Performance of columns packed with the new shell particles, Kinetex-C18

The performance of the new Kinetex-C₁₈ column was investigated. Packed with a new brand of porous shell particles, this column has an outstanding efficiency. Once corrected for the contribution of the instrument extra column volume, the minimum values of the reduced plate heights for a number of low molecular weight compounds (e.g., anthracene and naphtho[2,3-a]pyrene) were between 1.0 and 1.3, breaking the legendary record set 3 years ago by Halo-C₁₈ packed columns. The liquid-solid mass transfer of proteins (e.g., insulin and lyzozyme) is exceptionally fast on Kinetex-C₁₈ much faster than on the Halo-C₁₈ column. The different contributions of dispersion and mass transfer resistances to the column efficiency were determined and discussed. The possible reasons for this extremely high column efficiency are discussed.

Large-pore mesoporous SBA-15 silica particles with submicrometer size as stationary phases for high-speed CEC separation

A new mesoporous sphere-like SBA-15 silica was synthesized and evaluated in terms of its suitability as stationary phases for CEC. The unique and attractive properties of the silica particle are its submicrometer particle size of 400 nm and highly ordered cylindrical mesopores with uniform pore size of 12 nm running along the same direction. The bare silica particles with submicrometer size have been successfully employed for the normal-phase electrochromatographic separation of polar compounds with high efficiency (e.g., 210 000 for thiourea), which is matched well with its submicrometer particle size. The Van Deemeter plot showed the hindrance to mass transfer because of the existence of pore structure. The lowest plate height of 2.0 mu m was obtained at the linear velocity of 1.1 mm/s. On the other hand, because of the relatively high linear velocity (e.g., 4.0 mm/s) can be generated, high-speed separation of neutral compounds, anilines, and basic pharmaceuticals in CEC with C-18-modified SBA-15 silica as stationary phases was achieved within 36, 60, and 34 s, respectively.

Synthesis and characterisation of novel superficially porous silica based stationary phases for use in liquid chromatography

The concept of pellicular particles was suggested by Horváth and Lipsky over fifty years ago. The reasoning behind the idea of these particles was to improve column efficiency by shortening the pathways analyte molecules can travel, therefore reducing the effect of the A and C terms. Several types of shell particles were successfully marketed around this time, however with the introduction of high quality fully porous silica under 10 μm, shell particles faded into the background. In recent years a new generation of core shell particles have become popular within the separation science community. These particles allow fast and efficient separations that can be carried out on conventional HPLC systems. Chapter 1 of this thesis introduces the chemistry of chromatographic stationary phases, with an emphasis on silica bonded phases, particularly focusing on the current state of technology in this area. The main focus is on superficially porous silica particles as a support material for liquid chromatography. A summary of the history and development of these particles over the past few decades is explored, along with current methods of synthesis of shell particles. While commercial shell particles have a rough outer surface, Chapter 2 focuses on the novel approach to growth of smooth surface superficially porous particles in a step-by-step manner. From the Stöber methodology to the seeded growth technique, and finally to the layer-bylayer growth of the porous shell. The superficially porous particles generated in this work have an overall diameter of 2.6 μm with a 350 nm porous shell; these silica particles were characterised using SEM, TEM and BET analysis. The uniform spherical nature of the particles along with their surface area, pore size and particle size distribution are examined in this chapter. I discovered that these smooth surface shell particles can be synthesised to give comparable surface area and pore size in comparison to commercial brands. Chapter 3 deals with the bonding of the particles prepared in Chapter 2 with C18 functionality; one with a narrow and one with a wide particle size distribution. This chapter examines the chromatographic and kinetic performance of these silica stationary phases, and compares them to a commercial superficially porous silica phase with a rough outer surface. I found that the particle size distribution does not seem to be the major contributor to the improvement in efficiency. The surface morphology of the particles appears to play an important role in the packing process of these particles and influences the Van Deemter effects. Chapter 4 focuses on the functionalisation of 2.6 μm smooth surface superficially porous particles with a variety of fluorinated and phenyl silanes. The same processes were carried out on 3.0 μm fully porous silica particles to provide a comparison. All phases were accessed using elemental analysis, thermogravimetric analysis, nitrogen sorption analysis and chromatographically evaluated using the Neue test. I observed comparable results for the 2.6 μm shell pentaflurophenyl propyl silica when compared to 3.0 μm fully porous silica. Chapter 5 moves towards nano-particles, with the synthesis of sub-1 μm superficially porous particles, their characterisation and use in chromatography. The particles prepared are 750 nm in total with a 100 nm shell. All reactions and testing carried out on these 750 nm core shell particles are also carried out on 1.5 μm fully porous particles in order to give a comparative result. The 750 nm core shell particles can be synthesised quickly and are very uniform. The main drawback in their use for HPLC is the system itself due to the backpressure experienced using sub – 1 μm particles. The synthesis of modified Stöber particles is also examined in this chapter with a range of non-porous silica and shell silica from 70 nm – 750 nm being tested for use on a Langmuir – Blodgett system. These smooth surface shell particles have only been in existence since 2009. The results displayed in this thesis demonstrate how much potential smooth surface shell particles have provided more in-depth optimisation is carried out. The results on packing studies reported in this thesis aims to be a starting point for a more sophisticated methodology, which in turn can lead to greater chromatographic improvements.

