Structural and Electrical Investigation of C 60 –Graphene Vertical Heterostructures

Graphene, with its unique electronic and structural qualities, has become an important playground for studying adsorption and assembly of various materials including organic molecules. Moreover, organic/graphene vertical structures assembled by van der Waals interaction have potential for multifunctional device applications. Here, we investigate structural and electrical properties of vertical heterostructures composed of C60 thin film on graphene. The assembled film structure of C60 on graphene is investigated using transmission electron microscopy, which reveals a uniform morphology of C60 film on graphene with a grain size as large as 500 nm. The strong epitaxial relations between C60 crystal and graphene lattice directions are found, and van der Waals ab initio calculations support the observed phenomena. Moreover, using C60-graphene heterostructures, we fabricate vertical graphene transistors incorporating n-type organic semiconducting materials with an on/off ratio above 3 × 10(3). Our work demonstrates that graphene can serve as an excellent substrate for assembly of molecules, and attained organic/graphene heterostructures have great potential for electronics applications.

Transmission Spectra of Rb 87 atoms near an Optical Nanofiber.

We present measurements of the transmission spectra of 87Rb atoms at 780 nm in the vicinity of a nanofiber. A uniform distribution of fixed atoms around a nanofiber should produce a spectrum that is broadened towards the red due to shifts from the van der Waals potential. If the atoms are free, this also produces an attractive force that accelerates them until they collide with the fiber which depletes the steady-state density of near-surface atoms. It is for this reason that measurements of the van der Waals interaction are sparse. We confirm this by measuring the spectrum cold atoms from a magneto-optical trap around the fiber, revealing a symmetric line shape with nearly the natural linewidth of the transition. When we use an auxiliary 750 nm laser we are able to controllably desorb a steady flux of atoms from the fiber that reside near the surface (less than 50 nm) long enough to feel the van der Walls interaction and produce an asymmetric spectrum. We quantify the spectral asymmetry as a function of 750 nm laser power and find a maximum. Our model, which that takes into account the change in the density distribution, qualitatively explains the observations. In the future this can be used as a tool to more comprehensively study atom-surface interactions.

Protein-protein interaction investigated by steered molecular dynamics: the TCR-pMHC complex.

We present a novel steered molecular dynamics scheme to induce the dissociation of large protein-protein complexes. We apply this scheme to study the interaction of a T cell receptor (TCR) with a major histocompatibility complex (MHC) presenting a peptide (p). Two TCR-pMHC complexes are considered, which only differ by the mutation of a single amino acid on the peptide; one is a strong agonist that produces T cell activation in vivo, while the other is an antagonist. We investigate the interaction mechanism from a large number of unbinding trajectories by analyzing van der Waals and electrostatic interactions and by computing energy changes in proteins and solvent. In addition, dissociation potentials of mean force are calculated with the Jarzynski identity, using an averaging method developed for our steering scheme. We analyze the convergence of the Jarzynski exponential average, which is hampered by the large amount of dissipative work involved and the complexity of the system. The resulting dissociation free energies largely underestimate experimental values, but the simulations are able to clearly differentiate between wild-type and mutated TCR-pMHC and give insights into the dissociation mechanism.

