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21.
Flavio Sabatelli Jacopo Segato Leonardo Belpassi Alessandro Del Zotto Daniele Zuccaccia Paola Belanzoni 《Molecules (Basel, Switzerland)》2021,26(9)
The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl−, BF4−, OTf−, H2O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4− and OTf− have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf− and BF4−, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts. 相似文献
22.
Carlos Eduardo Barão Leandro Daniel de Paris João Henrique Dantas Matheus Mendonça Pereira Lucio Cardozo Filho Heizir Ferreira de Castro Gisella Maria Zanin Flavio Faria de Moraes Cleide Mara Faria Soares 《Applied biochemistry and biotechnology》2014,172(1):263-274
The use of lipases in industrial processes can result in products with high levels of purity and at the same time reduce pollutant generation and improve both selectivity and yields. In this work, lipase from Thermomyces lanuginosus was immobilized using two different techniques. The first involves the hydrolysis/polycondensation of a silica precursor (tetramethoxysilane (TMOS)) at neutral pH and ambient temperature, and the second one uses tetraethoxysilane (TEOS) as the silica precursor, involving the hydrolysis and polycondensation of the alkoxide in appropriate solvents. After immobilization, the enzymatic preparations were dried using the aerogel and xerogel techniques and then characterized in terms of their hydrolytic activities using a titrimetric method with olive oil and by the formation of 2-phenylethyl acetate in a transesterification reaction. The morphological properties of the materials were characterized using scanning electron microscopy, measurements of the surface area and pore size and volume, thermogravimetric analysis, and exploratory differential calorimetry. The results of the work indicate that the use of different silica precursors (TEOS or TMOS) and different drying techniques (aerogel or xerogel) can significantly affect the properties of the resulting biocatalyst. Drying with supercritical CO2 provided higher enzymatic activities and pore sizes and was therefore preferable to drying, using the xerogel technique. Thermogravimetric analysis and differential scanning calorimetry analyses revealed differences in behavior between the two biocatalyst preparations due to the compounds present. 相似文献
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Rafael M. de Almeida Victoria C. Ferrari Dr. Juliana dos S. Souza Dr. Flavio L. Souza Wendel A. Alves 《Chemphyschem》2020,21(6):476-483
Herein, a detailed investigation of the surface modification of a zinc oxide (ZnO) nanorod electrode with FeOOH nanoparticles dispersed in glycine was conducted to improve the water oxidation reaction assisted by sunlight. The results were systematically analysed in terms of the general parameters (light absorption, charge separation, and surface for catalysis) that govern the photocurrent density response of metal oxide as photoanode in a photoelectrochemical (PEC) cell. ZnO electrodes surface were modified with different concentration of FeOOH nanoparticles using the spin-coating deposition method, and it was found that 6-layer deposition of glycine-FeOOH nanoparticles is the optimum condition. The glycine plays an important role decreasing the agglomeration of FeOOH nanoparticles over the ZnO electrode surface and increasing the overall performance. Comparing bare ZnO electrodes with the ones modified with glycine-FeOOH nanoparticles an enhanced photocurrent density can be observed from 0.27 to 0.57 mA/cm2 at 1.23 VRHE under sunlight irradiation. The impedance spectroscopy data aid us to conclude that the higher photocurrent density is an effect associated with more efficient surface for chemical reaction instead of electronic improvement. Nevertheless, the charge separation efficiency remains low for this system. The present discovery shows that the combination of glycine-FeOOH nanoparticle is suitable and environmentally-friend cocatalyst to enhance the ZnO nanorod electrode activity for the oxygen evolution reaction assisted by sunlight irradiation. 相似文献
25.