Natural Language Generation and Fuzzy Sets : An Exploratory Study on Geographical Referring Expression Generation

This work was supported by the Spanish Ministry for Economy and Competitiveness (grant TIN2014-56633-C3-1-R) and by the European Regional Development Fund (ERDF/FEDER) and the Galician Ministry of Education (grants GRC2014/030 and CN2012/151). Alejandro Ramos-Soto is supported by the Spanish Ministry for Economy and Competitiveness (FPI Fellowship Program) under grant BES-2012-051878.

Direction giving: an attempt to increase user engagement

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Models and empirical data for the production of referring expressions

Article Accepted Date: 29 May 2014 Acknowledgements The authors gratefully acknowledge the support of the Cognitive Science Society for the organisation of the Workshop on Production of Referring Expressions: Bridging the Gap between Cognitive and Computational Approaches to Reference, from which this special issue originated. Funding Emiel Krahmer and Albert Gatt thank The Netherlands Organisation for Scientific Research (NWO) for VICI grant Bridging the Gap between Computational Linguistics and Psycholinguistics: The Case of Referring Expressions (grant number 277-70-007).

Production of Referring Expressions for an Unknown Audience : a Computational Model of Communal Common Ground

The research reported in this article is based on the Ph.D. project of Dr. RK, which was funded by the Scottish Informatics and Computer Science Alliance (SICSA). KvD acknowledges support from the EPSRC under the RefNet grant (EP/J019615/1).

Plot size matters: interference from intergenotypic competition in plant phenotyping studies

Genetic and physiological studies often comprise genotypes diverse in vigour, size and flowering time. This can make the phenotyping of complex traits challenging, particularly those associated with canopy development, biomass and yield, as the environment of one genotype can be influenced by a neighbouring genotype. Limited seed and space may encourage field assessment in single, spaced rows or in small, unbordered plots, whereas the convenience of a controlled environment or greenhouse makes pot studies tempting. However, the relevance of such growing conditions to commercial field-grown crops is unclear and often doubtful. Competition for water, light and nutrients necessary for canopy growth will be variable where immediate neighbours are genetically different, particularly under stress conditions, where competition for resources and influence on productivity is greatest. Small hills and rod-rows maximise the potential for intergenotypic competition that is not relevant to a crop’s performance in monocultures. Response to resource availability will typically vary among diverse genotypes to alter genotype ranking and reduce heritability for all growth-related traits, with the possible exception of harvest index. Validation of pot experiments to performance in canopies in the field is essential, whereas the planting of multirow plots and the simple exclusion of plot borders at harvest will increase experimental precision and confidence in genotype performance in target environments.

Recovery based on plot experiments is a poor predictor of landscape-level population impacts of agricultural pesticides

Current European Union regulatory risk assessment allows application of pesticides provided that recovery of nontarget arthropods in-crop occurs within a year. Despite the long-established theory of source-sink dynamics, risk assessment ignores depletion of surrounding populations and typical field trials are restricted to plot-scale experiments. In the present study, the authors used agent-based modeling of 2 contrasting invertebrates, a spider and a beetle, to assess how the area of pesticide application and environmental half-life affect the assessment of recovery at the plot scale and impact the population at the landscape scale. Small-scale plot experiments were simulated for pesticides with different application rates and environmental half-lives. The same pesticides were then evaluated at the landscape scale (10 km × 10 km) assuming continuous year-on-year usage. The authors' results show that recovery time estimated from plot experiments is a poor indicator of long-term population impact at the landscape level and that the spatial scale of pesticide application strongly determines population-level impact. This raises serious doubts as to the utility of plot-recovery experiments in pesticide regulatory risk assessment for population-level protection. Predictions from the model are supported by empirical evidence from a series of studies carried out in the decade starting in 1988. The issues raised then can now be addressed using simulation. Prediction of impacts at landscape scales should be more widely used in assessing the risks posed by environmental stressors.