Non-Covalent Interaction: Revealed by Rotational Spectroscopy

The pulsed jet Fourier transform microwave spectroscopy have been applied to several molecular complexes involving H2O, freons, methane, carboxylic acids, and rare gas. The obtained results showcase the suitability of this technique for studying the intermolecular interactions. The rotational spectra of three water adducts of halogenated organic molecules, i.e. chlorotrifluoroethylene, isoflurane and alfa,alfa,alfa,-trifluoroanisole, have been investigated. It has been found that, the halogenation of the partner molecules definitely changes the way in which water will link to the partner molecule. Quadrupole hyperfine structures and/or the tunneling splittings have been observed in the rotational spectra of difluoromethane-dichloromethane, chlorotrifluorometane-fluoromethane, difluoromethane-formaldehyde and trifluoromethane-benzene. These features have been useful to describe their intermolecular interactions (weak hydrogen bonds or halogen bonds), and to size the potential energy surfaces of their internal motions. The rotational spectrum of pyridine-methane pointed out that methane prefers to locate above the ring and link to pyridine through a C-H•••π weak hydrogen bond, rather than the C-H•••n interaction. This behavior, typical of complexes of pyridine with rare gases, suggests classifying CH4, in relation to its ability to form molecular complexes with aromatic molecules, as a pseudo rare gas. The conformational equilibria of three bi-molecules of carboxylic acids, acrylic acid-trifluoroacetic acid, difluoroacetic acid-formic acid and acrylic acid-fluoroacetic acid have been studied. The increase of the hydrogen bond length upon H→D isotopic substitution (Ubbelohde effect) has been deduced from the elongation of the carboxylic carbons C•••C distance. The van der Waals complex tetrahydrofuran-krypton shows that the systematic doubling of the rotational lines has been attributed to the residual pseudo-rotation of tetrahydrofuran in the complex, based on the values of the Coriolis coupling constants, and on the type (mu_b) of the interstate transitions.

Pentafluorophenyl phenyl interaction in biphenyl DNA

We prepared and investigated oligonucleotide duplexes of the sequence d(GATGAC(X)(n)GCTAG)d(CTAGC(Y)(n)GTCATC), in which X and Y designate biphenyl- (bph) and pentafluorobiphenyl- ((5F)bph) C-nucleotides, respectively, and n varies from 0-4. These hydrophobic base substitutes are expected to adopt a zipperlike, interstrand stacking motif, in which not only bph/bph or (5F)bph/(5F)bph homo pairs, but also (5F)bph/bph mixed pairs can be formed. By performing UV-melting curve analysis we found that incorporation of a single (5F)bph/(5F)bph pair leads to a duplex that is essentially as stable as the unmodified duplex (n=0), and 2.4 K more stable than the duplex with the nonfluorinated bph/bph pair. The T(m) of the mixed bph/(5F)bph pair was in between the T(m) values of the respective homo pairs. Additional, unnatural aromatic pairs increased the T(m) by +3.0-4.4 K/couple, irrespective of the nature of the aromatic residue. A thermodynamic analysis using isothermal titration calorimetry (ITC) of a series of duplexes with n=3 revealed lower (less negative) duplex formation enthalpies (DeltaH) in the (5F)bph/(5F)bph case than in the bph/bph case, and confirmed the higher thermodynamic stability (DeltaG) of the fluorinated duplex, suggesting it to be of entropic origin. Our data are compatible with a model in which the stacking of (5F)bph versus bph is dominated by dehydration of the aromatic units upon duplex formation. They do not support a model in which van der Waals dispersive forces (induced dipoles) or electrostatic (quadrupole) interactions play a dominant role

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

Structural details of an interaction between cardiolipin and an integral membrane protein

Anionic lipids play a variety of key roles in biomembrane function, including providing the immediate environment for the integral membrane proteins that catalyze photosynthetic and respiratory energy transduction. Little is known about the molecular basis of these lipid–protein interactions. In this study, x-ray crystallography has been used to examine the structural details of an interaction between cardiolipin and the photoreaction center, a key light-driven electron transfer protein complex found in the cytoplasmic membrane of photosynthetic bacteria. X-ray diffraction data collected over the resolution range 30.0–2.1 Å show that binding of the lipid to the protein involves a combination of ionic interactions between the protein and the lipid headgroup and van der Waals interactions between the lipid tails and the electroneutral intramembrane surface of the protein. In the headgroup region, ionic interactions involve polar groups of a number of residues, the protein backbone, and bound water molecules. The lipid tails sit along largely hydrophobic grooves in the irregular surface of the protein. In addition to providing new information on the immediate lipid environment of a key integral membrane protein, this study provides the first, to our knowledge, high-resolution x-ray crystal structure for cardiolipin. The possible significance of this interaction between an integral membrane protein and cardiolipin is considered.

