Environmental weathering of natural and artificial stones used in historical architecture: influence of microstructure and new restoration methods

For some study cases (the Cathedral of Modena, Italy, XII-XIV century; the Ducal Palace in Mantua, Italy, XVI century; the church of San Francesco in Fano, Italy, XIV-XIX century), considered as representative of the use of natural and artificial stones in historical architecture, the complex interaction between environ-mental aggressiveness, materials’ microstructural characteristics and degradation was investigated. From the results of such analyses, it was found that materials microstructure plays a fundamental role in the actual extent to which weathering mechanisms affect natural and artificial stones. Consequently, the need of taking into account the important role of material microstructure, when evaluating the environmental aggressiveness to natural and artificial stones, was highlighted. Therefore, a possible quantification of the role of microstructure on the resistance to environmental attack was investigated. By exposing stone samples, with significantly different microstructural features, to slightly acidic aqueous solutions, simulating clean and acid rain, a good correlation between weight losses and the product of carbonate content and specific surface area (defined as the “vulnerable specific surface area”) was found. Alongside the evaluation of stone vulnerability, the development of a new consolidant for weathered carbonate stones was undertaken. The use of hydroxya-patite, formed by reacting the calcite of the stone with an aqueous solution of di-ammonium hydrogen phosphate, was found to be a promising consolidating tech-nique for carbonates stones. Indeed, significant increases in the mechanical prop-erties can be achieved after the treatment, which has the advantage of simply con-sisting in a non-hazardous aqueous solution, able to penetrate deeply into the stone (> 2 cm) and bring significant strengthening after just 2 days of reaction. Furthermore, the stone sorptivity is not eliminated after treatment, so that water and water vapor exchanges between the stone and the environment are not com-pletely blocked.

N-Heterocyclic carbene complexes of rhodium: structures, dynamics and catalysis

A series of imidazolium salts of the type [BocNHCH2CH2ImR]X (Boc = t-Bu carbamates; Im = imidazole) (R = Me, X = I, 1a; R = Bn, X = Br, 1b; R = Trityl, X = Cl, 1c) and [BnImR’]X (R’ = Me, X = Br, 1d; R’ = Bn, X = Br, 1e; R’ = Trityl, X = Cl, 1g; R’ = tBu, X = Br, 1h) bearing increasingly bulky substituents were synthetized and characterized. Subsequently, these precursors were employed in the synthesis of silver(I)-N-heterocyclic (NHC) complexes as transmetallating reagents for the preparation of rhodium(I) complexes [RhX(NBD)(NHC)] (NHC = 1-(2-NHBoc-ethyl)-3-R-imidazolin-2-ylidene; X = Cl; R = Me, 4a; R = Bn, 4b; R = Trityl, 4c; X = I, R = Me, 5a; NHC = 1-Bn-3-R’-imidazolin-2-ylidene; X = Cl; R’ = Me, 4d, R’ = Bn, 4e, R’ = Trityl, 4g; R’ = tBu, 4h). VT NMR studies of these complexes revealed a restricted rotation barriers about the metal-carbene bond. While the rotation barriers calculated for the complexes in which R = Me, Bn (4a,b,d,e and 5a) matched the experimental values, this was not true for the complexes 4c,g, bearing a trityl group for which the values are much smaller than the calculated ones. Energy barriers for 4c,g, derived from a line shape simulation, showed a strong dependence on the temperature while for 4h the rotational energy barrier is stopped at room temperature. The catalytic activity of the new rhodium compounds was investigated in the hydrosilylation of terminal alkynes and in the addition of phenylboronic acid to benzaldehyde. The imidazolium salts 1d,e were also employed in the synthesis of new iron(II)-NHC complexes. Finally, during a six-months stay at the University of York a new ligand derived from Norharman was prepared and employed in palladium-mediated cross-coupling.