Traslaciones Poéticas: un recorrido por la Friedrichstrasse de Mies van der Rohe en 1921. Arquitectura, fotografía y cine, la percepción en la arquitectura

El presente ensayo pretende aportar una reflexión sobre el amplio territorio de la imagen en la arquitectura hoy. Para ello un buen ejemplo es el proyecto del Rascacielos de la Friedrichstrasse, realizado por Mies van der Rohe en el periodo de entre guerras de 1921/22. Muchas son las razones que han hecho de esta obra la elegida, pero una más actual sobresale del resto: que de los cientos de ensayos vertidos sobre esta obra solo se haya comentado -salvo alguna excepción- las características objetuales de lo directamente descrito por las vistas -como si fuera un fiel reflejo de la realidad- sin entrar a analizar la verdadera naturaleza física y simbólica de lo representado como expresión subjetiva –espacial- de una arquitectura. Si su importancia como punto de inflexión en el desarrollo inicial de una obra plenamente moderna es un motivo más que suficiente para dedicarle un estudio pormenorizado, ya que puede resultar crucial para comprender los inicios del autor en el Movimiento Moderno. Su presencia como un reducido conjunto de cuatro vistas perspectivas, mezcla de una fotografía del lugar y de un dibujo realizado sobre la misma, acarrea en nuestra opinión significaciones igual de importantes para la comprensión de esta arquitectura que todas aquellas ideas descritas sobre las mismas. Creadas en una época seminal, cuando el lenguaje de la fotografía y el cine están en pleno desarrollo, se puede afirmar que el conjunto de representaciones del Rascacielos de la Friedrichstrasse forman parte como referente histórico de una de las primeras arquitecturas virtuales que pertenecen de pleno derecho al Movimiento Moderno. Paradigma de las más absoluta actualidad, por encontrarse en esa frontera de lo nunca realizado, pero sí asumible espacialmente como realidad fotográfica, las imágenes del rascacielos se pueden considerar así como una de las primeras reflexiones sobre la naturaleza virtual del proyecto arquitectónico postindustrial. No siendo novedoso que la descripción fotográfica de una obra absorba y comunique por sí misma las múltiples propiedades que esta posee, como tampoco lo es que la mayoría de arquitecturas se den por conocidas actualmente a través de los medios. Sorprende que hasta hoy no se hayan analizado con la misma intensidad las múltiples razones que dieron lugar a unas imágenes cuya poética da forma por igual a la arquitectura que representan. Si la intención es reflexionar así sobre este hecho contemporáneo mediante un ejemplo paradigmático, certificado por la historia, nos veremos obligados a emplear una metodología acorde a la condición dual que toda imagen mediatizada produce en su lectura como mezcla fluctuante entre lo que se interpreta de manera autónoma a través de lo representado y de los significados que la imagen adquiere a lo largo de su recorrido como referente histórico. Esta ambivalencia interpretativa llevará a organizar este ensayo mediante dos bloques claramente diferenciados que, complementarios entre sí, siguen el orden de lectura que toda imagen de una arquitectura ofrece a través de los medios. Así, una primera parte, titulada La imagen de una arquitectura, analiza la interpretación que la historia y el autor han dado al rascacielos por medio de su uso en las diferentes exposiciones, revistas, tratados de estilos y monografías de las que ha formado parte. Este recorrido, que es el verdadero espacio donde estas arquitecturas residen, limitado -por una cuestión de poner orden- al estudio a los países que acogieron en vida al autor, servirá para establecer una primera narrativa que expone las diferentes posiciones que la crítica ha producido a lo largo del tiempo. La presencia del primer rascacielos junto al segundo, en la publicación que el arquitecto realiza de manera temprana en Frühlicht, obligará a incorporar esta segunda solución como una parte más del estudio. Cargada de las citas obligadas, de las diferentes personalidades que se han enfrentado a dichos proyectos, este primer análisis historiográfico establece un primer estado de la cuestión donde se revela una lectura ambivalente de los rascacielos. Si la interpretación directa de sus imágenes ha permitido profundizar en las características del vidrio y sus reflejos y en la desnudez de una estructura metálica como claros ejemplos de una expresión moderna y tecnológica de vidrio y el acero. Las particulares formas triangulares del primero y las formas sinuosas del segundo han dado lugar a una multitud de calificaciones, de ser ejemplo tanto de un Expresionismo como de un dadaísmo o constructivismo, que con el tiempo han ido creciendo hacia una admiración artística con una fuerte carga poética. Este lectura histórica, que remata con un breve periodo más actual donde se inicia el cuestionamiento de su carácter utópico y se recupera puntualmente su naturaleza como proyecto, servirá para plantear finalmente una serie de dudas que, sin respuesta aparente, exigen revisar la lectura de sus imágenes como parte de lo que realmente son: expresión de una nueva arquitectura que a partir de ese preciso momento entra de pleno derecho en el Movimiento Moderno. Por otro lado, la existencia en el discurso posterior del arquitecto de un proceso de formalizacion altamente valorado por su autor y la presencia de igual a igual de un lugar en las representaciones y planos de los rascacielos, que la historia parece haber obviado, servirán como razón más que suficiente para la revisión de unas relaciones iniciales con la vanguardia -todavía hoy poco definidas- así como para proponer la lectura renovada de dichas propuestas en altura por lo que también son: proyectos que responden a unas necesidades espaciales de un lugar y tiempo muy determinados. Esta segunda parte, denominada La