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131.
The complete assignment of the proton chemical shifts of coumarin ( 1 ), all monomethoxy derivatives and the six possible dimethoxyl substituted compounds at the aromatic ring was achieved at 60 MHz in a quantitative study utilizing Pr(fod)3 as the shift reagent. It was found that in addition to the complexation at the lactone carbonyl a second interaction of the lanthanide shift reagent occurs when two methoxyl groups are found in an ortho distribution. The results are discussed in comparison to data published for flavones in the presence of Pr(fod)3 shift reagent. 相似文献
132.
Preparation and characterization of individual peptide-wrapped single-walled carbon nanotubes 总被引:3,自引:0,他引:3
Zorbas V Ortiz-Acevedo A Dalton AB Yoshida MM Dieckmann GR Draper RK Baughman RH Jose-Yacaman M Musselman IH 《Journal of the American Chemical Society》2004,126(23):7222-7227
Two challenges for effectively exploiting the remarkable properties of single-walled carbon nanotubes (SWNTs) are the isolation of intact individual nanotubes from the raw material and the assembly of these isolated SWNTs into useful structures. In this study, we present atomic force microscopy (AFM) evidence that we can isolate individual peptide-wrapped SWNTs, possibly connected end-to-end into long fibrillar structures, using an amphiphilic alpha-helical peptide, termed nano-1. Transmission electron microscopy (TEM) and well-resolved absorption spectral features further corroborate nano-1's ability to debundle SWNTs in aqueous solution. Peptide-assisted assembly of SWNT structures, specifically in the form of Y-, X-, and intraloop junctions, was observed in the AFM and TEM images. 相似文献
133.
M. Pilar Gamasa Mariano Laguna Daniel Miguel Víctor Riera 《Transition Metal Chemistry》1981,6(6):374-376
Summary Bidentate ligands can readily replace acetone in thefac-[Mn(CO)3(chel)(OCMe2)]+ complexes or the perchlorate group fromfac-[Mn(CO)3(chel)(OClO3)] yieldingfac-[Mn(CO)3(chel)(L-L)]+ or [{fac-Mn(CO)3(chel)}2(L-L)]2+ [chel = 1,10-phenanthroline (phen), 2,2-bipyridine (bipy), 1,2-bis(diphenylphosphine)ethane (dpe); L-L = bis(diphenylphosphine)methane (dpm), dpe, 1,4-bis(diphenylphosphine)butane (dpb), succinonitrile (suc), and glutaronitrile (glu)]. Some of these mononuclear complexes are precursors for binuclear complexes which are linked by bridging phosphines or nitriles. 相似文献
134.
Fernández EJ Laguna A López-de-Luzuriaga JM Monge M Montiel M Olmos ME 《Inorganic chemistry》2005,44(5):1163-1165
The reaction of the complex [Au2Ag2(C6F5)4)N[triple bond]CCH3)2]n (1) with 1 equiv of CuCl in the presence of 1 equiv of pyrimidine ligand leads to the formation of the heteronuclear Au(I)-Cu(I) organometallic polymer [Cu{Au(C6F5)2}(N[triple bond]CCH3)(mu2-C4H4N2)]n (2) through a transmetalation reaction. Complex 2 displays unprecedented unsupported Au(I)...Cu(I) interactions of [Au(C6F5)2]- units with the acid Cu(I) sites in a [Cu(N[triple bond]CCH3)(mu2-pyrimidine)]n+(n) polymeric chain. Complex 2 has a rich photophysics in solution and in the solid state. 相似文献
135.
