3D-Strukturanalyse von Molluskenhämocyaninen aus elektronenmikroskopischen Bildern

Diese Arbeit präsentiert die bislang höchst aufgelösten KryoEM-Strukturen für ein Cephalopoden hämocyanin Dekamer (Nautilus pompilus Hämocyanin, NpH) und ein Gastropoden Hämocyanin Didekamer (keyhole limpet hemocyanin isoform 1). Durch die Methoden des “molecular modelling” und “rigid-body-fiting” wurde auch eine detaillierte Beschreibung beider Strukturen auf atomarem Niveau erstmalig möglich. Hämocyanine sind kupferhaltige Sauerstoff-Transportproteine die frei gelöst in Blut zahlreicher Arthropoden und Mollusken vorkommen. Allgemein sind Molluskenhämocyanine als Dekamere (Hohlzylinder aus 5 Untereinheiten-dimere) oder Didecamere (Zusammenlagerung von zwei Dekameren) zu finden. Durch Anlagerung weiterer Dekamere bilden sich teilweise tubuläre Multidekamere. Hämocyanine der Cephalopoden bestehen ausschließlich aus solitären Decameren. In Octopus und Nautilus bestehen die 10 Untereinheiten aus 7 funktionellen Einheiten(FU-a bis FU-g), wobei jede FU ein Sauerstoffmolekül binden kann. FUs a-f bilden die Wand des ringförmigen Moleküls und 10 Kopien der FU-g bilden einen sogenannten „inneren Kragenkomplex“. Das im Rahmen dieser Arbeit erstelltes molekulares Modell von NpH klärt die Struktur des Dekamers vollständig auf. Wir waren zum ersten Mal in der Lage das Untereinheiten-dimer, den Verlauf der Polypeptidkette und 15 unterschiedliche Kontaktstellen zwischen FUs zu identifizieren. Viele der inter-FU-Kontakte weisen Aminosäurenkonstellationen auf, die die Basis für die Übertragung allosterischer Wechselwirkungen zwischen FUs darstellen könnten und Hinweise für den Aufbau der allosterische Einheit geben. Potentielle Bindungsstellen für N-glykosidische Zucker und bivalente Kationen wurden auch identifiziert. Im Gegensatz zu NpH, kommen Gastropoden Hämocyanine (inkl. KLH) hauptsächlich als Didekamere vor und der Kragenkomplex wird in diesem Fall aus 2 FUs gebildet (Fu-g und FU-h). Die zusätzliche C'-terminale FU-h zeichnet sich durch eine spezielle Verlängerung von ~ 100 Aminosäuren aus. KLH stammt aus der kalifornische Schnecke Megathura crenulata und kommt seit mehreren Jahrzehnten als Immunostimulator in der immunologischen Grundlagenforschung und klinischen Anwendung zum Einsatz. KLH weist zwei Isoformen auf, KLH1 und KLH2. Das vorliegende Modell von KLH1 erlaubt die komplexe Architektur dieses riesigen Proteins in allen Details zu verstehen, sowie einen Vergleich zum dem NpH Dekamer auf atomare Ebene. Es wurde gefunden, dass das Untereinheitensegment a-b-c-d-e-f-g, sowie die equivalenten Kontaktstellen zwichen FUs stark konserviert sind. Dies deutet darauf hin, dass in Bezug auf die Übertragung allosterische Signale zwischen benachbarten FUs, grundlegende Mechanismen in beiden Molekülen beibehalten wurden. Weiterhin, konnten die Verbindungen zwischen den zwei Dekameren ertsmalig identifiziert werden. Schließlich, wurde die Topologie der N-glycosidischen Zucker, welche für die immunologische Eigenschaften von KLH1 von großer Bedeutung sind, auch aufgeklärt. Somit leistet die vorliegende Arbeit einen wesentlichen Schritt zum Verständnis der Quartärstruktur und Funktion der Molluskenhämocyanine.rn

Effect of mixing, particle interaction, and spatial dimension on the glass transition

