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71.
The development of useful synthetic tools to label amino acids within a peptide framework for the ultimate modification of proteins in a late-stage fashion is a challenging task of utmost importance within chemical biology. Herein, we report the first Pd-catalyzed C–H acylation of a collection of Tyr-containing peptides with aldehydes. This water-compatible tagging technique is distinguished by its site-specificity, scalability and full tolerance of sensitive functional groups. Remarkably, it provides straightforward access to a high number of oligopeptides with altered side-chain topology including mimetics of endomorphin-2 and neuromedin N, thus illustrating its promising perspectives toward the diversification of structurally complex peptides and chemical ligation.A novel Pd-catalyzed C–H acylation reaction with readily available aldehydes under an aqueous environment towards the assembly of non-protegenic acylated Tyr-containing oligopeptides is presented. 相似文献
72.
I. I. L. Cunha 《Journal of Radioanalytical and Nuclear Chemistry》2001,249(1):257-261
Sediment cores were collected at the Cananeia-Iguape Estuary and thelevels of 210Pb, 226Ra and 137Cs were measuredby gamma-ray spectrometry. The total 210Pb levels in sedimentsvaried from 13.5 to 122.5 Bq . kg —1 , for 226Raranged from 2.4 to 28 Bq . kg —1 and for 137Csfrom 0.28 to 6.1 Bq . kg —1 . Sedimentation rates were calculatedfrom the slope of the excess 210Pb profile in the core. The valuesobtained varied from 5 to 10 mm . y—1 , depending on thesediment deposition inputs in the local of sampling. 相似文献
73.
Juliana Vaz Bevilaqua Lidia M. Lima Aline Gomes Cunha Eliezer J. Barreiro Tito L. M. Alves Lucia Moreira Campos Paiva Denise M.Guimarães Freire 《Applied biochemistry and biotechnology》2005,121(1-3):117-128
The last step of the production of four phthalimide-derived acids, designed to act as antiasthma drugs, was performed by enzymatic hydrolysis of the respective methyl or ethyl esters. The esters 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic methyl ester (PHT-MET), 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic ethyl ester, 4-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester, and 2-(1,3-dioxo-1, 3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester were hydrolyzed by immobilized lipase. The enzymatic reaction could be used only to produce the desired 4-substituted compounds. The best result that was found to hydrolysis of PHT-MET, and, therefore, that ester was selected for optimization experiments in a three-phase system. Reactions were performed with solid biocatalyst (Lipozyme® RM IM), organic solvent phase (ethyl acetate), and aqueous phase (saturated Na2CO3 solution). To optimize the reaction conditions, an experimental design optimization procedure was used. The variables studied were the amount of enzyme, the temperature, and the volume of the aqueous solution. Time course experiments were then performed for different initial enzyme concentrations (0.5, 0.9, and 1.4 UH/mL of solvent). The optimized reaction conditions found were 20 mg of Lipozyme (0.9 UH/mLsolvent) and 5.0 mL of Na2CO3(sat) at 40°C for 6 h. 相似文献
74.
Jesús M. Ruiz Gonzalez Marcos Loroo Tania Crdova Gabriel Chuchani 《Journal of Molecular Structure》2005,732(1-3):55-61
Møller-Plesset MP2/6-31G method was used to examine the gas-phase elimination of 2-substituted alkyl ethyl N,N-dimethylcarbamates. The results of these calculations support a concerted non-synchronous six-membered cyclic transition state mechanism for carbamates containing a Cβ–H bond at the alkyl side of the ester. These substrates produce the N,N-dimethylcarbamic acid and the corresponding olefin. The unstable intermediate, N,N-dimethylcarbamic acid, rapidly decomposes through a four-membered cyclic transition state to dimethylamine and CO2 gas. Correlation of the logarithm of theoretical rate coefficients against original Taft's σ* values gave an approximate straight line (ρ*=−1.39, r=0.9558 at 360 °C). In addition to this fact, when log krel is plotted against the theoretical log krel for 2-substituted ethyl N,N-dimethylcarbamates a reasonable straight line (r=0.9919 at 360 °C) is obtained, suggesting similar mechanism. 相似文献
75.
