey was signed and submitted on August 23rd, 1826. The land totals 1/4 of an acre. The second survey map and description is of William Sanderson's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; line between Sanderson and Clendenning's land, line between Sanderson and Adam's land, canal. The survey was signed and submitted on August 23, 1826. The land totals 14 perches and 1 road. Surveyor notes are seen in pencil on the map. This image contains two seperate surveys.

Welland Canal Survey of Lands William McLellan

Survey map and description of William McLellan's land created by The Welland Canal Company. Included is a written description of the land along with a drawing of the land. Noteable features include; line between lots, canal. Surveyor notes are seen in pencil on the map.

Probate of Last Will and Testament - William Smith

Probate of Last Will and Testament of William Smith of the township of Lincoln. Mr. Smith was a farmer. His goods and chattels are left to his children and grandchildren. The document was registered May 9, 1865 - instrument no. 15383 and the original date of the document is January 20, 1856.

Some Incidents and Circumstances Written by William F. Haile in the Course of his Life, 1859

William Frederick Haile was born in Putney, Windham County, Vermont on November 4th, 1791. He was raised in Fairfield, Herkimer County, New York. At the age of 21 he entered the United States Army. He served in the War of 1812 as a lieutenant in the 11th United States Infantry. He was severely wounded in the Battle of Lundy’s Lane [not mentioned in this memoir]. After the war he settled in Plattsburgh, New York and became a lawyer. He was a judge from April 1837 to March of 1843. He was also the fifth collector of customs for the District of Champlain. He died on October 1861 at the age of 69. This document was written for the children of William Frederick Haile in January of 1859 [as noted on p.23]. The memoir ends in July of 1814 before the Battle of Lundy’s Lane. Haile’s memoir is laced with names of military personnel and he expresses his opinions freely.

Synthesis, structure and solution chemistry of mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands

In the title family, the ONO donor ligands are the acetylhydrazones of salicylaidehyde (H2L1) and 2-hydroxyacetophenone (H2L2) (general abbreviation, H2L). The reaction of bis(acetylacetonato)oxovanadium(IV) with a mixture of tridentate H2L and a bidentate NN donor [e.g., 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen), hereafter B] ligands in equimolar ratio afforded the tetravalent complexes of the type [(VO)-O-IV(L)(B)]; complexes (1)-(4) whereas, if B is replaced by 8-hydroxyquinoline(Hhq) (which is a bidentate ON donor ligand), the above reaction mixture yielded the pentavalent complexes of the type [(VO)-O-V(L)(hq)]; complexes (5) and (6). Aerial oxygen is most likely the oxidant (for the oxidation of V-IV -> V-V) in the synthesis of pentavalent complexes (5) and (6). [(VO)-O-IV(L)(B)] complexes are one electron paramagnetic and display axial EPR spectra, while the [(VO)-O-V(L)(hq)] complexes are diamagnetic. The X-ray structure of [(VO)-O-V(L-2)(hq)] (6) indicates that H2L2 ligand is bonded with the vanadium meridionally in a tridentate dinegative fashion through its phenolic-O, enolic-O and imine-N atoms. The general bond length order is: oxo < phenolato < enolato. The V-O (enolato) bond is longer than V-O (phenolato) bond by similar to 0.07 angstrom and is identical with V-O (carboxylate) bond. H-1 NMR spectrum of (6) in CDCl3 solution indicates that the binding nature in the solid state is also retained in solution. Complexes (1)(4) display two ligand-field transitions in the visible region near 820 and 480 nm in DMF solution and exhibit irreversible oxidation peak near +0.60 V versus SCE in DMSO solution, while complexes (5) and (6) exhibit only LMCT band near 535 nm and display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. The VO3+-VO2+ E-1/2 values shift considerably to more negative values when neutral NN donor is replaced by anionic ON donor species and it also provides better VO3+ binding via phenolato oxygen. For a given bidentate ligand, E-1/2 increases in the order: (L-2)(2-) < (L-1)(2-). (c) 2004 Elsevier B.V. All rights reserved.