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101.
Paola Rodríguez-Estupiñán Liliana Giraldo Juan C. Moreno-Piraján 《Journal of Thermal Analysis and Calorimetry》2013,114(1):245-251
In this study, immersion calorimetry was used to characterise different samples of commercial granular activated carbon (GAC) which undergo oxidation with HNO3 (GACOxN) and thermal treatments to modify its superficial group contents, as well as to determine the textural characteristics of the materials through nitrogen adsorption at 77 K and its superficial chemistry by Boehm titration and zero point of charge. Correlations between the immersion enthalpies and the results of the other techniques of characterisation were established. The immersion enthalpies in dichloromethane obtained were greater, which were found to be between ?88.36 and ?155.6 J g?1, in contrast to those in carbon tetrachloride, which were found to be between ?50.21 and ?94.29 J g?1. The dependence of the immersion enthalpies in water on the contents of total acidity and basicity surface groups was also established, and a good correlation between the accessible surface area determined by calorimetric technique and the BET area was found. 相似文献
102.
Dr. Ángel J. Jiménez Michael Sekita Dr. Esmeralda Caballero Dr. M. Luisa Marcos Dr. M. Salomé Rodríguez‐Morgade Prof. Dr. Dirk M. Guldi Prof. Tomás Torres 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14506-14514
In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of PtII disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of PtII between Pc and PDI impacts the results in a longer‐lived Pc . +/PDI . ? radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 . 相似文献
103.
This paper describes the experimental studies carried out to determine (238)Pu, (239/40)Pu, (241)Pu, (241)Am, (242)Cm and (244)Cm in samples from nuclear power plants (mainly spent ion exchange resins and evaporator concentrates) using an organophosphorus compound immobilized on an inert support. These materials are commercially available under the name TRU Resin (for Transuranium Specific) from Eichrom Industries, Darien, IL. An attempt is made to develop a rapid, accurate method of analysis, with minimum waste generation. Standard solutions of Pu and Am and one sample of spent ion exchange resin that contains fission, activation products, Pu, Am and Cm were analyzed to study the separation factors and interferences in the measurement of Pu, Am and Cm isotopes. 相似文献
104.
Textile/Metal–Organic‐Framework Composites as Self‐Detoxifying Filters for Chemical‐Warfare Agents 下载免费PDF全文
Elena López‐Maya Dr. Carmen Montoro Dr. L. Marleny Rodríguez‐Albelo Dr. Salvador D. Aznar Cervantes Dr. A. Abel Lozano‐Pérez Prof. José Luis Cenís Dr. Elisa Barea Prof. Jorge A. R. Navarro 《Angewandte Chemie (International ed. in English)》2015,54(23):6790-6794
The current technology of air‐filtration materials for protection against highly toxic chemicals, that is, chemical‐warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self‐cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal–organic framework (MOF) materials to develop advanced self‐detoxifying adsorbents of chemical‐warfare agents containing hydrolysable P? F, P? O, and C? Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air‐permeation properties of the textiles with the self‐detoxifying properties of the MOF material. 相似文献
105.
Sanches-Silva A Rodríguez-Bernaldo de Quirós A López-Hernández J Paseiro-Losada P 《Journal of chromatography. A》2004,1032(1-2):7-15
A reversed-phase high performance liquid chromatographic (RP-HLPC) method was compared with a gas chromatography-flame ionization detection (GC-FID) method for determining fatty acids in potato crisps. Different extraction procedures were used. Fatty acids were quantified by linear regression. Both methods presented good precision (R.S.D. < or = 5.88%) and recovery (> or = 82.31%). The precision using HPLC method was slightly better than for GC-FID method. There was good agreement between the fatty acid composition of potato crisps analysed by both methods. For most purposes the HPLC method would be better. However, when more fatty acids need to be analysed, GC is a more suitable method. 相似文献
106.
A novel synthetic process leading to the framework of benzo[c]cinnoline has been discovered and investigated. The process is composed of two separate reactions, the first of which is a partial reduction of the nitro groups of the 2,2'-dinitrobiphenyl, a process that we believe proceeds via a SET mechanism to yield the hydroxyamino and nitroso groups. In the following step the cyclization takes place under formation of the -N=N- bond. We believe that this process take place via a radical mechanism through the nitroso radical anion. The novel process affords either benzo[c]cinnoline or benzo[c]cinnoline N-oxide, both in high yields, 93% and 91%, respectively. To obtain benzo[c]cinnoline, the reaction is conducted with an alcohol as solvent and an alkoxide as the base, while for benzo[c]cinnoline N-oxide, water is used as solvent with sodium hydroxide as the base. To establish the latter procedure, statistical experimental design and multivariate modeling were utilized to reveal the response surface for the reaction and to determine the optimal conditions for the reaction. A proposal for the complex reaction mechanism is given. During the corroboration of the mechanism, a new deoxygenation reaction for converting benzo[c]cinnoline N-oxide into benzo[c]cinnoline was discovered. The reaction is conducted by treating the N-oxide with sodium ethoxide at elevated temperature to achieve near-quantitative conversion into benzo[c]cinnoline in a yield of 96%. 相似文献
107.
