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41.
Kirill P. Birin Yulia G. Gorbunova Aslan Yu. Tsivadze 《Magnetic resonance in chemistry : MRC》2010,48(7):505-515
A novel approach for the structural analysis of heteroleptic triple‐decker (porphyrinato)(phthalocyaninato) lanthanides(III) in solutions is developed. The developed approach consists in molecular mechanics (MM+) optimization of the geometry of the complex taking into account the lanthanide‐induced shift (LIS) datasets. LISs of the resonance peaks in 1H NMR spectra of a series of symmetric complexes [An4P]Ln[(15C5)4Pc]Ln[An4P], where An4P2? is 5,10,15,20‐tetrakis(4‐methoxyphenyl)porphyrinato‐dianion, [(15C5)4Pc]2? is 2,3,9,10,16,17,24,25‐tetrakis(15‐crown‐5)phthalocyaninato‐dianion and Ln = La, Ce, Pr, Nd, Sm, Eu, are analyzed. Analysis of LISs showed two sets of protons in the molecule with opposite signs of shift. Two‐nuclei analysis of LISs testifies isostructurality of the whole series of investigated complexes in solution despite contraction of the lanthanide ions. Model‐free separation of contact and dipolar contributions of LISs was performed with one‐nucleus technique and did not show changes in contact and dipolar terms within the investigated series. MM+ optimization of the molecular structure allowed the interpretation of features of LIS for each particular group of protons. Parameterization of MM + ‐optimized model of molecule with values of structure‐dependent dipolar contributions of LIS allows the development of the precise structural model of the triple‐decker complex in solution. This approach allows the determination of the geometry and structure of the sandwich macrocyclic tetrapyrrolic complexes together with conformational analysis of flexible peripheral substituents in solutions. The developed method can be applied with minor modifications for the determination of structural parameters of other types of lanthanides(III) complexes with tetrapyrrolic ligands and also supramolecular systems based on them. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
42.
Vitalii S. Tkach Dmitrii S. Suslov Gennadii V. Ratovskii Tuczek Felix 《Journal of organometallic chemistry》2008,693(12):2069-2073
A series of palladium complexes of general formula [(Acac)PdL1L2]+A−, where L1, L2 = phosphines and A = BF4, CF3SO3, were synthesized. Preliminary studies show that the complexes are active in selective dimerization of styrene and addition polymerization of norbornene. 相似文献
43.
Complex electromagnetic situation and the need in protecting information from unauthorized access require new engineering
solutions in the development of communication system. One of such approaches is associated with fractal communication systems
(FCSs) employing antijamming waveforms with fractal spectra as information carriers. Basic concepts of an FCS are considered
and the results of its practical implementation for computer communication via an aerial or a coaxial cable are discussed. 相似文献
44.
A facile synthetic route to N-polyfluoro(trimethylsilyl)ethyl azole derivatives was developed starting from N-bromo(chloro)polyfluoroethyl-substituted azoles. The silanes thus obtained were reacted with various electrophiles in the presence of the fluoride ion to yield the corresponding fluorinated carbinols, ketones, carboxylic acids, and methyl dithiocarboxylates as well as N-pentafluoroethylbenzimidazole. 相似文献
45.
46.
Alexey Leonidovich Bychkov Kirill G. Korolev Oleg I. Lomovsky 《Applied biochemistry and biotechnology》2010,162(7):2008-2014
A new method of obtaining biologically active mannanoligosaccharides is proposed. It involves mechanical activation of the
enzymatic hydrolysis of components forming the supramolecular structure of the cell wall. Processes that take place during
mechanical treatment and enzymatic hydrolysis of yeast biomass and lead to an increase in the availability of mannanoligosaccharides
of the yeast cell walls are investigated. The efficiency of the use of mechanoenzymatic approach to obtaining mannanoligosaccharide
preparations is evaluated. 相似文献
47.