arquitectura de una imagen, se plantea así más como una inmersión total en el mundo del proyecto que una simple descripción nominal del mismo. Conscientemente simétrica y opuesta a un primer bloque histórico, esta segunda parte -mucho más extensa y parte central de esta tesis- se concentra en el análisis de las imágenes como: aquel conjunto de eventos históricos que aplicados sobre la ciudad, el lugar, el rascacielos, y los procesos técnicos de la imagen dieron lugar a estas arquitecturas como razón de ser. Consecuentemente se tratará pues de bucear en las razones que, ocultas como proceso de formalización, llevaron a Mies a dar un paso más allá hacia a una nueva manera de hacer, ver y pensar su arquitectura, de expresar un espacio. La aproximación a estas imágenes radicará por tanto en resaltar al mismo tiempo la naturaleza de unas representaciones cuyas características fotográficas son el fiel reflejo de una época donde los nuevos medios visuales –cine y fotografía- empiezan a ser cuestionados por su excesiva utilización. La complejidad de unos hechos coincidentes en el tiempo obligará a dividir este estudio en un primer acercamiento general, a la respuesta dada por una mayoría de participantes al concurso, para así cotejar la importancia de una actitud proyectual y contextual común de Mies y sus compañeros. Mezcla de requerimientos y necesidades de la propia historia de la parcela, de las peculiaridades de un lugar y las exigencias programáticas del concurso; el siguiente paso consistirá en reconstruir el proceso de formalización del conjunto de dibujos que caracterizan ambos proyectos para así comprender los mecanismo que, suspendidos como traslaciones entre las diferentes representaciones, operan en la realización física de dichas imágenes y complementan como pensamiento la idea arquitectónica de los mismos. Con lo que se pretende ofrecer dos cosas: una interpretación que tenga en cuenta la novedosa naturaleza de la manera de pensar lo fotográfico en el arquitecto, así como la particular idiosincrasia del momento en que estas concurren. Dicho de otro modo, se realizará una aproximación de las vistas del primer rascacielos que tenga en cuenta la historia tecnológica y visual que rodea al evento y las características de una ejecución física todavía hoy sin aclarar del todo. El descubrimiento de una serie de incoherencias geométricas en las plantas, alzado y vistas del primer proyecto llevará a argumentar la presencia de un trampantojo que, nunca antes revelado, se entiende lleno de unas intenciones espaciales plenamente vanguardistas. Interpretación arquitectónica de las imágenes donde la presencia de una serie de elementos directamente ligados al lenguaje fotográfico y cinematográfico se traduce en una nueva lectura espacial plenamente dinámica llena de dislocación, ritmo y simultaneidad alejada de la idea de ver la forma como un elemento permanentemente fijo. Sugerencia que nos lleva directamente a la lectura del segundo proyecto de rascacielos como una clara continuación de lo imaginado en el primero. Para finalizar, tras una revisión biográfica -previa al proyecto- que desvela unas preocupaciones urbanas y un deseo de cambio anterior al concurso de la Friedrichstrasse, se comparan estas nuevas significaciones espaciales con una práctica de vanguardia que, coetánea a la convocatoria de 1921, demuestran unas investigaciones muy similares con unos mismos intereses cinematográficos. La lectura de las propuestas de tres artistas próximos en ese momento al arquitecto -como son Hans Richter, Moholy-Nagy y El Lissitzky- permiten demostrar unas preocupaciones muy similares a lo conseguido por Mies con los rascacielos que parecen haber servido de ejemplo y motivación mutua para el surgimiento de una nueva espacialidad -más fluida-. Esta lectura permitirá recuperar la importancia de estos dos proyectos como la expresión directa de una nueva manera de pensar y hacer su arquitectura que ya no tendrá vuelta atrás en la obra de Mies. A la vez que recuperar la potencialidad poética de unas vistas que, así definidas reiteradamente por la crítica, se revelan ahora como directas transmisoras de ese deseo de cambio arquitectónico evidenciado en los proyectos posteriores. Racionalización de una poética que al ir más allá de la forma directamente transcrita permite establecer una última reflexión general sobre como opera la imagen en la arquitectura, así como la pertinencia crítica de este proyecto para con el mundo virtual de hoy. En definitiva, más allá del poder evocador de estas representaciones, este será un estudio que pretende cuestionar las características que la imagen de la arquitectura puede proponer más allá de su literalidad por medio de la fascinante interacción que se produce entre la imagen y lo espacialmente imaginado. Encuentros, recursos e intereses de una respuesta plenamente arquitectónica que, además de dar luz a un cambio tan inclasificable como moderno, abre el camino a la interpretación de un proceso de formalizacion que, reiteradamente defendido por su autor justifican una intensidad poética dada por la historia y reafirman una preocupación artística a menudo desmentida por su autor. Dicho de otro modo, si profundizar en las razones arquitectónicas, históricas y técnicas que llevan a Mies a realizar sus rascacielos, por medio de su relación con la vanguardia y el cine, arrojan luz y explican el cambio que se está gestando en el arquitecto cara una nueva espacialidad fluida. Reflexionar sobre su naturaleza espacial -de estas imágenes ya icónicas- equivale a aportar una reflexión crítica sobre la naturaleza simbólica de la imagen de la arquitectura hoy. “Aunque el puesto clave que ocupa el Rascacielos de la Friedrichstrasse dentro de la historia de la arquitectura moderna nunca ha sido seriamente cuestionado, la opinion critica al respecto siempre ha estado dividida. Desde la publicacion de la monografia de Philip Johnson sobre Mies en 1947, el muro cortina como una piel transparente que reviste el esqueleto estructural has ido aclamado como un gran avance pionero. Otros puntos de vista sobre el edificio, subrayando su supuesta planta expresionista, lo han visto como un esfuerzo un poco menos aventurado. Asi calibrada, la propuesta de Mies para la Friedrichstrasse es radicalmente moderna en mas de un sentido enfatizado por Johnson.” 