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891.
892.
Kozlov YN Romakh VB Kitaygorodskiy A Buglyó P Süss-Fink G Shul'pin GB 《The journal of physical chemistry. A》2007,111(32):7736-7752
The vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA [identical with] pcaH) efficiently catalyzes the oxidation of 2-propanol by hydrogen peroxide to give acetone. UV-vis spectroscopic monitoring of the reaction as well as the kinetics lead to the conclusion that the crucial step of the process is the monomolecular decomposition of a diperoxovanadium(V) complex containing the pca ligand to afford the peroxyl radical, HOO(.-) and a V(IV) derivative. The rate-limiting step in the overall process may not be this (rapid) decomposition itself but (prior to this step) the slow hydrogen transfer from a coordinated H2O2 molecule to the oxygen atom of a pca ligand at the vanadium center: "(pca)(O=)V...O2H2" --> "(pca)(HO-)V-OOH". The V(IV) derivative reacts with a new hydrogen peroxide molecule to generate the hydroxyl radical ("V(IV)" + H2O2 --> "V(V)" + HO(-) + HO(.-)), active in the activation of isopropanol: HO(.-) + Me2CH(OH) --> H2O + Me2C(.-)(OH). The reaction with an alkane, RH, in acetonitrile proceeds analogously, and in this case the hydroxyl radical abstracts a hydrogen atom from the alkane: HO(.-) + RH --> H2O + R(.-). These conclusions are in a good agreement with the results obtained by Bell and co-workers (Khaliullin, R. Z.; Bell, A. T.; Head-Gordon, M. J. Phys. Chem. B 2005, 109, 17984-17992) who recently carried out a density functional theory study of the mechanism of radical generation in the reagent under discussion in acetonitrile. 相似文献
893.
Irene Mediavilla María Amparo Blzquez Alex Ruiz Luis Saúl Esteban 《Molecules (Basel, Switzerland)》2021,26(8)
Cistus ladanifer is a Mediterranean native plant from which valuable products, such as essential oil, are obtained. Manual harvesting of the plants in wild shrublands is usual during short periods of time. Their mechanised harvesting could increase the volume of harvested plants and prevent fires, further storage of the plants collected being necessary. The objective of this work is to study the influence of the storage period of mechanically harvested bales on the essential oil yield and qualitative composition. The harvesting trials were carried out with an adapted commercial harvester baler and the storage of the bales was performed indoors during 1–7 days, 15–30 days and 100–120 days. Afterwards, the bales were crushed (30 mm) and distilled in a 30 litre stainless steel still with saturated steam (0.5 bar). The essential oil components were identified by GC-MS and quantified by GC-FID. The storage of mechanically harvested Cistus ladanifer does not decrease the oil yield of steam distillation on a pilot scale. However, it leads to differences in the quantitative composition of the essential oils, decreasing the total monoterpene compounds content and increasing that of oxygenated sesquiterpenes, especially when the biomass is stored for 100–120 days, without affecting its qualitative composition. 相似文献
894.
Jennifer A. Klaus Taylor M. Brooks Muyang Zhou Alex J. Veinot Alexander M. Warman Adam Palayew Patrick T. Gormley B. Ninh Khuong Christopher M. Vogels Jason D. Masuda Felix J. Baerlocher Stephen A. Westcott 《Transition Metal Chemistry》2017,42(3):263-271
Six Schiff base compounds have been prepared from the condensation of o-vanillin, 2,3-dihydroxybenzaldehyde and 2,3,4-trihydroxybenzaldehyde with 4-aminosalicylic acid and 5-aminosalicylic acid (5-ASA). Addition of these Schiff bases to [Pd(OAc)2] afforded the corresponding bis(salicylaldiminato)palladium(II) complexes in moderate to excellent yields. All new palladium complexes have been characterized fully using standard spectroscopic methods, elemental analyses and a single-crystal X-ray diffraction study in the case of 2e, the palladium complex containing Schiff base ligands derived from 5-ASA and 2,3-dihydroxybenzaldehyde. All derivatives of 5-ASA were examined for potential antimicrobial activities against two species of fungi, Aspergillus niger and Saccharomyces cerevisiae, as well as two species of bacteria, Bacillus cereus (Gram-positive) and Pseudomonas aeruginosa (Gram-negative). 相似文献
895.
Alex Sandro Santos 《Archiv der Mathematik》2017,109(1):91-100
It was conjectured in the 80s that every critical metric of the total scalar curvature functional restricted to space of metrics with constant scalar curvature of unitary volume must be Einstein. We prove that such a conjecture is true under a second-order vanishing condition on the Weyl tensor. 相似文献
896.
Microporous carbon aerogel prepared through ambient pressure drying route as anode material for lithium ion cells 下载免费PDF全文
Ancy Smitha Alex Ananda Lekshmi M.S. Sekkar V. Bibin John Gouri C. Ilangovan S.A. 《先进技术聚合物》2017,28(12):1945-1950
Carbon aerogel synthesized through a cost‐effective and easy method was evaluated and found to be a promising anode material for lithium ion cells. Carbon aerogel was prepared by carbonizing resorcinol–formaldehyde (RF) aerogel under inert atmosphere. Resorcinol–formaldehyde aerogel in turn was prepared through sol gel polymerization of resorcinol with formaldehyde using sodium carbonate as catalyst adopting ambient pressure drying route. The structure and the morphology of the prepared carbon aerogel are investigated using X‐ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and surface area determined using N2–Brunauer–Emmett–Teller (BET) method. The TEM images reveal microporous morphology of the carbon aerogel particles. The evaluation of carbon aerogel as an anode material revealed promising specific capacity synergized with outstanding cyclability. The first cycle specific capacity was 288 mAh/g with an efficiency of 63% at C/10 rate. The material retained a capacity of 96.9% of the initial capacity with about 100% efficiency after 100 cycles, showing the excellent cyclability of the material. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献
897.
898.
We address the estimation of the loss parameter of a bosonic channel probed by Gaussian signals. We derive the ultimate quantum bound with precision and show that no improvement may be obtained by having access to the environmental degrees of freedom. We find that, for small losses, the variance of the optimal estimator is proportional to the loss parameter itself, a result that represents a qualitative improvement over the shot-noise limit. An observable based on the symmetric logarithmic derivative is obtained, which attains the ultimate bound and may be implemented using Gaussian operations and photon counting. 相似文献
899.
We present a concept of standing-wave optical frequency conversion in dispersive microcavities theoretically and experimentally, allowing efficient ultracompact nonlinear photonics. We developed a time-dependent model, incorporating the dispersion into the structure of the spatial cavity modes, where the conversion efficiency is enhanced by the optimization of a nonlinear cavity mode overlap. We designed and fabricated integrated double-resonance semiconductor microcavities for standing-wave second-harmonic generation. The measured efficiency exhibits a significant maximum near the cavity resonance owing to the intracavity power enhancement and the dispersion-induced wavelength detuning effect on the mode overlap, in good agreement with our theoretical predictions. 相似文献
900.
"Push-pull" phenyltetraene-based chromophores are too sensitive to be incorporated into Diels-Alder-type cross-linkable polymers due to the reactivity of its diene segment with maleimides. A facile synthetic route has been explored to incorporate a methoxy group into the R position of such chromophores, which reduces their diene reactivity during the poling and lattice hardening process. The poled polymers with one of such chromophores doped in a cross-linked polymer lattice showed ultrahigh electro-optic activities, up to 306 pm/V at 1310 nm. 相似文献