Syntheses, EPR spectral studies and crystal structures of manganese(II) complexes of neutral N,N donor bidentate Schiff bases and azide/thiocyanate as coligand

Four manganese(II) complexes Mn2(paa)2(N3)4 (1), [Mn(paa)2(NCS)2] 3/2H2O (2), Mn(papea)2(NCS)2 (3), [Mn(dpka)2(NCS)2] 1/2H2O(4) of three neutral N,N donor bidentate Schiff bases were synthesized and physico- chemically characterized by means of partial elemental analyses, electronic, infrared and EPR spectral studies. Compounds 3 and 4 were obtained as single crystals suitable for X-ray diffraction. Compound 4 recrystallized as Mn(dpka)2(NCS)2. Both the compounds crystallized in the monoclinic space groups P21 for 3 and C2/c for 4. Manganese(II) is found to be in a distorted octahedral geometry in both the monomeric complexes with thiocyanate anion as a terminal ligand coordinating through the nitrogen atom. EPR spectra in DMF solutions at 77 K show hyperfine sextets with low intensity forbidden lines lying between each of the two main hyperfine lines and the zero field splitting parameters (D and E) were calculated.

Design and Development of Spectral Signature Based Chipless RFID Tags

The main objective of this thesis is to design and develop spectral signature based chipless RFID tags Multiresonators are essential component of spectral signature based chipless tags. To enhance the data coding capacity in spectral signature based tags require large number of resonances in a limited bandwidth. The frequency of the resonators have to be close to each other. To achieve this condition, the quality factor of each resonance needs to be high. The thesis discusses about various types of multiresonators, their practical implementation and how they can be used in design. Encoding of data into spectral domain is another challenge in chipless tag design. Here, the technique used is the presence or absence encoding technique. The presence of a resonance is used to encode Logic 1 and absence of a speci c resonance is used to encode Logic 0. Di erent types of multiresonators such as open stub multiresonators, coupled bunch hairpin resonators and shorted slot ground ring resonator are proposed in this thesis.

Experimentelle und numerische Untersuchungen zur Dispersion von Dichteströmungen in einem stochastischen Modellaquifer

Es ist bekannt, dass die Dichte eines gelösten Stoffes die Richtung und die Stärke seiner Bewegung im Untergrund entscheidend bestimmen kann. Eine Vielzahl von Untersuchungen hat gezeigt, dass die Verteilung der Durchlässigkeiten eines porösen Mediums diese Dichteffekte verstärken oder abmindern kann. Wie sich dieser gekoppelte Effekt auf die Vermischung zweier Fluide auswirkt, wurde in dieser Arbeit untersucht und dabei das experimentelle sowohl mit dem numerischen als auch mit dem analytischen Modell gekoppelt. Die auf der Störungstheorie basierende stochastische Theorie der macrodispersion wurde in dieser Arbeit für den Fall der transversalen Makodispersion. Für den Fall einer stabilen Schichtung wurde in einem Modelltank (10m x 1.2m x 0.1m) der Universität Kassel eine Serie sorgfältig kontrollierter zweidimensionaler Experimente an einem stochastisch heterogenen Modellaquifer durchgeführt. Es wurden Versuchsreihen mit variierenden Konzentrationsdifferenzen (250 ppm bis 100 000 ppm) und Strömungsgeschwindigkeiten (u = 1 m/ d bis 8 m/d) an drei verschieden anisotrop gepackten porösen Medien mit variierender Varianzen und Korrelationen der lognormal verteilten Permeabilitäten durchgeführt. Die stationäre räumliche Konzentrationsausbreitung der sich ausbreitenden Salzwasserfahne wurde anhand der Leitfähigkeit gemessen und aus der Höhendifferenz des 84- und 16-prozentigen relativen Konzentrationsdurchgang die Dispersion berechnet. Parallel dazu wurde ein numerisches Modell mit dem dichteabhängigen Finite-Elemente-Strömungs- und Transport-Programm SUTRA aufgestellt. Mit dem kalibrierten numerischen Modell wurden Prognosen für mögliche Transportszenarien, Sensitivitätsanalysen und stochastische Simulationen nach der Monte-Carlo-Methode durchgeführt. Die Einstellung der Strömungsgeschwindigkeit erfolgte - sowohl im experimentellen als auch im numerischen Modell - über konstante Druckränder an den Ein- und Auslauftanks. Dabei zeigte sich eine starke Sensitivität der räumlichen Konzentrationsausbreitung hinsichtlich lokaler Druckvariationen. Die Untersuchungen ergaben, dass sich die Konzentrationsfahne mit steigendem Abstand von der Einströmkante wellenförmig einem effektiven Wert annähert, aus dem die Makrodispersivität ermittelt werden kann. Dabei zeigten sich sichtbare nichtergodische Effekte, d.h. starke Abweichungen in den zweiten räumlichen Momenten der Konzentrationsverteilung der deterministischen Experimente von den Erwartungswerten aus der stochastischen Theorie. Die transversale Makrodispersivität stieg proportional zur Varianz und Korrelation der lognormalen Permeabilitätsverteilung und umgekehrt proportional zur Strömungsgeschwindigkeit und Dichtedifferenz zweier Fluide. Aus dem von Welty et al. [2003] mittels Störungstheorie entwickelten dichteabhängigen Makrodispersionstensor konnte in dieser Arbeit die stochastische Formel für die transversale Makrodispersion weiter entwickelt und - sowohl experimentell als auch numerisch - verifiziert werden.