Wilson Cunico Claudia R. B. Gomes Solange M. S. V. Wardell John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):o411-o414
rac‐2‐Isopropyl‐3‐(2‐nitrobenzyl)‐1,3‐thiadiazolin‐4‐one, C13H16N2O3S, is a rare example of a racemate crystallizing in the space group P212121, with one molecule each of S and R configurations, whose conformations are almost mirror images, within the asymmetric unit. The molecules of S configuration are linked by two C—H...O hydrogen bonds into a three‐dimensional framework, and the molecules of R configuration are linked by two further C—H...O hydrogen bonds into a different type of three‐dimensional framework; the two frameworks are linked by a fifth C—H...O hydrogen bond. 相似文献
76.
Preparation and characterization of high-specific-surface-area activated carbons from K2CO3-treated waste polyurethane 总被引:2,自引:0,他引:2
Hayashi J Yamamoto N Horikawa T Muroyama K Gomes VG 《Journal of colloid and interface science》2005,290(2):437-443
An activated carbon with high specific surface area was prepared from polyurethane foam by chemical activation with K2CO3 and the influences of carbonization temperature and impregnation ratio on the pore structure of the prepared activated carbon were investigated. It was found that the specific surface area of the activated carbon was at a maximum value (about 2800 m(2)/g) at a carbonization temperature of 1073 K and at an impregnation ratio of 1.0. It was concluded that the polyurethane foam structure was modified during impregnation by K2CO3, K2CO3 promoted charring during carbonization, and then the weight loss behavior was changed below 700 and above 1000 K, carbon in the char was consumed by K2CO3 reduction, and this led to the high specific surface area. The prepared activated carbon had a very sharp micropore size distribution, compared with the commercial activated carbon having high specific surface area. The amounts of three organic vapors (benzene, acetone, and octane) adsorbed on the prepared activated carbons was much larger than those on the traditional coconut shell AC and the same as those on the commercial activated carbon except for octane. We surmised that the high specific surface area was due to the modification of the carbonization behavior of polyurethane foam by K2CO3. 相似文献
77.
Rutile Ni
x
Ti1-3x
Sb2x
O2 solid solution nanoparticles were synthesized by a sol-gel route using propylene oxide as a gelation agent. Titanium oxide
nanopowder and 12% TiCl3 solution were used as the source for titanium to investigate the influence of the titanium precursors on the formation of
the target materials. It was found that the nanoparticles prepared using 12% TiCl3 solution showed a much lower phase formation temperature (700°C) as compared to those prepared from TiO2 nanoparticles (1000°C). This lower phase formation temperature allowed a substantial reduction of the aggregation of the
particles during calcination leading to the formation of nearly mono-dispersed nanoparticles of about 20 nm. The results of
this work show that the epoxide assisted sol-gel method is capable to produce titanium-based ternary oxide solid solution
nanoparticles, owing to the formation of a highly homogeneous precursor gel intermediate. 相似文献
78.
Marcos Mandado Christian Van Alsenoy Paul Geerlings Frank De Proft Ricardo A Mosquera 《Chemphyschem》2006,7(6):1294-1305
A Hirshfeld decomposition scheme of the Hartree-Fock total molecular energy into atomic energies is presented. The calculations are performed by direct numerical integration and the results are compared for a set of 28 molecules containing different kinds of atoms. The calculated atomic energies show a strong dependency on changes of atomic electron population and hybridization. Linear correlations are found between the energy and the population for H, these being related to the electronegativity of this atom and to the external potential created by the remaining atoms. The proposed energy partitioning scheme appears to be useful for studies such as proton acidity, the anomeric effect and group transferability, and allows atomic virial ratios to be obtained. Finally, the atomic potential energies are found to mimic trends based on exact expressions as well as trends displayed by molecular quantities, thus lending credibility to the partitioning scheme used. 相似文献
79.
Mauricio Gomes Constantino Kleber Thiago de OliveiraAdilson Beatriz Gil Valdo José da Silva 《Tetrahedron letters》2003,44(13):2641-2643
A synthesis of a functionalized bicyclo[6.2.1]undecane, N-(7-hydroxymethyl-bicyclo[6.2.1]undeca-3,5,9-trien-2-yl)-4-methyl-benzenesulfonamide, is described. Starting with a [6+4] cycloaddition between cyclopentadiene and cycloheptatrienone, the final product was prepared in five steps with an overall 37% yield. The remarkable resistance to hydrolysis of an intermediate lactam was overcome by tosylating the amide and reducing with LiAlH4. 相似文献
80.