Synthesis and characterization of structurally well-defined polymer-layered silicate nanocomposites

Zusammenfassung Nanokomposite aus Polymeren und Schichtsilikaten werden zumeist auf der Basis natürlicher Tone wie Montmorillonit hergestellt. Für NMR- und EPR-Untersuchungen der Tensidschicht, die das Silikat mit dem Polymer kompatibilisiert, ist der Eisengehalt natürlicher Tone jedoch abträglich, weil er zu einer Verkürzung der Relaxationszeiten und zu einer Linienverbreiterung in den Spektren führt. Dieses Problem konnte überwunden werden, indem als Silikatkomponente eisenfreies, strukturell wohldefiniertes Magadiit hydrothermal synthetisiert und für die Kompositbildung eingesetzt wurde. Die Morphologie des Magadiits wurde durch Rasterelektronenmikroskopie charakterisiert und der Interkalationsgrad von schmelzinterkalierten Polymer-Nanokompositen wurde durch Weitwinkelröntgenstreuung bestimmt. Polymere mit Carbonylgruppen scheinen leichter zu interkalieren als solche ohne Carbonylgruppen. Polycaprolacton interkalierte sowohl in Oragnomagadiite auf der Basis von Ammoniumtensiden als auch in solche auf der Basis von Phosphoniumtensiden. Die Dynamik auf einer Nanosekundenzeitskala und die Struktur der Tensidschicht wurden mittels ortsspezifisch spinmarkierter Tensidsonden unter Nutzung von Dauerstrich- (CW) und Puls-Methoden der elektronenparamagnetischen Resonanzspektroskopie (EPR) untersucht. Zusätzlich wurde die statische 2H-Kernmagnetresonanz (NMR) an spezifisch deuterierten Tensiden angewendet, um die Tensiddynamik auf einer komplementären Zeitskala zwischen Mikrosekunden und Millisekunden zu erfassen. Sowohl die CW-EPR- als auch die 2H-NMR-Ergebnisse zeigen eine Beschleunigung der Tensiddynamik durch Interkalation von Polycaprolacton auf, während sich in den nichtinterkalierten Mikrokompositen mit Polystyrol die Tensiddynamik verlangsamt. Die Rotationskorrelationszeiten und Aktivierungsenergien offenbaren verschiedene Regime der Tensiddynamik. In Polystyrol-Mikrokompositen entspricht die Übergangstemperatur zwischen den Regimen der Glasübergangstemperatur von Polystyrol, während sie in Polycaprolacton-Nanokompositen bei der Schmelztemperatur von Polycaprolacton liegt. Durch die erhebliche Verlängerung der Elektronenspin-Relaxationszeiten bei Verwendung von eisenfreiem Magadiit können Messdaten hoher Qualität mit Puls-EPR-Experimenten erhalten werden. Insebsondere wurden die Vier-Puls-Elektron-Elektron-Doppelresonanz (DEER), die Elektronenspinechoenveloppenmodulation (ESEEM) und die Elektronen-Kern-Doppelresonanz (ENDOR) an spinmarkierten sowie spezifisch deuterierten Tensiden angewandt. Die ENDOR-Ergebnisse legen ein Model der Tensidschicht nahe, in dem zusätzlich zu den Oberflächenlagen auf dem Silikat eine wohldefinierte mittlere Lage existiert. Dieses Modell erklärt auch Verdünnungseffekte durch das Polymer in Kompositen mit Polycaprolacton und Polystyrol. Die umfangreiche Information aus den Magnetresonanztechniken ergänzt die Information aus konventionellen Charakterisierungstechniken wie Röntgendiffraktion und Transmissionselektronenmikroskopie und führt so zu einem detaillierteren Bild der Struktur und Dynamik der Tensidschicht in Nanokompositen aus Polymeren und Schichtsilikaten.

Untersuchung der Struktur und Assemblierung des Lichtsammelkomplexes II höherer Pflanzen mittels elektronenparamagnetischer Resonanz (EPR)