Quantification of the hydrophobic interaction by simulations of the aggregation of small hydrophobic solutes in water

The hydrophobic interaction, the tendency for nonpolar molecules to aggregate in solution, is a major driving force in biology. In a direct approach to the physical basis of the hydrophobic effect, nanosecond molecular dynamics simulations were performed on increasing numbers of hydrocarbon solute molecules in water-filled boxes of different sizes. The intermittent formation of solute clusters gives a free energy that is proportional to the loss in exposed molecular surface area with a constant of proportionality of 45 ± 6 cal/mol⋅Å2. The molecular surface area is the envelope of the solute cluster that is impenetrable by solvent and is somewhat smaller than the more traditional solvent-accessible surface area, which is the area transcribed by the radius of a solvent molecule rolled over the surface of the cluster. When we apply a factor relating molecular surface area to solvent-accessible surface area, we obtain 24 cal/mol⋅Å2. Ours is the first direct calculation, to our knowledge, of the hydrophobic interaction from molecular dynamics simulations; the excellent qualitative and quantitative agreement with experiment proves that simple van der Waals interactions and atomic point-charge electrostatics account for the most important driving force in biology.

Complex-order forced van der Pol oscillator

In this paper we consider a complex-order forced van der Pol oscillator. The complex derivative Dα1jβ, with α, β ∈ ℝ+, is a generalization of the concept of an integer derivative, where α = 1, β = 0. The Fourier transforms of the periodic solutions of the complex-order forced van der Pol oscillator are computed for various values of parameters such as frequency ω and amplitude b of the external forcing, the damping μ, and parameters α and β. Moreover, we consider two cases: (i) b = 1, μ = {1.0, 5.0, 10.0}, and ω = {0.5, 2.46, 5.0, 20.0}; (ii) ω = 20.0, μ = {1.0, 5.0, 10.0}, and b = {1.0, 5.0, 10.0}. We verified that most of the signal energy is concentrated in the fundamental harmonic ω0. We also observed that the fundamental frequency of the oscillations ω0 varies with α and μ. For the range of tested values, the numerical fitting led to logarithmic approximations for system (7) in the two cases (i) and (ii). In conclusion, we verify that by varying the parameter values α and β of the complex-order derivative in expression (7), we accomplished a very effective way of perturbing the dynamical behavior of the forced van der Pol oscillator, which is no longer limited to parameters b and ω.

Complex order van der Pol oscillator

In this paper a complex-order van der Pol oscillator is considered. The complex derivative Dα±ȷβ , with α,β∈R + is a generalization of the concept of integer derivative, where α=1, β=0. By applying the concept of complex derivative, we obtain a high-dimensional parameter space. Amplitude and period values of the periodic solutions of the two versions of the complex-order van der Pol oscillator are studied for variation of these parameters. Fourier transforms of the periodic solutions of the two oscillators are also analyzed.

Analysis of the Van der Pol oscillator containing derivatives of fractional order

In this paper a modified version of the classical Van der Pol oscillator is proposed, introducing fractional-order time derivatives into the state-space model. The resulting fractional-order Van der Pol oscillator is analyzed in the time and frequency domains, using phase portraits, spectral analysis and bifurcation diagrams. The fractional-order dynamics is illustrated through numerical simulations of the proposed schemes using approximations to fractional-order operators. Finally, the analysis is extended to the forced Van der Pol oscillator.

Estudo da influência de nanotubos de carbono funcionalizados nas propriedades de revestimentos de poliuretano

Dissertação de mestrado em Propriedades e Tecnologias de Polímeros

Essential oils of the Sextonia rubra (Mez ) van der Werff (Lauraceae)

The essential oils of the leaves and branches of Sextonia rubra were obtained by hydrodistillation and analyzed by GC-FID and GC-MS. In the leaves were identified as the major constituents α-pinene (21.7%), β-pinene (15.4%), α-copaene (12.5%) and germacrene D (12.1%). In the branches essential oil, α-copaene (22.9%), β-selinene (7.9%) and β-elemene (7.2%) were identified as the most abundant constituents. This paper describes for the first time the composition of these essential oils.