1 W.Tegethoff ABSTRACT This essay reflects on the broad territory of the image in today’s architecture. One good example is the Friedrichstrasse Skyscraper design by Mies van der Rohe in 1921/22, during the period between World Wars I and II. There are many reasons why this work has been chosen, but one of the most recent stands out above the rest: of the hundreds of essays written on this work, comments have been made only (with the odd exception) on the objectual characteristics of what has been directly described by the views (as if it were a genuine reflection of reality), without analysing the real physical and symbolic nature of the representation a subjective (spatial) expression of architecture. If its importance as a point of inflection in the initial development of a completely modern work is more than enough reason to make a detailed study, since it may be crucial for understanding the author’s beginnings in the Modern Movement. Its presence as a reduced set of four views, the combination of a photograph of the place and a drawing made of it, in our opinion, carry meanings that are as important for understanding this architecture as all the ideas described about them. Created during an early period, when the languages of photography and cinema were in full swing, it can be said that the perspectives of the Friedrichstrasse Skyscraper form a historical reference of one of the first virtual architectures that belong entirely to the Modern Movement. A paradigm of the most absolute modernity owing to the fact that it is on that frontier of the never-accomplished, but spatially assumable as photographic reality, the images of the skyscraper can be considered as one of the first reflections on the virtual nature of post-industrial architectural design. There is nothing new in the fact that the photographic description of work absorbs and communicates on its own the multiple properties it involves and there is nothing new in the fact that most architectures become known today through the media. It is surprising that no analysis has been made to date, with the same intensity, of the many reasons that led to a number of images whose poetry add form to the architecture they represent. If the intention is to reflect on this contemporary fact using a paradigmatic example certified by history, we will be forced to use a methodology that corresponds to the dual condition produced by the interpretation of all media images as a fluctuating combination of what is interpreted independently through the representation and meanings the image acquires as a historical reference. This ambivalent interpretation will lead this essay to be structured in two clearly different and complementary blocks that follow the reading order offered by any image of architecture in the media. Thus, a first part, titled The image of an architecture, analyses the interpretation history and the author have given to the skyscraper through its use in the various exhibitions, magazines, style agreements and monographs in which it has been included. This examination, which is the real space in which these architectures reside, is (to delimit and organise the study) restricted to countries in which the author lived during his lifetime and it will help establish a first narrative that considers the different interpretations made by critics over time. The presence of the first skyscraper next to the second one in the publication the architect makes early on in Frühlicht will require the second solution to be incorporated as another part of the study. Laden with necessary quotes by the various personalities who have examined said designs, this first historiographical analysis establishes an initial state of the question that reveals an ambivalent interpretation of skyscrapers. If the direct interpretation of the images has made it possible to closely examine the characteristics of the glass and its reflections and the nudity of a metal structure as clear examples of a modern and technological expression of glass and steel. The particular triangular shapes of the former and the sinuous shapes of the latter have generated many classifications that suggest it is an example of Expressionism, Dadaism or Constructivism, which have grown over time into artistic admiration laden with poetry. This historical reading, which concludes with a more recent short period that begins to question the utopian character and recovers its nature as a project, will finally consider a number of doubts that have no apparent answer and require a revision of the reading of the images as part of what they actually are: expression of a new architecture that becomes part of the Modern Movement as from that precise moment. In addition, the existence in the architect’s subsequent discourse of a formalisation process highly valued by the author and the equal presence of a place in the representations and plans of a skyscraper history seems to have forgotten, will stand as more than sufficient reason for a revision of initial relations with the avantgarde -not particularly well defined today- together with a renewed reading of said vertical proposals for what they also are: projects that respond to the special needs of a very specific place and time. This second part, titled The architecture of an image, is presented more as a total immersion in the project world than a mere nominal description of it. Deliberately symmetrical