Cannabinoid system combined to classic targets for a new MTDL strategy: design and synthesis of natural inspired molecules for Alzheimer's disease

In this thesis is described the design and synthesis of potential agents for the treatment of the multifactorial Alzheimer’s disease (AD). Our multi-target approach was to consider cannabinoid system involved in AD, together with classic targets. In the first project, designed modifications were performed on lead molecule in order to increase potency and obtain balanced activities on fatty acid amide hydrolase and cholinesterases. A small library of compounds was synthesized and biological results showed increased inhibitory activity (nanomolar range) related to selected target. The second project was focused on the benzofuran framework, a privileged structure being a common moiety found in many biologically active natural products and therapeutics. Hybrid molecules were designed and synthesized, focusing on the inhibition of cholinesterases, Aβ aggregation, FAAH and on the interaction with CB receptors. Preliminary results showed that several compounds are potent CB ligands, in particular the high affinity for CB2 receptors, could open new opportunities to modulate neuroinflammation. The third and the fourth project were carried out at the IMS, Aberdeen, under the supervision of Prof. Matteo Zanda. The role of the cannabinoid system in the brain is still largely unexplored and the relationship between the CB1 receptors functional modification, density and distribution and the onset of a pathological state is not well understood. For this reasons, Rimonabant analogues suitable as radioligands were synthesized. The latter, through PET, could provide reliable measurements of density and distribution of CB1 receptors in the brain. In the fifth project, in collaboration with CHyM of York, the goal was to develop arginine analogues that are target specific due to their exclusively location into NOS enzymes and could work as MRI contrasting agents. Synthesized analogues could be suitable substrate for the transfer of polarization by p-H2 molecules through SABRE technique transforming MRI a more sensitive and faster technique.

Strategies of Representation, Relationship, and Resistance: British Women Travelers and Mormon Plural Wives, c. 1870-1890

During the 1870s and 1880s, several British women writers traveled by transcontinental railroad across the American West via Salt Lake City, Utah, the capital of the Church of Jesus Christ of Latter-day Saints, or Mormons. These women subsequently wrote books about their travels for a home audience with a taste for adventures in the American West, and particularly for accounts of Mormon plural marriage, which was sanctioned by the Church before 1890. "The plight of the Mormon woman," a prominent social reform and literary theme of the period, situated Mormon women at the center of popular representations of Utah during the second half of the nineteenth century. "The Mormon question" thus lends itself to an analysis of how a stereotyped subaltern group was represented by elite British travelers. These residents of western American territories, however, differed in important respects from the typical subaltern subjects discussed by Victorian travelers. These white, upwardly mobile, and articulate Mormon plural wives attempted to influence observers' representations of them through a variety of narrative strategies. Both British women travel writers and Mormon women wrote from the margins of power and credibility, and as interpreters of the Mormon scene were concerned to established their representational authority.

The Advantages of Parametric Modeling for the Reconstruction of Historic Buildings

Consecrated in 1297 as the monastery church of the four years earlier founded St. Catherine’s monastery, the Gothic Church of St. Catherine was largely destroyed in a devastating bombing raid on January 2nd 1945. To counteract the process of disintegration, the departments of geo-information and lower monument protection authority of the City of Nuremburg decided to getting done a three dimensional building model of the Church of St. Catherine’s. A heterogeneous set of data was used for preparation of a parametric architectural model. In effect the modeling of historic buildings can profit from the so called BIM method (Building Information Modeling), as the necessary structuring of the basic data renders it into very sustainable information. The resulting model is perfectly suited to deliver a vivid impression of the interior and exterior of this former mendicant orders’ church to present observers.

Student notebook of Samuel Dunbar, 1721-1722

This leather-bound volume contains substantial transcriptions copied by Samuel Dunbar from textbooks while he was a student at Harvard in 1721 and 1722. There is a general index to texts at the end of the volume. Dunbar's notebook provides a window into the state of higher education in the eighteenth century and offers a firsthand account of academic life at Harvard College. Notably, he often indicated the number of days spent copying texts into his book.

Sundrypeices of the Plate given to the College, 1736 September 18

One-page inventory of the silver, including the weight of each object, donor, and dates; one passage is crossed out, and written diagonal to the inventory are the words "Fort London Farmer London." Docketed on the verso with an address to the Right Honorable Samuel Bishop of York.

