Understanding the twist-bend nematic phase: the characterisation of 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl) hexane (CB6OCB) and comparison with CB7CB

Acknowledgements The FFTEM data were obtained at the (Cryo) TEM facility at the Liquid Crystal Institute, Kent State University, supported by the Ohio Research Scholars Program Research Cluster on Surfaces in Advanced Materials. ODL acknowledges the support of NSF DMR-1410378 grant. The authors are grateful for financial support from MINECO/FEDER MAT2015-66208-C3-2-P and from the Gobierno Vasco (GI/IT-449-10)

Frederick Douglass and Ireland, 1845: The "Vertiginous Twist[s]" of an Irish Encounter

Frederick Douglas was a reader of and writer on the nineteenth-century political and social texts and contexts of oppression, which he experienced at home and witnesed while in Ireland and Britain, 1845-47. This thesis is unique in its identification of several surprising lacunae in the research and critical evaluation of Frederick Douglass’ activities of reading and writing and the texts and contexts that supported these activities. This thesis takes Douglass’ relationship with Ireland and the Irish as its starting point, and offers several moments in the transnational space engendered by Douglass’ readerly and writerly experience of the transatlantic axes of Ireland, Britain and America. This thesis draws upon archival research to recover information regarding Douglass’ trip and subjects his reading and writing on Ireland and the Irish to the critical rigours of narratolgical, cultural and discourse analysis. One lacuna is Douglass’ favourite and neglected school primer, the Columbian Orator, which Douglass signified upon across his autobiographical project. The speech by the Irish patriot and exile, Arthur O’Connor, included in the Orator, is crucial to Douglass’ understanding and expression of justice and equality. Genette’s narratological analysis gives theoretical traction to the ways in which, in his autobiographical representations of his British trip, Douglass recalibrates his autobiographies to reflect his changing perspectives on his life and work. Contrary to popular assumptions, Douglass did, in two letters to Garrison address and comment on Irish poverty. This thesis interrogates the strategic anglophilia of these letters. While the World’s Temperance Convention (WTC) refused to discuss African- American slavery, analysis of Douglass’ speech in Covent Garden and of the paratextual apparatus of the published proceedings of the WTC demonstrates the impossibility of separating these closely interrelated reform causes. When a newly discovered poem from Waterford that admonished the city for its disregard for Douglass’ message is juxtaposed with an uncomfortable moment in Cork, we understand that Douglass became a pawn to bolster sectarian rivalries between nationalist and establishment factions. Though Douglass believed imperial politics was the best vehicle for modernity, he recognised that it had failed Ireland: consequently, in Thoughts and Recollections of a Trip to Ireland (1886), he advocates for Home Rule for Ireland.

Twist di Harkaitz Cano: analisi del romanzo e proposta di traduzione del primo capitolo dallo spagnolo.

o scopo di questa tesi è quello di fornire un'analisi esaustiva del romanzo thriller Twist di Harkaitz Cano e proporre una traduzione del primo capitolo «Cambalache, 1983». Quest'ultimo, in particolare, offre un esempio dello stile di scrittura di Cano e rappresenta allo stesso tempo una notevole sfida per il traduttore e una coinvolgente lettura. La proposta di traduzione e l'analisi delle difficoltà incontrate nel corso del processo traduttivo sono precedute prima da una presentazione della produzione letteraria dell'autore e del contesto storico-sociale in cui nasce il romanzo, e poi da un breve ma interessante approfondimento su trama, stile e temi dell'opera, in cui non mancano collegamenti e spunti di riflessione sulla storia, sulla cultura e sulla società basca e spagnola.

Ellas a estudiar y bailar, ellos a hacer deporte: un estudio de las actividades extraescolares de los adolescentes mediante los presupuestos de tiempo

Los estudios sobre actividades extraescolares en la adolescencia muestran que el tiempo no escolar puede utilizarse para mejorar el rendimiento académico y el desarrollo de la persona, pero también es posible emplearlo en conductas de riesgo o adicciones. Estos matices diferenciales pueden analizarse mediante un presupuesto de tiempo (PT), que además de registrar las actividades practicadas, incorpora la diversidad de las mismas dentro del repertorio del adolescente, la distribución y la cantidad de tiempo destinado en distintos días y las personas que les acompañan en cada práctica. Con base en esta sensibilidad, nuestro objetivo fue conocer los usos del tiempo al salir de la escuela, atendiendo a las relaciones interpersonales y los patrones de repetición en las actividades extraescolares. Participaron 103 adolescentes (43 chicas, 60 chicos), entre 11 y 18 años (M = 14.1; DT = 2.0). Se utilizó un PT ad hoc, registrándose durante una semana las actividades -físico-deportivas, de formación o artísticas-, realizadas fuera del horario escolar, especificando con quién se realizaba cada actividad. Los resultados obtenidos muestran escasa multiactividad, diferencias entre chicas y chicos respecto a la realización de actividades, momentos y tiempos de prácticas; ciertos patrones de frecuencia temporal de práctica; diferencias en términos de horas de dedicación según actividad o género, y predominio de la presencia de los pares. Los datos recogidos muestran la utilidad de los PT para orientar estrategias de intervención dirigidas a potenciar o mejorar las jornadas extraescolares, y así incidir positivamente sobre los tiempos escolares y no escolares.