and opposite to a historic first bloc, this second part (much longer and central part of the thesis) it will focus on analysing images as: the set of historical events that affected the skyscraper, city, place and technical processes image to provide these architectures with their raison d’être. Consequently, the aim is to delve in the reasons which, hidden as a formalisation process, led Mies to move on to a new form of doing, seeing and thinking his architecture, of expressing a space. The approach to these images will therefore lie in highlighting the nature of a number of representations whose photographic features are the true reflection of a period in which the new visual media (cinema and photography) begin to be questioned due to excessive use. The complexity of facts that coincide in time will require this study to be divided into a first general approach, with a response given by most of the participants in the competition, to compare the importance of a common approach in terms of project and context of the response given by Mies and his colleagues. A combination of requirements and needs of the very history of the plot of land, the peculiarities of a place and the programmatic requirements of the competition; the next step will reconstruct the formalisation process of the set of drawings that characterise both to understand the mechanism which, suspended like translations between the different representations, operates in the realisation of said images and complements as thought their architectural idea. The aim is thus to offer two things: an interpretation that takes into account the new way in which the architect works with photography, together with the particular idiosyncrasy of the moment at which they occur. In other words, the approach will focus on the views of the first skyscraper, which takes into account the technological and visual history that surrounds the event and the characteristics of a physical execution that still remains unexplained in full. The subsequent discovery of a number of geometrical incoherences in the floor plans, elevations and views of the first project will lead to an argument for the presence of trompe l’oeil which, never before revealed, is seen as laden with completely avant-garde spatial intentions. Architectural interpretation of the images where the presence of a number of elements directly linked to the languages of photography and cinema is translated into a new spatial reading that is completely dynamic and full of dislocation, rhythm and simultaneity far-removed from the idea of seeing shape as a permanently fixed element. This suggestion takes us to directly to the second skyscraper design as a clear continuation of what he imagined in the first. To end, after a preliminary biographical revision (previous to the project) that reveals urban concerns and a desire for change before the Friedrichstrasse competition, a comparison is made of these new spatial meanings with avant-garde practice which, contemporary with the 1921 competition, show very similar investigations with the same cinematographic interest. The reading of the proposals of three artists close to the architect at that time -i.e. Hans Richter, Moholy-Nagy and El Lissitzky- reveals concerns that are very similar to what Mies achieved with the skyscrapers that seem to have been used as an example and mutual motivation for the creation of a new (more fluent) spatiality. This interpretation will make it possible to recover the importance of these two projects as the direct expression of a new way of thinking and doing his architecture that was to remain fixed in Mies’ work. This also gives rise to the possibility of recovering the poetic potential of views which, as defined repeatedly by the critics, now stand as the direct transmitters of the desire for architectural change shown in later projects. A rationalisation of poetry which, by going beyond the directly transcribed form, gives rise to the establishment of one general final reflection on how the image works in architecture, together with the critical relevance of this design for today’s virtual world. In short, beyond the evocative power of images this will be a study which questions the characteristics the image of architecture can propose beyond its literality through the fascinating interaction between the image and spatially imagined. Encounters, resources and interests of a completely architectural response that, besides sheds light to a change that is as non-classifiable as it is modern, shows the way to the interpretation of a formalisation process which, repeatedly defined by the author, justifies a poetic intensity and confirms an artistic concern often denied by the author. In other words, examining the architectural, historical and technical reasons that led Mies to create his skyscrapers, thanks to its relationship with the avant-garde and cinema, sheds light on and explains the change taking place in the architect with regard to a new fluent spatiality. Reflecting on the spatial nature -of these iconic images- is tantamount to a critical reflection on the symbolic nature of architecture today. “Although the key position of the Friedrichstrasse Office Building within the early history of modern architecture has never been seriously challenged, critical opinion on it has always been divided. Ever since the publication of Philip Johnson’s monograph on Mies in 1947, the curtain wall as a transparent skin sheathing the skeleton structure has frequently been hailed as a pioneering breakthrough. Other views of the building, stressing its supposedly Expressionist plan, have seen it as a somewhat less adventurous effort. In fact, the project has never been regarded in abroad context. Thus measured, Mies’s proposal fro Friedrichstrasse is radically modern in more than the one respect emphasized by Johnson.” 1 W.Tegethoff

