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31.
Verónica de la Fuente Dipl.‐Chem. Mark Waugh Dr. Graham R. Eastham Dr. Jonathan A. Iggo Dr. Sergio Castillón Prof. Dr. Carmen Claver Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6919-6932
Novel cis‐1,2‐bis(di‐tert‐butyl‐phosphinomethyl) carbocyclic ligands 6 – 9 have been prepared and the corresponding palladium complexes [Pd(O3SCH3)(L‐L)][O3SCH3] (L‐ L=diphosphine) 32 – 35 synthesised and characterised by NMR spectroscopy and X‐ray diffraction. These diphosphine ligands give very active catalysts for the palladium‐catalysed methoxycarbonylation of ethene. The activity varies with the size of the carbocyclic backbone, ligands 7 and 9 , containing four‐ and six‐membered ring backbones giving more active systems. The acid used as co‐catalyst has a strong influence on the activity, with excess trifluoroacetic acid affording the highest conversion, whereas excess methyl sulfonic acid inhibits the catalytic system. An in operando NMR spectroscopic mechanistic study has established the catalytic cycle and resting state of the catalyst under operating reaction conditions. Although the catalysis follows the hydride pathway, the resting state is shown to be the hydride precursor complex [Pd(O3SCH3)(L‐ L)][O3SCH3], which demonstrates that an isolable/detectable hydride complex is not a prerequisite for this mechanism. 相似文献
32.
Gonzalo Martínez‐García Verónica Serafín Lourdes Agüí Paloma Yáñez‐Sedeño José M. Pingarrón 《Electroanalysis》2015,27(5):1119-1126
An electrochemical immunosensor for ghrelin (GHRL) determination in saliva is reported. Anti‐GHRL was immobilized onto Protein G‐magnetic beads and a competitive immunoassay involving biotinylated GHRL and alkaline phosphatase‐streptavidin was implemented. Once conjugate was magnetically captured on a screen‐printed carbon electrode, GHRL quantization was accomplished by DPV of 1‐naphtol formed upon addition of 1‐naphtyl phosphate. A linear range between 10?3 and 103 ng/mL GHRL, and a LOD of 7 pg/mL, much smaller than those from commercial ELISA kits, were found. The usefulness of the immunosensor was demonstrated by analyzing human saliva spiked with GHRL at 0.01, 0.1, 1 and 10 ng/mL. 相似文献
33.
34.
Rivas MV De Leo LP Hamer M Carballo R Williams FJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10714-10721
Metalloporphyrin molecules have a wide range of potential applications in diverse technological areas ranging from electronics to optoelectronics, electrochemistry, photophysics, chemical sensors, and catalysis. In particular, self-assembled monolayers of porphyrin molecules have recently attracted considerable interest. In this work we have studied for the first time the self-assembly of a novel Cu deutero porphyrin functionalized with disulfide moieties using electrochemical techniques, UV-vis absorption spectroscopy, polarization modulation infrared reflection absorption spectroscopy, and photoelectron spectroscopies (XPS and UPS). Experimental results indicate that the molecule adsorbs retaining its molecular integrity without forming molecular aggregates via the formation of Au-S covalent bonds. Furthermore, the monolayer consists of a packed array of molecules adsorbed with the plane of the porphyrin molecule at an angle of around 30° with respect to the surface normal. Interestingly, adsorption induces reduction of the Cu center and its consequent removal from the center of the porphyrin ring resulting in porphyrin demetalation. Our results are important in the design of self-assembled monolayers of metallo porphyrins where not only blocking of the metal center by the functional groups that drive the self-assembly should be considered but also possible adsorption induced demetalation with the consequent loss in the properties imparted by the metal center. 相似文献
35.
A focused-microwave assisted extraction method using aggregates of the ionic liquid (IL) 1-hexadecyl-3-butylimidazolium bromide (HDBIm-Br) followed by high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection and single-channel fluorescence detection (FLD) has been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in toasted cereals (“gofios”) of different nature (wheat, barley, rye, and maize corn) from the Canary Islands, Spain. The optimized HPLC-UV-vis/single-channel FLD method takes 40 min for the chromatographic run with limits of detection varying between 0.02 and 4.01 ng mL−1 for the fluorescent PAHs from the European Union (EU) priority list in foods, and 20.5 ng mL−1 for the non-fluorescent PAH cyclopenta[c,d]pyrene (CPP). The optimized microwave step presented extractions recoveries ranging from 70.1 to 109% and precision values lower than 12.6% (as relative standard deviation), using an extraction time of 14 min. The extraction method also utilizes low amounts of sample (0.1 g), and low amounts of IL (77 mg), avoiding completely the use of organic solvents. 相似文献
36.
