A dimensional analysis of the benzylic hydroxylase active site in mortierella isabellina

The spatial limits of the active site in the benzylic hydroxylase enzyme of the fungus Mortierella isabellina were investigated. Several molecular probes were used in incubation experiments to determine the acceptability of each compound by this enzyme. The yields of benzylic alcohols provided information on the acceptability of the particular compound into the active site, and the enantiomeric excess values provided information on the "fit" of acceptable substrates. Measurements of the molecular models were made using Cambridge Scientific Computing Inc. CSC Chem 3D Plus modeling program. i The dimensional limits of the aromatic binding pocket of the benzylic hydroxylase were tested using suitably substituted ethyl benzenes. Both the depth (para substituted substrates) and width (ortho and meta substituted substrates) of this region were investigated, with results demonstrating absolute spatial limits in both directions in the plane of the aromatic ring of 7.3 Angstroms for the depth and 7.1 Angstroms for the width. A minimum requirement for the height of this region has also been established at 6.2 Angstroms. The region containing the active oxygen species was also investigated, using a series of alkylphenylmethanes and fused ring systems in indan, 1,2,3,4-tetrahydronaphthalene and benzocycloheptene substrates. A maximum distance of 6.9 Angstroms (including the 1.5 Angstroms from the phenyl substituent to the active center of the heme prosthetic group of the enzyme) has been established extending directly in ii front of the aromatic binding pocket. The other dimensions in this region of the benzylic hydroxylase active site will require further investigation to establish maximum allowable values. An explanation of the stereochemical distributions in the obtained products has also been put forth that correlates well with the experimental observations.

Investigation of Frustrated Quasi-One-Dimensional Quantum Spin-Chain Materials

Copper arsenite CuAs2O4 and Copper antimonite CuSb2O4 are S=1/2 (Cu2+ 3d9 electronic configuration) quasi-one-dimensional quantum spin-chain compounds. Both compounds crystallize with tetragonal structures containing edge sharing CuO6 octahedra chains which experience Jahn-Teller distortions. The basal planes of the octahedra link together to form CuO2 ribbon-chains which harbor Cu2+ spin-chains. These compounds are magnetically frustrated with competing nearest-neighbour and next-nearest-neighbour intrachain spin-exchange interactions. Despite the similarities between CuAs2O4 and CuSb2O4, they exhibit very different magnetic properties. In this thesis work, the physical properties of CuAs2O4 and CuSb2O4 are investigated using a variety of experimental techniques which include x-ray diffraction, magnetic susceptibility measurements, heat capacity measurements, Raman spectroscopy, electron paramagnetic resonance, neutron diffraction, and dielectric capacitance measurements. CuAs2O4 exhibits dominant ferromagnetic nearest-neighbour and weaker antiferromagnetic next-nearest-neighbour intrachain spin-exchange interactions. The ratio of the intrachain interactions amounts to Jnn/Jnnn = -4.1. CuAs2O4 was found to order with a ferromagnetic groundstate below TC = 7.4 K. An extensive physical characterization of the magnetic and structural properties of CuAs2O4 was carried out. Under the effect of hydrostatic pressure, CuAs2O4 was found to undergo a structural phase transition at 9 GPa to a new spin-chain structure. The structural phase transition is accompanied by a severe alteration of the magnetic properties. The high-pressure phase exhibits dominant ferromagnetic next-nearest-neighbour spin-exchange interactions and weaker ferromagnetic nearest-neighbour interactions. The ratio of the intrachain interactions in the high-pressure phase was found to be Jnn/Jnnn = 0.3. Structural and magnetic characterizations under hydrostatic pressure are reported and a relationship between the structural and magnetic properties was established. CuSb2O4 orders antiferromagnetically below TN = 1.8 K with an incommensurate helicoidal magnetic structure. CuSb2O4 is characterized by ferromagnetic nearest-neighbour and antiferromagnetic next-nearest-neighbour spin-exchange interactions with Jnn/Jnnn = -1.8. A (H, T) magnetic phase diagram was constructed using low-temperature magnetization and heat capacity measurements. The resulting phase diagram contains multiple phases as a consequence of the strong intrachain magnetic frustration. Indications of ferroelectricity were observed in the incommensurate antiferromagnetic phase.

