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91.
Dr. Miriam Corredor Dr. Daniel Carbajo Cecilia Domingo Dr. Yolanda Pérez Dr. Jordi Bujons Prof. Dr. Angel Messeguer Dr. Ignacio Alfonso 《Angewandte Chemie (International ed. in English)》2018,57(37):11973-11977
Despite heparin being the most widely used macromolecular drug, the design of small‐molecule ligands to modulate its effects has been hampered by the structural properties of this polyanionic polysaccharide. Now a dynamic covalent selection approach is used to identify a new ligand for heparin, assembled from extremely simple building blocks. The amplified molecule strongly binds to heparin (KD in the low μm range, ITC) by a combination of electrostatic, hydrogen bonding, and CH–π interactions as shown by NMR and molecular modeling. Moreover, this ligand reverts the inhibitory effect of heparin within an enzymatic cascade reaction related to blood coagulation. This study demonstrates the power of dynamic covalent chemistry for the discovery of new modulators of biologically relevant glycosaminoglycans. 相似文献
92.
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
93.
Gagliardi LG Castells CB Ràfols C Rosés M Bosch E 《Journal of separation science》2008,31(6-7):969-980
We propose a general simple equation for accurately predicting the retention factors of ionizable compounds upon simultaneous changes in mobile phase pH and column temperature at a given hydroorganic solvent composition. Only four independent experiments provide the input data: retention factors measured in two pH buffered mobile phases at extreme acidic and basic pH values (e. g., at least +/- 2 pH units far from the analyte pK(a)) and at two column temperatures. The equations, derived from the basic thermodynamics of the acid-base equilibria, additionally require the knowledge of the solute pK(a )and enthalpies of acid-base dissociation of both the solute and the buffer components in the hydroorganic solvent mixture. The performance of the predictive model is corroborated with the comparison between theoretical and experimental retention factors of several weak acids and bases of important pharmacological activity, in mobile phases containing different buffer solutions prepared in 25% w/w ACN in water and at several temperatures. 相似文献
94.
Donatella Senatra C. Ziparo Cecilia M. C. Gambi L. Lanzi 《Journal of Thermal Analysis and Calorimetry》2008,92(2):535-541
A water-in-oil microemulsion composed of water, AOT and decane with volume fraction φ=0.50 and molar ratio X=40.8 was analysed by DSC. The percolation and the bicontinuous transitions as well as the melting endotherms and the freezing
exotherms were measured. The main attention was focussed on the system energy balance. It was found that, by freezing the
samples after the occurrence of the percolative transition, the total heat released is significantly less than the heat absorbed
in the melting endotherms. A simple geometrical model was used as an analysis tool of the aforementioned energy difference.
Since the system studied exhibits a percolative transition of dynamic type, on approaching the percolation threshold temperature
(T≤T
p) and a static percolation for T≥T
p, the structural change from the connecting water-droplet-cluster to a connecting water channel was schematised in the model
as a change from a sphere-necklace to a water-cylindrical channel of equal volume and equal length. The surface energy associated
with the formation of the two different geometrical surfaces was evaluated and the amount of saved energy compared with the
experimentally measured one. 相似文献
95.
Rapid screening of membrane protein activity: electrophysiological analysis of OmpF reconstituted in proteoliposomes 总被引:1,自引:0,他引:1
Solvent-free planar lipid bilayers were formed in an automatic manner by bursting of giant unilamellar vesicles (GUVs) after gentle suction application through micron-sized apertures in a borosilicate glass substrate. Incubation of GUVs with the purified ion channel protein of interest yielded proteoliposomes. These proteoliposomes allow for immediate recording of channel activity after GUV sealing. This approach reduces the time-consuming, laborious and sometimes difficult protein reconstitution processes normally performed after bilayer formation. Bilayer recordings are attractive for investigations of membrane proteins not accessible to patch clamp analysis, like e.g. proteins from organelles. In the presented work, we show the example of the outer membrane protein OmpF from Escherichia coli. We reconstituted OmpF in proteoliposomes and observed the characteristic trimeric conductance levels and the typical gating induced by pH and transmembrane voltage. Moreover, OmpF is the main entrance for beta-lactam antibiotics and we investigated translocation processes of antibiotics and modulation of OmpF by spermine. We suggest that the rapid formation of porin containing lipid bilayers is of potential for the efficient electrophysiological characterization of the OmpF protein, for studying membrane permeation processes and for the rapid screening of antibiotics. 相似文献
96.