Rumores de serenata en La Alhambra para hacer bailar las piedras: noche música y ventana

Fondo Margaritainés Restrepo

Bailar o el arte de despojarse: ¡hormonas de la alegría trabajando!

Fondo Margaritainés Restrepo

2-Bromo-2-methyl-N-p-tolylpropanamide

In the title molecule, C(11)H(14)BrNO, there is twist between the mean plane of the amide group and the benzene ring [C(=O)-N-C...;C torsion angle = -31.2 (5)degrees]. In the crystal, intermolecular N-H...O and weak C-H...O hydrogen bonds link molecules into chains along [100]. The methyl group H atoms are disordered over two sets of sites with equal occupancy.

2-Bromo-2-methyl-N-(4-nitrophenyl)propanamide

The title compound, C(10)H(11)BrN(2)O(3), exhibits a small twist between the amide residue and benzene ring [the C-N-C-C torsion angle = 12.7 (4)degrees]. The crystal structure is stabilized by weak N-H center dot center dot center dot O, C-H center dot center dot center dot Br and C-H center dot center dot center dot O interactions. These lead to supramolecular layers in the bc plane.

2-(4-Methylphenyl)-1H-anthraceno-[1,2-d]imidazole-6,11-dione: a fluorescent chemosensor

In the title compound, C(22)H(14)N(2)O(2), the five rings of the molecule are not coplanar. There is a significant twist between the four fused rings, which have a slightly arched conformation, and the pendant aromatic ring, as seen in the dihedral angle of 13.16 (8)degrees between the anthraquinonic ring system and the pendant aromatic ring plane.

Contribution to dynamic characteristics of the cutting temperature in the drilling process considering one dimension heat flow

The machining of hardened steels has always been a great challenge in metal cutting, particularly for drilling operations. Generally, drilling is the machining process that is most difficult to cool due to the tool`s geometry. The aim of this work is to determine the heat flux and the coefficient of convection in drilling using the inverse heat conduction method. Temperature was assessed during the drilling of hardened AISI H13 steel using the embedded thermocouple technique. Dry machining and two cooling/lubrication systems were used, and thermocouples were fixed at distances very close to the hole`s wall. Tests were replicated for each condition, and were carried out with new and worn drills. An analytical heat conduction model was used to calculate the temperature at tool-workpiece interface and to define the heat flux and the coefficient of convection. In all tests using new and worn out drills, the lowest temperatures and decrease of heat flux were observed using the flooded system, followed by the MQL, considering the dry condition as reference. The decrease of temperature was directly proportional to the amount of lubricant applied and was significant in the MQL system when compared to dry cutting. (C) 2011 Elsevier Ltd. All rights reserved.

Improved finite element for 3D laminate frame analysis including warping for any cross-section

The most ordinary finite element formulations for 3D frame analysis do not consider the warping of cross-sections as part of their kinematics. So the stiffness, regarding torsion, should be directly introduced by the user into the computational software and the bar is treated as it is working under no warping hypothesis. This approach does not give good results for general structural elements applied in engineering. Both displacement and stress calculation reveal sensible deficiencies for both linear and non-linear applications. For linear analysis, displacements can be corrected by assuming a stiffness that results in acceptable global displacements of the analyzed structure. However, the stress calculation will be far from reality. For nonlinear analysis the deficiencies are even worse. In the past forty years, some special structural matrix analysis and finite element formulations have been proposed in literature to include warping and the bending-torsion effects for 3D general frame analysis considering both linear and non-linear situations. In this work, using a kinematics improvement technique, the degree of freedom ""warping intensity"" is introduced following a new approach for 3D frame elements. This degree of freedom is associated with the warping basic mode, a geometric characteristic of the cross-section, It does not have a direct relation with the rate of twist rotation along the longitudinal axis, as in existent formulations. Moreover, a linear strain variation mode is provided for the geometric non-linear approach, for which complete 3D constitutive relation (Saint-Venant Kirchhoff) is adopted. The proposed technique allows the consideration of inhomogeneous cross-sections with any geometry. Various examples are shown to demonstrate the accuracy and applicability of the proposed formulation. (C) 2009 Elsevier Inc. All rights reserved.

On Quasi-Hopf Superalgebras

In this work we investigate several important aspects of the structure theory of the recently introduced quasi-Hopf superalgebras (QHSAs), which play a fundamental role in knot theory and integrable systems. In particular we introduce the opposite structure and prove in detail (for the graded case) Drinfeld's result that the coproduct Delta ' =_ (S circle times S) (.) T (.) Delta (.) S-1 induced on a QHSA is obtained from the coproduct Delta by twisting. The corresponding "Drinfeld twist" F-D is explicitly constructed, as well as its inverse, and we investigate the complete QHSA associated with Delta '. We give a universal proof that the coassociator Phi ' = (S circle times S circle times S) Phi (321) and canonical elements alpha ' = S(beta), beta ' = S(alpha) correspond to twisting, the original coassociator Phi = Phi (123) and canonical elements alpha, beta with the Drinfeld twist F-D. Moreover in the quasi-tri angular case, it is shown algebraically that the R-matrix R ' = (S circle times S)R corresponds to twisting the original R-matrix R with F-D. This has important consequences in knot theory, which will be investigated elsewhere.

