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171.
Borys V. Zakharchenko Dmytro M. Khomenko Roman O. Doroshchuk Olga V. Severynovska Ilona V. Raspertova Victoria S. Starova Rostyslav D. Lampeka 《Chemical Papers》2017,71(10):2003-2009
The structure of four new palladium complexes [Pd(HL 2 )Cl 2 and Pd(L 1–3 ) 2 ] with 3-(2-pyridyl)-5-R-1,2,4-triazoles (R=H, CH3, Ph respectively HL 1 , HL 2 , HL 3 ) was proposed based on IR, NMR, UV spectroscopy and MALDI mass spectrometry data analysis. It is found that the complexation of HL 2 and HL 3 with Pd2+ ions results in a decrease of their fluorescence intensity and it is vice versa in case of HL 1 . Furthermore, the influence of the substituent (R) in the 3-(2-pirydyl)-5-R-1,2,4-triazoles on the fluorescent and protolytic properties of HL 1–3 was investigated. 相似文献
172.
Denysenko D Grzywa M Tonigold M Streppel B Krkljus I Hirscher M Mugnaioli E Kolb U Hanss J Volkmer D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(6):1837-1848
A highly porous member of isoreticular MFU‐4‐type frameworks, [Zn5Cl4(BTDD)3] (MFU‐4l(arge)) (H2‐BTDD=bis(1H‐1,2,3‐triazolo[4,5‐b],[4′,5′‐i])dibenzo[1,4]dioxin), has been synthesized using ZnCl2 and H2‐BTDD in N,N‐dimethylformamide as a solvent. MFU‐4l represents the first example of MFU‐4‐type frameworks featuring large pore apertures of 9.1 Å. Here, MFU‐4l serves as a reference compound to evaluate the origin of unique and specific gas‐sorption properties of MFU‐4, reported previously. The latter framework features narrow‐sized pores of 2.5 Å that allow passage of sufficiently small molecules only (such as hydrogen or water), whereas molecules with larger kinetic diameters (e.g., argon or nitrogen) are excluded from uptake. The crystal structure of MFU‐4l has been solved ab initio by direct methods from 3D electron‐diffraction data acquired from a single nanosized crystal through automated electron diffraction tomography (ADT) in combination with electron‐beam precession. Independently, it has been solved using powder X‐ray diffraction. Thermogravimetric analysis (TGA) and variable‐temperature X‐ray powder diffraction (XRPD) experiments carried out on MFU‐4l indicate that it is stable up to 500 °C (N2 atmosphere) and up to 350 °C in air. The framework adsorbs 4 wt % hydrogen at 20 bar and 77 K, which is twice the amount compared to MFU‐4. The isosteric heat of adsorption starts for low surface coverage at 5 kJ mol?1 and decreases to 3.5 kJ mol?1 at higher H2 uptake. In contrast, MFU‐4 possesses a nearly constant isosteric heat of adsorption of ca. 7 kJ mol?1 over a wide range of surface coverage. Moreover, MFU‐4 exhibits a H2 desorption maximum at 71 K, which is the highest temperature ever measured for hydrogen physisorbed on metal–organic frameworks (MOFs). 相似文献
173.
Andrey V. BogolubskySergey V. Ryabukhin Sergey E. PipkoOleg Lukin Alexander Shivanyuk Dmytro MykytenkoAndrey Tolmachev 《Tetrahedron》2011,67(20):3619-3623
A facile and versatile method for the synthesis of unsymmetrical ureas from readily available reagents is reported. In the first step trifluoroethylchloroformate is reacted with a stoichiometric amount of a primary amine to give an intermediate trifluoroethyl carbamate. The addition of a second amine (primary or secondary) to the trifluoroethyl carbamate furnishes corresponding unsymmetrical ureas in 75-85% yield. A simple workup procedure, the high yields obtained, and the purity of the isolated products are suitable for the parallel synthesis of combinatorial libraries of unsymmetrical ureas with high structural and functional diversity. 相似文献
174.