MEMS-based Tunable Optical Filter Arrays for Nano-Spectrometer in the Visible Spectral Range

Optische Spektrometer sind bekannte Instrumente für viele Anwendungen in Life Sciences, Produktion und Technik aufgrund ihrer guten Selektivität und Sensitivität zusammen mit ihren berührungslosen Messverfahren. MEMS (engl. Micro-electro-mechanical system)-basierten Spektrometer werden als disruptive Technologie betrachtet, in der miniaturisierte Fabry-Pérot Filter als sehr attraktiv für die optische Kommunikation und 'Smart Personal Environments', einschließlich des medizinischen Anwendungen, zu nennen sind. Das Ziel dieser Arbeit ist, durchstimmbare Filter-Arrays mit kostengünstigen Technologien herzustellen. Materialien und technologische Prozesse, die für die Herstellung der Filter-Arrays benötigt werden, wurden untersucht. Im Rahmen dieser Arbeit, wurden durchstimmbare Fabry Pérot Filter-Arrays für den sichtbaren Spektralbereich untersucht, die als Nano-Spektrometer eingesetzt werden. Darüber hinaus wurde ein Modell der numerischen Simulation vorgestellt, die zur Ermittlung eines optimales geometrisches Designs verwendet wurde, wobei sich das Hauptaugenmerk der Untersuchung auf die Durchbiegung der Filtermembranen aufgrund der mechanischen Verspannung der Schichten richtet. Die geometrische Form und Größe der Filtermembranen zusammen mit der Verbindungsbrücken sind von entscheidender Bedeutung, da sie die Durchbiegung beeinflussen. Lange und schmale Verbindungsbrücken führen zur stärkeren Durchbiegung der Filtermembranen. Dieser Effekt wurde auch bei der Vergrößerung der Durchmesser der Membran beobachtet. Die Filter mit spiralige (engl. curl-bent) Verbindungsbrücken führten zu geringerer Deformation als die mit geraden oder gebogenen Verbindungsbrücken. Durchstimmbare Si3N4/SiO2 DBR-basierende Filter-Arrays wurden erfolgreich hergestellt. Eine Untersuchung über die UV-NIL Polymere, die als Opferschicht und Haltepfosten-Material der Filter verwendet wurden, wurde durchgeführt. Die Polymere sind kompatibel zu dem PECVD-Verfahren, das für die Spiegel-Herstellung verwendet wird. Die laterale Strukturierung der DBR-Spiegel mittels des RIE (engl. Reactive Ion Etching)-Prozesses sowie der Unterätz-Prozess im Sauerstoffplasma zur Entfernung der Opferschicht und zum Erreichen der Luftspalt-Kavität, wurden durchgeführt. Durchstimmbare Filter-Arrays zeigten einen Abstimmbereich von 70 nm bei angelegten Spannungen von weniger als 20 V. Optimierungen bei der Strukturierung von TiO2/SiO2 DBR-basierenden Filtern konnte erzielt werden. Mit der CCP (engl. Capacitively Coupling Plasma)-RIE, wurde eine Ätzrate von 20 nm/min erreicht, wobei Fotolack als Ätzmaske diente. Mit der ICP (engl. Inductively Coupling Plasma)-RIE, wurden die Ätzrate von mehr als 60 nm/min mit einem Verhältniss der Ar/SF6 Gasflüssen von 10/10 sccm und Fotolack als Ätzmasken erzielt. Eine Ätzrate von 80 bis 90 nm/min wurde erreicht, hier diente ITO als Ätzmaske. Ausgezeichnete geätzte Profile wurden durch den Ätzprozess unter Verwendung von 500 W ICP/300 W RF-Leistung und Ar/SF6 Gasflüsse von 20/10 sccm erreicht. Die Ergebnisse dieser Arbeit ermöglichen die Realisierung eines breiten Spektralbereichs der Filter-Arrays im Nano-Spektrometer.

