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101.
Yago DiezAuthor Vitae J. Antoni SellarèsAuthor Vitae 《Discrete Applied Mathematics》2011,159(6):433-449
We propose a process for determining approximated matches, in terms of the bottleneck distance, under color preserving rigid motions, between two colored point sets A,B∈R2, |A|≤|B|. We solve the matching problem by generating all representative motions that bring A close to a subset B′ of set B and then using a graph matching algorithm. We also present an approximate matching algorithm with improved computational time. In order to get better running times for both algorithms we present a lossless filtering preprocessing step. By using it, we determine some candidate zones which are regions that contain a subset S of B such that A may match one or more subsets B′ of S. Then, we solve the matching problem between A and every candidate zone. Experimental results using both synthetic and real data are reported to prove the effectiveness of the proposed approach. 相似文献
102.
Mena ML Moreno-Gordaliza E Moraleja I Cañas B Gómez-Gómez MM 《Journal of chromatography. A》2011,1218(9):1281-1290
In this work a 2D electrophoretic separation procedure able to maintain the integrity of platinum-protein bonds has been developed. The method is based on the use of sequential OFFGEL isoelectric focussing (IEF) and PAGE. A systematic study of the reagents used for PAGE, for OFFGEL-IEF separation, and post-separation treatment of gels (such as enzymatic digestion and sample preparation for MS analysis) was tackled regarding their suitability for the identification of platinum binding proteins using standard proteins incubated with cisplatin. The distribution of platinum in high and low molecular weight fractions (separated by cut-off filters) was determined by ICP-MS, which allows evaluating platinum-protein bond stability under the conditions studied. SDS-PAGE in the absence of β-mercaptoethanol or dithiotreitol preserved the platinum-protein bonds. In addition, neither the influence of the electric field during the electrophoretic separation, nor the processes of fixing, staining and destaining of proteins in the gel did result in the loss of platinum from platinum binding proteins. SDS-PAGE under non-reducing conditions provides separation of platinum-binding proteins in very narrow bands with quantitative recoveries. Different amounts of platinum-bound proteins covering the range 0.3-2.0 μg were separated and mineralised for platinum determination, showing good platinum linearity. Limits of detection for a mixture of five standard proteins incubated with cisplatin were between the range of 2.4 and 13.9 pg of platinum, which were satisfactory for their application to biological samples. Regarding OFFGEL-IEF, a denaturing solution without thiourea and without dithiotreitol is recommended. The suitability of the OFFGEL-IEF for the separation of platinum binding proteins of a kidney cytosol was demonstrated. 相似文献
103.
Carbon nanofiber (CNF) layers have been directly synthesized on nickel foils by chemical vapor deposition at 450°C using different H(2) concentrations and reaction times. The addition of 5% H(2) produces thicker, rougher and more porous CNF layers than when 1% H(2) is used. The roughness and porosity increases with reaction time when 5%, 10% or 20% H(2) are used; however, this effect is less pronounced when 1% H(2) is used. CNFs are 50-55 nm in diameter and have a fishbone type structure. We have studied the influence of CNF layer thickness, porosity and surface roughness on the interaction with water by measuring the contact angle. The water wetting properties of the samples are more significantly influenced by the CNF layer thickness than both surface roughness and porosity. When the CNF layer is thicker than ca. 20 μm, the surface is hydrophobic and the contact angle increases with surface roughness and porosity. When the CNF layer is thinner than ca. 20 μm, the surface is hydrophilic and the contact angle decreases with increasing surface roughness and porosity. This behavior is attributed to penetration of water, making contact with the hydrophilic C layer between the CNF layer and the foil. 相似文献
104.
Serrano I López MI Ferrer Í Poater A Parella T Fontrodona X Solà M Llobet A Rodríguez M Romero I 《Inorganic chemistry》2011,50(13):6044-6054
The synthesis of a family of new Ru complexes containing the facial tridentate ligand with general formula [Ru(II)(T)(D)(X)](n+) (T = trispyrazolylmethane (tpm); D = ((4S,4'S)-(-)-4,4',5,5'-tetrahydro-4,4'-bis(1-methylethyl)-2,2'-bioxazole) (iPr-box-C) or N-(1-hydroxy-3-methylbutan-(2S)-(-)-2-yl)-(4S)-(-)-4-isopropyl-4,5-dihydrooxazole-2-carbimidate (iPr-box-O); X = Cl, H(2)O) has been described. All complexes have been spectroscopically characterized in solution through (1)H NMR and UV-vis techniques, and the redox properties of complexes have also been studied by means of cyclic voltammetry (CV). Furthermore, the chloro complexes presented here have been characterized in the solid state through monocrystal X-ray diffraction analysis. The oxazolinic iPr-box-C ligand undergoes a Ru-assisted hydrolysis reaction generating the corresponding amidate anionic ligand iPr-box-O, that keeps coordinated to the Ru metal center and that produces a strong σ-donation effect over it. The reactivity of the Ru-OH(2) complexes described in this paper together with other similar ones, previously synthesized by us, has been tested with regard to the epoxidation of different olefins. Complexes [Ru(II)(R-box-C)(tpm)OH(2)](BF(4))(2), R = Bz, 3'c/iPr, 3c, show high stereoselectivity in the epoxidation of cis-β-methylstyrene, with the exclusive formation of the cis-epoxide. However, there is a significant difference in regioselectivity between the two catalysts in the epoxidation of 4-vinylcyclohexene; complex 3'c leads to the regioselective oxidation at the ring alkene position, whereas complex 3c leads to the oxidation at the terminal position. Computational calculations indicate only small energy differences between the two possible products of 4-vinylcyclohexene epoxidation, but the energy barriers for the interaction of the catalytic systems with the alkene groups of 4-vinylcyclohexene agree with the reactivity differences found for the two catalysts having isopropyl or benzyl as substituent of the oxazole ligand. Computed local Fukui functions help to explain the observed reactivity trends. 相似文献
105.
