Semantic and conceptual structures in module design

This paper describes the employment of semantic and conceptual structures in module design, specifically course modules. Additionally, it suggests other uses of these structures in aiding teaching and learning.

I wanna be a protocol: online media and electronic structures of kinship

Heidegger famously identified Modernity with a technological leveling of being to a single order of a “standing reserve.” In a radically different tone, Gilles Deleuze articulated a single “plane of immanence” within which ontological distinctions between mind and body, God and world, interiority and exteriority become indiscernible. Taking such philosophical declarations as points of departure, this panel will consider how a collapse of ontological distinction emerged as a thematic and structural trope in literary and cinematic modernisms. We hope to consider how writers and film-makers of the 20th c. utilize the resources of their media to ask “the question of being” that troubled their philosophical contemporaries and heirs. In this vein, we will examine how these modernist ontologies of immanence describe the crisis of a subject saturated and eclipsed by a world which comprises her while also remaining strange or opaque. Papers will ask what is lost with the departure of a distinctly human sense of “being” and how the historical arrival of an alternative ontological order may be evident in the lived experience of modernity. In this sense, the relationship to departures and arrivals becomes the modern subject’s suspicion that he is unable to do either vis á vis the world.

IR/Raman spectroscopy and DFT calculations of cyclic di-amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L-Ser-L-Ser)

B3-LYP/cc-pVDZ calculations of the gas-phase structure and vibrational spectra of the isolated molecule cyclo(L-Ser-L-Ser), a cyclic di-amino acid peptide (CDAP), were carried out by assuming C-2 symmetry. It is predicted that the minimum-energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L-Beryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol(-1)) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X-ray crystallographic structure of cyclo(L-Ser-L-Ser), shows that the DKP ring displays a near-planar conformation, with both the two L-Beryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier-transform infrared (FT-IR) spectra of solid state and aqueous solution samples of cyclo(L-Ser-L-Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid-state samples show characteristic amide I vibrations which are split (Raman:1661 and 1687 cm(-1), IR:1666 and 1680 cm(-1)), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ~ 30 cm(-1), which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm(-1). The occurrence of this cis amide II mode at a wavenumber above 1500 cm(-1) concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C-alpha atoms, and is also indicative of a relatively unstrained DKP ring.

Versatile N,C,N coordination behavior of a monoanionic aryldiamine ligand in ruthenium(II) complexes: Syntheses and crystal structures of [Ru-II(C6H3(CH(2)NMe(2))(2)-2,6)X(L)] (L equals norbornadiene, X=Cl, SO3CF3; L=PPh(3), X=I) and [Ru-II{C6H3(CH(2)NMe(2))(2)-2,6}(2,2':6:2''-terpyridine)]Cl

The monoanionic ligand [C6H3(CH(2)NMe(2))(2)-2,6](-), a potentially terdentate N,C,N bonding system, has been employed to synthesize a series of new ruthenium(II) complexes [Ru{C6H3(CH(2)NMe(2))(2)-2,6}X(L)] (L = PPh(3) X = Cl (2a), I (2b); L = norbornadiene (nbd), X = Cl (4), eta(1)-OSO2CF3 (5)) and [Ru{C6H3(CH(2)NMe(2))(2)-2,6}(2,2':6',2 ''-terpyridine)]Cl (3). X-ray crystal structures of 2b and 3-5 have been determined, in which the N,C,N coordination geometry with respect to the metal center is found to differ considerably. In each complex the aryldiamine ligand is terdentate, eta(3)-N,C,N-bonded as a six electron donor system. However, depending on the other ligands in the Ru(II) coordination sphere, this ligand demonstrates considerable flexibility in adopting coordination geometries which range from meridional in 3 through pseudomeridional in 2b to pseudofacial in 4 and 5. In the structures of 4 and 5 significant distortions of the aryl ring, involving bending of the six-membered ring into a boatlike conformation, are found. The different combinations of the N,C,N ligand with sets of other ligands lead to a range of metal geometries, i.e. square pyramidal in 2b, octahedral in 3, and bicapped tetrahedral in 4 and 5.

Cation complexation by chemically modified calixarenes. 11. Complexation and extraction of alkali cations by calix[5]- and -[6]arene ketones. Crystal and molecular structures of calix[5]arene ketones and Na+ and Rb+ complexes

A series of four calix[5]arenes and three calix[6]arenes (R-calixarene-OCH2COR1) (R = H or Bu-t) with alkyl ketone residues (R-1 = Me or Bu-t) on the lower rim have been synthesized, and their affinity for complexation of alkali cations has been assessed through phase-transfer experiments and stability constant measurements. The conformations of these ketones have been probed by H-1 NMR and X-ray diffraction analysis, and by molecular mechanics calculations. Pentamer 3 (R R-1 = Bu-t) possesses a symmetrical cone conformation in solution and a very distorted cone conformation in the solid state. Pentamer 5 (R = H, R-1 = Bu-t) exists in a distorted 1,2-alternate conformation in the solid state, but in solution two slowly interconverting conformations, one a cone and the other presumed to be 1,2-alternate, can be detected. X-ray structure analysis of the sodium and rubidium perchlorate complexes of 3 reveal the cations deeply encapsulated by the ethereal and carbonyl oxygen atoms in distorted cone conformations which can be accurately reproduced by molecular mechanics calculations. The phase-transfer and stability constant data reveal that the extent of complexation depends on calixarene size and the nature of the alkyl residues adjacent to the ketonic carbonyls with tert-butyl much more efficacious than methyl.

Use of recycled demolition aggregate in precast products, phase II: Concrete paving blocks

A study undertaken at the University of Liverpool has investigated the potential for using construction and demolition waste (C&DW) as aggregate in the manufacture of a range of precast concrete products, i.e. building and paving blocks and pavement flags. Phase II, which is reported here, investigated concrete paving blocks. Recycled demolition aggregate can be used to replace newly quarried limestone aggregate, usually used in coarse (6 mm) and fine (4 mm-to-dust) gradings. The first objective, as was the case with concrete building blocks, was to replicate the process used by industry in fabricating concrete paving blocks in the laboratory. The compaction technique used involved vibration and pressure at the same time, i.e. a vibro-compaction technique. An electric hammer used previously for building blocks was not sufficient for adequate compaction of paving blocks. Adequate compaction could only be achieved by using the electric hammer while the specimens were on a vibrating table. The experimental work involved two main series of tests, i.e. paving blocks made with concrete- and masonry-derived aggregate. Variables that were investigated were level of replacement of (a) coarse aggregate only, (b) fine aggregate only, and (c) both coarse and fine aggregate. Investigation of mechanical properties, i.e. compressive and tensile splitting strength, of paving blocks made with recycled demolition aggregate determined levels of replacement which produced similar mechanical properties to paving blocks made with newly quarried aggregates. This had to be achieved without an increase in the cement content. The results from this research programme indicate that recycled demolition aggregate can be used for this new higher value market and therefore may encourage demolition contractors to develop crushing and screening facilities for this. (C) 2011 Published by Elsevier Ltd.