Significant discrepancies between van't Hoff and calorimetric enthalpies.

In this paper we show that the usual assumption in studies of the temperature variation of equilibrium constants for equilibria of the form A+B <-->AB that a plot of ln K vs. 1/T (K = equilibrium constant, T = temperature in degrees kelvin) is a straight line with slope equal to -delta HvH/R (delta HvH = van't Hoff or apparent enthalpy, R = gas constant) is not valid in many cases. In all the cases considered here, delta HvH is temperature dependent and is significantly different from the true or calorimetrically measured enthalpy, and the respective values for delta Cp are also significantly different.

Sphere plot of SN1987a event

IMB (Irvine, Michigan, Brookline), a collaboration between the University of Michigan, the University of California at Irvine, and the U.S. Department of Energy, was an experiment designed to determine the ultimate stability of matter. PMT [photomultiplier tubes] hits from SN [supernovae] event projected onto sphere.

Is modern medicine at risk of losing the plot?

Contemporary medicine has much to its credit, but has created an insatiable demand for new technologies and more health services, fed by commercial promotion, professional advocacy and sociopolitical pressure. Total health expenditure at the national level is now almost 10% of gross domestic product and is expected to top 16% by 2020. After recent inquiries into the failings of its public health system, the Queensland Government has committed itself to a 25% increase in expenditure on health over the next 5 years. But will it lead to better population health, and is it sustainable? The return-on-investment curve for modern health care may be flattening out, in an environment of growing numbers of older patients with chronic illnesses, maldistribution of services and hospital overcrowding. A change in thinking is required if current medical practice is to avoid imploding when confronted with the next major economic downturn. Health policy, service funding and clinical training must focus on critical appraisal of the effectiveness of health care technologies and the structure and financing of health care systems. Practising clinicians will be obliged to provide leadership in determining value for money in the choice of health care for specific patient populations and how that care is delivered.