Flavio Antonio Franchina Delphine Zanella Eliane Lazzari Pierre‐Hugues Stefanuto Jean‐Franois Focant 《Journal of separation science》2020,43(9-10):1790-1799
Headspace gas chromatography is frequently used for aroma profiling thanks to its ability to naturally exploit the volatility of aroma compounds, and also to provide chemical information on sample composition. Its main advantages rely on simplicity, no use of solvent, amenability to automation, and the cleanliness of the extract. In the present contribution, the most effective sampling (dynamic extraction), separation (multidimensional gas chromatography), and detection (mass spectrometry) techniques for untargeted analysis are exploited in combination, showing their potential in unraveling aroma profiles in fruit beers. To complete the overall analytical process, a neat workflow for data analysis is discussed and used for the successful characterization and identification of five different beer flavors (berries, cherry, banana, apple, and peach). From the technical viewpoint, the coupling of purge‐and‐trap, comprehensive two‐dimensional gas chromatography, and mass spectrometry makes the global methodology unique, and it is for the first time discussed. A (low‐)flow modulation approach allowed for the full transfer into the second dimension with mass‐spectrometry compatible flow (< 7 mL/min), avoiding the need of splitting before detection and making the overall method sensitive (1.2–5.2‐fold higher signal to noise ratio compared to unmodulated gas chromatography conditions) and selective. 相似文献
26.
Amyloglucosidase from Novo (Copenhagen, Denmark) was immobilized in controlled pore silica particles with the silane-glutaraldehyde
covalent method. Thermal stability of the free and immobilized enzyme (IE) was determined with 30% (w/v) α-amylase liquefied
cassava starch, pH 4.5, temperatures from 35 to 75°C. Free amyloglucosidase maintained its activity practically constant for
240 min and temperatures up to 50°C. The IE has shown higher stability retaining its activity for the same period up to 60°C.
Half-life for free enzyme was 20.6, 6.44, 2.07, 0.69, and 0.24 h for 55, 60, 65, 70, and 75°C, respectively, whereas the IE
at the same temperatures had half-lives of 116.4, 30.88, 8.52, 2.44, and 0.73 h. The energy of thermal deactivation was thus
50.6 and 57.6 kcal/mol, respectively for the free and IE, confirming stabilization by immobilization. 相似文献
27.
Yun Zou Meriem Gaida Flavio A. Franchina Pierre-Hugues Stefanuto Jean-Franois Focant 《Molecules (Basel, Switzerland)》2022,27(6)
Coffee, one of the most popular beverages in the world, attracts consumers by its rich aroma and the stimulating effect of caffeine. Increasing consumers prefer decaffeinated coffee to regular coffee due to health concerns. There are some main decaffeination methods commonly used by commercial coffee producers for decades. However, a certain amount of the aroma precursors can be removed together with caffeine, which could cause a thin taste of decaffeinated coffee. To understand the difference between regular and decaffeinated coffee from the volatile composition point of view, headspace solid-phase microextraction two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME-GC×GC-TOFMS) was employed to examine the headspace volatiles of eight pairs of regular and decaffeinated coffees in this study. Using the key aroma-related volatiles, decaffeinated coffee was significantly separated from regular coffee by principal component analysis (PCA). Using feature-selection tools (univariate analysis: t-test and multivariate analysis: partial least squares-discriminant analysis (PLS-DA)), a group of pyrazines was observed to be significantly different between regular coffee and decaffeinated coffee. Pyrazines were more enriched in the regular coffee, which was due to the reduction of sucrose during the decaffeination process. The reduction of pyrazines led to a lack of nutty, roasted, chocolate, earthy, and musty aroma in the decaffeinated coffee. For the non-targeted analysis, the random forest (RF) classification algorithm was used to select the most important features that could enable a distinct classification between the two coffee types. In total, 20 discriminatory features were identified. The results suggested that pyrazine-derived compounds were a strong marker for the regular coffee group whereas furan-derived compounds were a strong marker for the decaffeinated coffee samples. 相似文献
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We prove that given a compact n-dimensional boundaryless manifold M, n?2, there exists a residual subset R of Diff1(M) such that if f∈R admits a spectral decomposition (i.e., the non-wandering set admits a partition into a finite number of transitive compact sets), then this spectral decomposition is robust in a generic sense (tame behavior). This implies a C1-generic trichotomy that generalizes some aspects of a two-dimensional theorem of Mañé [Topology 17 (1978) 386-396].Lastly, Palis [Astérisque 261 (2000) 335-347] has conjectured that densely in Diffk(M) diffeomorphisms either are hyperbolic or exhibit homoclinic bifurcations. We use the aforementioned results to prove this conjecture in a large open region of Diff1(M). 相似文献