Propriétés géométriques des surfaces associées aux solutions des modèles sigma grassmanniens en deux dimensions

Dans cette thèse, nous analysons les propriétés géométriques des surfaces obtenues des solutions classiques des modèles sigma bosoniques et supersymétriques en deux dimensions ayant pour espace cible des variétés grassmanniennes G(m,n). Plus particulièrement, nous considérons la métrique, les formes fondamentales et la courbure gaussienne induites par ces surfaces naturellement plongées dans l'algèbre de Lie su(n). Le premier chapitre présente des outils préliminaires pour comprendre les éléments des chapitres suivants. Nous y présentons les théories de jauge non-abéliennes et les modèles sigma grassmanniens bosoniques ainsi que supersymétriques. Nous nous intéressons aussi à la construction de surfaces dans l'algèbre de Lie su(n) à partir des solutions des modèles sigma bosoniques. Les trois prochains chapitres, formant cette thèse, présentent les contraintes devant être imposées sur les solutions de ces modèles afin d'obtenir des surfaces à courbure gaussienne constante. Ces contraintes permettent d'obtenir une classification des solutions en fonction des valeurs possibles de la courbure. Les chapitres 2 et 3 de cette thèse présentent une analyse de ces surfaces et de leurs solutions classiques pour les modèles sigma grassmanniens bosoniques. Le quatrième consiste en une analyse analogue pour une extension supersymétrique N=2 des modèles sigma bosoniques G(1,n)=CP^(n-1) incluant quelques résultats sur les modèles grassmanniens. Dans le deuxième chapitre, nous étudions les propriétés géométriques des surfaces associées aux solutions holomorphes des modèles sigma grassmanniens bosoniques. Nous donnons une classification complète de ces solutions à courbure gaussienne constante pour les modèles G(2,n) pour n=3,4,5. De plus, nous établissons deux conjectures sur les valeurs constantes possibles de la courbure gaussienne pour G(m,n). Nous donnons aussi des éléments de preuve de ces conjectures en nous appuyant sur les immersions et les coordonnées de Plücker ainsi que la séquence de Veronese. Ces résultats sont publiés dans la revue Journal of Geometry and Physics. Le troisième chapitre présente une analyse des surfaces à courbure gaussienne constante associées aux solutions non-holomorphes des modèles sigma grassmanniens bosoniques. Ce travail généralise les résultats du premier article et donne un algorithme systématique pour l'obtention de telles surfaces issues des solutions connues des modèles. Ces résultats sont publiés dans la revue Journal of Geometry and Physics. Dans le dernier chapitre, nous considérons une extension supersymétrique N=2 du modèle sigma bosonique ayant pour espace cible G(1,n)=CP^(n-1). Ce chapitre décrit la géométrie des surfaces obtenues des solutions du modèle et démontre, dans le cas holomorphe, qu'elles ont une courbure gaussienne constante si et seulement si la solution holomorphe consiste en une généralisation de la séquence de Veronese. De plus, en utilisant une version invariante de jauge du modèle en termes de projecteurs orthogonaux, nous obtenons des solutions non-holomorphes et étudions la géométrie des surfaces associées à ces nouvelles solutions. Ces résultats sont soumis dans la revue Communications in Mathematical Physics.

Two Dimensional Large Amplitude Quasi Solitons in Thin Helium Films

Large amplitude local density fluctuations in a thin superfluid He film is considered. It is shown that these large amplitude fluctuations travel and behave like "quasi-solitons" under collision, even when the full nonlinearity arising from the Van der Waals potential is taken into account.

