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51.
Finze M 《Inorganic chemistry》2008,47(24):11857-11867
Salts of the carba-closo-dodecaborate anion with one or two phenyl- or trimethylsilylalkynyl substituents were synthesized by Pd-catalyzed Kumada-type cross-coupling reactions of the corresponding iodinated clusters with alkynyl Grignard reagents. Selective monofunctionalization in the 7- and 12-position of the {closo-CB(11)} cluster was achieved, resulting in salts of the anions: [1-R-12-R'C[triple bond]C-closo-CB(11)H(10)](-) (R = H, Ph; R' = Ph, Me(3)Si (1-4)), [12-Hal-7-PhC[triple bond]C-closo-CB(11)H(10)](-) (Hal = F (5), Cl (6), Br (7)), and [12-F-7-Me(3)SiC[triple bond]C-closo-CB(11)H(10)](-) (8). Furthermore, the disubstituted derivatives [7,12-(RC[triple bond]C)(2)-closo-CB(11)H(10)](-) (R = Ph (9), Me(3)Si (10)) are described. All salts were characterized by multi-NMR, IR, and Raman spectroscopy as well as by mass spectrometry (MALDI). The crystal structures of Cs(+)1 and [Et(4)N](+)6 were determined by single-crystal X-ray diffraction. The spectroscopic and structural properties are compared to values derived from DFT calculations and to data of related boron species with alkynyl groups. 相似文献
52.
Jarno Riefer Ludwig Zapf Dr. Raphael Wirthensohn Dr. Philipp T. Hennig Dr. Tatjana Ribbeck Dr. Jan A. P. Sprenger Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《European journal of organic chemistry》2023,26(17):e202300031
Cyanoborane adducts of the Lewis acids B(CN)3, BF(CN)2, and BH(CN)2 with pyridine and 4-cyanopyridine have been obtained in high yields. The syntheses were accomplished by oxidation of the readily available potassium salts of the cyano(hydrido)borate anions [BH(CN)3]− ( MHB ), [BFH(CN)2]− ( FHB ), and [BH2(CN)2]− ( DHB ) with bromine in the presence of the respective pyridine derivative C5H5N or 4-CN-C5H4N as starting material. All six cyanoborane adducts have been characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The reduction of the cyanoborane adducts has been investigated by cyclic voltammetry and the Lewis acidity of the different cyanoboranes has been assessed using the Gutmann-Beckett method. Selected experimental data and trends are compared to theoretical ones, for example fluoride ion affinities (FIAs). 相似文献
53.
Bioelectronic Interface Connecting Reversible Logic Gates Based on Enzyme and DNA Reactions
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Dr. Nataliia Guz Tatiana A. Fedotova Brian E. Fratto Orr Schlesinger Prof. Lital Alfonta Prof. Dmitry M. Kolpashchikov Prof. Evgeny Katz 《Chemphyschem》2016,17(14):2247-2255
It is believed that connecting biomolecular computation elements in complex networks of communicating molecules may eventually lead to a biocomputer that can be used for diagnostics and/or the cure of physiological and genetic disorders. Here, a bioelectronic interface based on biomolecule‐modified electrodes has been designed to bridge reversible enzymatic logic gates with reversible DNA‐based logic gates. The enzyme‐based Fredkin gate with three input and three output signals was connected to the DNA‐based Feynman gate with two input and two output signals—both representing logically reversible computing elements. In the reversible Fredkin gate, the routing of two data signals between two output channels was controlled by the control signal (third channel). The two data output signals generated by the Fredkin gate were directed toward two electrochemical flow cells, responding to the output signals by releasing DNA molecules that serve as the input signals for the next Feynman logic gate based on the DNA reacting cascade, producing, in turn, two final output signals. The Feynman gate operated as the controlled NOT gate (CNOT), where one of the input channels controlled a NOT operation on another channel. Both logic gates represented a highly sophisticated combination of input‐controlled signal‐routing logic operations, resulting in redirecting chemical signals in different channels and performing orchestrated computing processes. The biomolecular reaction cascade responsible for the signal processing was realized by moving the solution from one reacting cell to another, including the reacting flow cells and electrochemical flow cells, which were organized in a specific network mimicking electronic computing circuitries. The designed system represents the first example of high complexity biocomputing processes integrating enzyme and DNA reactions and performing logically reversible signal processing. 相似文献
54.