A partial least squares (PLS) Fourier transform Raman spectrometry procedure based on the measurement of solid samples contained inside standard glass vials, has been developed for direct and reagent-free determination of sodium saccharin and sodium cyclamate in table top sweeteners. A classical 22 design for standards was used for calibration, but this system provides accuracy errors higher than 13% w/w for the analysis of samples containing glucose monohydrate. So, an extended model incorporating glucose monohydrate (23 standards) was assayed for the determination of sodium saccharin and sodium cyclamate in all the samples. Mean centering spectra data pre-treatment has been employed to eliminate common spectral information and root mean square error of calibration (RMSEC) of 0.0064 and 0.0596 was obtained for sodium saccharin and sodium cyclamate, respectively. A mean accuracy error of the order of 1.1 and 1.9% w/w was achieved for sodium saccharin and sodium cyclamate, in the validation of the method using actual table top samples, being lower than those obtained using an external monoparametric calibration. FT-Raman provides a fast alternative to the chromatographic method for the determination of the sweeteners with a three times higher sampling throughput than that obtained in HPLC. On the other hand, FT-Raman offers an environmentally friendly methodology which eliminates the use of solvents. Furthermore, the stability of samples and standards into chromatographic standard glass vials allows their storage for future analysis thus avoiding completely the waste generation. 相似文献
136.
Gotor-Fernández V Ferrero M Fernández S Gotor V 《The Journal of organic chemistry》2002,67(4):1266-1270
An efficient synthesis of monoacylated 1alpha,25-dihydroxyvitamin D3 A-ring precursors 15, 16, 18, and 19 has been described through an enzymatic hydrolysis process. Candida antarctica A lipase (CAL-A) hydrolyzes the C-5 acetate ester in trans stereoisomers 9 and 13, with complete and high selectivity, respectively. In the case of cis isomers 11 and 14, Chromobacterium viscosum lipase (CVL) is the enzyme of choice, exhibiting opposite selectivity for these two enantiomers. This lipase selectively catalyzes the hydrolysis at the C-3 acetate in diester 11 and at C-5 position in diester 14. It is noteworthy that through a hydrolysis reaction CAL-A and CVL allow the synthesis of the four A-ring monoacetylated precursors of 1alpha,25-dihydroxyvitamin D3, precursors which are complementary to those obtained by the enzymatic acylation process. In addition, with excellent yield CVL selectively hydrolyzes the C-3 chloroacetate ester instead of the C-5 acetate in diester 22, a key intermediate in the synthesis of new A-ring modified 1alpha,25-dihydroxyvitamin D3 analogues. 相似文献
137.
Velázquez MM Ortega F Monroy F Rubio RG Pegiadou S Pérez L Infante MR 《Journal of colloid and interface science》2005,283(1):144-152
We report the formation of Langmuir monolayers of pure zwitterionic hexadecyl 1-N-L-tryptophan glycerol ether (C(16)-TGE) surfactant and mixed monolayers of cationic-zwitterionic surfactant obtained modifying the pH of the subphase. The pressure-area and surface potential-area isotherms and fluorescence microscopy measurements have been used to characterize the surface phase transitions in the monolayers. These transitions appeared at larger areas as the pH decreased from 6.0 to 2.0 and almost disappeared as the pH decreased further. The analysis of the surface potential and the infrared reflection-absorption spectroscopy data suggests that the phase transition is associated with a change of orientation of both the hydrocarbon chain and the aromatic group of the surfactant with respect to the air-water surface. The surface rheology of the monolayers was studied by quasielastic light scattering and by the oscillatory barrier technique. The results indicate that there is at least one relaxation process in the monolayer. 相似文献
138.