Der Haupt-Lichtsammelkomplex (LHCII) des Photosyntheseapparates höherer Pflanzen gehört zu den häufigsten Membranproteinen der Erde. Seine Kristallstruktur ist bekannt. Das Apoprotein kann rekombinant in Escherichia coli überexprimiert und somit molekularbiologisch vielfältig verändert werden. In Detergenzlösung besitzt das denaturierte Protein die erstaunliche Fähigkeit, sich spontan zu funktionalen Protein-Pigment-Komplexen zu organisieren, welche strukturell nahezu identisch sind mit nativem LHCII. Der Faltungsprozess findet in vitro im Zeitbereich von Sekunden bis Minuten statt und ist abhängig von der Bindung der Cofaktoren Chlorophyll a und b sowie verschiedenen Carotinoiden.rn Diese Eigenschaften machen LHCII besonders geeignet für Strukturuntersuchungen mittels der elektronenparamagnetischen Resonanz (EPR)-Spektrokopie. Diese setzt eine punktspezifische Spinmarkierung des LHCII voraus, die in dieser Arbeit zunächst optimiert wurde. Einschließlich der Beiträge Anderer stand eine breite Auswahl von über 40 spinmarkierten Mutanten des LHCII bereit, einen N-terminalen „Cys walk“ eingeschlossen. Weder der hierfür notwendige Austausch einzelner Aminosäuren noch die Anknüpfung des Spinmarkers beeinträchtigten die Funktion des LHCII. Zudem konnte ein Protokoll zur Präparation heterogen spinmarkierter LHCII-Trimere entwickelt werden, also von Trimeren, die jeweils nur ein Monomer mit einer Spinmarkierung enthalten.rn Spinmarkierte Proben des Detergenz-solubilisierten LHCII wurden unter Verwendung verschiedener EPR-Techniken strukturell analysiert. Als besonders aussagekräftig erwies sich die Messung der Wasserzugänglichkeit einzelner Aminosäurepositionen anhand der Electron Spin Echo Envelope Modulation (ESEEM). In Kombination mit der etablierten Double Electron-Electron Resonance (DEER)-Technik zur Detektion von Abständen zwischen zwei Spinmarkern wurde der membranständige Kernbereich des LHCII in Lösung eingehend untersucht und strukturell der Kristallstruktur für sehr ähnlich befunden. Die Vermessung kristallographisch nicht erfasster Bereiche nahe dem N-Terminus offenbarte die schon früher detektierte Strukturdynamik der Domäne in Abhängigkeit des Oligomerisierungsgrades. Der neue, noch zu vervollständigende Datensatz aus Abstandsverteilungen und ESEEM-Wasserzugänglichkeiten monomerer wie trimerer Proben sollte in naher Zukunft die sehr genaue Modellierung der N-terminalen Domäne des LHCII ermöglichen.rn In einem weiteren Abschnitt der Arbeit wurde die Faltung des LHCII-Apoproteins bei der LHCII-Assemblierung in vitro untersucht. Vorausgegangene fluoreszenzspektroskopi-sche Arbeiten hatten gezeigt, dass die Bindung von Chlorophyll a und b in aufeinanderfolgenden Schritten im Zeitbereich von weniger als einer Minute bzw. mehreren Minuten erfolgten. Sowohl die Wasserzugänglichkeit einzelner Aminosäurepositionen als auch Spin-Spin-Abstände änderten sich in ähnlichen Zeitbereichen. Die Daten deuten darauf hin, dass die Ausbildung der mittleren Transmembran-Helix mit der schnelleren Chlorophyll-a-Bindung einhergeht, während sich die Superhelix aus den beiden anderen Transmembranhelices erst im langsameren Schritt, zusammen mit der Chlorophyll-b-Bindung, ausbildet.rn

Synthetic strategies of new spin-labelled supramolecular systems

Molecular recognition and self-assembly represent fundamental issues for the construction of supramolecular systems, structures in which the components are held together through non-covalent interactions. The study of host-guest complexes and mechanical interlocked molecules, important examples in this field, is necessary in order to characterize self-assembly processes, achieve more control over the molecular organization and develop sophisticated structures by using properly designed building blocks. The introduction of paramagnetic species, or spin labelling, represents an attractive opportunity that allows their detection and characterization by the Electron Spin Resonance spectroscopy, a valuable technique that provides additional information to those obtained by traditional methods. In this Thesis, recent progresses in the design and the synthesis of new paramagnetic host-guest complexes and rotaxanes characterized by the presence of nitroxide radicals and their investigation by ESR spectroscopy are reported. In Chapter 1 a brief overview of the principal concepts of supramolecular chemistry, the spin labelling approach and the development of ESR methods applied to paramagnetic systems are described. Chapter 2 and 3 are focused on the introduction of radicals in macrocycles as Cucurbiturils and Pillar[n]arenes, due to the interesting binding properties and the potential employment in rotaxanes, in order to investigate their structures and recognition properties. Chapter 4 deals with one of the most studied mechanical interlocked molecules, the bistable [2]rotaxane reported by Stoddart and Heath based on the ciclobis (paraquat-p-phenylene) CBPQT4+, that represents a well known example of molecular switch driven by external stimuli. The spin labelling of analogous architectures allows the monitoring by ESR spectroscopy of the switch mechanism involving the ring compound by tuning the spin exchange interaction. Finally, Chapter 5 contains the experimental procedures used for the synthesis of some of the compounds described in Chapter 2-4.

