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961.
Irina V. Terekhova Marina N. Tikhova Tatyana V. Volkova Roman S. Kumeev German L. Perlovich 《Journal of inclusion phenomena and macrocyclic chemistry》2011,69(1-2):167-172
Possibility of encapsulation of riboflavin and alloxazine by ??- and ??-cyclodextrins in aqueous solution was studied by 1H NMR and solubility methods. Thermodynamic parameters of 1:1 inclusion complex formation (K, ??cG0, ??cH0 and ??cS0) were obtained and analyzed in terms of influence of reagent??s structure on complexation process. It was shown that ??-cyclodextrin displays low binding affinity to riboflavin and alloxazine. On the contrary, ??-cyclodextrin forms with riboflavin and alloxazine more stable inclusion complexes. Binding is accompanied by the negative enthalpy and entropy changes that are determined by predominance of van der Waals interactions and possible H-bonding. The presence of ribityl substituent in riboflavin molecule prevents the deep penetration of this compound into macrocyclic cavity. Proposed on the basis of 1H NMR data the partial insertion of the hydrophobic part of riboflavin and alloxazine molecules into the ??-cyclodextrin cavity causes the enhancement of aqueous solubility of the encapsulated substances. In comparison with ??-cyclodextrin, the solubilizing effect of ??-cyclodextrin is more pronounced due to its higher binding affinity to alloxazine and riboflavin. 相似文献
962.
Ananikov VP Makarov AV Beletskaya IP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12623-12630
The puzzling question of alkyne insertion into Pd-P and Pd-H bonds leading to the formation of new Pd-C, C-P, and C-H bonds was explored by theoretical calculations at the CCSD(T) and B3LYP levels of theory. The key factors responsible for selectivity of catalytic hydrofunctionalization of alkynes were resolved and studied in details for the models of hydrophosphorylation, hydrophosphinylation, and hydrophospination reactions. In contrast with the generally accepted mechanistic picture, the calculations have shown that several pathways are possible depending on the nature and geometrical arrangement of the phosphorus group. It was found that the product of alkyne insertion into the metal-hydrogen bond should be easily formed under kinetic-control conditions, while the product of alkyne insertion into the metal-phosphorus bond may be formed in certain cases under thermodynamic control. For the first time, the calculations have revealed the role of the oxygen atom in the reactivity of P=P(O)R(2) groups and the role of the interactions involving the lone pair of the P=PR(2) group in the reagent. The fundamental properties of the Pd-P, C-P, and P-H bonds were reported, and the larger bond strength upon increasing the number of oxygen atoms bound to phosphorus (P=PR(2), P(O)R(2), and P(O)(OR)(2)) have been shown. The relationship between bond energy, acidity, and reactivity of the studied phosphorus compounds has been determined. 相似文献
963.
Chernyshova IV Ponnurangam S Somasundaran P 《Journal of the American Chemical Society》2011,133(24):9536-9544
The impact of deposition and aggregation on (bio)chemical properties of semiconducting nanoparticles (NPs) is perhaps among the least studied aspects of aquatic chemistry of solids. Employing a combination of in situ FTIR and ex situ X-ray photoelectron spectroscopy (XPS) and using the Mn(II) oxygenation on hematite (α-Fe(2)O(3)) and anatase (TiO(2)) NPs as a model catalytic reaction, we discovered that the catalytic and sorption performance of the semiconducting NPs in the dark can be manipulated by depositing them on different supports or mixing them with other NPs. We introduce the electrochemical concept of the catalytic redox activity to explain the findings and to predict the effects of (co)aggregation and deposition on the catalytic and corrosion properties of ferric (hydr)oxides. These results offer new possibilities for rationally tailoring the technological performance of semiconducting metal oxide NPs, provide a new framework for modeling their fate and transport in the environment and living organisms, and can be helpful in discriminating between weakly and strongly adsorbed species in spectra. 相似文献
964.
Irina Nenciu 《Monatshefte für Mathematik》2013,170(3-4):425-436
The connection of orthogonal polynomials on the unit circle to the defocusing Ablowitz–Ladik integrable system involves the definition of a Poisson structure on the space of Verblunsky coefficients. In this paper, we compute the complete set of Poisson brackets for the monic orthogonal and the orthonormal polynomials on the unit circle, as well as for the second kind polynomials and the Wall polynomials. This answers a question posed by Cantero and Simon (J Approx Theory 158(1):3–48, 2009), for the case of measures with finite support. We also show that the results hold for the case of measures with periodic Verblunsky coefficients. 相似文献
965.
Anatolii E. Shipov Mikhail V. Makarov Pavel V. Petrovskii Ekaterina Yu. Rybalkina Yulia V. Nelyubina Irina L. Odinets 《Heteroatom Chemistry》2013,24(3):191-199
Two novel series of phosphorus‐substituted 3,5‐bis(arylidene)piperid‐4‐ones bearing 1,3,2‐oxazaphosphorinane cycle either directly attached to the piperidone core through the P N bond (diamidophosphates 4 ) or connected with it via thiocarbamoyl linker (thioureas 5 ) were obtained by the phosphorylation of NH precursors with 2‐oxo‐1,3,2‐oxazaphosphorinane chloride or the reaction of the former ones with the corresponding cyclic isothiocyanate. According to the results of cytotoxicity screening against human carcinoma cell lines (A549, CaOv3, KB), thioureas 5 were more active than the diamidophosphates 4 bearing the same arylidene rings, with compounds with electron‐withdrawing side groups displaying IC50 in the micromolar range of 1.2–7 μM. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:191–199, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21082 相似文献
966.