Tom Urbnek Jií Trousil Dmytro Rak Kristýna Gunr Rafa Konefa Miroslav louf Marin Sedlk Olga ebestov Janoukov Martin Hrubý 《Macromolecular bioscience》2020,20(5)
Polymeric drug carriers exhibit excellent properties that advance drug delivery systems. In particular, carriers based on poly(ethylene oxide)‐block‐poly(ε‐caprolactone) are very useful in pharmacokinetics. In addition to their proven biocompatibility, there are several requirements for the efficacy of the polymeric drug carriers after internalization, e.g., nanoparticle behavior, cellular uptake, the rate of degradation, and cellular localization. The introduction of γ‐butyrolactone units into the hydrophobic block enables the tuning of the abovementioned properties over a wide range. In this study, a relatively high content of γ‐butyrolactone units with a reasonable yield of ≈60% is achieved by anionic ring‐opening copolymerization using 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene as a very efficient catalyst in the nonpolar environment of toluene with an incorporated γ‐butyrolactone content of ≈30%. The content of γ‐butyrolactone units can be easily modulated according to the feed ratio of the monomers. This method enables control over the rate of degradation so that when the content of γ‐butyrolactone increases, the rate of degradation increases. These findings broaden the application possibilities of polyester‐polyether‐based nanoparticles for biomedical applications, such as drug delivery systems. 相似文献
175.
Dmytro Havrylyuk Borys Zimenkovsky Roman Lesyk 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):638-650
A series of new 2-{4-oxo-2-[(4-oxothiazolidin-2-ylidene)-hydrazono]-thiazolidin-5-yl}-N-arylacetamides ( 4a–e ), 5-(2-oxo-2-aryl-ethyl)-2-[(4-oxothiazolidin-2-ylidene)-hydrazono]-thiazolidine-4-ones ( 5a–d ), 2-(4-oxo-2-[(2-oxothiazolidin-4-ylidene)-hydrazono]-thiazolidin-5-yl)-N-arylacetamides ( 7a–e ), and 5-(2-oxo-2-aryl-ethyl)-2-[(2-oxothiazolidin-4-ylidene)-hydrazono]-thiazolidine-4-ones ( 8a–d ) have been synthesized starting from 2-thioxothiazolidin-4-one and 4-thioxothiazolidin-2-one through a multistep reaction sequence. 2-Thioxothiazolidin-4-one was alkylated via the intermediate formation of the triethylammonium salt 1 by ethyl chloroacetate. Compound 2 and 4-thioxothiazolidin-2-one reacted with thiosemicarbazides to give the 1-(4-thiazolidinone-2-ylidene)-4-R-thiosemicarbazones ( 3a,b ) and 1-(2-thiazolidinone-4-ylidene)thiosemicarbazones ( 6a,b ), respectively. Following [2+3]-cyclization of thiazolidinone-substituted thiosemicarbazones ( 3a,b and 6a,b) with N-arylmaleimides and aroylacrylic acids as equivalents of dielectrophilic synthon [C2]2 +, novel non-fused bicyclic thiazolidinones ( 4a–e, 5a–d, 7a–e, 8a–d ) were synthesized. The structures of the new compounds ( 4a–e, 5a–d, 7a–e, 8a–d ) were established on the basis of their elemental analysis and 1H NMR and mass spectral data. Eight of the synthesized compounds were tested, and three of them displayed different levels of antitumor activity. The most efficient antitumor agent—2-{4-oxo-3-furylmethyl-2-[(4-oxothiazolidin-2-ylidene)-hydrazono]-thiazolidin-5-yl}-N-4-chlorophenylacetamide ( 4d ) was found to be active against leukemia, melanoma, lung, colon, CNS, ovarian, renal, prostate, and breast cancer cell lines with mean lgGI50 and lgTGI values of –5.35 and –4.78, respectively. 相似文献
176.
Ablikim M Achasov MN Alberto D An Q An ZH Bai JZ Baldini R Ban Y Becker J Berger N Bertani M Bian JM Bondarenko O Boyko I Briere RA Bytev V Cai X Calcaterra AC Cao GF Cao XX Chang JF Chelkov G Chen G Chen HS Chen JC Chen ML Chen SJ Chen Y Chen YB Cheng HP Chu YP Cronin-Hennessy D Dai HL Dai JP Dedovich D Deng ZY Denysenko I Destefanis M Ding Y Dong LY Dong MY Du SX Fan RR Fang J Fang SS Feng CQ Fu CD Fu JL Gao Y Geng C Goetzen K Gong WX Greco M Grishin S Gu MH Gu YT Guan YH Guo AQ Guo LB Guo YP 《Physical review letters》2011,107(18):182001
We present results of a study of the decay J/ψ → ωηπ+ π- using a sample of (225.2 ± 2.8) × 10(6) J/ψ events collected by the BESIII detector, and report the observation of a new process J/ψ → ωX(1870) with a statistical significance of 7.2σ, in which X(1870) decays to a(0)(±)(980)π±. Fitting to ηπ+ π- mass spectrum yields a mass M = 1877.3 ± 6.3(stat)(-7.4)(+3.4)(syst) MeV/c(2), a width Γ = 57 ± 12(stat)(-4)(+19)(syst) MeV/c(2), and a product branching fraction B(J/ψ → ωX) × B(X→a(0)(±)(980)π±) × B(a(0) (±)(980) → ηπ±) = [1.50 ± 0.26(stat)(-0.36)(+0.72) (syst)] × 10(-4). Signals for J/ψ → ωf(1)(1285) and J/ψ → ω η(1405) are also clearly observed and measured. 相似文献
177.