Popery a complex falsehood: or an attempt to clear and evidence, that it is so, in a lecture had at Harvard College in Cambridge, New England, on May 10th, 1769

The hand-sewn notebook contains a 30-page manuscript draft of the Dudleian lecture delivered by Samuel Mather on May 10, 1769 at Harvard College. The sermon begins with the Biblical text 2 Thess. 11:11, 12. The copy includes a small number of edits and struck-out words. The item has unattached pages and is in fragile condition. The lecture was never published.

Diocesan Episcopacy: as Founded on the supposed Episcopacy of Timothy & Titus, subverted in a sermon preached at Harvard College May 9, 1770 at the Lecture founded by Paul Dudley

Two handwritten drafts of the Dudleian lecture delivered by Amos Adams on May 9, 1770 at Harvard College written in the same hand. The sermon begins with the Biblical text Titus 1:5. The first copy (HUC 5340.70) is bound between black paper covers and includes edits and citations written on interleaved pages. The second copy (HUC 5340.70.2) appears to be a subsequent draft of the address with additional edits.

A discourse on natural religion: delivered in the Chapel of the University at Cambridge, September 5, 1787

The hand-sewn notebook contains a 35-page manuscript draft of the Dudleian lecture delivered by Simeon Howard on September 5, 1787 at Harvard College. The sermon begins with the Biblical text Acts 17:28. The copy includes a small number of edits and struck-out words. The covers are no longer with the item. The lecture was not printed.

A discourse on natural religion: delivered in the chapel of the University in Cambridge, September 3r, 1795, at the lecture founded by the Honourable Paul Dudley, Esqr

The hand-sewn notebook contains a manuscript draft of the Dudleian lecture delivered by Thomas Barnard on September 3, 1795 at Harvard College. The sermon begins with the Biblical text Acts 14-57. The copy includes a small number of edits and struck-out words. The covers are no longer with the item.

Account book of Andrew Croswell, 1794-1802

Andrew Croswell kept this account book while an undergraduate at Harvard College. It contains entries from 1794, the year he entered, until his graduation in 1798. There is also one entry on the back cover apparently made in 1802. The entries, divided by school term, are very detailed. Croswell indicates the cost of the following, among many other expenses and purchases: transportation, most often to Hingham and Plymouth; payment for "passing the bridge"; candles; hiring a horse; wood and having it cut; laundry; quills and pencils; paper and ink; razors, haircuts, hair ribbons; a trunk; clothing and cloth for trousers; furniture; tickets to the theater; door locks; a bowl and spoon; "batts and balls" and "other necessaries"; tobacco; toothbrushes; shoe and boot repair; fruit; wine, brandy and rum; cheese; coffee and tea; butter; lemons; sugar; and wafers. There are also entries for college-related costs, including the payment of quarter bills, buttery bills, Hasty Pudding Club dues, and a fee to the President of Harvard College related to Croswell's graduation. There are also entries pertaining to the cost of celebrating various special occasions, including Election Day, Christmas Eve, "Independent Day," and George Washington's birthday.

European and North American Railway, New England and Eastern Canada, 1850 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Map of the European and North American Railway : showing its connection with the railways of the United States & Canada, [by] A.C. Morton, engineer. It was published in 1850 by Bowen & Co. Scale [ca. 1:1,625,000]. Covers New England, eastern New York, and the Maritime Provinces. The image inside the map neatline is georeferenced to the surface of the earth and fit to the USA Contiguous Albers Equal Area Conic projection (Meters). All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, or other information associated with the principal map. This map shows features such as completed, in progress, and proposed railroads, selected towns, drainage, state boundaries, and more. Includes inset: Map showing the plan for shortening the transit between New York & London. This layer is part of a selection of digitally scanned and georeferenced historic maps of New England from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of regions, originators, ground condition dates, scales, and purposes.

The Turkish Empire in Europe, Asia, and Africa: dividid into all its governments, together with the other territories that are tributary to it, as also the dominions of ye Emperor of Marocco [sic] according to the newest and most exact observations

by H. Moll.