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101.
102.
Mixtures of Zn(II) and 8-hydroxyquinoline (8QOH) in a 1:2 proportion, in aqueous solutions, result in fast complexation, followed by precipitation. Addition of 0.05 M sodium dodecyl sulfate (SDS), N-dodecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-12), N-hexadecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-16) or Triton X-100 results in considerable retardation of precipitation. In the presence of SDS, SB3-12, SB3-16 and Triton X-100 the 8QOH chelates are only kinetically stable in solution and after 24 h, the precipitation is almost quantitative. Conversely, upon addition of the cationic surfactant hexadecyltrimethylammonium bromide (CTABr), the absorbance of the complex remains constant even after at least six months. The interaction of the ligand 8QOH (and of the (8QO)(2)Zn(II) complex) with the cationic surfactant was studied by ultraviolet and NMR spectroscopy and 8QOH has a pK(a)=9.05 in the presence of the cationic surfactant and the ligand intercalates in the micelle, being preferentially located near the headgroup of the micelle. Although the solubilization site of the (8QO)(2)Zn(II) complex is similar to that of 8QOH, the interaction of the aromatic moiety with the CTA(+) headgroup is much stronger, due to the increased electron density in the aromatic ring of the ligand. As a consequence of this interaction, sphere to rod transition and an increase in microscopic and macroscopic viscosity are observed.  相似文献   
103.
We present herein a new catalyst-free and solvent-free approach for the synthesis of allylic thioethers directly from allylic alcohols and thiols. The methodology allows the synthesis of different allylic thioethers in good to excellent yields under microwave irradiation. Theoretical calculations for the allylic carbocation helped to explain the regioselectivity observed when nonsymmetric substrates are used in the reaction.  相似文献   
104.
Reaction and crystallization of 1,2-bis(2,6-dicarboxypyridin-4-yl)ethyne with Co(II) produces crystals containing monomers of 4-(2,6-dicarboxypyridin-4-yl)ethynylpyridine-2,6-dicarboxylatotriaqua cobalt(II) monohydrate complex (1), [Co(C16H6N2O8)(H2O)3]·H2O, instead of a rigid 1-D metal–organic framework consisting of a linear coordination polymer. This complex crystallizes in the monoclinic space group C2/c with a=6.8028(9) ?, b=36.781(5) ?, c=7.5135(9) 2.474(2)° and Z=4. The complex sits on a symmetry axis such that the two halves of the molecule are related by two-fold rotation symmetry. The molecules form layers in which the molecules are joined by intermolecular O–H⋯O interactions involving hydrogen bonds between CO2H⋯CO2 , H2O⋯CO2 , H2O⋯CO2H and H2O⋯H2O groups.Supplementary material CCDC-289569 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data request/cif, by e-mailing data request@ccdc.cam.ac.uk or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 IEZ, UK; fax: +44(0)1223-336033.  相似文献   
105.
106.
    
A novel hexa‐armed and star‐shaped polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms emanating from a phosphazene core (N3P3‐(PCL‐Chol)6) was synthesized by a combination of ring‐opening polymerization and “click” chemistry techniques. For this purpose, the terminal ? OH groups of the synthesized precursor (N3P3‐(PCL‐OH)6) were converted into Chol through a series of reaction. Both N3P3‐(PCL‐OH)6 and N3P3‐(PCL‐Chol)6 were then employed in the preparation of supramolecular inclusion complexes (ICs) with β‐cyclodextrin (β‐CD). The latter formed ICs with β‐CD in higher yield. The host–guest stoichiometry (ε‐CL:β‐CD, mol:mol) in the ICs of N3P3‐(PCL‐Chol)6 was found to be 1.2. The formation of supramolecular ICs of N3P3‐(PCL‐Chol)6 with β‐CD was confirmed by using Fourier transform infrared (FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopic methods, wide‐angle X‐ray diffraction (WAXD), and thermal analysis techniques. WAXD data showed that the obtained ICs with N3P3‐(PCL‐Chol)6 had a channel‐type crystalline structure, indicating the suppression of the original crystallization of N3P3‐(PCL‐Chol)6 in β‐CD cavities. Moreover, the thermal stabilities of ICs were found to be higher than those of the free star polymer and β‐CD. Furthermore, the surface properties of N3P3‐(PCL‐Chol)6 and its ICs with β‐CD were investigated by static contact angle measurements. The obtained results proved that the wettability of N3P3‐(PCL‐Chol)6 successfully increased with the formation of its ICs with β‐CD. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3406–3420  相似文献   
107.
    
The kinetics of the reaction of 1,1,1-trichloro-4-methoxy-3-penten-2-one with various aliphatic and aromatic amines was studied at 25°C in water, dimethyl sulphoxide, methanol, ethanol, chloroform, toluene and hexane. The formation of the corresponding 1,1,1-trichloro-4-amino-3-penten-2-one is explained in terms of an addition–elimination mechanism.  相似文献   
108.
The rate of specific hydrogen ion catalyzed hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane and equilibrium protonation of 1-hydroxy-2-naphthoate ion in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3-, are increased markedly by NaClO4 which induces anionic character and uptake of H3O+ in the micelles. Other salts, for example, NaNO3, NaBr, and NaCl, have similar but much smaller effects on this uptake of H3O+.  相似文献   
109.
This work describes the effect of a variety of metal ions as quenchers of the fluorescence of naphthalene, in aqueous micellar solutions of sodium dodecyl sulfate (SDS). The quenching by the metal ions can be adequately described by the Stern-Volmer equation and the best signal to noise ratios are obtained with low micellized detergent concentrations. Apparent Stern-Volmer constants decrease in the order: Fe3+ > Cu2+ > Pb2+ > Cr3+ > Ni2+ and directly reflect the relative sensitivity of the method for these ions. Detection limits (defined as three times the standard deviation of the blank for n= 10) for the fluorescence quenching of naphthalene by the metal ions in aqueous micellar SDS are in the range of 1.0 x 10(-6) to 1.0 x 10(-5) mol dm(-3). The proposed fluorescence quenching method shows good repeatibility for a variety of added quencher metal ions, indicating that anionic micelle-enhanced fluorescence quenching by metal ions constitutes an analytical method of rather general application.  相似文献   
110.
Static and free vibration analyses of straight and circular beams on elastic foundation are investigated. The Timoshenko beam theory is adopted in the derivation of the governing equation. Ordinary differential equations in scalar form obtained in the Laplace domain are solved numerically using the complementary functions method. The static and free vibration analyses of beams on elastic foundation are analyzed through various examples.  相似文献   
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