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911.
Dr. Antonio Zucca Dr. Luca Maidich Laura Canu Dr. Giacomo L. Petretto Prof. Sergio Stoccoro Prof. Maria Agostina Cinellu Dr. Guy J. Clarkson Dr. Jonathan P. Rourke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5501-5510
Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a “rollover”/“retro‐rollover” reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR3)] resulted in a rare C(sp2)?C(sp3) bond formation to give the bidentate nitrogen ligands 3‐methyl‐2,2′‐bipyridine, 3,6‐dimethyl‐2,2′‐bipyridine, and 3‐methyl‐2‐(2′‐pyridyl)‐quinoline, which were isolated and characterized. The nature of the phosphane PR3 is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of C?H bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize. 相似文献
912.
Franciele Maria Pelissari Paulo José do Amaral Sobral Florencia Cecilia Menegalli 《Cellulose (London, England)》2014,21(1):417-432
Cellulose nanofibers were isolated from banana peel using a combination of chemical treatments, such as alkaline treatment, bleaching, and acid hydrolysis. The suspensions of chemically treated fibers were then passed through a high-pressure homogenizer 3, 5, and 7 times, to investigate the effect of the number of passages on the properties of the resulting cellulose nanofibers. The cellulose nanofibers isolated in this study had a dry basis yield of 5.1 %. Transmission electron microscopy showed that all treatments effectively isolated banana fibers in the nanometer scale. The micrographs of the process steps used to isolate the nanofibers revealed gradual removal of amorphous components. Increasing number of passages in the homogenizer shortened the cellulose nanofibers while furnishing more stable aqueous suspensions with zeta potential values ranging from ?16.1 to ?44.1 mV. All the samples presented aspect ratio in the range of long nanofibers, hence being potentially applicable as reinforcing agents in composites. X-ray diffraction studies revealed that homogenized nanofiber suspensions were more crystalline than non-homogenized suspensions. Fourier transform infrared spectroscopy confirmed that alkaline treatment and bleaching removed most of the hemicellulose and lignin components present in the banana fibers. Thermal analyses revealed that the developed nanofibers exhibit enhanced thermal properties. In general, the nanoparticles isolated from the banana peel have potential application as reinforcing elements in a variety of polymer composite systems. 相似文献
913.
Thermal Ethane Activation by Bare [V2O5]+ and [Nb2O5]+ Cluster Cations: on the Origin of Their Different Reactivities
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Dr. Xiao‐Nan Wu Dr. Shi‐Ya Tang Dr. Hai‐Tao Zhao Dr. Thomas Weiske Dr. Maria Schlangen Prof. Dr. Helmut Schwarz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6672-6677
The gas‐phase reactivity of [V2O5]+ and [Nb2O5]+ towards ethane has been investigated by means of mass spectrometry and density functional theory (DFT) calculations. The two metal oxides give rise to the formation of quite different reaction products; for example, the direct room‐temperature conversions C2H6→C2H5OH or C2H6→CH3CHO are brought about solely by [V2O5]+. In distinct contrast, for the couple [Nb2O5]+/C2H6, one observes only single and double hydrogen‐atom abstraction from the hydrocarbon. DFT calculations reveal that different modes of attack in the initial phase of C?H bond activation together with quite different bond‐dissociation energies of the M?O bonds cause the rather varying reactivities of [V2O5]+ and [Nb2O5]+ towards ethane. The gas‐phase generation of acetaldehyde from ethane by bare [V2O5]+ may provide mechanistic insight in the related vanadium‐catalyzed large‐scale process. 相似文献
914.
Juliano Fiorelli Catarina Abdala Gomide Francisco Antonio Rocco Lahr Maria Fátima do Nascimento Diogo de Lucca Sartori Julian Eduardo Mejia Ballesteros Stephen Bonila Bueno Ugo Leandro Belini 《Cellulose (London, England)》2014,21(5):3269-3277
Anatomical and physico-chemical properties of residual natural fibers (sugarcane bagasse, coconut fibers and peanut hulls) were characterized in order to evaluate their potential for use in the production of particleboard. The bulk density was determined by helium pycnometer and the chemical characteristics by using an electronic pH meter (for pH determination) on fibers dissolved in acidic and neutral detergents (to determine the levels of cellulose, hemicellulose and lignin). The anatomical characteristics were established using scanning electron microscopy coupled with an X-ray detector system, as well as energy dispersive X-ray spectroscopy. Results indicated similarities and differences between physico-chemical and anatomical characteristics of the residual lignocellulosic fibers when compared with the Pinus sp. wood commercially employed in particleboard production. Bulk density and pH for residual lignocellulosic fibers and Pinus sp. wood presented analogous values. Similar amounts of cellulose and lignin were identified between waste fibers and Pinus sp. wood. The presence of silica was identified in coconut fiber, peanut hull and sugarcane bagasse waste fibers, and may affect the mechanical characteristics of panels. Coconut and sugarcane bagasse fibers show surface pores with diameters ranging from 1.2 to 2.1 μm, below the 5 μm identified for Pinus sp. wood. Both fibers present pores distributed over their entire surface, whereas peanut hull fibers have no pores on their surface. This characteristic contributes to resin dispersion among particles, reflecting positively on the physical–mechanical properties of the panels. Particleboards produced with residual lignocellulosic fibers present similar physical–mechanical properties to those of Pinus sp. wood panels. 相似文献
915.