Topological Invariants in Hydrodynamics and Hydromagnetics

In this thesis we are studying possible invariants in hydrodynamics and hydromagnetics. The concept of flux preservation and line preservation of vector fields, especially vorticity vector fields, have been studied from the very beginning of the study of fluid mechanics by Helmholtz and others. In ideal magnetohydrodynamic flows the magnetic fields satisfy the same conservation laws as that of vorticity field in ideal hydrodynamic flows. Apart from these there are many other fields also in ideal hydrodynamic and magnetohydrodynamic flows which preserves flux across a surface or whose vector lines are preserved. A general study using this analogy had not been made for a long time. Moreover there are other physical quantities which are also invariant under the flow, such as Ertel invariant. Using the calculus of differential forms Tur and Yanovsky classified the possible invariants in hydrodynamics. This mathematical abstraction of physical quantities to topological objects is needed for an elegant and complete analysis of invariants.Many authors used a four dimensional space-time manifold for analysing fluid flows. We have also used such a space-time manifold in obtaining invariants in the usual three dimensional flows.In chapter one we have discussed the invariants related to vorticity field using vorticity field two form w2 in E4. Corresponding to the invariance of four form w2 ^ w2 we have got the invariance of the quantity E. w. We have shown that in an isentropic flow this quantity is an invariant over an arbitrary volume.In chapter three we have extended this method to any divergence-free frozen-in field. In a four dimensional space-time manifold we have defined a closed differential two form and its potential one from corresponding to such a frozen-in field. Using this potential one form w1 , it is possible to define the forms dw1 , w1 ^ dw1 and dw1 ^ dw1 . Corresponding to the invariance of the four form we have got an additional invariant in the usual hydrodynamic flows, which can not be obtained by considering three dimensional space.In chapter four we have classified the possible integral invariants associated with the physical quantities which can be expressed using one form or two form in a three dimensional flow. After deriving some general results which hold for an arbitrary dimensional manifold we have illustrated them in the context of flows in three dimensional Euclidean space JR3. If the Lie derivative of a differential p-form w is not vanishing,then the surface integral of w over all p-surfaces need not be constant of flow. Even then there exist some special p-surfaces over which the integral is a constant of motion, if the Lie derivative of w satisfies certain conditions. Such surfaces can be utilised for investigating the qualitative properties of a flow in the absence of invariance over all p-surfaces. We have also discussed the conditions for line preservation and surface preservation of vector fields. We see that the surface preservation need not imply the line preservation. We have given some examples which illustrate the above results. The study given in this thesis is a continuation of that started by Vedan et.el. As mentioned earlier, they have used a four dimensional space-time manifold to obtain invariants of flow from variational formulation and application of Noether's theorem. This was from the point of view of hydrodynamic stability studies using Arnold's method. The use of a four dimensional manifold has great significance in the study of knots and links. In the context of hydrodynamics, helicity is a measure of knottedness of vortex lines. We are interested in the use of differential forms in E4 in the study of vortex knots and links. The knowledge of surface invariants given in chapter 4 may also be utilised for the analysis of vortex and magnetic reconnections.

Optical response of two-dimensional few-electron concentric double quantum rings: A local-spin-density-functional theory study

We have investigated the dipole charge- and spin-density response of few-electron two-dimensional concentric nanorings as a function of the intensity of a erpendicularly applied magnetic field. We show that the dipole response displays signatures associated with the localization of electron states in the inner and outer ring favored by the perpendicularly applied magnetic field. Electron localization produces a more fragmented spectrum due to the appearance of additional edge excitations in the inner and outer ring.

High-Speed Semiconductor Lasers based on Low-Dimensional Active Materials for Optical Telecommunication