In this thesis, the influence of composition changes on the glass transition behavior of binary liquids in two and three spatial dimensions (2D/3D) is studied in the framework of mode-coupling theory (MCT).The well-established MCT equations are generalized to isotropic and homogeneous multicomponent liquids in arbitrary spatial dimensions. Furthermore, a new method is introduced which allows a fast and precise determination of special properties of glass transition lines. The new equations are then applied to the following model systems: binary mixtures of hard disks/spheres in 2D/3D, binary mixtures of dipolar point particles in 2D, and binary mixtures of dipolar hard disks in 2D. Some general features of the glass transition lines are also discussed. The direct comparison of the binary hard disk/sphere models in 2D/3D shows similar qualitative behavior. Particularly, for binary mixtures of hard disks in 2D the same four so-called mixing effects are identified as have been found before by Götze and Voigtmann for binary hard spheres in 3D [Phys. Rev. E 67, 021502 (2003)]. For instance, depending on the size disparity, adding a second component to a one-component liquid may lead to a stabilization of either the liquid or the glassy state. The MCT results for the 2D system are on a qualitative level in agreement with available computer simulation data. Furthermore, the glass transition diagram found for binary hard disks in 2D strongly resembles the corresponding random close packing diagram. Concerning dipolar systems, it is demonstrated that the experimental system of König et al. [Eur. Phys. J. E 18, 287 (2005)] is well described by binary point dipoles in 2D through a comparison between the experimental partial structure factors and those from computer simulations. For such mixtures of point particles it is demonstrated that MCT predicts always a plasticization effect, i.e. a stabilization of the liquid state due to mixing, in contrast to binary hard disks in 2D or binary hard spheres in 3D. It is demonstrated that the predicted plasticization effect is in qualitative agreement with experimental results. Finally, a glass transition diagram for binary mixtures of dipolar hard disks in 2D is calculated. These results demonstrate that at higher packing fractions there is a competition between the mixing effects occurring for binary hard disks in 2D and those for binary point dipoles in 2D.

Zweikernige 3d-Übergangsmetall-Komplexe mit Derivaten des para-Phenylendiamins als redoxaktive Brückenliganden

Die vorliegende Arbeit beschäftigt sich mit der Darstellung zweikerniger Koordinationsverbindungen, bei denen zweiwertige Ionen der 3d-Übergangsmetalle über einen bestimmten Liganden verbrückt sind. Dieser Brückenligand, das N,N,N‘,N‘-Tetrakis-(2-methylpyridyl)-benzol-1,4-diamin (TPBD), besteht aus einem p-Phenylendiamin-Gerüst, an dessen Stickstoffe je zwei Methylpyridin-Gruppen gebunden sind. In diesen zwei jeweils dreizähnigen Bindungstaschen wurden 3d-Übergangsmetallionen komplexiert, wobei deren Koordinationssphäre mit einem zweizähnigen capping-Liganden vom Typ des 1,10-Phenanthrolins und einem einzähnigen dritten Liganden abgesättigt wird. Die strukturellen, magnetischen und elektronischen Eigenschaften der so erhaltenen homometallischen Komplexe mit Mn(II), Fe(II), Co(II), Ni(II), Cu(II) und Zn(II) wurden untersucht. Dabei wurde besonderes Augenmerk auf die Veränderung dieser Eigenschaften bei dem Einsatz unterschiedlicher capping- und dritter Liganden gerichtet. Die schwach antiferromagnetische Wechselwirkung der metallzentrierten Spins über den Brückenliganden führt dabei stets zu einem diamagnetischen Grundzustand, was diese als mögliche Einzelmolekülmagnete ausschließt. Mit der Oxidierbarkeit des Liganden zu seiner radikalischen Spezies besteht die Möglichkeit, einen zusätzlichen Spin in dem System zu erzeugen, woraus ein Spingrundzustand von ungleich null resultiert. Es zeigte sich, dass die Lebensdauer der radikalischen Spezies eine starke Abhängigkeit sowohl von den eingesetzten Metallionen als auch den weiteren Liganden besitzt. Auch vier Derivate des ursprünglichen Brückenliganden konnten synthetisiert und deren Oxidierbarkeit zu den entsprechenden Radikalformen gezeigt werden. Neben der Darstellung homometallischer Komplexe gelang zudem die Synthese und Strukturaufklärung dreier heterometallischer zweikerniger Komplexe mit Mn(II), Co(II) und Ni(II) als Metallionen. Es konnte gezeigt werden, dass diese auch ohne die Oxidation des Brückenliganden bei schwacher antiferromagnetischer Wechselwirkung der Spins einen paramagnetischen Spingrundzustand besitzen.

