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111.
112.
Anastasia Grishina Dr. Stancho Stanchev Lukáš Kumprecht Dr. Miloš Buděšínský Dr. Michaela Pojarová Dr. Michal Dušek Dr. Michaela Rumlová Ivana Křížová Dr. Lubomír Rulíšek Dr. Tomáš Kraus 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12292-12304
New tubular host molecules, which are composed of two β‐cyclodextrin macrocycles that are connected through two disulfide bonds, have been prepared by the air‐promoted oxidation of 6I,6IV‐dideoxy‐6I,6IV‐disulfanyl‐β‐cyclodextrin in aqueous solution. This reaction leads to three products: monomeric intramolecular disulfide and two dimeric species, which are termed as “non‐eclipsed” and “eclipsed” cyclodextrin duplexes. Oxidation at a concentration of the starting thiol of 0.1 mM gave the intramolecular disulfide as the major product whereas a concentration in the millimolar range afforded the dimeric species as the dominant products. The tubular structure of the “non‐eclipsed” isomer was unequivocally determined by X‐ray analysis. The binding affinities of the duplexes to a wide range of compounds, including fluorescent dyes and clinically used drugs Imatinib and Esomeprazol, were studied in water by ITC. For most guest compounds, the experimentally determined Ka values were in the range 107–108 M ?1. These binding affinities are significantly higher than those found in the literature for analogous complexes with native cyclodextrins. In cases of binding of neutral or anionic guest molecules cyclodextrin duplexes outperformed cucurbiturils. A complex between a duplex and Nile blue was used to investigate its ability to penetrate the cytoplasmic membrane of HeLa cells. We found that the complex accumulated in the cell membrane but did not pass into cytosol. Importantly, the complex did not decompose to a significant extent under high dilution in the cellular environment. 相似文献
113.
Importance of the Anchor Group Position (Para versus Meta) in Tetraphenylmethane Tripods: Synthesis and Self‐Assembly Features 下载免费PDF全文
Marcin Lindner Dr. Michal Valášek Jan Homberg Kevin Edelmann Dr. Lukas Gerhard Prof. Dr. Wulf Wulfhekel Dr. Olaf Fuhr Tobias Wächter Prof. Dr. Michael Zharnikov Dr. Viliam Kolivoška Dr. Lubomír Pospíšil Dr. Gábor Mészáros Dr. Magdaléna Hromadová Prof. Dr. Marcel Mayor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(37):13218-13235
The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl‐protected thiol groups in either meta or para positions relative to the central sp3 carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in position 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self‐assembly features of both derivatives are analyzed on Au (111) surfaces by low‐temperature ultra‐high‐vacuum STM, high‐resolution X‐ray photoelectron spectroscopy, near‐edge X‐ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well‐ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single‐molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment. 相似文献
114.
Frontispiece: Copper(II) and Zinc(II) Complexes of Conformationally Constrained Polyazamacrocycles as Efficient Catalysts for RNA Model Substrate Cleavage in Aqueous Solution at Physiological pH 下载免费PDF全文
115.
Radim Horák Kamil Kořistek Veronika Šamšulová Ludmila Slaninová Martin Grepl Lubomír Kvapil Petr Funk Pavel Hradil Miroslav Soural 《Journal of heterocyclic chemistry》2020,57(4):1605-1615
Compounds bearing [1,3]dioxolo-quinoline scaffolds have been found in quinoline-based natural products; the only exception is the [1,3]dioxolo[4,5-c]quinoline moiety with a rare occurrence in both natural and synthetic derivatives. In this article, we report the preparation of diversely substituted and functionalized [1,3]dioxolo[4,5-c]quinolines using [1,3]dioxolo[4,5-c]quinoline-4-carbaldehyde (DQC) as the common intermediate. DQC was synthesized on a large scale from anthranilic acid and chloroacetone as the starting materials, with the rearrangement of acetonyl-anthranilate as the key step. The developed method allows for the simple preparation of [1,3]dioxolo[4,5-c]quinolines with various C2 substituents on the quinoline scaffold. Additionally, the synthetic route was successfully applied to the preparation of 3-hydroxyquinoline-4(1H)-ones. The target compounds were tested against representative Gram-positive/negative bacteria, and two derivatives exhibited submicromolar minimum inhibitory concentrations against Micrococcus luteus. 相似文献
116.