Isothermal Titration Calorimetry Study of a Bistable Supramolecular System: Reversible Complexation of Cryptand[2.2.2] with Potassium Ions
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Maria G. del Rosso Dr. Artur Ciesielski Dr. Silvia Colella Prof. Jack M. Harrowfield Prof. Paolo Samorì 《Chemphyschem》2014,15(13):2743-2748
Isothermal titration calorimetry (ITC) is used to investigate the thermodynamics of the complexation of potassium ions by 1,10‐diaza‐4,7,13,16,21,24‐hexaoxabicyclo[8.8.8]hexacosane (cryptand[2.2.2]) in aqueous solution. By changing the pH of the solution it was possible to trigger the reversible complexation/decomplexation of the cryptand in consecutive in situ experiments and to assess for the first time the use of ITC to monitor the thermodynamics of a bistable system. 相似文献
916.
Maria Laura Di Lorenzo Paolo Rubino Romain Luijkx Marion Hélou 《Colloid and polymer science》2014,292(2):399-409
The influence of chain structure on crystal polymorphism of poly(lactic acid) (PLA) with high l-lactic acid content (97.8–100 %) is detailed in this contribution. Upon usual processing conditions of PLA, only α and α′ crystals grow, which makes these two polymorphs of major interest for research. The two crystal modifications have similar chain packing, which complicates their quantitative analysis by diffraction methods. The two crystal modifications are instead easily identified by analysis of the crystallization kinetics, which varies not only with temperature, but also with crystal polymorphism. The dependence of the rate of ordering on temperature shows two distinct maxima around 105–110 and 120–125 °C, which are related to growth of α′ and α crystals, respectively. Addition of d-lactic acid co-units leads to a decrease of the overall crystallization rate of PLA, as well as of the rate of spherulite growth (G) of both the crystal modifications. The relative crystallization rates of α and α′ forms are highly affected by stereoregularity, especially in the PLA grades that have a high crystallization rate. A high d-lactic acid content results not only in an overall slower crystal growth, but also in a varied temperature range where each of the two crystal modifications prevail, with a shift to lower temperatures of both the maxima of the G vs. temperature plots, indicating that inclusion of d-lactic acid units in the PLA chain affects crystallization rate of both α and α′ crystal modifications. 相似文献
917.
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
918.
919.
Maria I. B. Bernardi Vinícius D. Araújo Caue Ribeiro Waldir Avansi Elson Longo Nilson J. A. de Albuquerque Simoni M. P. Meneghetti Rusiene M. Almeida Humberto V. Fajardo 《Chemical Papers》2014,68(9):1213-1218
Wurtzite-type Zn1?x Mn x O (x = 0, 0.03, 0.05, 0.07) nanostructures were successfully synthesised using a simple microwave-assisted hydrothermal route and their catalytic properties were investigated in the cellulose conversion. The morphology of the nanocatalysts is dopant-dependent. Pure ZnO presented multi-plate morphology with a flower-like shape of nanometric sizes, while the Zn0.97Mn0.03O sample is formed by nanoplates with the presence of spherical nanoparticles; the Zn0.95Mn0.05O and Zn0.93Mn0.07O samples are mainly formed by nanorods with the presence of a small quantity of spherical nanoparticles. The catalyst without Mn did not show any catalytic activity in the cellulose conversion. The Mn doping promoted an increase in the density of weak acid sites which, according to the catalytic results, favoured promotion of the reaction. 相似文献
920.
Dongyi Liu Dr. Ahmed M. El-Zohry Maria Taddei Clemens Matt Laura Bussotti Dr. Zhijia Wang Prof. Jianzhang Zhao Prof. Omar F. Mohammed Prof. Mariangela Di Donato Prof. Stefan Weber 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11688-11696
We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long-lived triplet charge-transfer (3CT) state, based on the electron spin control using spin-orbit charge transfer intersystem crossing (SOCT-ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT-ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long-lived 3CT state (0.94 μs in deaerated n-hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time-resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron-spin polarization pattern was observed for the naphthalimide-localized triplet state. Our spiro compact dyad structure and the electron spin-control approach is different to previous methods for which invoking transition-metal coordination or chromophores with intrinsic ISC ability is mandatory. 相似文献