Large-Size AlGaN/GaN HEMT Large-Signal Electrothermal Characterization and Modeling for Wireless Digital Communications

The rapid growth in high data rate communication systems has introduced new high spectral efficient modulation techniques and standards such as LTE-A (long term evolution-advanced) for 4G (4th generation) systems. These techniques have provided a broader bandwidth but introduced high peak-to-average power ratio (PAR) problem at the high power amplifier (HPA) level of the communication system base transceiver station (BTS). To avoid spectral spreading due to high PAR, stringent requirement on linearity is needed which brings the HPA to operate at large back-off power at the expense of power efficiency. Consequently, high power devices are fundamental in HPAs for high linearity and efficiency. Recent development in wide bandgap power devices, in particular AlGaN/GaN HEMT, has offered higher power level with superior linearity-efficiency trade-off in microwaves communication. For cost-effective HPA design to production cycle, rigorous computer aided design (CAD) AlGaN/GaN HEMT models are essential to reflect real response with increasing power level and channel temperature. Therefore, large-size AlGaN/GaN HEMT large-signal electrothermal modeling procedure is proposed. The HEMT structure analysis, characterization, data processing, model extraction and model implementation phases have been covered in this thesis including trapping and self-heating dispersion accounting for nonlinear drain current collapse. The small-signal model is extracted using the 22-element modeling procedure developed in our department. The intrinsic large-signal model is deeply investigated in conjunction with linearity prediction. The accuracy of the nonlinear drain current has been enhanced through several issues such as trapping and self-heating characterization. Also, the HEMT structure thermal profile has been investigated and corresponding thermal resistance has been extracted through thermal simulation and chuck-controlled temperature pulsed I(V) and static DC measurements. Higher-order equivalent thermal model is extracted and implemented in the HEMT large-signal model to accurately estimate instantaneous channel temperature. Moreover, trapping and self-heating transients has been characterized through transient measurements. The obtained time constants are represented by equivalent sub-circuits and integrated in the nonlinear drain current implementation to account for complex communication signals dynamic prediction. The obtained verification of this table-based large-size large-signal electrothermal model implementation has illustrated high accuracy in terms of output power, gain, efficiency and nonlinearity prediction with respect to standard large-signal test signals.

Optimization of the Mechanical and Optical Properties of Tunable Optical Sensor Arrays (TOSA) for a Nanospectrometer in the Visible and Near Infrared Spectral Range

Tunable Optical Sensor Arrays (TOSA) based on Fabry-Pérot (FP) filters, for high quality spectroscopic applications in the visible and near infrared spectral range are investigated within this work. The optical performance of the FP filters is improved by using ion beam sputtered niobium pentoxide (Nb2O5) and silicon dioxide (SiO2) Distributed Bragg Reflectors (DBRs) as mirrors. Due to their high refractive index contrast, only a few alternating pairs of Nb2O5 and SiO2 films can achieve DBRs with high reflectivity in a wide spectral range, while ion beam sputter deposition (IBSD) is utilized due to its ability to produce films with high optical purity. However, IBSD films are highly stressed; resulting in stress induced mirror curvature and suspension bending in the free standing filter suspensions of the MEMS (Micro-Electro-Mechanical Systems) FP filters. Stress induced mirror curvature results in filter transmission line degradation, while suspension bending results in high required filter tuning voltages. Moreover, stress induced suspension bending results in higher order mode filter operation which in turn degrades the optical resolution of the filter. Therefore, the deposition process is optimized to achieve both near zero absorption and low residual stress. High energy ion bombardment during film deposition is utilized to reduce the film density, and hence the film compressive stress. Utilizing this technique, the compressive stress of Nb2O5 is reduced by ~43%, while that for SiO2 is reduced by ~40%. Filters fabricated with stress reduced films show curvatures as low as 100 nm for 70 μm mirrors. To reduce the stress induced bending in the free standing filter suspensions, a stress optimized multi-layer suspension design is presented; with a tensile stressed metal sandwiched between two compressively stressed films. The stress in Physical Vapor Deposited (PVD) metals is therefore characterized for use as filter top-electrode and stress compensating layer. Surface micromachining is used to fabricate tunable FP filters in the visible spectral range using the above mentioned design. The upward bending of the suspensions is reduced from several micrometers to less than 100 nm and 250 nm for two different suspension layer combinations. Mechanical tuning of up to 188 nm is obtained by applying 40 V of actuation voltage. Alternatively, a filter line with transmission of 65.5%, Full Width at Half Maximum (FWHM) of 10.5 nm and a stopband of 170 nm (at an output wavelength of 594 nm) is achieved. Numerical model simulations are also performed to study the validity of the stress optimized suspension design for the near infrared spectral range, wherein membrane displacement and suspension deformation due to material residual stress is studied. Two bandpass filter designs based on quarter-wave and non-quarter-wave layers are presented as integral components of the TOSA. With a filter passband of 135 nm and a broad stopband of over 650 nm, high average filter transmission of 88% is achieved inside the passband, while maximum filter transmission of less than 1.6% outside the passband is achieved.