We propose a notion of algebra of twisted chiral differential operators over algebraic manifolds with vanishing 1st Pontrjagin class. We show that such algebras possess
families of modules depending on infinitely many complex parameters, which we classify in terms of the corresponding algebra
of twisted differential operators. If the underlying manifold is a flag manifold, our construction recovers modules over an
affine Lie algebra parameterized by opers over the Langlands dual Lie algebra. The spaces of global sections of “smallest”
such modules are irreducible
[^(\mathfrakg)]{{\hat{{\mathfrak{g}}}}} -modules, and all irreducible
\mathfrakg{{\mathfrak{g}}} -integrable
[^(\mathfrakg)]{{\hat{{\mathfrak{g}}}}} -modules at the critical level arise in this way. 相似文献
178.
The pyrazolo[1,5-a]pyrimidine class of compounds has been identified as a privileged structure for library synthesis on the basis of several key characteristics of the core molecule. A chemical set in excess of 400 compounds was synthesized to give 3,6,7-substituted pyrazolo[1,5-a]pyrimidinecarboxamides 9. To facilitate the rapid preparation of this library, a preparative strategy included the synthesis of activated p-nitrophenyl esters, followed by subsequent scavenging of the p-nitrophenol leaving group. Excess reagents were also removed using scavenging reagents that were found to be compatible with the synthetic methodology and that afforded target compounds in acceptable purity and yields. 相似文献
179.
Reorientation of 9-(trideuteromethyl)purine and 7-(trideuteromethyl)purine molecules in methanol-d4 solutions has been investigated on the basis of the interpretation of the nuclear spin relaxation rates of their 14N (or 1H) and 13C nuclei. The transverse quadrupole relaxation rates of 14N nuclei have been obtained from the line shape analysis of their 14N NMR spectra. Alternatively, the information on the longitudinal 14N relaxation rates has been obtained via the scalar relaxation of the second kind of protons coupled to 14N. The longitudinal dipolar relaxation rates of the protonated 13C nuclei in the investigated molecules have been determined by measuring their overall relaxation rates and NOE enhancement factors. The molecular geometries, scalar coupling constants, and EFG tensors needed for quantitative interpretation of the above data have been calculated theoretically [DFT B3LYP/6-311++G(2d,p) or B3PW91/6-311+G(df,pd)] including the impact of the solvent by using discrete solvation and the polarizable continuum model. The reorientation of the investigated purines has been described as rotational diffusion of an asymmetrical top. It has been found that to get a fully consistent interpretation of the relaxation data, effective C-H bond lengths being 3% longer than the calculated ones had to be used in analysis to compensate for the ground-state vibrations. The obtained rotational diffusion coefficients and orientations of the principal diffusion axes show that the investigated molecules reorient anisotropically and that the mode of their solvation is remarkably different, in spite of their structural similarity. 相似文献
180.
The morphology of a highly asymmetric double crystallizable poly(epsilon-caprolactone-b-ethylene oxide) (PCL-b-PEO) block copolymer has been studied with in situ simultaneously small and wide-angle x-ray scattering as well as atomic force microscopy. The molecular masses Mn of the PCL and PEO blocks are 24,000 and 5800, respectively. X-ray scattering and rheological measurements indicate that no microphase separation occurs in the melt. Decreasing the temperature simultaneously triggers off a crystallization of PCL and microphase separation between the PCL and PEO blocks. Coupling and competition between microphase separation and crystallization results in a morphology of PEO spheres surrounded by PCL partially crystallized in lamella. Further decreasing temperature induces the crystallization of PEO spheres, which have a preferred orientation due to the confinements from hard PCL crystalline lamella and from soft amorphous PCL segments in different sides. The final morphology of this highly asymmetric block copolymer is similar to the granular morphology reported for syndiotactic polypropylene and other (co-) polymers. This implies a similar underlying mechanism of coupling and competition of various phase transitions, which is worth further exploration. 相似文献