Beryllium, thorium and protactinium isotope ratios in sediments from the Galapagos microplate

Biogenic particle fluxes from highly productive surface waters, boundary scavenging, and hydrothermal activity are the main factors influencing the deposition of radionuclides in the area of the Galapagos microplate, eastern Equatorial Pacific. In order to evaluate the importance of these three processes throughout the last 100 kyr, concentrations of the radionuclides 10Be, 230Th, and 231Pa, and of Mn and Fe were measured at high resolution in sediment samples from two gravity cores KLH 068 and KLH 093. High biological productivity in the surface waters overlying the investigated area has led to 10Be and 231Pa fluxes exceeding production during at least the last 30 kyr and probably the last 100 kyr. However, during periods of high productivity at the up welling centers off Peru and extension of the equatorial high-productivity zone, a relative loss of 10Be and 231Pa may have occurred in these sediment cores because of boundary scavenging. The effects of hydrothermal activity were investigated by comparing the 230Thex concentrations to the Mn/Fe ratios and by comparing the fluxes of 230Th and 10Be which exceed production. The results suggest an enhanced hydrothermal influence during isotope stages 4 and 5 and to a lesser extent during isotope stage 1 in core KLH 093. During isotope stages 2 and 3, the hydrothermal supply of Mn was deposited elsewhere, probably because of changes in current regime or deep water oxygenation. A strong increase of the Mn/Fe ratio at the beginning of climatic stage 1 which is not accompanied by an increase of the 230Thex concentration is interpreted to be an effect of Mn remobilization and reprecipitation in the sediment.

Matriz de Butler de Banda Ancha en Banda X para Antenas Reconfigurables

The work presented in this document shows the complete simulation of a Butler matrix. This circuit will be used in the feeding of a steerable on board antenna in X band. The antenna consists of printed elements grouped in an array. This terminal works in a frequency band from 7.25 up to 8.4 GHz (15% of bandwidth), where both bands, reception (7.25 – 7.75 GHz) and transmission (7.9–8.4 GHz), are included simultaneously. The whole antenna reaches 31 dBi, with a beam width smaller than 10º and a dual circular polarization. This antenna also includes the capability of electronic steering in elevation ±45º and mechanically motorized junction 360º in azimuth.

An investigation of the nitroxide-mediated preirradiation grafting of styrene onto PFA

Simultaneous and preirradiation grafting of styrene onto fluorinated polyolefins does not enable control of the molecular weights or polydispersities of the styrene grafts. The nitroxide-mediated grafting of styrene onto PFA with TEMPO and TEISO using a preirradiation method has been investigated as a means of controlling the graft properties and especially to produce grafts with improved suitability for SPOC. The yields of graft were found to be in the range 15-20% for nitroxide concentrations between 5 x 10(-3) and 2 x 10(-2) M and were similar for the two nitroxides studied. Raman mapping was used to obtain the depth profile for the styrene grafts. The grafts were found to be principally located within the PFA substrate, and little graft was formed at the PFA surface. Fmoc loading tests were performed to assess the suitability of the grafted PFA as a support for SPOC, but these showed no significant loading was achieved, thus indicating that the graft properties are not suitable for SPOC. However, the study has important implications for the applications of PFA-grafted polymers in other areas, such as chemically resistant ion-exchange and separation membranes.

Modeling of optical detection of spin-polarized carrier injection into light-emitting devices

We investigate the emission of multimodal polarized light from light emitting devices due to spin-aligned carrier injection. The results are derived through operator Langevin equations, which include thermal and carrier-injection fluctuations, as well as nonradiative recombination and electronic g-factor temperature dependence. We study the dynamics of the optoelectronic processes and show how the temperature-dependent g factor and magnetic field affect the degree of polarization of the emitted light. In addition, at high temperatures, thermal fluctuation reduces the efficiency of the optoelectronic detection method for measuring the degree of spin polarization of carrier injection into nonmagnetic semicondutors.

Archaeology and age of a new hominin from Flores in eastern Indonesia

Excavations at Liang Bua, a large limestone cave on the island of Flores in eastern Indonesia, have yielded evidence for a population of tiny hominins, sufficiently distinct anatomically to be assigned to a new species, Homo floresiensis(1). The finds comprise the cranial and some post-cranial remains of one individual, as well as a premolar from another individual in older deposits. Here we describe their context, implications and the remaining archaeological uncertainties. Dating by radiocarbon (C-14), luminescence, uranium-series and electron spin resonance (ESR) methods indicates that H. floresiensis existed from before 38,000 years ago (kyr) until at least 18 kyr. Associated deposits contain stone artefacts and animal remains, including Komodo dragon and an endemic, dwarfed species of Stegodon. H. floresiensis originated from an early dispersal of Homo erectus ( including specimens referred to as Homo ergaster and Homo georgicus)(1) that reached Flores, and then survived on this island refuge until relatively recently. It overlapped significantly in time with Homo sapiens in the region(2,3), but we do not know if or how the two species interacted.

