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911.
Dr. Martin Piesch Dr. Amélie Nicolay Dr. Maria Haimerl Dr. Michael Seidl Dr. Gábor Balázs Prof. T. Don Tilley Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(45):e202201144
The bridging MeCN ligand in the dicopper(I) complexes [(DPFN)Cu2(μ,η1 : η1-MeCN)][X]2 (X=weakly coordinating anion, NTf2 ( 1 a ), FAl[OC6F10(C6F5)]3 ( 1 b ), Al[OC(CF3)3]4 ( 1 c )) was replaced by white phosphorus (P4) or yellow arsenic (As4) to yield [(DPFN)Cu2(μ,η2 : η2-E4)][X]2 (E=P ( 2 a – c ), As ( 3 a – c )). The molecular structures in the solid state reveal novel coordination modes for E4 tetrahedra bonded to coinage metal ions. Experimental data and quantum chemical computations provide information concerning perturbations to the bonding in coordinated E4 tetrahedra. Reactions with N-heterocyclic carbenes (NHCs) led to replacement of the E4 tetrahedra with release of P4 or As4 and formation of [(DPFN)Cu2(μ,η1 : η1-MeNHC)][X]2 ( 4 a,b ) or to an opening of one E−E bond leading to an unusual E4 butterfly structural motif in [(DPFN)Cu2(μ,η1 : η1-E4DippNHC)][X]2 (E=P ( 5 a,b ), E=As ( 6 )). With a cyclic alkyl amino carbene (EtCAAC), cleavage of two As−As bonds was observed to give two isomers of [(DPFN)Cu2(μ,η2 : η2-As4EtCAAC)][X]2 ( 7 a,b ) with an unusual As4-triangle+1 unit. 相似文献
912.
Michael G. Pfeffer Tanja Kowacs Dr. Maria Wächtler Dr. Julien Guthmuller Prof. Dr. Benjamin Dietzek Prof. Dr. Johannes G. Vos Prof. Dr. Sven Rau 《Angewandte Chemie (International ed. in English)》2015,54(22):6627-6631
A molecular photocatalyst consisting of a RuII photocenter, a tetrapyridophenazine bridging ligand, and a PtX2 (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies. 相似文献
913.
Multi‐responses Methodology Applied in the Electroanalytical Determination of Hair Dye by Using Printed Carbon Electrode Modified with Graphene 下载免费PDF全文
Felipe Fantinato Hudari Sergio Luis Costa Ferreira Maria Valnice Boldrin Zanoni 《Electroanalysis》2016,28(5):1085-1092
This paper describes a rapid and sensitive method for determination of the hair dye Basic Blue 41 in wastewater samples using screen‐printed carbon electrodes modified with graphene (SPCE/Gr). The method is based on the reversible reduction of azo groups of the dye at potential of ?0.23 V/?0.26 V, where both the anodic and cathodic currents increased 1,300 % when compared to screen‐printed carbon (SPCE) and glassy carbon electrodes (GCE). The optimization of a square wave voltammetric method was performed by means of 23 factorial design, Doehlert matrix and multi‐response assays, and the best parameters were: frequency (54.8 Hz), step potential (6 mV), pulse amplitude (43.7 mV) and pH 4.5. The analytical curve was constructed from 3.00×10?8 to 2.01×10?6 mol L?1, with detection and quantification limits of 5.00×10?9 and 1.70×10?8 mol L?1, respectively. The repeatability of the method evaluated for 10 consecutive measurements at concentrations of 1.70×10?7 mol L?1 and 1.70×10?6 mol L?1, showed relative standard deviation of 3.56 and 0.57 %, respectively. The sensor based in SPCE/Gr was successfully applied in wastewater samples collected from a drinking water treatment plant and validated by comparison with HPLC‐DAD method with good accuracy. 相似文献
914.
Two Ru(II) complexes, [Ru(bpy)2L](ClO4)2 (1) and [Ru(bpy)2L'](BF4)2 (2), where bpy is 2,2'-bipyridine, L is diacetyl dihydrazone, and L' 1:2 is the condensate of L and acetone, are synthesized. From X-ray crystal structures, both are found to contain distorted octahedral RuN(6)(2+) cores. NMR spectra show that the cations in 1 and 2 possess a C2 axis in solution. They display the expected metal-to-ligand charge transfer (1MLCT) band in the 400-500 nm region. Complex 1 is nonemissive at room temperature in solution as well as at 80 K. In contrast, complex 2 gives rise to an appreciable emission upon excitation at 440 nm. The room-temperature emission is centered at 730 nm (lambda(em)(max)) with a quantum yield (Phi(em)) of 0.002 and a lifetime (tau(em)) of 42 ns in an air-equilibrated methanol-ethanol solution. At 80 K, Phi(em) = 0.007 and tau(em) = 178 ns, with a lambda(em)(max) of 690 nm, which is close to the 0-0 transition, indicating an 3MLCT excited-state energy of 1.80 eV. The radiative rate constant (5 x 10(4) s(-1)) at room temperature and 80 K is almost temperature independent. From spectroelectrochemistry, it is found that bpy is easiest to reduce in 2 and that L is easiest in 1. The implications of this are that in 2 the lowest (3)MLCT state is localized on a bpy ligand and in 1 it is localized on L. Transient absorption results also support these assignments. As a consequence, even though 2 shows a fairly strong and long-lived emission from a Ru(II) --> bpy CT state, the Ru(II) --> L CT state in 1 shows no detectable emission even at 80 K. 相似文献
915.
