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41.
Svetlana I. Dorovskikh Denis E. Tryakhov Darya D. Klyamer Alexander S. Sukhikh Irina V. Mirzaeva Natalia B. Morozova Tamara V. Basova 《Molecules (Basel, Switzerland)》2022,27(7)
To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH3CXCHCO(R))2] with β-diketone [tfa−1,1,1-trifluoro-2,4-pentanedionato (1); pfpa−5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba−5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and β-iminoketone [i-tfa−1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa−5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (4); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato (6)] ligands were synthesized with 70–80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd β-diketonates contained both cis and trans isomers, while only trans isomers were detected in the solutions of Pd β-iminoketonates. The molecules 2–6 and new polymorphs of complexes 3 and 5 were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands. The H…F contacts were the main ones involved in the formation of packages of molecules 1–2, and C…F, F…F, NH…F contacts appeared in the structures of complexes 4–6. The stability of complexes and their polymorphs in the crystal phases were estimated from DFT calculations. The TG data showed that the volatility differences between Pd β-iminoketonates and Pd β-diketonates were minimized with the elongation of the fluorine chain in the ligands. 相似文献
42.
Tamara Borisova Sergey Fridrikh Yuli Gotlib Grigoriy Medvedev Natalja Nikonorova Sergey Skorokhodov Vjacheslav Zuev 《Macromolecular Symposia》1993,72(1):67-80
A series of thermotropic main chain polymers with extended dimethylsiloxane segments was investigated. The study of dielectric properties of polymers revealed the relationship between their ability to form a mesophase and their molecular mobility. The peculiar behaviour of dielectric α-relaxation parameters during the transition from mesomorphic to isotropic members of this polymeric series was shown. The theoretical approaches were developed for understanding macrochain dynamics of liquid crystalline polymers. The theoretical and experimental results are in good agreement. 相似文献
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Limiting the Number of Potential Binding Modes by Introducing Symmetry into Ligands: Structure‐Based Design of Inhibitors for Trypsin‐Like Serine Proteases
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Norbert Furtmann Daniela Häußler Tamara Scheidt Dr. Marit Stirnberg Prof. Dr. Torsten Steinmetzer Prof. Dr. Jürgen Bajorath Prof. Dr. Michael Gütschow 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(2):610-625
In the absence of X‐ray data, the exploration of compound binding modes continues to be a challenging task. For structure‐based design, specific features of active sites in different targets play a major role in rationalizing ligand binding characteristics. For example, dibasic compounds have been reported as potent inhibitors of various trypsin‐like serine proteases, the active sites of which contain several binding pockets that can be targeted by cationic moieties. This results in several possible orientations within the active site, complicating the binding mode prediction of such compounds by docking tools. Therefore, we introduced symmetry in bi‐ and tribasic compounds to reduce conformational space in docking calculations and to simplify binding mode selection by limiting the number of possible pocket occupations. Asymmetric bisbenzamidines were used as starting points for a multistage and structure‐guided optimization. A series of 24 final compounds with either two or three benzamidine substructures was ultimately synthesized and evaluated as inhibitors of five serine proteases, leading to potent symmetric inhibitors for the pharmaceutical drug targets matriptase, matriptase‐2, thrombin and factor Xa. This study underlines the relevance of ligand symmetry for chemical biology. 相似文献
45.
Tamara Koledin 《Linear and Multilinear Algebra》2017,65(11):2187-2198
In this paper we focus on connected signed graphs of fixed number of vertices, positive edges and negative edges that maximize the largest eigenvalue (also called the index) of their adjacency matrix. In the first step we determine these signed graphs in the set of signed generalized theta graphs. Concerning the general case, we use the eigenvector techniques for getting some structural properties of resulting signed graphs. In particular, we prove that positive edges induce nested split subgraphs, while negative edges induce double nested signed subgraphs. We observe that our concept can be applied when considering balancedness of signed graphs (the property that is extensively studied in both mathematical and non-mathematical context). 相似文献
46.
[reaction: see text] A new poly(ethylene glycol)-supported porphyrin has been prepared and its ability as a promoter in photooxidation reactions has been studied. The PEG-supported catalyst exhibits high activity, comparable to that of a nonanchored sensitizer, and it is easily removable by filtration from the reaction mixture. The polymer-bound porphyrin has been recycled up to six times with no loss of chemical and stereochemical efficiency. 相似文献
47.
While fluorescence can be clearly observed in resonance-stabilized acyclic anions, its occurrence is insufficient for unambiguous assignment of either ion-pairing type or anion geometry. As in cyclic, aromatic anions, the requirement for contact ion-pairing is less severe in the excited state than in the ground state. The fluorescence lifetimes of acyclic anions are affected more by the associated cation than by the type of ion-pairing. 相似文献
48.
Fitzgerald TN Brooks DH Triedman JK 《IEEE transactions on bio-medical engineering》2004,51(5):847-855
Isochronal cardiac activation maps can be constructed from local activation times associated with spatial locations, and are frequently used to study cardiac arrhythmias. Cardiac velocity vector mapping has been proposed as an alternative method to study cardiac activation in both clinical and research environments. Velocity vectors inherently contain more information than scalar measures of latency, but it is unknown how vector maps and isochronal maps compare when they are used to identify patterns and features associated with arrhythmias. In order to quantitatively compare these two visualization methods, eight cardiologists were asked to complete forced-choice tasks in which they selected ablation sites based on synthetic vector or isochronal maps. Maps varied in arrhythmia complexity, number of vectors or activation times included, and errors in magnitude or angle for maps of velocity vectors. Quantitative comparison was achieved by using psychometric functions to characterize the learning curve and the total number of measurements needed in order to choose a correct ablation site. For simple arrhythmias, performance with vector maps was superior to isochronal maps. Subjects required fewer measurements, and learned more rapidly by studying vector maps. For more complex arrhythmias, there was no significant difference in performance between vector and isochronal maps. However, arrhythmia features were clearer with vector maps, even though this clarity did not necessarily change the ablation site choice. When errors were added to vector maps, performance was satisfactory for angle errors < 55 degrees, and speed errors did not affect performance. 相似文献
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The Kauffman model describes a system of randomly connected nodes with dynamics based on Boolean update functions. Though it is a simple model, it exhibits very complex behavior for "critical" parameter values at the boundary between a frozen and a disordered phase, and is therefore used for studies of real network problems. We prove here that the mean number and mean length of attractors in critical random Boolean networks with connectivity one both increase faster than any power law with network size. We derive these results by generating the networks through a growth process and by calculating lower bounds. 相似文献