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901.
Wang D Xin HL Yu Y Wang H Rus E Muller DA Abruña HD 《Journal of the American Chemical Society》2010,132(50):17664-17666
A simple method for the preparation of PdCo@Pd core-shell nanoparticles supported on carbon based on an adsorbate-induced surface segregation effect has been developed. The stability of these PdCo@Pd nanoparticles and their electrocatalytic activity for the oxygen reduction reaction (ORR) were enhanced by decoration with a small amount of Pt deposited via a spontaneous displacement reaction. The facile method described herein is suitable for large-scale, lower-cost production and significantly lowers the Pt loading and thus the cost. The as-prepared PdCo@Pd and Pd-decorated PdCo@Pd nanocatalysts have a higher methanol tolerance than Pt/C in the ORR and are promising cathode catalysts for fuel cell applications. 相似文献
902.
Abarca A Galakhov M Gómez-Sal P Martín A Mena M Poblet JM Santamaría C Sarasa JP 《Angewandte Chemie (International ed. in English)》2000,39(3):534-537
Incorporation of M(CO)(3) fragments by trinuclear Ti complexes [{Ti(3)Cp(μ(3)-CR)}(μ-O)(3)] and [{Ti(3)Cp(μ(3)-N)}(μ-NH)(3)] (Cp*=eta(5)-C(5)Me(5)) leads to the formation of an unprecedented class of heterometallic clusters with cubane structure [e.g., Eq. (a)]. Density functional calculations on these complexes indicate the existence of electron delocalization in the Ti(3)M cores (M=Cr, Mo, W). 相似文献
903.
A simple and sensitive spectrophotometric method for determination of copper(II) is based on the formation of a blue coloured complex of Cu(II) with 9-phenyl-2,3,7-trihydroxy-6-fluorone (PF) in the presence of cetylpyridinium chloride (CP) and Triton X-100, has been developed. Optimum concentrations of PF, CP, Triton X-100 and pH ensuring maximum absorbance were defined. The complex Cu(II)-PF-CP-Triton X-100 shows maximum absorbance at 595 nm with a molar absorptivity value of 9.67x10(4) l mol(-1) cm(-1). The detection limit of the method is 0.028 mug ml(-1). Beer's law is obeyed for copper concentrations in the range 0.04-0.4 mug ml(-1). The studies of the effect of foreign ions on determination of copper, show that the selectivity of the method is poor. The cations of alkali metals and anions Br(-), Cl(-), I(-), F(-), NO(2)(-), NO(3)(-), CH(3)COO(-), SO(4)(2-), S(2)O(3)(2-), PO(4)(3-), citrates (examined in 1000-fold molar excess over copper) do not affect the determination. All cations forming complexes with PF have an interfering effect. The statistical evaluation of the method was carried out for six determinations using 10 mug of Cu and the following results were obtained: the standard deviation, SD=0.042, the confidence interval mu(95)=10.1+/-0.1 mug Cu. The method has been applied for determination of copper in blood serum. 相似文献
904.
Andrade Eiroa A Vázquez Blanco E López Mahía P Muniategui Lorenzo S Prada Rodríguez D Fernández Fernández E 《Talanta》2000,51(4):677-684
In this work, the combination of the excellent band narrowing features of derivative spectrometry with constant-energy synchronous fluorescence spectrometry for the simultaneous determination of different polycyclic aromatic hydrocarbons (PAHs) in a mixture of 18 is assessed. This mode of scanning allowed for the identification and quantification of 10 PAHs and the grouping of some of these. 相似文献
905.
García Ruano JL Gamboa AE Gutiérrez LG Martín Castro AM Rodríguez Ramos JH Yuste F 《Organic letters》2000,2(6):733-736
A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group. 相似文献
906.
