Probing active galactic nuclei with H2O megamasers.

We describe the characteristics of the rapidly rotating molecular disk in the nucleus of the mildly active galaxy NGC4258. The morphology and kinematics of the disk are delineated by the point-like watervapor emission sources at 1.35-cm wavelength. High angular resolution [200 microas where as is arcsec, corresponding to 0.006 parsec (pc) at 6.4 million pc] and high spectral resolution (0.2 km.s-1 or nu/Deltanu = 1.4 x 10(6)) with the Very-Long-Baseline Array allow precise definition of the disk. The disk is very thin, but slightly warped, and is viewed nearly edge-on. The masers show that the disk is in nearly perfect Keplerian rotation within the observable range of radii of 0.13-0.26 pc. The approximately random deviations from the Keplerian rotation curve among the high-velocity masers are approximately 3.5 km.s-1 (rms). These deviations may be due to the masers lying off the midline by about +/-4 degrees or variations in the inclination of the disk by +/-4 degrees. Lack of systematic deviations indicates that the disk has a mass of <4 x 10(6) solar mass (M[symbol: see text]). The gravitational binding mass is 3.5 x 10(7) M[symbol: see text], which must lie within the inner radius of the disk and requires that the mass density be >4 x 10(9) M[symbol: see text].pc-3. If the central mass were in the form of a star cluster with a density distribution such as a Plummer model, then the central mass density would be 4 x 10(12) M[symbol: see text].pc-3. The lifetime of such a cluster would be short with respect to the age of the galaxy [Maoz, E. (1995) Astrophys. J. Lett. 447, L91-L94]. Therefore, the central mass may be a black hole. The disk as traced by the systemic velocity features is unresolved in the vertical direction, indicating that its scale height is <0.0003 pc (hence the ratio of thickness to radius, H/R, is <0.0025). For a disk in hydrostatic equilibrium the quadrature sum of the sound speed and Alfven velocity is <2.5 km.s-1, so that the temperature of the disk must be <1000 K and the toroidal magnetic field component must be <250 mG. If the molecular mass density in the disk is 10(10) cm-3, then the disk mass is approximately 10(4) M[symbol: see text], and the disk is marginally stable as defined by the Toomre stability parameter Q (Q = 6 at the inner edge and 1 at the outer edge). The inward drift velocity is predicted to be <0.007 km.s-1, for a viscosity parameter of 0.1, and the accretion rate is <7 x 10(-5) M[symbol: see text].yr-1. At this value the accretion would be sufficient to power the nuclear x-ray source of 4 x 10(40) ergs-1 (1 erg = 0.1 microJ). The volume of individual maser components may be as large as 10(46) cm3, based on the velocity gradients, which is sufficient to supply the observed luminosity. The pump power undoubtedly comes from the nucleus, perhaps in the form of x-rays. The warp may allow the pump radiation to penetrate the disk obliquely [Neufeld, D. A. & Maloney, P. R. (1995) Astrophys. J. Lett. 447, L17-L19]. A total of 15 H2O megamasers have been identified out of >250 galaxies searched. Galaxy NGC4258 may be the only case where conditions are optimal to reveal a well-defined nuclear disk. Future measurement of proper motions and accelerations for NGC4258 will yield an accurate distance and a more precise definition of the dynamics of the disk

Velocity distributions in a plate heat exchanger channel

The development of a Laser Doppler Anemometer technique to measure the velocity distribution in a commercial plate heat exchanger is described. Detailed velocity profiles are presented and a preliminary investigation is reported on flow behaviour through a single cell in the channel matrix. The objective of the study was to extend previous investigations of plate heat exchanger flow patterns in the laminar range with the eventual aim of establishing the effect of flow patterns on heat transfer performance, thus leading to improved plate heat exchanger design and design methods. Accurate point velocities were obtained by Laser Anemometry in a perspex replica of the metal channel. Oil was used as a circulating liquid with a refractive index matched to that of the perspex so that the laser beams were not distorted. Cell-by-cell velocity measurements over a range of Reynolds number up to ten showed significant liquid mal-distribution. Local cell velocities were found to be as high as twenty seven times average velocity, contrary to the previously held belief of four times. The degree of mal-distribution varied across the channel as well as in the vertical direction, and depended on the upward or downward direction of flow. At Reynolds numbers less than one, flow zig-zagged from one side of the channel to the other in wave form, but increases in Reynolds number improved liquid distribution. A detailed examination of selected cells showed velocity variations in different directions, together with variation within individual cells. Experimental results are also reported on the flow split when passing through a single cell in a section of a channel . These observations were used to explain mal-distribution in the perspex channel itself.