The scope of this work is the fundamental growth, tailoring and characterization of self-organized indium arsenide quantum dots (QDs) and their exploitation as active region for diode lasers emitting in the 1.55 µm range. This wavelength regime is especially interesting for long-haul telecommunications as optical fibers made from silica glass have the lowest optical absorption. Molecular Beam Epitaxy is utilized as fabrication technique for the quantum dots and laser structures. The results presented in this thesis depict the first experimental work for which this reactor was used at the University of Kassel. Most research in the field of self-organized quantum dots has been conducted in the InAs/GaAs material system. It can be seen as the model system of self-organized quantum dots, but is not suitable for the targeted emission wavelength. Light emission from this system at 1.55 µm is hard to accomplish. To stay as close as possible to existing processing technology, the In(AlGa)As/InP (100) material system is deployed. Depending on the epitaxial growth technique and growth parameters this system has the drawback of producing a wide range of nano species besides quantum dots. Best known are the elongated quantum dashes (QDash). Such structures are preferentially formed, if InAs is deposited on InP. This is related to the low lattice-mismatch of 3.2 %, which is less than half of the value in the InAs/GaAs system. The task of creating round-shaped and uniform QDs is rendered more complex considering exchange effects of arsenic and phosphorus as well as anisotropic effects on the surface that do not need to be dealt with in the InAs/GaAs case. While QDash structures haven been studied fundamentally as well as in laser structures, they do not represent the theoretical ideal case of a zero-dimensional material. Creating round-shaped quantum dots on the InP(100) substrate remains a challenging task. Details of the self-organization process are still unknown and the formation of the QDs is not fully understood yet. In the course of the experimental work a novel growth concept was discovered and analyzed that eases the fabrication of QDs. It is based on different crystal growth and ad-atom diffusion processes under supply of different modifications of the arsenic atmosphere in the MBE reactor. The reactor is equipped with special valved cracking effusion cells for arsenic and phosphorus. It represents an all-solid source configuration that does not rely on toxic gas supply. The cracking effusion cell are able to create different species of arsenic and phosphorus. This constitutes the basis of the growth concept. With this method round-shaped QD ensembles with superior optical properties and record-low photoluminescence linewidth were achieved. By systematically varying the growth parameters and working out a detailed analysis of the experimental data a range of parameter values, for which the formation of QDs is favored, was found. A qualitative explanation of the formation characteristics based on the surface migration of In ad-atoms is developed. Such tailored QDs are finally implemented as active region in a self-designed diode laser structure. A basic characterization of the static and temperature-dependent properties was carried out. The QD lasers exceed a reference quantum well laser in terms of inversion conditions and temperature-dependent characteristics. Pulsed output powers of several hundred milli watt were measured at room temperature. In particular, the lasers feature a high modal gain that even allowed cw-emission at room temperature of a processed ridge wave guide device as short as 340 µm with output powers of 17 mW. Modulation experiments performed at the Israel Institute of Technology (Technion) showed a complex behavior of the QDs in the laser cavity. Despite the fact that the laser structure is not fully optimized for a high-speed device, data transmission capabilities of 15 Gb/s combined with low noise were achieved. To the best of the author`s knowledge, this renders the lasers the fastest QD devices operating at 1.55 µm. The thesis starts with an introductory chapter that pronounces the advantages of optical fiber communication in general. Chapter 2 will introduce the fundamental knowledge that is necessary to understand the importance of the active region`s dimensions for the performance of a diode laser. The novel growth concept and its experimental analysis are presented in chapter 3. Chapter 4 finally contains the work on diode lasers.

Magnetic interactions between transition metal impurities and clusters mediated by low-dimensional metallic hosts: A first principles theoretical investigation

The magnetic properties and interactions between transition metal (TM) impurities and clusters in low-dimensional metallic hosts are studied using a first principles theoretical method. In the first part of this work, the effect of magnetic order in 3d-5d systems is addressed from the perspective of its influence on the enhancement of the magnetic anisotropy energy (MAE). In the second part, the possibility of using external electric fields (EFs) to control the magnetic properties and interactions between nanoparticles deposited at noble metal surfaces is investigated. The influence of 3d composition and magnetic order on the spin polarization of the substrate and its consequences on the MAE are analyzed for the case of 3d impurities in one- and two-dimensional polarizable hosts. It is shown that the MAE and easy- axis of monoatomic free standing 3d-Pt wires is mainly determined by the atomic spin-orbit (SO) coupling contributions. The competition between ferromagnetic (FM) and antiferromagnetic (AF) order in FePtn wires is studied in detail for n=1-4 as a function of the relative position between Fe atoms. Our results show an oscillatory behavior of the magnetic polarization of Pt atoms as a function of their distance from the magnetic impurities, which can be correlated to a long-ranged magnetic coupling of the Fe atoms. Exceptionally large variations of the induced spin and orbital moments at the Pt atoms are found as a function of concentration and magnetic order. Along with a violation of the third Hund’s rule at the Fe sites, these variations result in a non trivial behavior of the MAE. In the case of TM impurities and dimers at the Cu(111), the effects of surface charging and applied EFs on the magnetic properties and substrate-mediated magnetic interactions have been investigated. The modifications of the surface electronic structure, impurity local moments and magnetic exchange coupling as a result of the EF-induced metallic screening and charge rearrangements are analysed. In a first study, the properties of surface substitutional Co and Fe impurities are investigated as a function of the external charge per surface atom q. At large inter-impurity distances the effective magnetic exchange coupling ∆E between impurities shows RKKY-like oscillations as a function of the distance which are not significantly affected by the considered values of q. For distances r < 10 Å, important modifications in the magnitude of ∆E, involving changes from FM to AF coupling, are found depending non-monotonously on the value and polarity of q. The interaction energies are analysed from a local perspective. In a second study, the interplay between external EF effects, internal magnetic order and substrate-mediated magnetic coupling has been investigated for Mn dimers on Cu(111). Our calculations show that EF (∼ 1eV/Å) can induce a switching from AF to FM ground-state magnetic order within single Mn dimers. The relative coupling between a pair of dimers also shows RKKY-like oscillations as a function of the inter-dimer distance. Their effective magnetic exchange interaction is found to depend significantly on the magnetic order within the Mn dimers and on their relative orientation on the surface. The dependence of the substrate-mediated interaction on the magnetic state of the dimers is qualitatively explained in terms of the differences in the scattering of surface electrons. At short inter-dimer distances, the ground-state configuration is determined by an interplay between exchange interactions and EF effects. These results demonstrate that external surface charging and applied EFs offer remarkable possibilities of manipulating the sign and strength of the magnetic coupling of surface supported nanoparticles.