A new 3D modelling paradigm for discrete model

Until few years ago, 3D modelling was a topic confined into a professional environment. Nowadays technological innovations, the 3D printer among all, have attracted novice users to this application field. This sudden breakthrough was not supported by adequate software solutions. The 3D editing tools currently available do not assist the non-expert user during the various stages of generation, interaction and manipulation of 3D virtual models. This is mainly due to the current paradigm that is largely supported by two-dimensional input/output devices and strongly affected by obvious geometrical constraints. We have identified three main phases that characterize the creation and management of 3D virtual models. We investigated these directions evaluating and simplifying the classic editing techniques in order to propose more natural and intuitive tools in a pure 3D modelling environment. In particular, we focused on freehand sketch-based modelling to create 3D virtual models, interaction and navigation in a 3D modelling environment and advanced editing tools for free-form deformation and objects composition. To pursuing these goals we wondered how new gesture-based interaction technologies can be successfully employed in a 3D modelling environments, how we could improve the depth perception and the interaction in 3D environments and which operations could be developed to simplify the classical virtual models editing paradigm. Our main aims were to propose a set of solutions with which a common user can realize an idea in a 3D virtual model, drawing in the air just as he would on paper. Moreover, we tried to use gestures and mid-air movements to explore and interact in 3D virtual environment, and we studied simple and effective 3D form transformations. The work was carried out adopting the discrete representation of the models, thanks to its intuitiveness, but especially because it is full of open challenges.

Iodide interaction with natural pyrite

29I is one of the major dose-determining nuclides in the safety analysis of deep storage of radioactive waste. Iodine forms anionic species that hardly sorb on the surfaces of common host-rock minerals. Recently, interest has arisen on the role of pyrite, an accessory mineral capable of binding anionic selenium. Whereas the interaction of selenium with pyrite is well documented, corresponding results on iodine sorption are still scarce and controversial. Pyrite is present in argicilleous rocks which are being considered in many countries as potential host rocks for a radioactive waste repository. The uptake of iodide (I−) on natural pyrite was investigated under nearly anoxic conditions (O2 < 5 ppm) over a wide concentration range (10−11–10−3 M total I−) using 125I as the radioactive tracer. Weak but measurable sorption was observed; distribution coefficients (R d) were less than 0.002 m3 kg−1 and decreased with increasing total iodide concentration. Iodide sorption was connected to the presence of oxidized clusters on the pyrite surface, which were presumably formed by reaction with limited amounts of dissolved oxygen. The results obtained indicated that pyrite cannot be considered as an effective scavenger of 129I under the geochemical conditions prevailing in underground radioactive waste geologic storage.

Clinical and biochemical description of a novel CYP21A2 gene mutation 962_963insA using a new 3D model for the P450c21 protein

OBJECTIVE: A severely virilized 46, XX newborn girl was referred to our center for evaluation and treatment of congenital adrenal hyperplasia (CAH) because of highly elevated 17alpha-hydroxyprogesterone levels at newborn screening; biochemical tests confirmed the diagnosis of salt-wasting CAH. Genetic analysis revealed that the girl was compound heterozygote for a previously reported Q318X mutation in exon 8 and a novel insertion of an adenine between nucleotides 962 and 963 in exon 4 of the CYP21A2 gene. This 962_963insA mutation created a frameshift leading to a stop codon at amino acid 161 of the P450c21 protein. AIM AND METHODS: To better understand structure-function relationships of mutant P450c21 proteins, we performed multiple sequence alignments of P450c21 with three mammalian P450s (P450 2C8, 2C9 and 2B4) with known structures as well as with human P450c17. Comparative molecular modeling of human P450c21 was then performed by MODELLER using the X-ray crystal structure of rabbit P450 2B4 as a template. RESULTS: The new three dimensional model of human P450c21 and the sequence alignment were found to be helpful in predicting the role of various amino acids in P450c21, especially those involved in heme binding and interaction with P450 oxidoreductase, the obligate electron donor. CONCLUSION: Our model will help in analyzing the genotype-phenotype relationship of P450c21 mutations which have not been tested for their functional activity in an in vitro assay.

Design and implementation of a 3D computer game controller using inertial MEMS sensors

Though 3D computer graphics has seen tremendous advancement in the past two decades, most available mechanisms for computer interaction in 3D are high cost and targeted for industry and virtual reality applications. Recent advances in Micro-Electro-Mechanical-System (MEMS) devices have brought forth a variety of new low-cost, low-power, miniature sensors with high accuracy, which are well suited for hand-held devices. In this work a novel design for a 3D computer game controller using inertial sensors is proposed, and a prototype device based on this design is implemented. The design incorporates MEMS accelerometers and gyroscopes from Analog Devices to measure the three components of the acceleration and angular velocity. From these sensor readings, the position and orientation of the hand-held compartment can be calculated using numerical methods. The implemented prototype is utilizes a USB 2.0 compliant interface for power and communication with the host system. A Microchip dsPIC microcontroller is used in the design. This microcontroller integrates the analog to digital converters, the program memory flash, as well as the core processor, on a single integrated circuit. A PC running Microsoft Windows operating system is used as the host machine. Prototype firmware for the microcontroller is developed and tested to establish the communication between the design and the host, and perform the data acquisition and initial filtering of the sensor data. A PC front-end application with a graphical interface is developed to communicate with the device, and allow real-time visualization of the acquired data.

