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101.
Phosphane-free oxime-derived palladacycle 2 is an efficient precatalyst for the copper-free acylation of terminal alkynes with different carboxylic acid chlorides in toluene in the presence of 3 equiv of TEA as base, giving the corresponding ynones in good yields. The coupling reaction can normally be performed under air or under inert atmosphere when very low catalyst loadings (10(-3) mol % Pd) (turnover numbers (TONs) up to 23,000, turnover frequencies (TOFs) up to 958 h(-1)) or sensitive carboxylic acid chlorides are used. In addition, Pd(OAc)(2) has been shown as an efficient catalyst for the ligandless process, although usually working under higher loading conditions. This new protocol allows one to perform the synthesis of ynones at 110 degrees C, at room temperature, or under microwave irradiation conditions. 相似文献
102.
The phase of quantum gates is one key issue for the implementation of quantum algorithms. In this paper we first investigate the phase evolution of global molecular quantum gates, which are realized by optimally shaped femtosecond laser pulses. The specific laser fields are calculated using the multitarget optimal control algorithm, our modification of the optimal control theory relevant for application in quantum computing. As qubit system we use vibrational modes of polyatomic molecules, here the two IR-active modes of acetylene. Exemplarily, we present our results for a Pi gate, which shows a strong dependence on the phase, leading to a significant decrease in quantum yield. To correct for this unwanted behavior we include pressure on the quantum phase in our multitarget approach. In addition the accuracy of these phase corrected global quantum gates is enhanced. Furthermore we could show that in our molecular approach phase corrected quantum gates and basis set independence are directly linked. Basis set independence is also another property highly required for the performance of quantum algorithms. By realizing the Deutsch-Jozsa algorithm in our two qubit molecular model system, we demonstrate the good performance of our phase corrected and basis set independent quantum gates. 相似文献
103.
Analysis of mono- and disaccharides in milk-based formulae by high-performance liquid chromatography with refractive index detection 总被引:1,自引:0,他引:1
A simple and reproducible method for the qualitative and quantitative analysis of free mono- and disaccharides (fructose, glucose, galactose, sucrose, lactulose and lactose) in milk-based formulae by high-performance liquid chromatography (HPLC) with refractive index (RI) detection was developed and validated. The method showed good linearity with determination coefficients exceeding 0.99. The limits of detection (DL) in these sugars were 0.17, 0.13, 0.06, 0.16, 0.05 and 0.25 mg/ml, respectively; and the limits of quantification (QL), 0.27, 0.24, 0.20, 0.26, 0.22 and 0.38 mg/ml. The relative standard deviations (R.S.D.s) for repeatability in fructose, sucrose, lactulose and lactose were 0.78, 0.99, 2.91 and 0.46 and the R.S.D.s for reproducibility were 4.8, 6.15, 7.04 and 2.49, respectively. Recoveries in all sugars were between 93 and 113%. 相似文献
104.
Relevant aspects of the critical behavior of the site percolation model in aL×M geometry (LM) are studied. It is shown that this geometry favors the growth of percolating clusters in theL-direction with respect to those growing in theM-direction, causing pronounced finite-size effects on the percolation probabilities. Scaling functions have an additional parameter, namelyM, which introduces a dependence of these functions on the aspect ratioL/M. At criticality, the probability of a site belonging to the percolation clusters (P
L,M
) behaves likeP
L,M
L
/v
(L/M) with =5/36 andv=4/3, where is a suitable scaling function. Using scaling arguments it is conjectured and then tested by means of Monte Carlo simulations, the following asymptotic behavior (L/M)(L/M), (L,M, =1), for the leading term. Systematic deviations of the Monte Carlo data from the conjectured behavior are due to second order corrections to the leading term which can also be under-stood on the basis of scaling ideas. Finite-size dependent critical probabilities are also functions ofL/M as it follows from scaling arguments which are corroborated by the simulations.Financially supported by the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET) de la República Argentina 相似文献
105.
Chemotherapeutic drugs for cancer treatment have been traditionally originated by the isolation of natural products from different environmental niches, by chemical synthesis or by a combination of both approaches thus generating semisynthetic drugs. In the last years, a number of gene clusters from several antitumor biosynthetic pathways, mainly produced by actinomycetes and belonging to the polyketides family, are being characterized. Genetic manipulation of these antitumor biosynthetic pathways will offer in the near future an alternative for the generation of novel antitumor derivatives and thus complementing current methods for obtaining novel anticancer drugs. Novel antitumor derivatives have been produced by targetted gene disruption and heterologous expression of single (or a few) gene(s) in another hosts or by combining genes from different, but structurally related, biosynthetic pathways ("combinatorial biosynthesis"). These strategies take advantage from the "relaxed substrate specificity" that characterize secondary metabolism enzymes. 相似文献
106.