We carried out density functional theory (DFT) calculations to investigate the thermodynamics and the kinetics of the double aquation reaction of the anticancer drug NAMI-A. Three explicit water molecules were included in the calculations to improve the PB solvation energies. Our calculations show that the chloride substitution reactions on the considered Ru(III) octahedral complex follow a dissociative interchange mechanism, I(d), passing through a loose heptacoordinate transition state. We calculated an activation enthalpy and free energy for the first aquation step of 101.5 and 103.7 kJ mol(-1), respectively, values that are in good agreement with the available experimental results. The activation enthalpy and free energy for the second aquation step were found significantly higher, 118.7 and 125.0 kJ mol(-1), again in agreement with the experimental evidence indicating a slower rate for the second aquation. 相似文献
97.
Bombelli C Bernardini C Elemento G Mancini G Sorrenti A Villani C 《Journal of the American Chemical Society》2008,130(9):2732-2733
Chiral recognition was observed in a biomembrane model. Micellar aggregates formed by enantiopure N-alkyl-N,N-dimethyl-N-(1-phenyl)ethylammonium bromide were in fact able to convert the racemic mixture of bilirubin-IXalpha into an enantiomerically enriched mixture. The stereochemical preference and the extent of enantiomeric enrichment depend on the length of the hydrophobic portion of the surfactant and on the concentration conditions, and changes in the stereochemical bias are reversible. 相似文献
98.
Orozco J Fernández-Sánchez C Mendoza E Baeza M Céspedes F Jiménez-Jorquera C 《Analytica chimica acta》2008,607(2):176-182
This work reports on the development of a graphite-polystyrene composite electrode of planar configuration, containing silver(II) oxide and copper(II) oxide catalysts (AgO-CuO), for the measurement of electrochemical oxygen demand (EOD). Optimisation studies of the composite composition as well as conditions for its processing on planar substrates and generation of an appropriate electrochemical active area resulted in the scalable fabrication of robust composite electrodes. These were evaluated with glucose as target analyte. They showed competitive low limits of detection in a linear concentration range from 5 mg L−1 to 1400 mg L−1 of O2. Besides, they were stable for at least one year. The determination of EOD in wastewater samples coming from production lines of parenteral food and winemaking was successfully carried out. 相似文献
99.
100.
Pablo Giménez-Gómez Manuel Gutiérrez-Capitán Fina Capdevila Anna Puig-Pujol César Fernández-Sánchez Cecilia Jiménez-Jorquera 《Analytica chimica acta》2016
l-lactic acid is monitored during malolactic fermentation process of wine and its evolution is strongly related with the quality of the final product. The analysis of l-lactic acid is carried out off-line in a laboratory. Therefore, there is a clear demand for analytical tools that enabled real-time monitoring of this process in field and biosensors have positioned as a feasible alternative in this regard. The development of an amperometric biosensor for l-lactate determination showing long-term stability is reported in this work. The biosensor architecture includes a thin-film gold electrochemical transducer selectively modified with an enzymatic membrane, based on a three-dimensional matrix of polypyrrole (PPy) entrapping lactate oxidase (LOX) and horseradish peroxidase (HRP) enzymes. The experimental conditions of the biosensor fabrication regarding the pyrrole polymerization and the enzymes entrapment are optimized. The biosensor response to l-lactate is linear in a concentration range of 1 × 10−6–1 × 10−4 M, with a detection limit of 5.2 × 10−7 M and a sensitivity of – (13500 ± 600) μA M−1 cm−2. The biosensor shows an excellent working stability, retaining more than 90% of its original sensitivity after 40 days. This is the determining factor that allowed for the application of this biosensor to monitor the malolactic fermentation of three red wines, showing a good agreement with the standard colorimetric method. 相似文献