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91.
A reverse flow injection spectrophotometric enzymatic method is proposed to quantify total phenols in urine samples. The polyphenol oxidase (PPO; EC 1.14.18.1) obtained as a crude extract from sweet potato root (Ipomoea batatas) was used as enzymatic catalyze. The detection limit, the sample throughput and relative standard deviation were 7.7 mg l−1 of total phenols, 49 h−1 and 0.9%, respectively. The method was applied to real samples and a recovery study was carried out in order to its validation. 相似文献
92.
57Fe Mössbauer spectroscopy is used to study the interactions, geometry, and the coordination characteristics of the Fe-complexes of biopolymers such as chitosan, glucosamine, and chondritin sulfate. In addition, a computational effort is undertaken for predicting the geometries and energies of the metal complexes by the Density Functional Theory (DFT) methods as implemented in the Gaussian 2003 quantum mechanical program. Both experimental and computational results suggest that the structure of the metal complexes resemble closely the structure of the active sites of metalloenzymes in 2+ or 3+ oxidation states and is at least tetracoordinated and can possibly have six ligands. 相似文献
93.
The validity of the paraxial approximation for laser beams in free space is studied via an integral criterion based on the propagation invariants of Helmholtz and paraxial wave equations. This approach allows one to determine the paraxial limit for beams with nondefined spot size and for beams described by more parameters in addition to typical longitudinal wavelength and transverse waist. As examples, the paraxiality of higher-order Hermite, Laguerre, and Bessel-Gaussian beams was completely determined. This method could be extended to nonlinear optics and Bose condensates. 相似文献
94.
Postsynthetic Improvement of the Physical Properties in a Metal–Organic Framework through a Single Crystal to Single Crystal Transmetallation
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Thais Grancha Dr. Jesús Ferrando‐Soria Prof. Dr. Hong‐Cai Zhou Prof. Dr. Jorge Gascon Dr. Beatriz Seoane Dr. Jorge Pasán Dr. Oscar Fabelo Prof. Dr. Miguel Julve Dr. Emilio Pardo 《Angewandte Chemie (International ed. in English)》2015,54(22):6521-6525
A single crystal to single crystal transmetallation process takes place in the three‐dimensional (3D) metal–organic framework (MOF) of formula MgII2{MgII4[CuII2(Me3mpba)2]3}?45 H2O ( 1 ; Me3mpba4?=N,N′‐2,4,6‐trimethyl‐1,3‐phenylenebis(oxamate)). After complete replacement of the MgII ions within the coordination network and those hosted in the channels by either CoII or NiII ions, 1 is transmetallated to yield two novel MOFs of formulae Co2II{CoII4[CuII2(Me3mpba)2]3}?56 H2O ( 2 ) and Ni2II{NiII4[CuII2(Me3mpba)2]3}? 54 H2O ( 3 ). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties. 相似文献
95.
Micelle‐Triggered β‐Hairpin to α‐Helix Transition in a 14‐Residue Peptide from a Choline‐Binding Repeat of the Pneumococcal Autolysin LytA
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Héctor Zamora‐Carreras Dr. Beatriz Maestro Dr. Erik Strandberg Prof. Anne S. Ulrich Dr. Jesús M. Sanz Dr. M. Ángeles Jiménez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8076-8089
Choline‐binding modules (CBMs) have a ββ‐solenoid structure composed of choline‐binding repeats (CBR), which consist of a β‐hairpin followed by a short linker. To find minimal peptides that are able to maintain the CBR native structure and to evaluate their remaining choline‐binding ability, we have analysed the third β‐hairpin of the CBM from the pneumococcal LytA autolysin. Circular dichroism and NMR data reveal that this peptide forms a highly stable native‐like β‐hairpin both in aqueous solution and in the presence of trifluoroethanol, but, strikingly, the peptide structure is a stable amphipathic α‐helix in both zwitterionic (dodecylphosphocholine) and anionic (sodium dodecylsulfate) detergent micelles, as well as in small unilamellar vesicles. This β‐hairpin to α‐helix conversion is reversible. Given that the β‐hairpin and α‐helix differ greatly in the distribution of hydrophobic and hydrophilic side chains, we propose that the amphipathicity is a requirement for a peptide structure to interact and to be stable in micelles or lipid vesicles. To our knowledge, this “chameleonic” behaviour is the only described case of a micelle‐induced structural transition between two ordered peptide structures. 相似文献
96.