Selecting Relevant Genes with a Spectral Approach

Array technologies have made it possible to record simultaneously the expression pattern of thousands of genes. A fundamental problem in the analysis of gene expression data is the identification of highly relevant genes that either discriminate between phenotypic labels or are important with respect to the cellular process studied in the experiment: for example cell cycle or heat shock in yeast experiments, chemical or genetic perturbations of mammalian cell lines, and genes involved in class discovery for human tumors. In this paper we focus on the task of unsupervised gene selection. The problem of selecting a small subset of genes is particularly challenging as the datasets involved are typically characterized by a very small sample size ?? the order of few tens of tissue samples ??d by a very large feature space as the number of genes tend to be in the high thousands. We propose a model independent approach which scores candidate gene selections using spectral properties of the candidate affinity matrix. The algorithm is very straightforward to implement yet contains a number of remarkable properties which guarantee consistent sparse selections. To illustrate the value of our approach we applied our algorithm on five different datasets. The first consists of time course data from four well studied Hematopoietic cell lines (HL-60, Jurkat, NB4, and U937). The other four datasets include three well studied treatment outcomes (large cell lymphoma, childhood medulloblastomas, breast tumors) and one unpublished dataset (lymph status). We compared our approach both with other unsupervised methods (SOM,PCA,GS) and with supervised methods (SNR,RMB,RFE). The results clearly show that our approach considerably outperforms all the other unsupervised approaches in our study, is competitive with supervised methods and in some case even outperforms supervised approaches.

Weighted Logratio Biplots, Correspondence Analysis and Spectral Maps

Starting with logratio biplots for compositional data, which are based on the principle of subcompositional coherence, and then adding weights, as in correspondence analysis, we rediscover Lewi's spectral map and many connections to analyses of two-way tables of non-negative data. Thanks to the weighting, the method also achieves the property of distributional equivalence

Quantification of the bond-angle dispersion by Raman spectroscopy and the strain energy of amorphous silicon

A thorough critical analysis of the theoretical relationships between the bond-angle dispersion in a-Si, Δθ, and the width of the transverse optical Raman peak, Γ, is presented. It is shown that the discrepancies between them are drastically reduced when unified definitions for Δθ and Γ are used. This reduced dispersion in the predicted values of Δθ together with the broad agreement with the scarce direct determinations of Δθ is then used to analyze the strain energy in partially relaxed pure a-Si. It is concluded that defect annihilation does not contribute appreciably to the reduction of the a-Si energy during structural relaxation. In contrast, it can account for half of the crystallization energy, which can be as low as 7 kJ/mol in defect-free a-Si

Anisotropic dispersion, space competition, and the slowdown of the Neolithic transition

The front speed of the Neolithic (farmer) spread in Europe decreased as it reached Northern latitudes, where the Mesolithic (huntergatherer) population density was higher. Here, we describe a reaction diffusion model with (i) an anisotropic dispersion kernel depending on the Mesolithic population density gradient and (ii) a modified population growth equation. Both effects are related to the space available for the Neolithic population. The model is able to explain the slowdown of the Neolithic front as observed from archaeological data

Perceptual correlates of spectral changes in complex tones

This paper reviews a study of tonal precepts such as pitch and timbre as a means of facilitating auditory discrimination tasks.

Evaluation of suitable spectral intervals for near-IR laboratory detection of water vapour continuum absorption

The water vapour continuum absorption is an important component of molecular absorption of radiation in atmosphere. However, uncertainty in knowledge of the value of the continuum absorption at present can achieve 100% in different spectral regions leading to an error in flux calculation up to 3-5 W/m2 global mean. This work uses line-by-line calculations to reveal the best spectral intervals for experimental verification of the CKD water vapour continuum models in the currently least studied near-infrared spectral region. Possible sources of errors in continuum retrieval taken into account in the simulation include the sensitivity of laboratory spectrometers and uncertainties in the spectral line parameters in HITRAN-2004 and Schwenke-Partridge database. It is shown that a number of micro-windows in near-IR can be used at present for laboratory detection of the water vapour continuum with estimated accuracy from 30 to 5%.