108.
Mass spectrometry detection of minor new meridianins from the antarctic colonial ascidians Aplidium falklandicum and Aplidium meridianum 下载免费PDF全文
Laura Núñez‐Pons Rosa María Nieto Conxita Avila Carlos Jiménez Jaime Rodríguez 《Journal of mass spectrometry : JMS》2015,50(1):103-111
Taking into account the broad biological activities found in the meridianin indole alkaloids isolated to date, we have re‐examined the organic extracts of an Antarctic collection of the tunicates Aplidium meridianum and A. falklandicum (Chordata: Ascidiacea) by HPLC in conjunction with a high‐resolution mass spectrometer (HPLC‐MS). A new set of analogs of meridianins A–G has been detected, and their structures are proposed on the basis of the molecular formulae identified by LC‐HRMS analysis using a C18 column with a gradient of water/acetonitrile and an LTQ‐FT‐MS Orbitrap detector. Remarkably, dimers derived from meridianin A and from meridianin B or E were also detected. Our findings provide further evidence of the broad variability within the meridianin‐like derivatives of this highly bioactive alkaloid family. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
109.
Rodríguez JC Zeng Y Wilks A Rivera M 《Journal of the American Chemical Society》2007,129(38):11730-11742
Relaxation compensated Carr-Purcell-Meiboom-Gill (rc-CPMG) NMR experiments have been used to investigate micros-ms motions in heme oxygenase from Pseudomonas aeruginosa (pa-HO) in its ferric state, inhibited by CN- (pa-HO-CN) and N3- (pa-HO-N3), and in its ferrous state, inhibited by CO (pa-HO-CO). Comparative analysis of the data from the three forms indicates that the nature of the coordinated distal ligand affects the micros-ms conformational freedom of the polypeptide in regions of the enzyme far removed from the heme iron and distal ligand. Interpretation of the dynamical information in the context of the crystal structure of resting state pa-HO shows that residues involved in the network of structural hydrogen-bonded waters characteristic of HOs undergo micros-ms motions in pa-HO-CN, which was studied as a model of the highly paramagnetic S = 5/2 resting state form. In comparison, similar motions are suppressed in the pa-HO-CO and pa-HO-N3 complexes, which were studied as mimics of the obligatory oxyferrous and ferric hydroperoxide intermediates, respectively, in the catalytic cycle of heme degradation. These findings suggest that in addition to proton delivery to the nascent Fe(III)-OO(-) intermediate during catalysis, the hydrogen-bonding network serves two additional roles: (i) propagate the electronic state (reactive state) in each of the distinct steps of the catalytic cycle to key but remote sections of the polypeptide via small rearrangements in the network of hydrogen bonds and (ii) modulate the conformational freedom of the enzyme, thus allowing it to adapt to the demanding changes in axial coordination state and substrate transformations that take place during the catalytic cycle. This idea was probed by disrupting the hydrogen-bonding network in pa-HO by replacing R80 with L. NMR spectroscopic studies conducted with R80L-pa-HO-N3 and R80L-pa-HO-CO revealed that the mutant exhibits nearly global conformational disorder, which is absent in the equivalent complexes of the wild type enzyme. The "chaotic" disorder in the R80L mutant is likely related to its significantly lower efficiency to hydroxylate heme in the presence of H2O2, relative to the wild type enzyme. 相似文献
110.
Gutiérrez L Alzuet G Borrás J Castiñeiras A Rodríguez-Fortea A Ruiz E 《Inorganic chemistry》2001,40(13):3089-3096
New Cu(II) complexes of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl]benzenesulfonamide, HL) [Cu(2)(CH(3)COO)(2)(L)(2)].2dmf (1) and ([Cu(L)(2)].2H(2)O)(infinity) (2) were prepared and structurally characterized. Compound 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 8.9486(9) A, b = 15.0956(12) A, c = 16.542(3) A, beta = 105.584(15) degrees, and Z = 2. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 13.8097(8) A, b = 14.5765(4) A, c = 13.7853(15) A, beta = 96.033(9) degrees, and Z = 1. In compound 1 two copper ions are linked by two syn-syn acetates and two nonlinear NCN bridging groups pertaining to the deprotonated sulfamethazine ligands. Each copper center presents a nearly square planar geometry. Magnetic susceptibility data for 1 show a strong antiferromagnetic coupling with 2J = -216.7 cm(-)(1). The EPR spectra at the X- and Q-band frequencies present the signals corresponding to the dinuclear entity, being the zero-field splitting parameter, D = 0.265 cm(-)(1). The antiferromagnetic exchange coupling is discussed using DFT calculations on some model compounds with NCN bridging ligands and also on model structures with mixed mu-acetato and NCN bridges. The copper in the polymeric compound 2 is five coordinate. The CuN(5) chromophore has a highly distorted square pyramidal geometry with small axial N-Cu-N angles of 65.53(14) and 59.90(13) degrees. In the structure a sulfamethazinate anion binds to one copper through the sulfonamido and pyrimidine N atoms and to an adjacent copper via the amino N atom. 相似文献