Wind plant interaction with series-compensated power systems

Wind power based generation has been rapidly growing world-wide during the recent past. In order to transmit large amounts of wind power over long distances, system planners may often add series compensation to existing transmission lines owing to several benefits such as improved steady-state power transfer limit, improved transient stability, and efficient utilization of transmission infrastructure. Application of series capacitors has posed resonant interaction concerns such as through subsynchronous resonance (SSR) with conventional turbine-generators. Wind turbine-generators may also be susceptible to such resonant interactions. However, not much information is available in literature and even engineering standards are yet to address these issues. The motivation problem for this research is based on an actual system switching event that resulted in undamped oscillations in a 345-kV series-compensated, typical ring-bus power system configuration. Based on time-domain ATP (Alternative Transients Program) modeling, simulations and analysis of system event records, the occurrence of subsynchronous interactions within the existing 345-kV series-compensated power system has been investigated. Effects of various small-signal and large-signal power system disturbances with both identical and non-identical wind turbine parameters (such as with a statistical-spread) has been evaluated. Effect of parameter variations on subsynchronous oscillations has been quantified using 3D-DFT plots and the oscillations have been identified as due to electrical self-excitation effects, rather than torsional interaction. Further, the generator no-load reactance and the rotor-side converter inner-loop controller gains have been identified as bearing maximum sensitivity to either damping or exacerbating the self-excited oscillations. A higher-order spectral analysis method based on modified Prony estimation has been successfully applied to the field records identifying dominant 9.79 Hz subsynchronous oscillations. Recommendations have been made for exploring countermeasures.

Visual Fixation for 3D Video Stabilization

Visual fixation is employed by humans and some animals to keep a specific 3D location at the center of the visual gaze. Inspired by this phenomenon in nature, this paper explores the idea to transfer this mechanism to the context of video stabilization for a handheld video camera. A novel approach is presented that stabilizes a video by fixating on automatically extracted 3D target points. This approach is different from existing automatic solutions that stabilize the video by smoothing. To determine the 3D target points, the recorded scene is analyzed with a stateof- the-art structure-from-motion algorithm, which estimates camera motion and reconstructs a 3D point cloud of the static scene objects. Special algorithms are presented that search either virtual or real 3D target points, which back-project close to the center of the image for as long a period of time as possible. The stabilization algorithm then transforms the original images of the sequence so that these 3D target points are kept exactly in the center of the image, which, in case of real 3D target points, produces a perfectly stable result at the image center. Furthermore, different methods of additional user interaction are investigated. It is shown that the stabilization process can easily be controlled and that it can be combined with state-of-theart tracking techniques in order to obtain a powerful image stabilization tool. The approach is evaluated on a variety of videos taken with a hand-held camera in natural scenes.

Language Learning in 3D Virtual World

Second Life (SL) is an ideal platform for language learning. It is called a Multi-User Virtual Environment, where users can have varieties of learning experiences in life-like environments. Numerous attempts have been made to use SL as a platform for language teaching and the possibility of SL as a means to promote conversational interactions has been reported. However, the research so far has largely focused on simply using SL without further augmentations for communication between learners or between teachers and learners in a school-like environment. Conversely, not enough attention has been paid to its controllability which builds on the embedded functions in SL. This study, based on the latest theories of second language acquisition, especially on the Task Based Language Teaching and the Interaction Hypothesis, proposes to design and implement an automatized interactive task space (AITS) where robotic agents work as interlocutors of learners. This paper presents a design that incorporates the SLA theories into SL and the implementation method of the design to construct AITS, fulfilling the controllability of SL. It also presents the result of the evaluation experiment conducted on the constructed AITS.

Chiral Templating Activity of Tris(bipyridine)ruthenium(II) Cation in the Design of Three-Dimensional (3D) Optically Active Oxalate-Bridged {[Ru(bpy) 3 ][Cu 2 x Ni 2(1 - x ) (C 2 O 4 ) 3 ]} n (0 ≤ x ≤ 1; bpy = 2,2‘-bipyridine): Structural, Optical, and Magnetic Studies