A sensitive procedure is presented for the voltammetric determination of nickel. The procedure involves an adsorptive accumulation of nickel 1-nitroso-2-napthol (NN) complex on a bismuth film electrode prepared ex situ by electrodeposition. The most suitable operating conditions and parameters such as pH, ligand concentration (CNN), adsorptive potential (Eads), adsorptive time (tads), scan rate and others were selected and the determination of nickel in aqueous solutions using the standard addition method was possible. The adsorbed Ni-NN complex gives a well defined cathodic stripping peak current at −0.70 V, which was used for the determination of nickel in the concentration range of 10.0-70.0 μg L−1 (pH 7.5; CNN 6.5 μmol L−1; Eads −0.30 V; tads 60 s) with a detection limit of 0.1 μg L−1. The relative standard deviation for a solution containing 10.0 μg L−1 of Ni(II) was 3.5% (n = 4). The proposed method was validated determining Ni(II) in certified reference waste water (SPS-WW1) and Certified Reference Water for Trace Elements (TMDA 51.3) with satisfactory results. Then lake water samples were analyzed. 相似文献
37.
López-Carrillo V Huguet N Mosquera Á Echavarren AM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(39):10972-10978
The carbene or carbocationic nature of the intermediates in the gold-catalyzed cycloisomerization of 1,5-enynes can be revealed, depending on the ligands on the gold catalysts. Gold complexes with highly electron-donating ligands promote reactions that proceed via intermediates with carbene-like character, leading to products with a bicyclo[3.1.0]hexene skeleton. The intermediate cyclopropyl endo-gold carbenes formed in this cyclization have been trapped, for the first time, to give biscyclopropane derivatives in a reaction that proceeds in a concerted fashion, according to DFT calculations. 相似文献
38.
Analysis of the products generated by mutants of aristolochene synthase from P. roqueforti (PR-AS) revealed the prominent structural role played by the aliphatic residue Leu 108 in maintaining the productive conformation of farnesyl diphosphate to ensure C1-C10 (σ-bond) ring-closure and hence (+)-aristolochene production. 相似文献
39.
López-Darias J Anderson JL Pino V Afonso AM 《Analytical and bioanalytical chemistry》2011,401(9):2965-2976
Two solid-phase microextraction (SPME) sorbent coatings based on polymeric ionic liquids (PILs) have been utilized for the
analysis of complex coffee aroma samples. The PIL-based SPME coatings examined, namely, poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium
bis[(trifluoromethyl)sulfonyl]imide) [poly(VBHDIm+ NTf2−)], with ∼14-μm thickness, and poly(1-vinyl-3-hexylimidazolium chloride) [poly(ViHIm+ Cl−)], with ∼8-μm thickness, were employed for the headspace determination of up to 49 analytes from four different coffee beans:
two French roast coffees of different brands, Sumatra coffee, and decaffeinated Sumatra coffee. The analysis was conducted
using gas chromatography coupled to mass spectrometry. For comparative purposes, the commercial polyacrylate (PA, 85-μm film
thickness) SPME coating was utilized under the same extraction conditions. The three SPME coatings tested behaved quite differently
as a function of the families of compounds extracted. Thus, the poly(VBHDIm+ NTf2−) coating was extremely selective for aldehydes while also exhibiting good extraction efficiencies for acids. The poly-(ViHIm+ Cl−) coating exhibited superior performance for aromatic alcohols, and the PA coating worked better for heterocyclic aromatics.
Both PIL-based SPME sorbent coatings demonstrated exceptional selectivity and extraction efficiency when dealing with complex
coffee aromas in spite of their small film thicknesses. 相似文献
40.
We will prove that normal complex contact metric manifolds that are Bochner flat must have constant holomorphic sectional curvature 4 and be Kähler. If they are also complete and simply connected, they must be isometric to the odd-dimensional complex projective space \({{\mathbb{C}P^{2n+1}}}\)(4) with the Fubini-Study metric. On the other hand, it is not possible for normal complex contact metric manifolds to be conformally flat. 相似文献