Ferrando-Soria J Ruiz-García R Cano J Stiriba SE Vallejo J Castro I Julve M Lloret F Amorós P Pasán J Ruiz-Pérez C Journaux Y Pardo E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(6):1608-1617
The concept of "molecular magnetic sponges" was introduced for the first time in 1999 by the creative imagination of the late Olivier Kahn. It refers to the exotic spongelike behavior of certain molecule-based materials that undergo a dramatic change of their magnetic properties upon reversible dehydration/rehydration processes. Here we report a unique example of a manganese(II)-copper(II) mixed-metal-organic framework of formula [Na(H(2)O)(4)](4)[Mn(4){Cu(2)(mpba)(2)(H(2)O)(4)}(3)]·56.5H(2)O (1) (mpba=N,N'-1,3-phenylenebis(oxamate)). Compound 1 possesses a 3D Mn(II)(4)Cu(II)(6) pillared layer structure with mixed square and octagonal pores of approximate dimensions 1.2×1.2 nm and 2.1×3.0 nm, respectively, hosting a large amount of crystallization H(2)O molecules and hydrated Na(I) countercations as guests. It reversibly switches from a crystalline hydrated phase with long-range ferromagnetic ordering at a rather high critical temperature (T(c)) of 22.5 K to an amorphous dehydrated phase with T(c) as low as 2.3 K, which is accompanied by a breathing-type dynamic effect involving a large crystal volume (ca. 45%) and color changes after water desorption/adsorption. The combination of both the open-framework structure and the spongelike optical, mechanical, and magnetic switching behavior in this new class of oxamato-based porous magnets offers fascinating possibilities in designing multifunctional materials for host-guest molecular sensing. 相似文献
907.
Scotti L Tullius Scotti M de Oliveira Lima E Sobral da Silva M do Carmo Alves de Lima M da Rocha Pitta I Olímpio de Moura R Gonzaga Batista de Oliveira J Duarte da Cruz RM Bezerra Mendonça Junior FJ 《Molecules (Basel, Switzerland)》2012,17(3):2298-2315
Fifty 2-[(arylidene)amino]-4,5-cycloalkyl[b]thiophene-3-carbonitrile derivatives were screened for their in vitro antifungal activities against Candida krusei and Cryptococcus neoformans. Based on experimentally determined minimum inhibitory concentration (MIC) values, we conducted computer-aided drug design studies [molecular modelling, chemometric tools (CPCA, PCA, PLS) and QSAR-3D] that enable the prediction of three-dimensional structural characteristics that influence the antifungal activities of these derivatives. These predictions provide direction with regard to the syntheses of new derivatives with improved biological activities, which can be used as therapeutic alternatives for the treatment of fungal infections. 相似文献
908.
909.
An extensive series of radical salts formed by the organic donor bis(ethylenedithio)tetrathiafulvalene (ET), the paramagnetic tris(oxalato)ferrate(III) anion [Fe(C(2)O(4))(3)](3-), and halobenzene guest molecules has been synthesized and characterized. The change of the halogen atom in this series has allowed the study of the effect of the size and charge polarization on the crystal structures and physical properties while keeping the geometry of the guest molecule. The general formula of the salts is ET(4)[A(I)Fe(C(2)O(4))(3)]·G with A/G = H(3)O(+)/PhF (1); H(3)O(+)/PhCl (2); H(3)O(+)/PhBr (3), and K(+)/PhI (4), (crystal data at room temperature: (1) monoclinic, space group C2/c with a = 10.3123(2) ?, b = 20.0205(3) ?, c = 35.2732(4) ?, β = 92.511(2)°, V = 7275.4(2) ?(3), Z = 4; (2) monoclinic, space group C2/c with a = 10.2899(4) ?, b = 20.026(10) ?, c = 35.411(10) ?, β = 92.974°, V = 7287(4) ?