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131.
Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging
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Dr. Jingjing Jia Dr. Edward R. White Dr. Adam J. Clancy Dr. Noelia Rubio Theo Suter Dr. Thomas S. Miller Kit McColl Prof. Paul F. McMillan Dr. Veronika Brázdová Prof. Furio Corà Dr. Christopher A. Howard Robert V. Law Dr. Cecilia Mattevi Prof. Milo S. P. Shaffer 《Angewandte Chemie (International ed. in English)》2018,57(39):12656-12660
Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties. 相似文献
132.
Jesús Valdés-Martínez Manuel Rubio Raul Cetina Rosado Javier Salcedo-Loaiza Rubén A. Toscano Georgina Espinosa-Pérez Simón Hernandez-Ortega Klaus Ebert 《Journal of chemical crystallography》1994,27(11):627-634
The crystal structure of 5-methyl-acetophenonethiosemicarbazone monohydrate,A, and salicylaldehyde-2-methylthiosemicarbazone monohydrate,B, were determined using single crystal X-ray diffraction.A crystallizes in the monoclinic space groupC2/c, with lattice parametersa=14.161(2),b=15.753(1) ?,c=11.084(1) ?, β=112.59(1)° andZ=4, yielding a calculated density ofD
calc=1.352 mg/m3.B crystallizes in the triclinic space groupP1, witha=7.233(2) ?,b=7.371(2) ?,c=11.841(2) ?, α=82.77(2)°, β=78.33(2)°, γ=63.06(2)° andD
calc=1.371 mg/m3 forZ=2,. In bothA andB the immine nitrogen and the sulfur atom areanti with respect to N2-C8. WhileA presents the usual intramolecular six membered hydrogen bond ring,B has instead an intermolecular hydrogen bond between the hydroxy moiety of the salicyladehyde and a water molecule. AM1 calculations
agree with the experimental conformations observed in both compounds.
Contribution No. 1619 of the Instituto de Química, UNAM. 相似文献
133.
William P. Freeman Yi Joon Ahn J. Andrew Whitaker Ramel J. Rubio Eike B. Bauer Fook S. Tham 《Journal of organometallic chemistry》2008,693(14):2415-2423
Four new phosphazirconocenes, [(4,5,6-trihydro-1-phosphapentalenyl)2ZrCl2] (8), [(4,5,6,7-tetrahydro-1-phosphindolyl)2ZrCl2] (9), [(4,5,6,7,8-pentahydro-1-phosphazulenyl)2ZrCl2] (10), (2,4-dimethylphospholyl)2ZrCl2 (11), were prepared and characterized. A crystal structure of [(4,5,6,7-tetrahydro-1-phosphindolyl)2ZrCl2] (9), was obtained that revealed disorder (rac and meso isomers in the same crystal) and demonstrates unambiguously the meso configuration in the bent early transition metal phosphametallocenes. Lacking a spectroscopic probe of the rotational dynamics in phosphametallocenes, propylene polymerization was chosen to provide a record of the stereoselective insertions and by inference insight into the phosphametallocene dynamics. Phosphazirconocenes 8-11 were evaluated, and the rac/meso mixture of [(4,5,6,7-tetrahydro-1-phosphindolyl)2ZrCl2] (9) was found to produce a mixture of isotactic (iPP) and atactic (aPP) polypropylenes. 13C NMR spectral analysis of the stereo-errors contained in the iPP fraction indicated enantiomorphic site control as the source of the stereoselectivity. The rotational dynamics of the η5-phospholyl ligand of the parent phosphazirconocene, [(C4H4P)2ZrCl2], was examined as a first order surrogate of reasonable computing complexity for the catalytically active species. The phosphazirconocene was examined using a restricted Hartree-Fock method with a split basis set of 6-311+G(d,p) for C, H, Cl, P and of LANL2DZ for Zr. The rotational potential energy surface was found to be unsymmetrical with a maximum barrier of 8.8 kcal mol−1, which is about an order of magnitude greater than that reported for Cp2ZrCl2. The projection of the calculated rotational dynamics onto a 1-phosphatetrahydroindenyl system is illustrated. This model leads to an interpretation of the polymerization results and the rotational dynamics in phosphametallocenes. 相似文献
134.
García-Fonseca S Ballesteros-Gómez A Rubio S Pérez-Bendito D 《Analytica chimica acta》2008,617(1-2):3-10
Coacervates made up of reverse micelles of decanoic acid were assessed as a new strategy for the simplification of wine sample treatment in the determination of Ochratoxin A (OTA). Simultaneous extraction/concentration of this contaminant was based on both hydrophobic and hydrogen bond OTA:coacervate interactions. Parameters affecting extraction efficiency and concentration factors were studied. Concentrations of decanoic acid and tetrahydrofuran (THF) were the most influential parameters, being 0.5% of acid and 5% of THF the selected ones. The procedure was very robust, so that the extractions were not influenced by the pH and the nature or concentration of matrix components. OTA recoveries from different types of wines (white, rosé and red) ranged between 85 and 100% and the actual concentration factors varied from 105 to 125 for sample volumes of 15 mL. The detection limits for OTA, after liquid chromatography/fluorimetry (LC/FL) analysis of the coacervate (20 microL), were 4.5 ng L(-1) in white and rosé wines and 15 ng L(-1) in red wines, values which were far below the threshold limit established for OTA by EU directives (2.0 microg L(-1)). No clean-up of the extracts was required for any of the samples analysed. The overall sample treatment took about 15-20 min and several samples could be simultaneously treated using conventional lab equipment. The precision of the method, expressed as relative standard deviation, was about 5%. The approach developed was successfully applied to the determination of OTA in different wine samples from the South of Spain. The concentrations found ranged between 0.015 and 0.091 microg L(-1). 相似文献
135.