Surface‐Functionalized Nanoparticles by Olefin Metathesis: A Chemoselective Approach for In Vivo Characterization of Atherosclerosis Plaque
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Dr. Beatriz Salinas Dr. Jesús Ruiz‐Cabello Ana V. Lechuga‐Vieco Dr. Marina Benito Dr. Fernando Herranz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(29):10450-10456
The use of click chemistry reactions for the functionalization of nanoparticles is particularly useful to modify the surface in a well‐defined manner and to enhance the targeting properties, thus facilitating clinical translation. Here it is demonstrated that olefin metathesis can be used for the chemoselective functionalization of iron oxide nanoparticles with three different examples. This approach enables, in one step, the synthesis and functionalization of different water‐stable magnetite‐based particles from oleic acid‐coated counterparts. The surface of the nanoparticles was completely characterized showing how the metathesis approach introduces a large number of hydrophilic molecules on their coating layer. As an example of the possible applications of these new nanocomposites, a focus was taken on atherosclerosis plaques. It is also demonstrated how the in vitro properties of one of the probes, particularly its Ca2+‐binding properties, mediate their final in vivo use; that is, the selective accumulation in atherosclerotic plaques. This opens promising new applications to detect possible microcalcifications associated with plaque vulnerability. The accumulation of the new imaging tracers is demonstrated by in vivo magnetic resonance imaging of carotids and aorta in the ApoE?/? mouse model and the results were confirmed by histology. 相似文献
97.
Beatriz Fernández Pablo Rodríguez-González J. Ignacio García Alonso Julien Malherbe Sergio García-Fonseca Rosario Pereiro Alfredo Sanz-Medel 《Analytica chimica acta》2014
We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6–21% for pressed pellets and 3–21% for fused solids were obtained from n = 3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches. 相似文献
98.
Beatriz Fresco-Cala Juan Manuel Jimenez-Soto Soledad Cardenas Miguel Valcarcel 《Mikrochimica acta》2014,181(9-10):1117-1124
We have evaluated the behavior of single-walled carbon nanohorns as a sorbent for headspace and direct immersion (micro)solid phase extraction using volatile organic compounds (VOCs) as model analytes. The conical carbon nanohorns were first oxidized in order to increase their solubility in water and organic solvents. A microporous hollow polypropylene fiber served as a mechanical support that provides a high surface area for nanoparticle retention. The extraction unit was directly placed in the liquid sample or the headspace of an aqueous standard or a water sample to extract and preconcentrate the VOCs. The variables affecting extraction have been optimized. The VOCs were then identified and quantified by GC/MS. We conclude that direct immersion of the fiber is the most adequate method for the extraction of VOCs from both liquid samples and headspace. Detection limits range from 3.5 to 4.3 ng L?1 (excepted for toluene with 25 ng L?1), and the precision (expressed as relative standard deviation) is between 3.9 and 9.6 %. The method was applied to the determination of toluene, ethylbenzene, various xylene isomers and styrene in bottled, river and tap waters, and the respective average recoveries of spiked samples are 95.6, 98.2 and 86.0 %. Figure
Schematic representation of the direct immersion / headspace (micro)solid phase extraction using oxidized single walled carbon nanohorns supported on a microporous hollow fiber for the extraction of volatile organic compound from water samples. 相似文献
99.
用于甲烷分解和甲烷二氧化炭重整的碳材料催化剂研究进展 总被引:1,自引:0,他引:1
The decomposition and CO2 reforming of methane,respectively,are promising alternatives to industrial steam methane reforming. In recent years,research has been focused on the development of catalysts that can operate without getting deactivated by carbon deposition,where,in particular,carbon catalysts have shown positive results. In this work,the role of carbon materials in heterogeneous catalysis is assessed and publications on methane decomposition and CO2 reforming of methane over carbon materials are reviewed. The influence of textural properties(BET surface area and micropore volume,etc.) and oxygen surface groups on the catalytic activity of carbon materials are discussed. In addition,this review examines how activated carbon and carbon black catalysts,which are the most commonly used carbon catalysts,are deactivated. Characteristics of the carbon deposits from methane are discussed and the influence of the reactivity to CO2 of fresh carbon and carbonaceous deposits for high and steady conversion during CO2 reforming of CH4 are also considered. 相似文献
100.
Pérez-Ojeda ME Trastoy B López-Arbeloa Í Bañuelos J Costela Á García-Moreno I Chiara JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(47):13258-13268
New hybrid organic–inorganic dyes based on an azide‐functionalized cubic octasilsesquioxane (POSS) as the inorganic part and a 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BDP) chromophore as the organic component have been synthesized by copper(I)‐catalyzed 1,3‐dipolar cycloaddition of azides to alkynes. We have studied the effects of the linkage group of BDP to the POSS unit and the degree of functionalization of this inorganic core on the ensuing optical properties by comparison with model dyes. The high fluorescence of the BDP dye is preserved in spite of the linked chain at its meso position, even after attaching one BDP moiety to the POSS core. The laser action of the new dyes has been analyzed under transversal pumping at 532 nm in both the liquid phase and when incorporated into solid polymeric matrices. The monosubstituted new hybrid dye exhibits high lasing efficiency of up to 56 % with high photostability, with its laser output remaining at the initial value after 4×105 pump pulses in the same position of the sample at a repetition rate of 30 Hz. However, functionalization of the POSS core with eight fluorophores leads to dye aggregation, as quantum mechanical simulation has revealed, worsening the optical properties and extinguishing the laser action. The new hybrid systems based on dye‐linked POSS nanoparticles open up the possibility of using these new photonic materials as alternative sources for optoelectronic devices, competing with dendronized or grafted polymers. 相似文献