Three-dimensional oxalate-based {[Ru(bpy)3][Cu2xNi2(1-x)(ox)3]}n (0≤ x ≤ 1, ox = C2O42-, bpy = 2,2‘bipyridine) were synthesized. The structure was determined for x = 1 by X-ray diffraction on single crystal. The compound crystallizes in the cubic space group P4132. It shows a three-dimensional 10-gon 3-connected (10,3) anionic network where copper(II) has an unusual tris(bischelated) environment. X-ray powder diffraction patterns and their Rietveld refinement show that all the compounds along the series are isostructural and single-phased. According to X-ray absorption spectroscopy, copper(II) and nickel(II) have an octahedral environment, respectively elongated and trigonally distorted. As shown by natural circular dichroism, the optically active forms of {[Ru(bpy)3][CuxNi2(1-x)(ox)3]}n are obtained starting from resolved Δ- or Λ-[Ru(bpy)3]2+. The Curie−Weiss temperatures range between −55 (x = 1) and −150 K (x = 0). The antiferromagnetic exchange interaction thus decreases when the copper contents increases in agreement with the crystallographic structure of the compounds and the electronic structure of the metal ions. At low temperature, the compounds exhibit complex long-range ordered magnetic behavior.

3D-modeling of Mercury's solar wind sputtered surface-exosphere environment

The efficiency of sputtered refractory elements by H+ and He++ solar wind ions from Mercury's surface and their contribution to the exosphere are studied for various solar wind conditions. A 3D solar wind-planetary interaction hybrid model is used for the evaluation of precipitation maps of the sputter agents on Mercury's surface. By assuming a global mineralogical surface composition, the related sputter yields are calculated by means of the 2013 SRIM code and are coupled with a 3D exosphere model. Because of Mercury's magnetic field, for quiet and nominal solar wind conditions the plasma can only precipitate around the polar areas, while for extreme solar events (fast solar wind, coronal mass ejections, interplanetary magnetic clouds) the solar wind plasma has access to the entire dayside. In that case the release of particles form the planet's surface can result in an exosphere density increase of more than one order of magnitude. The corresponding escape rates are also about an order of magnitude higher. Moreover, the amount of He++ ions in the precipitating solar plasma flow enhances also the release of sputtered elements from the surface in the exosphere. A comparison of our model results with MESSENGER observations of sputtered Mg and Ca elements in the exosphere shows a reasonable quantitative agreement. (C) 2015 Elsevier Ltd. All rights reserved.

A multimodal tablet-based interface for designing and reviewing 3D engineering models

The ability to view and interact with 3D models has been happening for a long time. However, vision-based 3D modeling has only seen limited success in applications, as it faces many technical challenges. Hand-held mobile devices have changed the way we interact with virtual reality environments. Their high mobility and technical features, such as inertial sensors, cameras and fast processors, are especially attractive for advancing the state of the art in virtual reality systems. Also, their ubiquity and fast Internet connection open a path to distributed and collaborative development. However, such path has not been fully explored in many domains. VR systems for real world engineering contexts are still difficult to use, especially when geographically dispersed engineering teams need to collaboratively visualize and review 3D CAD models. Another challenge is the ability to rendering these environments at the required interactive rates and with high fidelity. In this document it is presented a virtual reality system mobile for visualization, navigation and reviewing large scale 3D CAD models, held under the CEDAR (Collaborative Engineering Design and Review) project. It’s focused on interaction using different navigation modes. The system uses the mobile device's inertial sensors and camera to allow users to navigate through large scale models. IT professionals, architects, civil engineers and oil industry experts were involved in a qualitative assessment of the CEDAR system, in the form of direct user interaction with the prototypes and audio-recorded interviews about the prototypes. The lessons learned are valuable and are presented on this document. Subsequently it was prepared a quantitative study on the different navigation modes to analyze the best mode to use it in a given situation.

An attitude-based reasoning strategy to enhance interaction with augmented objects

This paper describes a mobile-based system to interact with objects in smart spaces, where the offer of resources may be extensive. The underlying idea is to use the augmentation capabilities of the mobile device to enable it as user-object mediator. In particular, the paper details how to build an attitude-based reasoning strategy that facilitates user-object interaction and resource filtering. The strategy prioritizes the available resources depending on the spatial history of the user, his real-time location and orientation and, finally, his active touch and focus interactions with the virtual overlay. The proposed reasoning method has been partially validated through a prototype that handles 2D and 3D visualization interfaces. This framework makes possible to develop in practice the IoT paradigm, augmenting the objects without physically modifying them.

Experimental Prototype Merging Stereo Panoramic Video and Interactive 3D Content in a 5-sided CAVETM

Immersion and interaction have been identified as key factors influencing the quality of experience in stereoscopic video systems. An experimental prototype designed to explore the influence of these factors in 3D video applications is described here1. The focus is on the real-time insertion algorithm of new 3D models into the original video streams. Using this algorithm, our prototype is aimed to explore a new interaction paradigm ? similar to the augmented reality approach ? with 3D video applications.