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141.
Infinite Time Register Machines (ITRM's) are a well-established machine model for infinitary computations. Their computational strength relative to oracles is understood, see e.g. , and . We consider the notion of recognizability, which was first formulated for Infinite Time Turing Machines in [6] and applied to ITRM's in [3]. A real x is ITRM-recognizable iff there is an ITRM-program P such that Py stops with output 1 iff y=x, and otherwise stops with output 0. In [3], it is shown that the recognizable reals are not contained in the ITRM-computable reals. Here, we investigate in detail how the ITRM -recognizable reals are distributed along the canonical well-ordering <L of Gödel's constructible hierarchy L . In particular, we prove that the recognizable reals have gaps in <L, that there is no universal ITRM in terms of recognizability and consider a relativized notion of recognizability. 相似文献
142.
Fabian Niedermair Roman Trattnig Kurt Mereiter Martin Schmuck Stefan Sax Emil J. W. List Christian Slugovc 《Monatshefte für Chemie / Chemical Monthly》2010,43(6):847-858
Abstract
Luminescent organoplatinum complexes featuring 8-quinolinolates as chelating ligands have been synthesized and characterized. Substitution of the quinolinolate ligand has been achieved in the 5 position, where benzoyl substituents were introduced by reacting 8-hydroxyquinoline and the corresponding benzoyl chloride in a Friedel–Crafts acylation. The resulting complexes, κ2(N,C2)-(2-(4-tert-butylphenyl)pyridine)-κ2(N,O)-(5-(4-tert-butylphenyl)(8-quinolinolato-5-yl)methanone)platinum(II) and κ2(N,C2)-(3-hexyloxy-2-phenylpyridine)-κ2(N,O)-((8-quinolinolato-5-yl)phenylmethanone)platinum(II), have been investigated by nuclear magnetic resonance and infrared spectroscopy, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, X-ray analysis, thermal analysis, cyclic voltammetry, UV–vis absorption spectroscopy, and luminescence measurements in solution and in the solid state. The solid-state structures of the complexes were found to be dominated by π–π intermolecular interactions. Organic light-emitting devices based on the complexes and a matching host material gave red to near-infrared electroluminescence with low-onset voltages (4–5 V) and continuous wave luminance intensities exceeding 500 cd/m2. 相似文献143.
Nicolas Preux Aurélie Rolle Cindy Merlin Messaoud Benamira Marcin Malys Claude Estournes Annick Rubbens Rose-Noëlle Vannier 《Comptes Rendus Chimie》2010,13(11):1351-1358
In this study, with the aim to enhance the ionic conduction of known structures by defect chemistry, the La2O3-Ta2O5 system was considered with a focus on the La3TaO7 phase whose structure is of Weberite type. In order to predict possible preferential substitution sites and substitution elements, atomistic simulation was used as a first approach. A solid solution La3−xSrxTaO7−x/2 was confirmed by X-ray diffraction and Raman spectroscopy; it extends for a substitution ratio up to x = 0.15. Whereas La3TaO7 is a poor oxide ion conductor (σ700 °C = 2 × 10−5S.cm−1), at 700 °C, its ionic conductivity is increased by more than one order of magnitude when 3.3% molar strontium is introduced in the structure (σ700 °C = 2 × 10−4S.cm−1). 相似文献
144.
W Sicking H Somnitz C Schmuck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(35):10937-10948
The mammalian heme enzyme myeloperoxidase (MPO) catalyzes the reaction of Cl(-) to the antimicrobial-effective molecule HOCl. During the catalytic cycle, a reactive intermediate "Compound?I" (Cpd?I) is generated. Cpd?I has the ability to destroy the enzyme. Indeed, in the absence of any substrate, Cpd?I decays with a half-life of 100?ms to an intermediate called Compound?II (Cpd?II), which is typically the one-electron reduced Cpd?I. However, the nature of Cpd?II, its spectroscopic properties, and the source of the additional electron are only poorly understood. On the basis of DFT and time-dependent (TD)-DFT quantum chemical calculations at the PBE0/6-31G* level, we propose an extended mechanism involving a new intermediate, which allows MPO to protect itself from self-oxidation or self-destruction during the catalytic cycle. Because of its similarity in electronic structure to Cpd?II, we named this intermediate Cpd?II'. However, the suggested mechanism and our proposed functional structure of Cpd?II' are based on the hypothesis that the heme is reduced by charge separation caused by reaction with a water molecule, and not, as is normally assumed, by the transfer of an electron. In the course of this investigation, we found a second intermediate, the reduced enzyme, towards which the new mechanism is equally transferable. In analogy to Cpd?II', we named it Fe(II') . The proposed new intermediates Cpd?II' and Fe(II') allow the experimental findings, which have been well documented in the literature for decades but not so far understood, to be explained for the first time. These encompass a)?the spontaneous decay of Cpd?I, b)?the unusual (chlorin-like) UV/Vis, circular dichroism (CD), and resonance Raman spectra, c)?the inability of reduced MPO to bind CO, d)?the fact that MPO-Cpd?II reduces SCN(-) but not Cl(-) , and e)?the experimentally observed auto-oxidation/auto-reduction features of the enzyme. Our new mechanism is also transferable to cytochromes, and could well be viable for heme enzymes in general. 相似文献
145.
