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101.
A synthetic procedure leading to the preparation of a new family of enantiopure mono-N-tosylated-1,2-diamines derived from (R)-(+)-limonene is described. (+)-Limonene was transformed into the appropriate N-tosyl derivative using N-tosylaziridination based on chloramine-T trihydrate. Subsequent ring opening by sodium azide afforded the corresponding isomeric azides. Finally, reduction of the azide function gave enantiomerically pure mono-N-tosylated-1,2-diamines. The ligands obtained proved to be effective in the asymmetric transfer hydrogenation protocol on aromatic ketones and imines. 相似文献
102.
Adamczyk Z Barbasz J Cieśla M 《Langmuir : the ACS journal of surfaces and colloids》2011,27(11):6868-6878
Adsorption of fibrinogen, modeled as a linear chain of touching beads of various sizes, was theoretically studied using the random sequential adsorption (RSA) model. The adsorption process was assumed to consist of two steps: (i) formation of an irreversibly bound fibrinogen monolayer under the side-on orientation, which is independent of the bulk protein concentration and (ii) formation of the reversibly bound, end-on monolayer, whose coverage was dependent on the bulk concentration. Calculation based on the RSA model showed that the maximum surface concentration of the end-on (reversible) monolayer equals N(⊥∞) = 6.13 × 10(3) μm(-2) which is much larger than the previously found value for the side-on (irreversible) monolayer, equal to N(∞) = 2.27 × 10(3) μm(-2). Hence, the maximum surface concentration of fibrinogen in both orientations is determined to be 8.40 × 10(3) μm(-2) corresponding to the protein coverage of 5.70 mg m(-2) assuming 20% hydration. Additionally, the surface blocking function (ASF) was determined for the end-on fibrinogen adsorption, approximated for the entire range of coverage by the interpolating polynomial. For the coverage approaching the jamming limit, the surface blocking function (ASF) was shown to vanish proportionally to (θ(⊥∞) - θ(⊥))(2). These calculation allowed one to theoretically predict adsorption isotherms for the end-on regime of fibrinogen and adsorption kinetics under various transport conditions (diffusion and convection). Using these theoretical results, a quantitative interpretation of experimental data obtained by TIRF and ellipsometry was successfully performed. The equilibrium adsorption constant for the end-on adsorption regime was found to be 8.04 × 10(-3) m. On the basis of this value, the depth of the adsorption energy minimum, equal to -17.4 kT, was predicted, which corresponds to ΔG = -41.8 kJ mol(-1). This is in accordance with adsorption energy derived as the sum of the van der Waals and electrostatic interactions. Besides having significance for predicting fibrinogen adsorption, theoretical results derived in this work also have implications for basic science providing information on mechanisms of anisotropic protein molecule adsorption on heterogeneous surfaces. 相似文献
103.
Nanoparticle self-assembly at fluid-fluid interfaces has been traditionally exploited in emulsification, encapsulation and oil recovery, and more recently in emerging applications including functional nanomaterials and biphasic catalysis. We provide a review of the literature focusing on the open challenges that still hamper the broader applicability of this potentially transformative technology, and we outline strategies to achieve improved control over interfacial self-assembly of nanoparticles. First, we discuss means to promote spontaneous adsorption by tuning the interfacial energies of the nanoparticles with the fluids using capping ligands, and the occurrence of energy barriers. We then examine the interactions between interfacial nanoparticles and how they affect the formation of equilibrium interfacial suspensions versus non-equilibrium two-dimensional phases, such as weakly attractive glasses and gels. Important differences with colloidal interactions in a bulk suspension arise due to the discontinuity in solvent properties at the interface. For instance, ligand brushes rearrange in asymmetric configurations, and thus play a significant role in determining interparticle interactions. Finally, we briefly discuss the link between interfacial microstructure and the dynamic response of particle-laden interfaces, including interfacial rheology and the fate of nanoparticle monolayers upon out-of-plane deformation. 相似文献
104.
Anna A. Kończyk Joanna Szawkało Jan K. Maurin Zbigniew Czarnocki 《Helvetica chimica acta》2013,96(7):1348-1354
The highly functionalized tetrahydropyridine 4 was obtained in an indium(III) chloride catalyzed multi‐component reaction from benzaldehyde, 4‐methoxyaniline, and ethyl acetoacetate (=ethyl 3‐oxobutanoate) in the presence of [1,1′‐binaphthalene]‐2,2′‐diol (binol). It was found that binol played a beneficial role in this reaction, allowing a substantial decrease of the amount of indium salt. Also, simple organic Brønsted acids may serve as effective organocatalysts in this process. 相似文献
105.