U-series dating of Locality 15 at Zhoukoudian, China, and implications for hominid evolution

This paper reports U-series dates on speleothem samples from Locality 15 at Zhoukoudian, one of the richest Paleolithic sites in northern China. The age of the lower part of Layer 2 is securely bracketed between 155,000 and 284,000 yr. The underlying Layer 3 dates back at least 284,000 yr. Layer 4, further below, should be older still, possibly by a cycle on the SPECMAP time scale before 284,000 yr ago. These ages, much greater than the previous estimates of 110,000-140,000 yr from U-series and electron spin resonance dating of fossil teeth, suggest that Locality 15 was broadly contemporaneous with Locality 4 (New Cave) and with the uppermost strata of Locality 1 (Peking Man site). The physical evolution and cultural development evidenced by the timing of the Zhoukoudian localities are in line with the opinion of Chinese anthropologists for a regional transition from Homo erectus to archaic Homo sapiens. (C) 2004 University of Washington. All rights reserved.

The physical and chemical properties of eumelanin

In this article, we review the current state of knowledge concerning the physical and chemical properties of the eumelanin pigment. We examine properties related to its photoprotective functionality, and draw the crucial link between fundamental molecular structure and observable macroscopic behaviour. Where necessary, we also briefly review certain aspects of the pheomelanin literature to draw relevant comparison. A full understanding of melanin function, and indeed its role in retarding or promoting the disease state, can only be obtained through a full mapping of key structure-property relationships in the main pigment types. We are engaged in such an endeavor for the case of eumelanin.

Evaluation of TerraSAR-X Observations for Wetland InSAR Application

This paper assesses the potential of using spaceborne X-band synthetic aperture radar (SAR) data for monitoring water-level changes over wetlands. Our analysis is based on three sets of TerraSAR-X (TSX) observations acquired over South Florida's Everglades wetlands during an eight-month period in 2008. The first set was acquired in single HH polarization stripmap mode over our northern study area, consisting of managed wetlands and urban environments. The second set was acquired in dual-polarization stripmap mode over the western half of the same area, consisting mostly of managed wetlands. The third set was also acquired with dual-polarization stripmap mode over our southern study area, consisting of natural flow freshand salt-water wetlands in the southern Everglades. The first data set was used for a proof-of-concept study to verify that X-band data can generate coherent interferograms in wetland areas. Interferometric processing of this data set shows a high level of coherence (> 0.35) over both wetland and urban regions, maintaining interferometric phase in all three interferograms spanning 11 days. Surprisingly, phase is maintained over some of the wetlands even for interferograms spanning 33 days. The other two data sets were used to evaluate interferometric coherence of all four polarization modes and to determine dominant scattering mechanism in each wetland environment. Our results show high coherence values (> 0.4) in all polarization modes, with highest values in HH, then VV, and lowest in HV or VH. Interferograms calculated from multipolarization data show very similar fringe patterns regardless of the polarization type, suggesting that the phase information in all polarization data reflects water-level changes in wetlands and that volume scattering may be less important than commonly believed. We also used the two multipolarization data sets to conduct the Pauli decomposition, finding a strong dependence of scattering mechanism on vegetation t- - ype. The high interferometric coherence level of all polarization data suggests that a significant part of the X-band scattered signal interacts with lower sections of the vegetation (trunks and branches), because scattering from wind-affected canopies cannot support such a high coherence level. The high spatial resolution of TSX, combined with its 11-day repeat orbit, makes this X-band sensor surprisingly suitable for wetland interferometric SAR applications.

First-principles calculation of alloy scattering in GexSi1-x

First-principles electronic structure methods are used to find the rates of intravalley and intervalley n-type carrier scattering due to alloy disorder in Si1-xGex alloys. The required alloy scattering matrix elements are calculated from the energy splitting of nearly degenerate Bloch states which arises when one average host atom is replaced by a Ge or Si atom in supercells containing up to 128 atoms. Scattering parameters for all relevant Delta and L intravalley and intervalley alloy scattering are calculated. Atomic relaxation is found to have a substantial effect on the scattering parameters. f-type intervalley scattering between Delta valleys is found to be comparable to other scattering channels. The n-type carrier mobility, calculated from the scattering rate using the Boltzmann transport equation in the relaxation time approximation, is in excellent agreement with experiments on bulk, unstrained alloys.