Plant cyclotides: A unique family of cyclic and knotted proteins that defines the cyclic cystine knot structural motif

Several macrocyclic peptides (similar to 30 amino acids), with diverse biological activities, have been isolated from the Rubiaceae and Violaceae plant families over recent years. We have significantly expanded the range of known macrocyclic peptides with the discovery of 16 novel peptides from extracts of Viola hederaceae, Viola odorata and Oldenlandia affinis. The Viola plants had not previously been examined for these peptides and thus represent novel species in which these unusual macrocyclic peptides are produced. Further, we have determined the three-dimensional struc ture of one of these novel peptides, cycloviolacin O1, using H-1 NMR spectroscopy. The structure consists of a distorted triple-stranded beta-sheet and a cystine-knot arrangement of the disulfide bonds. This structure is similar to kalata B1 and circulin A, the only two macrocyclic peptides for which a structure was available, suggesting that despite the sequence variation throughout the peptides they form a family in which the overall fold is conserved. We refer to these peptides as the cyclotide family and their embedded topology as the cyclic cystine knot (CCK) motif. The unique cyclic and knotted nature of these molecules makes them a fascinating example of topologically complex proteins. Examination of the sequences reveals they can be separated into two subfamilies, one of which tends to contain a larger number of positively charged residues and has a bracelet-like circularization of the backbone. The second subfamily contains a backbone twist due to a cis-Pro peptide bond and may conceptually be regarded as a molecular Moebius strip. Here we define the structural features of the two apparent subfamilies of the CCK peptides which may be significant for the likely defense related role of these peptides within plants. (C) 1999 Academic Press.

Assessment of the ability to model proteins with leucine-rich repeats in light of the latest structural information

The three-dimensional structures of leucine-rich repeat (LRR) -containing proteins from five different families were previously predicted based on the crystal structure of the ribonuclease inhibitor. using an approach that combined homology-based modeling, structure-based sequence alignment of LRRs, and several rational assumptions. The structural models have been produced based on very limited sequence similarity, which, in general. cannot yield trustworthy predictions. Recently, the protein structures from three of these five families have been determined. In this report we estimate the quality of the modeling approach by comparing the models with the experimentally determined structures. The comparison suggests that the general architecture, curvature, interior/exterior orientations of side chains. and backbone conformation of the LRR structures can be predicted correctly. On the other hand. the analysis revealed that, in some cases. it is difficult to predict correctly the twist of the overall super-helical structure. Taking into consideration the conclusions from these comparisons, we identified a new family of bacterial LRR proteins and present its structural model. The reliability of the LRR protein modeling suggests that it would be informative to apply similar modeling approaches to other classes of solenoid proteins.

Synthesis and structural properties of patellamide a derivatives and their copper(II) compounds

The synthesis, characterization and copper(II) coordination chemistry of three new cyclic peptide ligands, PatJ(1) (cyclo-(Ile -Thr- (Gly)Thz-lle-Thr(Gly)Thz)), PatJ(2) (cyclo-(Ile-Thr(Gly)Thz-(D)-Ile-Thr-(Gly)Thz)), and PatL (cyclo-(Ile-Ser-(Gly)Thz-Ile-Ser(Gly)Thz)) are reported. All of these cyclic peptides and PatN (cyclo-(Ile-Ser(Gly)Thz-Ile-Thr-(Gly)Thz)) are derivatives of patellamide A and have a [24]azacrown-8 macrocyclic structure. All four synthetic cyclic peptides have two thiazole rings but, in contrast to patellamide A, no oxazoline rings. The molecular structure of PatJ1, determined by X-ray crystallography, has a saddle conformation with two close-to-co-parallel thiazole rings, very similar to the geometry of patellamide D. The two coordination sites of PatJ1 with thiazole-N and amide-N donors are each well preorganized for transition metal ion binding. The coordination of copper(II) was monitored by UV/Vis spectroscopy, and this reveals various (meta)stable mono- and dinuclear copper(II) complexes whose stoichiometry was confirmed by mass spectra. Two types of dinuclear copper(II) complexes, [Cu-2(H4L)(OH2)(n)](2+) (n = 6, 8) and [Cu-2(H4L)(OH2)(n)] (n=4, 6; L=PatN, PatL, PatJ1, PatJ2) have been identified and analyzed structurally by EPR spectroscopy and a combination of spectra simulations and molecular mechanics calculations (MM-EPR). The four structures are similar to each other and have a saddle conformation, that is, derived from the crystal structure of PatJ(1) by a twist of the two thiozole rings. The small but significant structural differences are characterized by the EPR simulations.