A cautionary note on methods of comparing programmatic efficiency between two or more groups of DMUs in data envelopment analysis

In some applications of data envelopment analysis (DEA) there may be doubt as to whether all the DMUs form a single group with a common efficiency distribution. The Mann-Whitney rank statistic has been used to evaluate if two groups of DMUs come from a common efficiency distribution under the assumption of them sharing a common frontier and to test if the two groups have a common frontier. These procedures have subsequently been extended using the Kruskal-Wallis rank statistic to consider more than two groups. This technical note identifies problems with the second of these applications of both the Mann-Whitney and Kruskal-Wallis rank statistics. It also considers possible alternative methods of testing if groups have a common frontier, and the difficulties of disaggregating managerial and programmatic efficiency within a non-parametric framework. © 2007 Springer Science+Business Media, LLC.

Programmatic efficiency comparisons between unequally sized groups of DMUs in DEA

Data envelopment analysis (DEA) is a popular non-parametric technique for determining the efficiency of a homogeneous set of decision-making units (DMUs). In many practical cases, there is some doubt if the all the DMUs form a single group with a common efficiency distribution. The Mann-Whitney rank statistic has been used in DEA both to test if two groups of DMUs come from a common efficiency distribution and also to test if the two groups have a common frontier, each of which are likely to have important but different policy implications for the management of the groups. In this paper it is demonstrated that where the Mann-Whitney rank statistic is used for the second of these it is likely to overestimate programmatic inefficiency, particularly of the smaller group. A new non-parametric statistic is proposed for the case of comparing the efficient frontiers of two groups, which overcomes the problems we identify in the use of the Mann-Whitney rank statistic for this purpose. © 2005 Operational Research Society Ltd. All rights reserved.

Application of nanoimprinting technique for fabrication of trifocal diffractive lens with sine-like radial profile

The fabrication of submicron-height sine-like relief of a trifocal diffractive zone plate using a nanoimprinting technique is studied. The zone plate is intended for use in combined trifocal diffractive-refractive lenses and provides the possibility to form trifocal intraocular lenses with predetermined light intensity distribution between foci. The optical properties of the designed zone plate having the optical powers 3 D, 0, -3D in the three main diffraction orders are theoretically and experimentally investigated. The results of the theoretical investigations are in good agreement with experimental measurements. The effects of the pupil size (lens diameter) as well as the wavelength-dependent behavior of the zone plate are also discussed.

Gráfico de controle modificado para processos com estruturas complexas de autocorrelação

This work proposes a modified control chart incorporating concepts of time series analysis. Specifically, we considerer Gaussian mixed transition distribution (GMTD) models. The GMTD models are a more general class than the autorregressive (AR) family, in the sense that the autocorrelated processes may present flat stretches, bursts or outliers. In this scenario traditional Shewhart charts are no longer appropriate tools to monitoring such processes. Therefore, Vasilopoulos and Stamboulis (1978) proposed a modified version of those charts, considering proper control limits based on autocorrelated processes. In order to evaluate the efficiency of the proposed technique a comparison with a traditional Shewhart chart (which ignores the autocorrelation structure of the process), a AR(1) Shewhart control chart and a GMTD Shewhart control chart was made. An analytical expression for the process variance, as well as control limits were developed for a particular GMTD model. The ARL was used as a criteria to measure the efficiency of control charts. The comparison was made based on a series generated according to a GMTD model. The results point to the direction that the modified Shewhart GMTD charts have a better performance than the AR(1) Shewhart and the traditional Shewhart.

La distribution et la diffusion du livre québécois dans la sphère numérique : le cas de l’Entrepôt numérique (ANEL – De Marque)