Frank J. Millero Sara Sotolongo David J. Stade Carmen A. Vega 《Journal of solution chemistry》1991,20(11):1079-1092
The oxidation of Fe(II) with H2O2 has been measured in NaCl and NaClO4 solutions as a function of pH, temperature T (K) and ionic strength (M, mol-L–1). The rate constants, k (M–1-sec–1), d[Fe(II)]/DT=-k[Fe(II)][2O2]at pH=6.5 have been fitted to equations of the formlog k = log k0+ AI
1/2+BI+CI
1/2/T
Where log k0=15.53-3425/T in water; A=–2.3, –1.35; B=0.334, 0.180; and C=391, 235, respectively, for NaCl (=0.09) and NaClO4 ( =0.08). Measurements made in NaCl solutions with added anions yield rates in the order B(OH)
4
–
>HCO
3
–
>ClO
4
–
>Cl–>NO
3
–
>SO
4
2–
and are attributed to the relative strength of the interactions of Fe2+ or FeOH+ with these anions. The FeB(OH)
4
+
species is more reactive while the FeCO
3
0
, FeCl+, FeNO
3
+
and FeSO
4
0
species are less reactive than the FeOH+ ion pair. The general trend is similar to our earlier studies of the oxidation of Fe(II) with O2 except for B(OH)
4
–
. The effect of pH on the logk was found to be a quadratic function of the concentration of H+ or OH– from pH=4 to 8. These results have been attributed to the different rate constants for Fe2+ (k0) and FeOH+ (k1) which are related to the measured k by, k=k0Fe + k1FeOH, where i is the molar fraction of species i. The rates increase due to the greater reactivity of FeOH+ compared to Fe2+. k0 is independent of composition and ionic strength but k1 is a function of ionic strength and composition due to the interactions of FeOH+ with various anions. 相似文献
107.
Fernando Hernndez Flix L. Buenadicha Carmen Avendao Mnica Sllhuber 《Tetrahedron: Asymmetry》2002,12(24):3387-3398
An excess of base allows the regio- and diastereoselective alkylation at C(4) of the glycine templates 1-methyl(isopropyl)-2,4-dihydro-1H-pyrazino[2,1-b]quinazoline-3,6-diones 9a and 9b without the need for N(2)-protecting groups. While the alkylation of 9a gave exclusively the 1,4-anti-isomers, the isopropyl derivative 9b required much longer reaction times and occurred with lower diastereoselectivity. Fiscalin B 3 was obtained by alkylation of 9b with N-Boc-3-indolylmethyl bromide followed by indole deprotection. 相似文献
108.
Four new supramolecular compounds of Cu(II)-Ni(II) have been synthesized and characterized: [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(ClO(4))(2) (1), [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(PF(6))(2) (2), [Cu(oxpn)Ni(mu-NCS)(NCS) (tmen)](n) (3), and [Cu(Me(2)oxpn)Ni(mu-NCS)(NCS)(tmen)](n) (4), where oxpn = N,N'-bis(3-aminopropyl)oxamidate, Me(2)oxpn = N,N'-bis(3-amino-2,2'-dimethylpropyl)oxamidate, and tmen = N,N,N',N'-tetramethylethylenediamine. Their crystal structures were solved. Complexes 1 and 2 have the same tetranuclear cationic part but a different counteranion. The cationic part consists of two [Cu(Me(2)oxpn)Ni] moieties linked by SCN(-) bridged ligands and intra-tetranuclear hydrogen bonds. In the case of complex 3, a two-dimensional system was built, the thiocyanate ligand linking the dinuclear units gives a chain, and the chains are linked together by hydrogen bonds; intrachain hydrogen bonds are also present. For complex 4, the thiocyanate ligands produce intermolecular linkages between the dinuclear entities, giving a one-dimensional system; intrachain hydrogen bonds are also present. The magnetic properties of the four complexes were studied by susceptibility measurements vs temperature. DFT calculations were made to study the contribution of the SCN(-) and hydrogen bond bridges in the magnetic coupling. 相似文献
109.
Loreto Salazar Modesta Espada Carmen Avendao Jos Elguero 《Journal of heterocyclic chemistry》1990,27(4):1109-1110
N-Amination of the 3(5)-amino-1,2,4-triazolide anion with hydroxylamine-O-sulfonic acid is studied. This method provided an access to the previously unknown 1,5-diamino-1,2,4-triazole. 相似文献
110.
[structure: see text] The first enantioselective total synthesis of (-)-Centrolobine is described. The key reaction is the synthesis of the cis-disubstituted tetrahydropyran framework by intramolecular cyclization of the enantiopure hydroxyketone 3 with Et3SiH and TMSOTf. The stereoselective reduction of the beta-ketosulfoxide 4 is the source of chirality. Revision of the absolute configuration of (-)-Centrolobine is proposed. 相似文献