Rodríguez Patino JM Molina Ortiz SE Carrera Sánchez C Rodríguez Niño MR Añón MC 《Journal of colloid and interface science》2003,268(1):50-57
In this paper we present surface dilatational properties of soy globulins (beta-conglycinin, glycinin, and reduced glycinin with 10 mM of dithiothreitol (DTT)) adsorbed onto the air-water interface, as a function of adsorption time. The experiments were performed at constant temperature (20 degrees C), pH (8.0), and ionic strength (0.05 M). The surface rheological parameters were measured as a function of protein concentration (ranging from 1 to 1x10(-3)% wt/wt). We found that the surface dilatational modulus, E, increases, and the phase angle, phi, decreases with time, theta, which may be associated with protein adsorption. These phenomena have been related to protein adsorption, unfolding, and/or protein-protein interactions (at long-term adsorption) as a function of protein concentration in solution. From a rheological point of view, the surface viscoelastic characteristics of soy globulin films adsorbed at the air-water interface are practically elastic. The main conclusion is that the dilatational properties of the adsorbed films depend on the molecular structure of the protein. 相似文献
916.
Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants 总被引:3,自引:0,他引:3
Wise SA Poster DL Schantz MM Kucklick JR Sander LC Lopez de Alda M Schubert P Parris RM Porter BJ 《Analytical and bioanalytical chemistry》2004,378(5):1251-1264
Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10–20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material. 相似文献
917.
Luiz Pereira Ramos Helena Maria Wilhelm 《Applied biochemistry and biotechnology》2005,123(1-3):807-819
In recent years, the concept of producing biodiesel from renewable lipid sources has regained international attention. In
Brazil, a national program was launched in 2002 to evaluate the technical, economic, and environmental competitiveness of
biodiesel in relation to the commercially available diesel oil. Several research projects were initiated nationwide to investigate
and/or optimize biodiesel production from renewable lipid sources and ethanol derived from sugarcane (ethyl esters). Once
implemented, this program will not only decrease our dependence on petroleum derivatives but also create new market opportunities
for agribusiness, opening new jobs in the countryside, improving the sustainability of our energy matrix, and helping the
Brazilian government to support important actions against poverty. This article discusses the efforts to develop the Brazilian
biodiesel program in the context of technical specifications as well as potential oilseed sources. 相似文献
918.
Ecaterina Stela Dragan Maria Valentina Dinu Andrzej W. Trochimczuk 《European Polymer Journal》2009,45(7):2119-114
Cu(II), Co(II) and Ni(II) complexes of chelating resins (CR) bearing iminodiacetate (IDA) ligands were prepared. The CR-metal complexes were characterized by FT-IR spectroscopy, X-ray diffraction (XRD), thermal behavior (TG and DTG) under nitrogen atmosphere, and electron paramagnetic resonance (EPR). FT-IR spectra of the CR-metal complexes showed the characteristic bands of CR were still present but red-shifted after the metal complexation, and new bands assigned to Me-N bonds were observed. Thermal behavior of the metal-CR complexes supported the metal complexation, metal complexation leading to the decrease of the thermal stability of the CR, the lowest thermal stability being found when the highest amount of Cu(II) was loaded. Based on the EPR results and the thermal behavior of Cu(II)-CR complexes, the scheme for the complexation of Cu(II) on the CR was suggested. 相似文献
919.
Investigation of anthropic effects connected with metal ions concentration, organic matter and grain size in Bormida river sediments 总被引:9,自引:0,他引:9
Emilio Marengo Maria Carla Gennaro Elisa Robotti Piero Rossanigo Caterina Rinaudo Manuela Roz-Gastaldi 《Analytica chimica acta》2006,560(1-2):172-183
An investigation on the sediment composition and grain size was carried out along the Bormida river (Piedmont, Northern Italy). The samples were taken both in the riverbed and on its banks. Multivariate statistical exploratory methods permitted to identify possible sources of primary pollution. In particular, principal component analysis (PCA) showed that there are probably at least three anthropogenic main causes of pollution, one connected with Cr, Ni and Sn, the second with cadmium and the last one with mercury. Some correlations were found between heavy metal ion concentrations and organic matter and/or the sediment grain size. Differences between the samples collected in the riverbed and on the banks were identified and the relationships between the principal components and the distance of the samples from the riverbed and from the hot spot represented by the ACNA industrial site were also analyzed. 相似文献
920.
Kinga Nawalany Aleksandra Rusin Mariusz Kpczyski Alexei Mikhailov Gabriela Kramer-Marek Mirosaw
nietura Jan Potowicz Zdzisaw Krawczyk Maria Nowakowska 《Journal of photochemistry and photobiology. B, Biology》2009,97(1):8-17
Two photosensitizing systems: (1) tetrakis(4-hydroxyphenyl)porphyrin (p-THPP) encapsulated in sterically stabilized liposomes (SSL) and (2) p-THPP functionalized by covalent attachment of poly(ethylene glycol) (p-THPP–PEG2000) were studied in vitro. The dark and photo cytotoxicity of these systems were evaluated on two cell lines: HCT 116, a human colorectal carcinoma cell line, and DU 145, a prostate cancer cell line and compared with these determined for free p-THPP. It was demonstrated that both encapsulation in liposomes as well as attachment of PEG chain result in pronounced reduction of the dark cytotoxicity of the parent porphyrin. The liposomal formulation showed higher than p-THPP–PEG2000 photocytotoxicity towards both cell lines used in the studies. 相似文献