En 2008, le Québec fait son entrée dans le marché du livre numérique. Cette année-là, l’Association nationale des éditeurs de livres du Québec (ANEL) s’associe avec l’entreprise De Marque pour créer l’Entrepôt numérique (www.entrepotnumerique.com), une plateforme de diffusion et de distribution de livres numériques québécois. Sa structure permet de stocker et de gérer les fichiers numériques, tout en offrant aux éditeurs une interface personnalisée afin que chacun puisse commercialiser ses titres en quelques étapes simples. Dès le départ, les instigateurs de ce projet font le pari de mettre en place une infrastructure de diffusion-distribution propre aux Québécois et qui répond à l’internationalisation du marché du livre. Mais les enjeux sont nombreux pour les professionnels du système-livre du Québec qui tentent de s’adapter aux nouvelles structures et de se frayer un chemin dans la sphère numérique. À la fois d’ordre technologique, économique et culturel, ces enjeux posent la double question de la commercialisation d’une nouvelle forme de livre et de la présence de la culture québécoise sur le web. En effet, face à la multiplication des titres et devant l’espace infini de la Toile, comment assurer la circulation et la promotion du livre numérique ? Comment adapter les circuits traditionnels à un nouveau format de livre qui se distingue de la forme fixe du livre imprimé que l’on connaît ? Et comment, surtout, la culture québécoise peut-elle prendre place auprès de géants internationaux comme Amazon, Google ou Apple ? Ayant précisément pour mandat d’offrir une solution de diffusion numérique simple et efficace aux éditeurs québécois et canadiens-français, l’Entrepôt numérique distribue la production de 148 éditeurs, donnant ainsi aux lecteurs un accès à un catalogue mutualisé comptant 17 144 publications. Plus de 750 000 livres numériques ont été vendus depuis 2009 et de nombreuses ententes de partenariat ont été signées avec 194 revendeurs provenant de 58 pays. Or, en assurant la circulation et la commercialisation des titres dans l’espace numérique, l’Entrepôt numérique participe à la mutation du secteur de la diffusion-distribution au Québec. Il illustre ainsi les évolutions techniques, économiques et structurelles du marché. S’intéresser à l’Entrepôt numérique comme objet d’étude, c’est donc s’intéresser aux enjeux (technologiques, culturels, économiques) pouvant se dégager des nouvelles stratégies de circulation et de commercialisation du livre numérique implantées au sein de la filière québécoise.  Trois chapitres composent ce mémoire. Le premier propose un historique de l’Entrepôt numérique. En décrivant à la fois les enjeux de départ, les acteurs impliqués et l’évolution de la plateforme, il permet de situer les conditions culturelles, commerciales et éditoriales ayant permis le développement de cette plateforme. Le deuxième chapitre, qui examine les mécanismes de distribution via l’Entrepôt numérique, met en lumière les différents jalons qui marquent le passage de la distribution traditionnelle à la distribution du livre numérique. Enfin, le troisième chapitre porte sur les mécanismes de diffusion du livre numérique de la plateforme et illustre ainsi les nouvelles conditions de promotion du livre dans la sphère numérique. En somme, la présentation de l’historique de l’Entrepôt numérique et l’examen des mécanismes de diffusion et de distribution de la plateforme permettent d’offrir une meilleure préhension des transformations et enjeux émanant de l’industrie du livre numérique au Québec, entre 2007 et 2015.

Anisotropic Assembly of Colloidal Nanoparticles: Exploiting Substrate Crystallinity

We show that the crystal structure of a substrate can be exploited to drive the anisotropic assembly of colloidal nanoparticles. Pentanethiol-passivated Au particles of approximately 2 nm diameter deposited from toluene onto hydrogen-passivated Si(111) surfaces form linear assemblies (rods) with a narrow width distribution. The rod orientations mirror the substrate symmetry, with a high degree of alignment along principal crystallographic axes of the Si(111) surface. There is a strong preference for anisotropic growth with rod widths substantially more tightly distributed than lengths. Entropic trapping of nanoparticles provides a plausible explanation for the formation of the anisotropic assemblies we observe.

Protonenleitung in imidazolhaltigen Materialien als Modellsysteme für wasserfreie Brennstoffzellenmembranen

Es wird ein neues Konzept für ein protonenleitendes Polymer vorgestellt, das ohne eine zweite, flüssige Phase auskommt. Es beruht darauf, basische Gruppen (Imidazol) über flexible Spacer kovalent an ein Polymerrückgrat zu binden und durch Dotierung mit einer geringen Menge Säure Ladungsträger (Protonen) in dieses System einzubringen.Um die für die Leitfähigkeit und ihren Mechanismus verantwortlichen Größen zu identifizieren, wurde ein Satz von niedermolekularen Modellverbindungen definierter Struktur und hoher Reinheit synthetisiert und im reinen Zustand sowie nach Dotierung mit geringen Mengen Säure umfassend charakterisiert. Untersucht wurden die thermischen Eigenschaften, die Leitfähigkeit, die Diffusion der jeweiligen Modellverbindung sowie ggf. der zugesetzten Säure, das Protonierungsgleichgewicht und die dielektrischen Eigenschaften. Insbesondere wurden durch den Vergleich von Leitfähigkeits- und Diffusionsdaten unter Anwendung der Nernst-Einstein-Beziehung Rückschlüsse auf den Leitmechanismus gezogen.Es wurden Leitfähigkeiten von bis zu 6.5E-3 S/cm bei 120°C erreicht. Der Anteil der Strukturdiffusion (vergleichbar mit dem Grotthus-Mechanismus in Wasser) an der protonischen Leitfähigkeit betrug bis zu über 90%. Als entscheidende Faktoren für die Leitfähigkeit wurden die Glastemperatur und, mit geringerer Priorität, der Imidazolgehalt des Materials identifiziert. Die Temperaturabhängigkeit aller untersuchten Transportgrößen ließ sich durch die Vogel-Tamman-Fulcher-Gleichung exzellent beschreiben.Die vorgestellten Daten bilden die Grundlage für den Entwurf eines entsprechenden Polymers.