Lubomír Kubáček 《Applications of Mathematics》2003,48(2):81-95
In nonlinear regression models with constraints a linearization of the model leads to a bias in estimators of parameters of the mean value of the observation vector. Some criteria how to recognize whether a linearization is possible is developed. In the case that they are not satisfied, it is necessary to decide whether some quadratic corrections can make the estimator better. The aim of the paper is to contribute to the solution of the problem. 相似文献
117.
Christopher J. Shaffer Prokopis C. Andrikopoulos Jan Řezáč Lubomír Rulíšek František Tureček 《Journal of the American Society for Mass Spectrometry》2016,27(4):633-645
Noncovalent complexes of hydrophobic peptides GLLLG and GLLLK with photoleucine (L*) tagged peptides G(L* n L m )K (n = 1,3, m = 2,0) were generated as singly charged ions in the gas phase and probed by photodissociation at 355 nm. Carbene intermediates produced by photodissociative loss of N2 from the L* diazirine rings underwent insertion into X?H bonds of the target peptide moiety, forming covalent adducts with yields reaching 30%. Gas-phase sequencing of the covalent adducts revealed preferred bond formation at the C-terminal residue of the target peptide. Site-selective carbene insertion was achieved by placing the L* residue in different positions along the photopeptide chain, and the residues in the target peptide undergoing carbene insertion were identified by gas-phase ion sequencing that was aided by specific 13C labeling. Density functional theory calculations indicated that noncovalent binding to GL*L*L*K resulted in substantial changes of the (GLLLK + H)+ ground state conformation. The peptide moieties in [GL*L*LK + GLLLK + H]+ ion complexes were held together by hydrogen bonds, whereas dispersion interactions of the nonpolar groups were only secondary in ground-state 0 K structures. Born-Oppenheimer molecular dynamics for 100 ps trajectories of several different conformers at the 310 K laboratory temperature showed that noncovalent complexes developed multiple, residue-specific contacts between the diazirine carbons and GLLLK residues. The calculations pointed to the substantial fluidity of the nonpolar side chains in the complexes. Diazirine photochemistry in combination with Born-Oppenheimer molecular dynamics is a promising tool for investigations of peptide–peptide ion interactions in the gas phase. 相似文献
118.
Natália Káňavová Anna Krejčí Martina Benedeková Marek Doležel Lubomír Machuča 《Chemical Papers》2015,69(4):553-559
The impact of electrodialysis module characteristics on mass transfer was examined using the limiting current method. The current-voltage curves of different electrodialysis modules were measured and limiting currents were determined using the derivative method. The mass transfer coefficients were calculated and the parameters of their dependence on linear flow velocity were estimated. From these the impact of spacer thickness, spacer net type, membrane type, and module geometry were evaluated. It was found that the impact of spacer thickness was almost negligible within the examined range, but a decrease in the mass transfer coefficient could be expected in the case of thicker spacers. By contrast, the spacer net type and type of membrane were found to be very important parameters able to significantly influence the mass transfer. By modifying the module geometry, the mass transfer coefficient could also be altered and, only in this case, the exponential parameter of the dependence was changing. The parameters thus determined may be used to calculate the limiting current in a wide range of operational conditions and may help predict the performance of different electrodialysis module types. 相似文献
119.
Jaya Mehara Adarsh Koovakattil Surendran Teun van Wieringen Deeksha Setia Dr. Cina Foroutan-Nejad Dr. Michal Straka Prof. Dr. Lubomír Rulíšek Prof. Dr. Jana Roithová 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201794
Gold(II) complexes are rare, and their application to the catalysis of chemical transformations is underexplored. The reason is their easy oxidation or reduction to more stable gold(III) or gold(I) complexes, respectively. We explored the thermodynamics of the formation of [AuII(L)(X)]+ complexes (L=ligand, X=halogen) from the corresponding gold(III) precursors and investigated their stability and spectral properties in the IR and visible range in the gas phase. The results show that the best ancillary ligands L for stabilizing gaseous [AuII(L)(X)]+ complexes are bidentate and tridentate ligands with nitrogen donor atoms. The electronic structure and spectral properties of the investigated gold(II) complexes were correlated with quantum chemical calculations. The results show that the molecular and electronic structure of the gold(II) complexes as well as their spectroscopic properties are very similar to those of analogous stable copper(II) complexes. 相似文献
120.