136.
On the Exciton Coupling between Two Chlorophyll Pigments in the Absence of a Protein Environment: Intrinsic Effects Revealed by Theory and Experiment
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Dr. Bruce F. Milne Christina Kjær Jørgen Houmøller Dr. Mark H. Stockett Dr. Yoni Toker Prof. Angel Rubio Prof. Steen Brøndsted Nielsen 《Angewandte Chemie (International ed. in English)》2016,55(21):6248-6251
Exciton coupling between two or more chlorophyll (Chl) pigments is a key mechanism associated with the color tuning of photosynthetic proteins but it is difficult to disentangle this effect from shifts that are due to the protein microenvironment. Herein, we report the formation of the simplest coupled system, the Chl a dimer, tagged with a quaternary ammonium ion by electrospray ionization. Based on action spectroscopic studies in vacuo, the dimer complexes were found to absorb 50–70 meV to the red of the monomers under the same conditions. First‐principles calculations predict shifts that somewhat depend on the relative orientation of the two Chl units, namely 50 and 30 meV for structures where the Chl rings are stacked and unstacked, respectively. Our work demonstrates that Chl association alone can produce a large portion of the color shift observed in photosynthetic macromolecular assemblies. 相似文献
137.
J. N. Orce M. Kumar Raju N. A. Khumalo T. S. Dinoko P. Jones R. A. Bark E. A. Lawrie S. N. T. Majola L. M. Robledo B. Rubio M. Wiedeking J. Easton E. A. Khaleel B. V. Kheswa N. Kheswa M. S. Herbert J. J. Lawrie P. L. Masiteng M. R. Nchodu J. Ndayishimye D. Negi S. P. Noncolela S. S. Ntshangase P. Papka D. G. Roux O. Shirinda P. S. Sithole S. W. Yates 《The European Physical Journal A - Hadrons and Nuclei》2016,52(6):166
138.
Pedraza A Sicilia MD Rubio S Pérez-Bendito D 《Analytical and bioanalytical chemistry》2007,389(7-8):2297-2302
A selective method for the determination of l-glutamate in foodstuffs has been developed. It was based on the competition established between the analyte and the dye Coomassie
brilliant blue G (CBBG) to interact with the surfactant didodecyldimethylammonium bromide (DDABr). The measurement parameter
was the amount of DDABr required to reach a given dye-to-surfactant binding degree. It was obtained by photometric titration
on the basis of the changes observed in the spectral characteristics of the dye when CBBG–DDABr aggregates were formed. The
calibration graph obtained was linear in the l-glutamate concentration interval 0.2–5 mM (detection limit 0.05 mM). The high selectivity of the proposed method (other amino
acids and food additives did not interfere at the concentrations present in foodstuffs) permitted the direct analysis of food
samples after dissolution of the analyte in hot water. The accuracy of the surfactant to the dye binding degree method was
demonstrated by determining l-glutamate in different kinds of foodstuffs (liquid and dried soups, seasonings, pasta sauces and dried mushroom creams) and
comparing the results obtained with those provided by the commercial Boehringer Mannheim essay. 相似文献
139.
The surfactant to dye binding degree (SDBD) method is proposed for the routine monitoring of anionic surfactants in aqueous environmental samples and their analytical features compared with those provided by the standard methylene blue (MB) method. This new analytical approach is based on the effect that anionic surfactants exert on the binding degree of the cationic surfactant didodecyldimethylammonium bromide (DDABr) to the anionic dye Coomassie Brilliant Blue G (CBBG). The formation of DDABr-CBBG aggregates is monitored photometrically. The analytical applicability of the proposed method was demonstrated by determining anionic surfactants in tap, river and swamp water, and raw and treated sewage. The mean recoveries obtained ranged between 99 and 101%. The SDBD method offers important advantages over the classical MB method: it is more sensitive, selective, precise, simple and rapid; the analytical response is independent of the molecular structure of the anionic surfactants, and the volume of sample required for analysis and the consumption of organic solvents are significantly reduced. 相似文献
140.
Díez-Pascual AM Monroy F Ortega F Rubio RG Miller R Noskov BA 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3802-3808
A brief summary of dilational surface viscoelatic properties of spread and adsorbed surfactant polymer films at the air-water interface is reported. The viscoelastic moduli have been measured as a function of frequency and surface pressure. The combination of several techniques, oscillating drop and barrier experiments and electrocapillary waves (ECW), has allowed us to investigate a broad frequency range. The dynamic elasticity epsilon shows a slight change with frequency and a noticeable pressure dependence for both kinds of monolayers. In the spread films, elasticity increases steeply with surface pressure, and reaches a constant value before the polymer begins to dissolve into the bulk. On the other hand, the adsorbed films exhibit a pronounced elasticity maximum, followed by a considerable decay when a loose surface structure is formed. The position of the maximum depends on the polymer chemical composition and molecular weight. The results on the overlapping surface pressure range confirm the dynamic equivalence of spread and adsorbed monolayers. At low surface concentration, the agreement between static and dynamic elasticity is quite satisfactory, but the values diverge considerably at higher surface pressures. The loss modulus omegakappa decreases monotonically with increasing omega, becoming zero (it can even take apparent negative values) for the highest frequencies. The frequency dependence of the elasticity has been well described by the diffusive control model of Lucassen-van den Tempel (LVT). However, its predictions for omegakappa do not coincide with the experimental data. The differences between experimental and theoretical values increase at low frequencies. 相似文献