Dimensional structure of the Brief Symptom Inventory with Spanish college students. 'Estructura dimensional del Brief Symptom Inventory con universitarios espa??oles'

Resumen tomado de la publicaci??n. Resumen tambi??n en ingl??s

Propiedades psicom??tricas y estructura dimensional de la adaptaci??n espa??ola del Cuestionario de Estrategias de Afrontamiento en Competici??n Deportiva

Resumen tomado de la publicaci??n

Exercise sheet 4

Exercises and solutions in LaTex

Exercise sheet 4 pdf

Exercises and solutions in PDF

Three substituted 4-pyrazolylbenzoates: hydrogen-bonded supramolecular structures in one, two and three dimensions

The molecules of ethyl 4-(5-amino-3-methyl-1H-pyrazol-1yl) benzoate, C13H15N3O2, are linked by two independent N-H center dot center dot center dot O hydrogen bonds into a chain of edge-fused and alternating R-4(2)(8) and R-2(2)(20) rings. A combination of N-H center dot center dot center dot N and N-H center dot center dot center dot O hydrogen bonds links the molecules of methyl 4-(5-amino-3-tert-butyl-1H-pyrazol-1-yl) benzoate, C15H19N3O2, into sheets of alternating R-2(2)(20) and R-6(6)(32) rings. In 4-(5-amino-3-methyl-1H-pyrazol-1-yl) benzoic acid monohydrate, C11H11N3O2 center dot H2O, the molecular components are linked into a three-dimensional framework structure by a combination of five independent hydrogen bonds, two of O-H center dot center dot center dot N type and one each of O-H center dot center dot center dot O, N-H center dot center dot center dot O and N-H center dot center dot center dot N types

Problemas sobre metrología dimensional.

La obra plantea una serie de cien problemas solucionados, seleccionados como los más significativos de los siguientes temas: Unidades (problemas 1-2-3), Dilataciones (p. 4-5-6-7-8-9-10), Errores (p. 11-12-13), Sensibilidades (p. 14-15-16-17-18), Ajustes y Tolerancias (p. 19-20-21-22-23-24-25-26-27-28), Redondez (p. 29-30), Rugosidad (p. 31-32-33-34-35-36-37-38-39), Pie de rey (p. 40-41-42-43-44-45), Palmer (p. 46-47-47-48-49-50-51-52), Proyector de perfiles (p. 53-54-55-56-57-58-59), Comparadores (p. 60-61-62-63-64-65-66), Medidad angulares (p. 67-68-69-70-71-72), Control de radios de cilindros y esferas (73-74-75-76-77-78-79-80), Verificación de engranajes (p. 81-82-83-84-85-86-87-88-89), Verificación de roscas (p. 90-91-92-93-94-95-96-97-98-99), Verificación de máquinas herramientas (p. 100).

Efecto de diferentes agresivos químicos sobre la estabilidad dimensional de diversas resinas termoendurecibles reforzadas.

Se trata de un estudio sobre las alteraciones y sustituciones de los materiales clásicos por materiales de nueva factura. La metodología seguida ha partido de analizar los distintos materiales a través de un estudio de pruebas a los mismos. Finalmente se concluye con la importancia y necesidad de continuar en esta línea de investigación debido a la sustitución paulatina del material aluminio por los materiales plásticos.