Francàs L Sala X Escudero-Adán E Benet-Buchholz J Escriche L Llobet A 《Inorganic chemistry》2011,50(7):2771-2781
The preparation of three new octadentate tetranucleating ligands made out of two Ru-Hbpp-based units [where Hbpp is 3,5(bispyridyl)pyrazole], linked by a xylyl group attached at the pyrazolate moiety, of general formula (Hbpp)(2)-u-xyl (u = p, m, or o) is reported, together with its dinucleating counterpart substituted at the same position with a benzyl group, Hbpp-bz. All of these ligands have been characterized with the usual analytical and spectroscopic techniques. The corresponding tetranuclear ruthenium complexes of general formula {[Ru(2)(trpy)(2)(L)](2)(μ-(bpp)(2)-u-xyl)}(n+) [L = Cl or OAc, n = 4; L = (H(2)O)(2), n = 6] and their dinuclear homologues {[Ru(2)(trpy)(2)(L)](μ-bpp-bz)}(n+) [L = Cl or OAc, n = 2; L = (H(2)O)(2), n = 3] have also been prepared and thoroughly characterized both in solution and in the solid state. In solution, all of the complexes have been characterized spectroscopically by UV-vis and NMR and their redox properties investigated by means of cyclic voltammetry techniques. In the solid state, monocrystal X-ray diffraction analysis has been carried out for two dinuclear complexes {[Ru(2)(trpy)(2)(L)](μ-bpp-bz)}(2+) (L = Cl and OAc) and for the tetranuclear complex {[Ru(2)(trpy)(2)(μ-OAc)](2)(μ-(bpp)(2)-m-xyl)}(4+). The capacity of the tetranuclear aqua complexes {[Ru(2)(trpy)(2)(H(2)O)(2)](2)(μ-(bpp)(2)-u-xyl)}(6+) and the dinuclear homologue {[Ru(2)(trpy)(2)(H(2)O)(2)](μ-bpp-bz)}(3+) to act as water-oxidation catalysts has been evaluated using cerium(IV) as the chemical oxidant in pH = 1.0 triflic acid solutions. It is found that these complexes, besides generating significant amounts of dioxygen, also generate carbon dioxide. The relative ratio of [O(2)]/[CO(2)] is dependent not only on para, meta, or ortho substitution of the xylylic group but also on the concentration of the starting materials. With regard to the tetranuclear complexes, the one that contains the more sterically constrained ortho-substituted ligand generates the highest [O(2)]/[CO(2)] ratio. 相似文献
106.
Oliveira E Nuñez C Rodríguez-González B Capelo JL Lodeiro C 《Inorganic chemistry》2011,50(18):8797-8807
Emissive molecular probes based on amino acid moieties are very appealing because of their application as new building blocks in peptide synthesis. Two new bioinspired coumarin probes (L1 and L2) were synthesized and fully characterized by elemental analysis, infrared, (1)H NMR, (13)C NMR, UV-vis absorption and emission spectroscopy, matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF-MS), lifetime measurements, and X-ray crystal diffraction. Their sensing ability toward alkaline earth, transition, and post-transition metal ions (Ca(2+), Zn(2+), Cd(2+), Cu(2+), Ni(2+), Hg(2+), Ag(+), and Al(3+)) and their acid-base behavior (H(+), OH(-)) were explored in absolute ethanol by absorption and fluorescence spectroscopy. Compound L1 shows a strong complexation constant with the soft metal ions Zn(2+), Cd(2+), and Ag(+). Compound L2 shows a high fluorescence quantum yield, and it could be used as a non-pH-dependent fluorescent biological probe. Very small gold nanoparticles (AuNPs) using compounds L1 and L2 as stabilizers were obtained by using a reductive method and were characterized by UV-vis, light scattering, and transmission electron microscopy (TEM). Dynamic light scattering and TEM studies show that the formation of small nanoparticles is around 4.27 ± 0.64 nm for L1 and around 2.69 ± 0.96 nm for L2. The new stable Cou@AuNPs behaved as supramolecular chemosensors, which have been selective for the heavy element Hg(2+), with a concomitant change of color from pink to dark red/brown and an increase of size up to 100-fold. 相似文献
107.
Bernet L Lalrempuia R Ghattas W Mueller-Bunz H Vigara L Llobet A Albrecht M 《Chemical communications (Cambridge, England)》2011,47(28):8058-8060
The catalytic water oxidation activity of mononuclear ruthenium complexes comprising a pyridine-functionalized abnormal triazolylidene ligand can be adjusted by modification of the triazolylidene substituents, which is readily achieved through click-type cycloaddition chemistry, affording some of the most active ruthenium catalysts known thus far for water oxidation (TONs > 400, TOFs close to 7000 h(-1)). 相似文献
108.
Understanding water oxidation mechanisms: The power of two cooperating metal centers. 相似文献
109.
Isidoro Lpez Mehmed Z. Ertem Somnath Maji Jordi Benet‐Buchholz Anke Keidel Uwe Kuhlmann Peter Hildebrandt Christopher J. Cramer Victor S. Batista Antoni Llobet 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(1):209-213
The homogeneous catalysis of water oxidation by transition‐metal complexes has experienced spectacular development over the last five years. Practical energy‐conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water‐oxidation catalyst that is generated by self‐assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water‐oxidation catalyst that does not decompose over extended periods of time. 相似文献
110.