(3), Z = 4; (3) monoclinic, space group C2/c with a = 10.2875(3) ?, b = 20.0546(15) ?, c = 35.513(2) ?, β = 93.238(5)°, V = 7315.0(7) ?(3), Z = 4; (4) monoclinic, space group C2/c with a = 10.2260(2) ?, b = 19.9234(2) ?, c = 35.9064(6) ?, β = 93.3664(6)°, V = 7302.83(18) ?(3), Z = 4). The crystal structures at 120 K evidence that compounds 1-3 undergo a structural transition to a lower symmetry phase when the temperature is lowered (crystal data at 120 K: (1) triclinic, space group P1 with a = 10.2595(3) ?, b = 11.1403(3) ?, c = 34.9516(9) ?, α = 89.149(2)°, β = 86.762(2)°, γ = 62.578(3)°, V = 3539.96(19) ?(3), Z = 2; (2) triclinic, space group P1 with a = 10.25276(14) ?, b = 11.15081(13) ?, c = 35.1363(5) ?, α = 89.0829(10)°, β = 86.5203(11)°, γ = 62.6678(13)°, V = 3561.65(8) ?(3), Z = 2; (3) triclinic, space group P1 with a = 10.25554(17) ?, b = 11.16966(18) ?, c = 35.1997(5) ?, α = 62.7251(16)°, β = 86.3083(12)°, γ = 62.7251(16)°, V = 3575.99(10) ?(3), Z = 2; (4) monoclinic, space group C2/c with a = 10.1637(3) ?, b = 19.7251(6) ?, c = 35.6405(11) ?, β = 93.895(3)°, V = 7128.7(4) ?(3), Z = 4). A detailed crystallographic study shows a change in the symmetry of the crystal for compound 3 at about 200 K. This structural transition arises from the partial ordering of some ethylene groups in the ET molecules and involves a slight movement of the halobenzene guest molecules (which occupy hexagonal cavities in the anionic layers) toward one of the adjacent organic layers, giving rise to two nonequivalent organic layers at 120 K (compared to only one at room temperature). The structural transition at about 200 K is also observed in the electrical properties of 1-3 and in the magnetic properties of 1. The direct current (dc) conductivity shows metallic behavior in salts 1-3 with superconducting transitions at about 4.0 and 1.0 K in salts 3 and 1, respectively. Salt 4 shows a semiconductor behavior in the temperature range 300-50 K with an activation energy of 64 meV. The magnetic measurements confirm the presence of high spin S = 5/2 [Fe(C(2)O(4))(3)](3-) isolated monomers together with a Pauli paramagnetism, typical of metals, in compounds 1-3. The magnetic properties can be very well reproduced in the whole temperature range with a simple model of isolated S = 5/2 ions with a zero field splitting plus a temperature independent paramagnetism (Nα) with the following parameters: g = 1.965, |D| = 0.31 cm(-1), and Nα = 1.5 × 10(-3) emu mol(-1) for 1, g = 2.024, |D| = 0.65 cm(-1), and Nα = 1.4 × 10(-3) emu mol(-1) for 2, and g = 2.001, |D| = 0.52 cm(-1), and Nα = 1.5 × 10(-3) emu mol(-1) for 3. 相似文献
910.
P Alvarez-Fitz L Alvarez S Marquina J Luna-Herrera VM Navarro-García 《Molecules (Basel, Switzerland)》2012,17(7):8464-8470
Biotransformation processes have been successfully utilized to obtain products of pharmaceutical, chemical, food, and agricultural interest, which are difficult to obtain by classic chemical methods. The compound with antituberculous activity, 9-methoxy-tariacuripyrone (1), isolated from Aristolochia brevipes, was submitted to biotransformation with the yeast Saccharomyces cerevisiae under culture, yielding 5-amino-9-methoxy-3,4-dihydro-2H-benzo[h]chromen-2-one (2). The structure of (2) was elucidated on the basis of spectroscopic analyses. The results mainly show the reduction of the double bond and the nitro group of compound (1). Metabolite (2) demonstrated an increase in anti-tuberculous activity (MIC = 3.12 μg/mL) against the drug-sensitive Mycobacterium tuberculosis (H37Rv) strain, with respect to that shown by (1). 相似文献