We report a comprehensive formalism for the dynamics of metal speciation across an interphase formed between a complexing soft film layer and an electrolyte solution containing indifferent ions and metal ions that form complexes with charged molecular ligands distributed throughout the film. The analysis integrates the intricate interplay between metal complexation kinetics and diffusive metal transfer from/toward the ligand film, together with the kinetics of metal electrostatic partitioning across the film/solution interphase. This partitioning is determined by the settling dynamics of the interfacial electric double layer (EDL), as governed by time-dependent conduction-diffusion transports of both indifferent and reactive metal ions. The coupling between such chemodynamic and electrodynamic processes is evaluated via derivation of the dielectric permittivity increment for the ligand film/electrolyte interphase that is perturbed upon application of an ac electric field (pulsation ω) between electrodes supporting the films. The dielectric response is obtained from the ω-dependent distributions of all ions across the ligand film, as ruled by coupled Poisson-Nernst-Planck equations amended for a chemical source term involving the intra-film complex formation and dissociation pulsations (ω(a) and ω(d) respectively). Dielectric spectra are discussed for bare and film coated-electrodes over a wide range of field pulsations and Deborah numbers De = ω(a,d)/ω(diff), where ω(diff) is the electric double layer relaxation pulsation. The frequency-dependent dynamic or inert character of the formed metal complexes is then addressed over a time window that ranges from transient to fully relaxed EDL. The shape and magnitude of the dielectric spectra are further shown to reflect the lability of dynamic complexes, i.e. whether the overall speciation process at a given pulsation ω is primarily rate-limited either by complexation kinetics or by ion-transport dynamics. The limits, strengths and extensions of the approach are further discussed within the context of metal speciation dynamics at soft planar and particulate complexing interphases. 相似文献
146.
Schmuck C Rehm T Gröhn F Klein K Reinhold F 《Journal of the American Chemical Society》2006,128(5):1430-1431
The self-complementary flexible bis-zwitterion 1 forms discrete nanometer-sized cyclic dimers via ion pair driven self-assembly even in polar solvents. The existence of such dimers was confirmed by DOSY NMR, FAB-MS, and scattering experiments (DLS, SANS) which all indicate the concentration-dependent formation of cyclic dimers with a hydrodynamic radius of rH approximately 2.5 nm in solution. 相似文献
147.
148.
Highly Strained Heterocycles Constructed from Boron–Boron Multiple Bonds and Heavy Chalcogens 下载免费PDF全文
Prof. Dr. Holger Braunschweig Philipp Constantinidis Theresa Dellermann Dr. William C. Ewing Prof. Dr. Ingo Fischer Merlin Hess Dr. Fergus R. Knight Anna Rempel Christoph Schneider Stefan Ullrich Dr. Alfredo Vargas Prof. J. Derek Woollins 《Angewandte Chemie (International ed. in English)》2016,55(18):5606-5609
The reactions of a diborene with elemental selenium or tellurium are shown to afford a diboraselenirane or diboratellurirane, respectively. These reactions are reminiscent of the sequestration of subvalent oxygen and nitrogen in the formation of oxiranes and aziridines; however, such reactivity is not known between alkenes and the heavy chalcogens. Although carbon is too electronegative to affect the reduction of elements with lower relative electronegativity, the highly reducing nature of the B?B double bond enables reactions with Se0 and Te0. The capacity of multiple bonds between boron atoms to donate electron density is highlighted in reactions where diborynes behave as nucleophiles, attacking one of the two Te atoms of diaryltellurides, forming salts consisting of diboratellurenium cations and aryltelluride anions. 相似文献
149.
Dr. Merlin Kleoff Patrick Voßnacker Prof. Dr. Sebastian Riedel 《Angewandte Chemie (International ed. in English)》2023,62(17):e202216586
Chlorine plays a central role for the industrial production of numerous materials with global relevance. More recently, polychlorides have been evolved from an area of academic interest to a research topic with enormous industrial potential. In this minireview, the value of trichlorides for chlorine storage and chlorination reactions are outlined. Particularly, the inexpensive ionic liquid [NEt3Me][Cl3] shows a similar and sometimes even advantageous reactivity compared to chlorine gas, while offering a superior safety profile. Used as a chlorine storage, [NEt3Me][Cl3] could help to overcome the current limitations of storing and transporting chlorine in larger quantities. Thus, trichlorides could become a key technique for the flexibilization of the chlorine production enabling an exploitation of renewable, yet fluctuating, electrical energy. As the loaded storage, [NEt3Me][Cl3], is a proven chlorination reagent, it could directly be employed for downstream processes, paving the path to a more practical and safer chlorine industry. 相似文献
150.