Präparation, Charakterisierung und elektronische Eigenschaften von dünnen Schichten des Hochtemperatursupraleiters HgReBa 2 Ca n-1 Cu n O y

Ziel dieser Arbeit war die Pr"{a}paration, Charakterisierung und Untersuchung der elektronischen Eigenschaften von d"{u}nnen Schichten des Hochtemperatursupraleiters HgReBa$_{2}$Ca$_{n-1}$Cu$_{n}$O$_{y}$, die mittels gepulster Laser-Deposition hergestellt wurden. Die HgRe1212-Filme zeigen in der AC-Suszeptibilit"{a}t einen scharfen "{U}bergang in die supraleitende Phase bei 124 K mit einer "{U}bergangsbreite von 2 K. Die resistiven "{U}berg"{a}nge der Proben wurden mit zunehmender St"{a}rke des externen Magnetfeldes breiter. Aus der Steigung der Arrheniusplots konnte die Aktivierungsenergie f"{u}r verschiedene Feldst"{a}rken bestimmt werden. Weiterhin wurde die Winkelabh"{a}ngigkeit des Depinning-Feldes $B_{dp}(theta)$ der Filme gemessen. Hieraus wurde ein Anisotropiewert von $gamma$ = 7.7 bei 105 K ermittelt. Dies ist relevant, um den f"{u}r Anwendungen wichtigen Bereich im $T$-$B$-$theta$-Phasenraum des Materials absch"{a}tzen zu k"{o}nnen. Die kritische Stromdichte $J_{c}$ der d"{u}nnen Filme aus HgRe-1212 wurde mit Hilfe eines SQUID-Magnetometers gemessen. Die entsprechenden $M$-$H$ Kurven bzw. das magnetische Moment dieser Filme wurde f"{u}r einen weiten Temperatur- und Feldbereich mit einem magnetischen Feld senkrecht zum Film aufgenommen. F"{u}r einen HgRe-1212-Film konnte bei 5 K eine kritische Stromdichte von 1.2 x 10$^{7}$ A/cm$^{2}$ und etwa 2 x 10$^{6}$ A/cm$^{2}$ bei 77 K ermittelt werden. Es wurde die Magnetfeld- und die Temperaturabh"{a}ngigkeit des Hall-Effekts im normalleitenden und im Mischzustand in Magnetfeldern senkrecht zur $ab$-Ebene bis zu 12 T gemessen. Oberhalb der kritischen Temperatur $T_{c}$ steigt der longitudinale spezifische Widerstand $rho_{xx}$ linear mit der Temperatur, w"{a}hrend der spezifische Hall-Widerstand $rho_{yx}$ sich umgekehrt proportional zur Temperatur "{a}ndert. In der N"{a}he von $T_{c}$ und in Feldern kleiner als 3 T wurde eine doppelte Vorzeichen"{a}nderung des spezifischen Hall-Widerstandes beobachtet. Der Hall-Winkel im Normalzustand, cot $theta_{H}= alpha T^{2} + beta$, folgt einer universellen $textit{T }^{2}$-Abh"{a}ngigkeit in allen magnetischen Feldern. In der N"{a}he des Nullwiderstand-Zustandes h"{a}ngt der spezifische Hall-Widerstand $rho_{yx}$ "{u}ber ein Potenzgesetz mit dem longitudinalen Widerstand $rho_{xx}$ zusammen. Das Skalenverhalten zwischen $rho_{yx}$ und $rho_{xx}$ weist eine starke Feld-Abh"{a}ngigkeit auf. Der Skalenexponent $beta$ in der Gleichung $rho_{yx}$ =A $rho_{xx}^{beta}$ steigt von 1.0 bis 1.7, w"{a}hrend das Feld von 1.0 bis 12 T zunimmt.