Ashton PR Balzani V Clemente-León M Colonna B Credi A Jayaraman N Raymo FM Stoddart JF Venturi M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(3):673-684
Aliphatic amines, incorporating one or three (branched) acylated beta-D-glucopyranosyl residues, were coupled with the acid chloride of ferrocenecarboxylic acid and with the diacid chloride of 1,1'-ferrocenedicarboxylic acid to afford four dendrimer-type, carbohydrate-coated ferrocene derivatives in good yields (54-92%). Deprotection of the peracylated beta-D-glucopyranosyl residues was achieved quantitatively by using Zemplén conditions, affording four water-soluble ferrocene derivatives. When only one of the two cyclopentadienyl rings of the ferrocene unit is substituted, strong complexes are formed with beta-cyclodextrin in H2O, as demonstrated by liquid secondary ion mass spectrometry (LSIMS), 1H NMR spectroscopy, electrochemical measurements, and circular dichroism spectroscopy. Molecular dynamics calculations showed that the unsubstituted cyclopentadienyl ring is inserted through the cavity of the toroidal host in these complexes. The electrochemical behavior of the protected and deprotected ferrocene-containing dendrimers was investigated in acetonitrile and water, respectively. The diffusion coefficient decreases with increasing molecular weight of the compound. The potential for oxidation of the ferrocene core, the rate constant of heterogeneous electron transfer, and the rate constant for the energy-transfer reaction with the luminescent excited state of the [Ru(bpy)3]2+ complex (bpy = 2,2'-bipyridine) are strongly affected by the number (one or two) of substituents and by the number (one or three) of carbohydrate branches present in the substituents. These effects are assigned to shielding of the ferrocene core by the dendritic branches. Electrochemical evidence for the existence of different conformers for one of the dendrimers in aqueous solution was obtained. 相似文献
139.
Andrés R Galakhov MV Gómez-Sal MP Martín A Mena M del Carmen Morales-Varela M Santamaría C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):805-811
The photochemical treatment of mu(3)-alkylidyne complexes [[TiCp*(mu-O)](3)(mu(3)-CR)] (R=H (1), Me (2), Cp*=eta(5)-C(5)Me(5)) with the amines (2,6-Me(2)C(6)H(3))NH(2), Et(2)NH, and Ph(2)NH and the imine Ph(2)C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti(3)Cp*O(3)], and the formation of new oxoderivatives [[TiCp*(3)(mu-CHR)(R'NR")] (R"=2,6-Me(2)C(6)H(3), R'=H, R=H (3), Me (4); R'=R"=Et, R=H (5), Me (6); R'=R"=Ph, R=H (7), Me (8)) and [[TiCp*(mu-O)](3)(mu-CHR)(N=CPh(2))] (R=H (9), R=Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the mu-methylene [[TiCp*(mu-O)](3)(mu-CH(2))(HNtBu)] (11) complex and finally, the alkyl derivative [[TiCp*(mu-O)](3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes 1 or 2 in the presence of diamines o-C(6)H(4)(NH(2))(2) and H(2)NCH(2)CH(2)NH(2) (en) affords [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(6)H(4)NH)] (13) and [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(2)H(4)NH)] (14) by either methane or ethane elimination, respectively. In the reaction of 1 with en, an intermediate complex [[TiCp*(mu-O)](3)(mu-CH(2))(NHCH(2)CH(2)NH(2))] (15) is detected by (1)H NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R'(2)NH or the imine Ph(2)C=NH; however, heating of solutions of 3 or 4 in [D(6)]benzene or a equimolecular mixture of both at 170 degrees C produces methane, ethane, or both, and the complex [[TiCp*(mu-O)](3)[mu(3)-eta(2)-NC(6)H(3)(Me)CH(2)]] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis. 相似文献
140.
José Barluenga Pablo Barrio Rubén Vicente Luis A. López Miguel Tomás 《Journal of organometallic chemistry》2004,689(23):3793-3799
Fischer carbene complexes 1 underwent a clean ligand dimerization reaction yielding functionalized olefins and trienes 4 in the presence of copper (I) catalysts. If treated with trifluoroacetic acid (TFA), trienes 4c, d, f undergo a cyclization process (Nazarov reaction) which furnishes cyclopentenone derivatives 6c, d, 7c, d and 8 in good yields. Finally, the Fischer aminocarbene 9 efficiently cyclodimerizes to the substituted arene 10 in the presence of CuBr. 相似文献