Vladimir A. Bershtein Alexander M. Fainleib Polycarpos Pissis Irina M. Bei Florent Dalmas Larisa M. Egorova 《Journal of Macromolecular Science: Physics》2013,52(3):555-575
Polycyanurate‐modified montmorrilonite (PCN‐MMT) nanocomposites were synthesized by polymerization of dicyanate ester of bisphenol A in the presence of MMT dispersed by ultrasound. Techniques of IR spectroscopy, WAXD, and TEM were applied to study polymerization kinetics and structure of the nanocomposites prepared, whereas their dynamics and thermal/mechanical properties over the ?30 to 420°C range were studied by using DSC, laser‐interferometric creep rate spectroscopy (CRS), and dielectric relaxation spectroscopy (DRS) techniques. It was shown that a small amount of MMT additive acts as a catalyst of polymerization and results in the formation of complicated intercalated/exfoliated structures, as well as strongly modifies the dynamics in the PCN network. Pronounced dynamic heterogeneity was observed for PCN/MMT nanocomposites. Along with the main PCN glass transition, two new glass transitions, at much higher and much lower temperatures, were revealed as a consequence of constrained dynamics in matrix interfacial nanolayers and due to incomplete local cross‐linking in the PCN matrix, respectively. In addition, increased sub‐T g mobility was observed in these nanocomposites. A two‐fold rise of modulus of elasticity as well as increasing thermal stability and arising microplasticity at low temperatures, promoting, obviously, improved crack resistance in a brittle PCN network, were found for the PCN‐MMT nanocomposites. 相似文献
967.
968.
Maxim Polikarpov Irina Snigireva Anatoly Snigirev 《Journal of synchrotron radiation》2014,21(3):484-487
A new method of harmonics rejection based on X‐ray refractive optics has been proposed. Taking into account the fact that the focal distance of the refractive lens is energy‐dependent, the use of an off‐axis illumination of the lens immediately leads to spatial separation of the energy spectrum by focusing the fundamental harmonic at the focal point and suppressing the unfocused high‐energy radiation with a screen absorber or slit. The experiment was performed at the ESRF ID06 beamline in the in‐line geometry using an X‐ray transfocator with compound refractive lenses. Using this technique the presence of the third harmonic has been reduced to 10?3. In total, our method enabled suppression of all higher‐order harmonics to five orders of magnitude using monochromator detuning. The method is well suited to third‐generation synchrotron radiation sources and is very promising for the future ultimate storage rings. 相似文献
969.
Vladimir V. Tatarchuk Anastasiya P. Sergievskaya Irina A. Druzhinina Vladimir I. Zaikovsky 《Journal of nanoparticle research》2011,13(10):4997-5007
The kinetics of the growth of gold nanoparticles during the reduction of tetrachloroauric acid by hydrazine in dispersed aqueous
solution encapsulated by reverse micelles of Triton N-42 surfactant (with decane as dispersion medium) was studied by means
of spectrophotometry. According to DLS data, at a set value of solubilization capacity V
s/V
o = 0.005 initial micelles have an aqueous core hydrodynamic diameter d
c = 3.6±0.2 nm. The final particles obtained after full reduction of AuIII have a metallic core of defect-free single-crystalline gold with a narrow size distribution and average core diameter d
Au = 7.7 ± 1.4 nm as shown by TEM. The rate of the particle growth is limited by the rate of gold reduction. The process kinetics
corresponds to the model consisting of two stages of reduction AuIII → AuI → Au0. The stages involve the formation and redox decay of the intermediate complexes Au(N2H4)Cl3 and Au(N2H4)Cl, and each stage proceeds via two routes: (1) homogeneous in the dispersed aqueous phase, and (2) heterogeneous on the
particle surfaces. Reactions taking route (2) are autocatalytic because they proceed with participation of the surface atoms
of particles as the final products of AuIII reduction. The dependencies of observed rate constants on reagent concentrations, temperature, and solubilization capacity
of the micellar solution are studied. 相似文献
970.
Olga N. Glotova Irina P. Korneva Nikolay Ya. Sinyavsky Bernadeta Dobosz Ryszard Krzyminiewski Maciej Jadzyn Michal Ostafin Boleslaw Nogaj 《Central European Journal of Physics》2011,9(2):387-391
In this paper experimental results obtained by both 75As NQR and EPR spectroscopy are presented for the three-component system As-Sb-Se. The 75As NQR spectra of glasses of structures (As2Se3)0.78 (Sb2Se3)0.22, (As2Se3)0.75 (Sb2Se3)0.25, (As2Se3)0.5 (Sb2Se3)0.5 have broad lines with two Sb-NQR lines (corresponding to the Sb2Se3 units) and two 75As-NQR lines (corresponding to the As2Se3 units). Differences in the EPR spectra of the different glasses arise because of the different amounts of arsenic and antimony
in their structure. 相似文献