Unprecedented Efficient Structure Controlled Phosphorescence of Silver(I) Clusters Stabilized by Carba‐closo‐dodecaboranylethynyl Ligands
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Michael Hailmann Natalia Wolf Rebecca Renner Thomas C. Schäfer Benjamin Hupp Dr. Andreas Steffen Prof. Dr. Maik Finze 《Angewandte Chemie (International ed. in English)》2016,55(35):10507-10511
{Ag2(12‐C≡C‐closo‐1‐CB11H11)}n and selected pyridine ligands have been used for the synthesis of photostable AgI clusters that, with one exception, exhibit for AgI compounds unusual room‐temperature phosphorescence. Extraordinarily intense phosphorescence was observed for a distorted pentagonal bipyramidal AgI7 cluster that shows an unprecedented quantum yield of Φ=0.76 for AgI clusters. The luminescence properties correlate with the structures of the central AgIn motifs as shown by comparison of the emission properties of the clusters with different numbers of AgI ions, different charges, and electronically different pyridine ligands. 相似文献
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The eigenvalue analysis of rolling tires is one part of the simulation of tire rolling noise radiation for the reduction of traffic noise. In this paper the general strategies of numerical eigenvalue analysis for nonsymmetric matrices are shown. The special effects observed on rotating bodies are discussed in details. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
58.
Quantum groups (or more precisely, function algebras on quantum groups), i.e. bialgebras with certain additional properties, can be gained by deforming an appropriate function algebra on a group. In a similar way, we show that a polynomial-like algebra on the (function algebra of the) Manin plane leads to a so-called trialgebra (as suggested by Crane and Frenkel), i.e. an algebraic structure possessing a coproduct and two products in a compatible way. We show how to deform this trialgebra to a noncocommutative and totally noncommutative (i.e. in both products) one. Trialgebras are of interest for various reasons, e.g. the search for topological invariants for four manifolds or the duality operation for non-Abelian lattice gauge theories, recently suggested by the authors. 相似文献
59.
Gudrun Schürer Peter Gedeck Maik Gottschalk Timothy Clark 《International journal of quantum chemistry》1999,75(1):17-31
The variational method for the calculation of the electronic polarizability of molecules within the NDDO‐based semiempirical MO methods MNDO, AM1, and PM3 was parametrized to improve its accuracy. A training set of 156 compounds was used to fit 34 parameters simultaneously for 12 elements using a simplex optimization. The resulting parameters were tested for a test set of 83 molecules and the calculated polarizabilities compared with the experimental data. For AM1, the RMS deviation between experimental and calculated polarizabilities was reduced from 2.99 (using the original variational treatment) to 0.70 Å3 for the test set and from 2.81 to 0.40 Å3 for the training set. MNDO and PM3 gave similar improvements. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 17–31, 1999 相似文献
60.
Point-of-care testing (POCT) in patients with ischemic heart disease is driven by the time-critical need for fast, specific,
and accurate results to initiate therapy instantly. According to current guidelines, the results of the cardiac marker testing
should be available to the physician within 30 min (“vein-to-brain” time) to initiate therapy within 60–90 min (“door-to-needle”
time) after the patient has arrived at the emergency room or intensive care unit. This article reviews the current efforts
to meet this goal (1) by implementing POCT of established biochemical markers such as cardiac troponins, creatine kinase MB,
and myoglobin, in accelerated diagnosis and management workflow schemes, (2) by improving current POCT methods to obtain more
accurate, more specific, and even faster tests through the integration of optical and electrochemical sensor technology, and
(3) by identifying new markers for the very early and sensitive detection of myocardial ischemia and necrosis. Furthermore,
the specific requirements for cardiac POCT in regard to analytical performance, comparability, and diagnostic sensitivity/specificity
are discussed. For the future, the integration of new immunooptical and electrochemical chip technology might speed up diagnosis
even further. However, every new development will have to meet the stringent method validation criteria set for corresponding
central laboratory testing. 相似文献