Bedeutung der synovialen Strukturqualität für die Ernährung des Chondrozyten

In dieser Arbeit wird eine Einteilung der degenerativen strukturellen Veränderungen der Synovialmembran vorgestellt. Anhand der Kriterien Fibrosierung des Stromas, Rückgang des Gefäßnetzes, Auftreten von Hyalinose und chondroider Metaplasie mit und ohne Nachweis von CPPD Kristallen wurden Präparate der Synovialmembran von 59 Patienten mit Nachweis degenerativer strukturellen Veränderungen in 4 Stadien eingeteilt. rnHyalinose (Stadium 3) konnte in den untersuchten Schnitten nur relativ selten beobachtet werden, so dass am ehesten von einem Vorstadium zur chondroiden Metaplasie auszugehen ist. rnDie Verteilung der Erkrankungsdauer und des Alters in den verschiedenen Stadien lassen darauf schließen, dass höhere Stadien mit höherem Alter und längerer Erkrankungsdauer korrelieren. rnAus der vorhandenen Literatur ergeben sich Hinweise, welche Faktoren zu der Entstehung der strukturellen Veränderungen beitragen können: rnAus dem Netzwerk der Zytokine scheinen TGF-beta und die BMP’s an der Zunahme der Fibrose und an der Entstehung chondroider Metaplasie beteiligt zu sein. Makrophagen scheinen dabei eine wichtige Rolle zu spielen. Dies weist darauf hin, dass entzündliche und strukturelle Veränderungen miteinander vernetzt sind. rnBei der Entstehung der chondroiden Metaplasie kommen zusätzlich mechanische Einflüsse in Form von zyklischen Kompressionen als Einflussfaktor in Frage. rnDie Regulierung der Angiogenese ist noch zu wenig verstanden, um den Gefäßrückgang bei fortgeschrittenen strukturellen Veränderungen zu erklären. Erklärungsansätze sind zum einen zunehmende mechanische Schädigung bei zunehmender Inkongruenz der Gelenkflächen. Zum anderen könnte eine beginnende chondroide Metaplasie mit Expression von Chondromodulin I eine entscheidende Rolle spielen. rnInsgesamt muss man davon ausgehen, dass die zunehmenden strukturellen Veränderungen die Ernährung des Knorpels erschweren. Dabei ist an erster Stelle der Rückgang des Gefäßnetzes zu nennen. Dies erschwert nicht nur die Versorgung mit Nährstoffen, sondern auch den Abtransport von Stoffwechselprodukten. Ab einem gewissen Punkt ist aber auch davon auszugehen, dass die Funktion der Deckzellschicht beeinträchtigt wird. Wenn die Konzentration der Hyaluronsäure in der Synovia dadurch sinkt, kann dies durch eine vermehrte Permeabilität der Synovialmembran zum verstärkten Ausstrom von Wasser aus der Gelenkhöhle führen. Durch ein Ödem des umliegenden Gewebes kann dadurch der Blutfluss im Bereich des Gelenks zusätzlich vermindert werden. rnAuch die zunehmende Fibrosierung der Synovialmembran kann einen Einfluss auf die Permeabilität der Synovialmembran haben. Ob und in welchen Stadien der Veränderungen das einen relevanten Einfluss für die Ernährung der Chondrozyten hat, ist noch unklar.rn

Das Kluftsystem im Bereich des Naturdenkmals "Saurierfährten Münchehagen"

The joints at the site of the dinosaur tracks in Muenchehagen form a conspicuous rhomboid pattern in a widely exposed bedding surface of the local quarry. An approximately west-trending set of joints is radially orientated with regard to the shape of the Rehburg salt pillow indicating a genetic relation to salt flow. The second set of joints trends approximately NW and is associated with arrays of dextral shear joints. Its formation is attributed to salt pillow formation and/or a regional deformation plan. This deformation plan presumably existed during the Alpine orogeny. The preservation potential of the dinosaur tracks is considerably decreased by the joint System.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Reversible B/Z-DNA transition under the low salt condition and non-B-form polydApolydT selectivity by a cubane-like europium-L-aspartic acid complex

We report here that a cubane-like europium-L-aspartic acid complex at physiological pH can discriminate between DNA structures as judged by the comparison of thermal denaturation, binding stoichiometry, temperature-dependent fluorescence enhancement, and circular dichroism and gel electrophoresis studies. This complex can selectively stabilize non-B-form DNA polydApolydT but destabilize polydGdCpolydGdC and polydAdTpolydAdT. Further studies show that this complex can convert B-form polydGdCpolydGdC to Z-form under the low salt condition at physiological temperature 37 degrees C, and the transition is reversible, similar to RNA polymerase, which turns unwound DNA into Z-DNA and converts it back to B-DNA after transcription. The potential uses of a left-handed helix-selective probe in biology are obvious. Z-DNA is a transient structure and does not exist as a stable feature of the double helix. Therefore, probing this transient structure with a metal-amino acid complex under the low salt condition at physiological temperature would provide insights into their transitions in vivo and are of great interest.