Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions. 相似文献
ABSTRACT The asymptotic homogenization method is applied to complex dielectric periodic composites. An equivalence to coupled dielectric problems with real coefficients is shown. This is similar to a piezoelectric problem: an out-plane mechanical displacement and an in-plane electric potential establishing a correspondence principle. Closed-form formulas for the complex dielectric effective tensor in the case of a square array of circular inclusions embedded in a matrix are given. These formulas are written in terms of a real and symmetric matrix which facilitates the implementation of the computational scheme. We also get similar formulas for multilayered complex dielectric composites. The real closed-form formulas are advantageous for estimating gain and loss enhancement properties of active and passive composites in certain volume fraction intervals. Numerical computations are performed and the results are compared with other approaches showing the usefulness of the obtained formulas. This may be of interest in the context of metamaterials. 相似文献
Dipetalolactone and 4‐methyldipetalolactone are prepared in excellent yield by a one‐pot tandem propargylation/Claisen rearrangement/cyclization reaction of the corresponding 5,7‐dihydroxycoumarins with 3‐chloro‐3‐methylbut‐1‐yne in the presence of Cs2CO3 under microwave irradiation. The analogous reactions of propargyl chloride with esculetins or 5,7‐dihydroxycoumarins led to dipropargyloxy derivatives. The later by treatment with gold nanoparticles supported on TiO2 or BF3.Et2O in N,N‐dimethylformamide (DMF) under microwave irradiation resulted in very good to excellent yield to the corresponding fused dipyranocoumarins. The reactions of esculetins with 3‐chloro‐3‐methylbut‐1‐yne gave mainly exomethylene fused dioxino[g]coumarins. 相似文献
A simple, sensitive, specific, and cost‐effective analytical methodology was developed for the analysis of human plasma samples spiked with imatinib by CZE with on‐line UV detection in the context of Therapeutic Drug Monitoring. Several analytical conditions such as the ionic strength (I) and the pH of the BGE composed of citric acid and ε‐amino caproic acid were studied in regards of the presence of sodium chloride (NaCl) in plasma samples (1% m/v). Computer simulations (Simul software) were used to confirm the experimental results and to understand imatinib electrophoretic behavior in the presence of NaCl. Furthermore, the advantages of adding ACN to the sample containing NaCl to combine efficient protein precipitation and on‐line CZE stacking of imatinib were demonstrated. LOD and LOQ values of 48 and 191 ng/mL were obtained from plasma sample supernatant after protein precipitation with ACN, which is much lower than mean imatinib plasma level observed for patients treated by imatinib mesylate (about 1000 ng/mL). Good linearity was obtained in the concentration range 191–5000 ng/mL (R2 > 0.997). RSD of less than 1.68% and 2.60% (n = 6) for migration times and corrected peak areas, respectively, were observed at the LOQ. 相似文献
We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal–N-heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base-assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of transition-metal- and main-group-centered NHC compounds and could become the synthetic route of choice to form M–NHC bonds. 相似文献
AbstractExperimental studies conducted on some species of Mediterranean red algae allowed to identify Sphaerococcus coronopifolius Stackhouse as a valid alternative to the Pacific alga Gloiopeltis furcata (Postels & Ruprecht) J. Agardh, for the extraction of a material usable as natural consolidant and adhesive in the field of restoration. Promising results have been observed by comparing the extracts obtained from these two algae after the same extraction procedure. Chemical analysis (FTIR) revealed that S. coronopifolius has qualities similar to G. furcata. Even more promising results for S. coronopifolius compared to G. furcata were observed after the analysis of pH and conductivity, and the adhesion tests carried out on both extracts. 相似文献
Among alternative techniques to overcome the difficulties associated with thermal regeneration, non-thermal plasma can be considered as one of the most promising technology. The coke trapped in the zeolite micropores can be oxidized at room temperature with a low energy consumption using a dielectric barrier discharge reactor with a pin to plate geometry. The influence of various experimental parameters for coke removal efficiency and ozone production was investigated: input power, gap between the two electrodes, gas flow rate, catalyst mass and compactness. We showed that the efficiency was not strongly increased by increasing the deposited power from 23 to 36 W, but it depends strongly on the mass, so the depth of the wafer. The elimination of coke becomes more difficult as soon as the compactness is increased. The removal of coke is not uniform within the wafer, the one localized into the depth of the wafer is difficult to remove and requires higher input power (>?30 W).