Kirill Nikitin Helge Müller-Bunz Gérard Jaouen Michael J. McGlinchey 《Journal of organometallic chemistry》2010,695(4):595-608
The McMurry coupling of (tetraphenylcyclobutadiene)cobalt(cyclopentadienyl) ketones, (C4Ph4)Co[C5H4C(O)R], where R = Me, 3a, or Et, 3b, with a range of substituted benzophenones furnished a series of cobaltifens, organometallic analogues of tamoxifen whereby a phenyl ring has been replaced by an organo-cobalt sandwich moiety. These systems of the general formula (η4-C4Ph4)Co[η5-C5H4C(R)C(Ar)Ar′], where R = Me or Et, and Ar = Ar′ = p-C6H4X where X is OH, 2a and 2b, OMe, 2c and 2d, OBn, 2e and 2f, or O(CH2)2NMe2, 12a and 12b, and where Ar = C6H4OH and Ar′ = C6H4O(CH2)2NMe2, 2g and 2h, have been characterised by NMR spectroscopy and/or X-ray crystallography. The effect of 2a and 2b, 2g and 2h, and 12a and 12b on the growth of MCF-7 (hormone-dependent) and MDA-MB-231 (hormone-independent breast cancer cells) was studied. The dihydroxycobaltifens 2a and 2b exhibit a strong estrogenic effect on MCF-7 cells while the aminoalkyl-hydroxycobaltifens, 2g and 2h, were found to be only slightly cytotoxic on MDA-MB-231 cells (IC50 = 27.5 and 17 μM); surprisingly, however, the bis-(dimethylaminoethoxy)cobaltifens, 12a and 12b were shown to be highly cytotoxic towards both cell lines (IC50 = 3.8 and 2.5 μM). 相似文献
48.
Spin correlations of top quarks produced in hadron collisions have not been observed experimentally with large significance. In this Letter, we propose a new variable that may enable demonstration of the existence of spin correlations with 3–4 σ significance using just a few hundred dilepton events both at the Tevatron and the LHC. Such number of dilepton events has been observed at the Tevatron. At the LHC, it will become available once integrated luminosity of a few hundred inverse picobarns is collected. 相似文献
49.
Brunsveld L Kuhlmann J Alexandrov K Wittinghofer A Goody RS Waldmann H 《Angewandte Chemie (International ed. in English)》2006,45(40):6622-6646
Chemical biology can be defined as the study of biological phenomena from a chemical approach. Based on the analysis of relevant biological phenomena and their structural foundation, unsolved problems are identified and tackled through a combination of chemistry and biology. Thus, new synthetic methods and strategies are developed and employed for the construction of compounds that are used to investigate biological procedures. Solid-phase synthesis has emerged as the preferred method for the synthesis of lipidated peptides, which can be chemoselectively ligated to proteins of the Ras superfamily. The generated peptides and proteins have solved biological questions in the field of the Ras-superfamily GTPases that are not amendable to chemical or biological techniques alone. 相似文献
50.
Structure Elucidator: a versatile expert system for molecular structure elucidation from 1D and 2D NMR data and molecular fragments 总被引:2,自引:0,他引:2
Elyashberg ME Blinov KA Williams AJ Molodtsov SG Martin GE Martirosian ER 《Journal of chemical information and computer sciences》2004,44(3):771-792
StrucEluc is an expert system that allows the computer-assisted elucidation of chemical structures based on the inputs of a series of spectral data including 1D and 2D NMR and mass spectra. The system has been enabled to allow a chemist to utilize fragments stored in a fragment database as well as user-defined fragments submitted by the chemist in the structure elucidation process. The association of fragments in this way has been shown to dramatically speed up the process of structure generation from 2D NMR data and has helped to minimize or eliminate the need for user intervention thereby further enabling the vision of automated elucidation. The use of fragments has frequently transformed very difficult 2D NMR elucidation challenges into easily solvable tasks. A strategy to utilize molecular fragments has been developed and optimized based on specific challenging examples. This strategy will be described here using real world examples. Experience gained by solving more than 150 structure elucidation problems from a variety of literature sources is also reviewed in this work. 相似文献