Structure of colloid silica determined by viscosity measurements 总被引:3,自引:0,他引:3
The viscosity of nanosized colloid silica suspensions, used as binders in the investment casting, was determined as a function of their weight fraction reaching 52%. A new capillary viscometer was used whose construction eliminated sedimentation effects. The experiments have been carried out at fixed pH 10.0 and controlled ionic strength. It was found that for a low silica concentration range (weight fraction below 5%) the suspension viscosity increased more rapidly than the Einstein theory predicts. This anomalous behavior could not be explained in terms of the primary electroviscous effect predicted to be a few orders of magnitude smaller as observed. This discrepancy was accounted for by postulating a fuzzy, gel-like structure of colloid silicas used in our experiments. Hence, the apparent hydrodynamic radius of silica particles in aqueous suspensions was found to be larger than the primary particle size in accordance with previous observations. Based on this postulate, an apparent density of the silica sols was found to be 1.32-1.37 g/cm(3) instead of 2.2-2.32 g/cm(3) as determined from the suspension dilution method. This behavior was interpreted in terms of the core/shell model with high shell porosity, reaching 85%. Similarly, for higher concentration ranges, silica viscosity increased more rapidly with increased sol concentration than predicted by the Batchelor model derived for hard particles. The deviation was attributed to the secondary electroviscous effect stemming from the electrostatic interactions among silica particles in sheared suspensions. This effect has quantitatively been interpreted in terms of Russel's theory. On the other hand, for the high concentration range the experimental results were well accounted for by the Dougherty-Krieger model. By exploiting our experimental findings a sensitive method of determining the structure and apparent density of silica sols in aqueous media was proposed. 相似文献
106.
Plate impact experiments on the (210), (100), and (111) planes were performed to examine the role of crystalline anisotropy on the shock-induced decomposition of cyclotrimethylenetrinitramine (RDX) crystals. Time-resolved emission spectroscopy was used to probe the decomposition of single crystals shocked to peak stresses ranging between 7 and 20 GPa. Emission produced by decomposition intermediates was analyzed in terms of induction time to emission, emission intensity, and the emission spectra shapes as a function of stress and time. Utilizing these features, we found that the shock-induced decomposition of RDX crystals exhibits considerable anisotropy. Crystals shocked on the (210) and (100) planes were more sensitive to decomposition than crystals shocked on the (111) plane. The possible sources of the observed anisotropy are discussed with regard to the inelastic deformation mechanisms of shocked RDX. Our results suggest that, despite the anisotropy observed for shock initiation, decomposition pathways for all three orientations are similar. 相似文献
107.
Beata Kolesińska Katarzyna Kasperowicz Adam Mazur Zbigniew J. Kamiński 《Tetrahedron letters》2010,51(1):20-4513
The concept of a chiral coupling reagent for the enantioselective synthesis of peptides with a predictable configuration and enantiomeric purity from racemic substrates is presented. The reagent was prepared by treatment of strychninium tetrafluoroborate with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence of sodium bicarbonate yielding N-(4,6-dimethoxy-1,3,5-triazin-2-yl)strychninium tetrafluoroborate in high yield, which is stable at room temperature, and in a broad range of solvents gave enriched Z-Ala-Phe-OMe (dr from 95/5 to 60/40) in high yield with d-configuration on the alanine residue starting from rac-Z-Ala-OH. 相似文献
108.
109.
Beata Orlińska Jan Zawadiak Roman Mazurkiewicz Zbigniew Stec Henryk Koroniak 《Monatshefte für Chemie / Chemical Monthly》2009,97(2):1459-1463
Abstract
Thermal decomposition of 1-methyl-1-(4-methyl-1-naphthyl)ethyl hydroperoxide under gas chromatography-mass spectroscopy (GC–MS) conditions gives 2-((4-methyl-1-naphthyl)oxy)propene as the main product (50.5%), without any detectable traces of the isomeric 2-((5-methyl-1-naphthyl)oxy)propene. This finding excludes the rearrangement pathway of 1-methyl-1-(1-naphthyl)ethyl hydroperoxides to the corresponding 2-(1-naphthyloxy)propenes, which involves formation of a naphthofuran derivative as an intermediate and transfer of the isopropenyloxy group to the 8 position. This result, as well as our previous density functional theory (DFT) calculations, points to the rearrangement pathway involving an oxirane-type intermediate as the most plausible pathway to 2-(1-naphthyloxy)propenes. This rearrangement is responsible for the unusual inhibition effects of 1-methyl-1-(1-naphthyl)ethyl hydroperoxide on the liquid-phase oxidation of isopropylarenes with oxygen. 相似文献110.
Izabela Brzozowska Zbigniew A. Figaszewski 《Colloids and surfaces. B, Biointerfaces》2003,27(4):303-309
The measurements of the interfacial tension at the air/aqueous subphase interface as the function of pH were performed. The interfacial tension of the air–aqueous subphase interface was divided into contributions of individuals. A simple model of the influence of pH on the phosphatidylcholine monolayer at the air/hydrophobic chains of phosphatidylcholine is presented. The contributions of additive phosphatidylcholine forms (both interfacial tension values and molecular area values) depend on pH. The interfacial tension values and the molecular areas values for LH+, LOH− forms of phosphatidylcholine were calculated. The assumed model was verified experimentally. 相似文献