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101.
With through space and through bond experiments in two-dimensional NMR we analyze the transformation from the thorium phosphate-hydrogen phosphate hydrate (TPHPH) to the β form of the thorium phosphate diphosphate (β-TPD) in relation with the phosphorus networks. These techniques are complementary: the through space coupling gives an insight on the dipolar phosphorus networks while the through bond coupling is particularly efficient in the detection of the P2O7 groups. With these experiments we show that in a first step, by heating the precursor TPHPH above 250 °C, it transforms into an form of TPD. This transformation is due to the complete condensation of hydrogen phosphate groups HPO4 into P2O7 entities. By heating -TPD above 950 °C it transforms into its well-known β form. The form is characterized by a hygroscopic behavior: some water molecules are present near the P2O7 groups that makes non-equivalent their phosphorus nuclei. PO4 dipolar networks are always present in the form. The main effect of these PO4 and P2O7 units is to give the system a channel structure and the water enters in them. 相似文献
102.
Valdivia NP Williams EG Herdic PC 《The Journal of the Acoustical Society of America》2008,123(1):109-120
Boundary element methods (BEMs) based near-field acoustic holography (NAH) requires the measurement of the pressure field over a closed surface in order to recover the normal velocity on a nearby conformal surface. There are practical cases when measurements are available over a patch from the measurement surface in which conventional inverse BEM based NAH (IBEM) cannot be applied directly, but instead as an approximation. In this work two main approximations based on the indirect-implicit methods are considered: Patch IBEM and IBEM with Cauchy data. Patch IBEM can be applied with a continuation procedure, which as its predecessor patch NAH (a well known technique that can be used on separable geometries of the wave equation) continues the pressure field using an iterative procedure, or it can be applied by a direct procedure. On the other hand, IBEM with Cauchy data requires measurements over two conformal patches and it will be shown that this technique will be reliable regardless of the position of the source. The theory behind each method will be justified and validated using a cylindrical surface with numerical data generated by point sources, and using experimental data from a cylindrical fuselage excited by a point force. 相似文献
103.
104.
Dr. Massimo Rigo Evi R. M. Habraken Dr. Koyel Bhattacharyya Manuela Weber Dr. Andreas W. Ehlers Dr. Nicolas Mézailles Dr. J. Chris Slootweg Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8769-8779
A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur) was calculated to get insight into the steric properties, [LNi(CO)3] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts. 相似文献
105.
Dr. Ting Liang Dr. Dominique Collin Melodie Galerne Dr. Gad Fuks Dr. Andreas Vargas Jentzsch Prof. Dr. Mounir Maaloum Alain Carvalho Prof. Dr. Nicolas Giuseppone Dr. Emilie Moulin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14341-14348
C3-Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π–π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude. 相似文献
106.
Dr. Marc Presset Dr. Jérôme Paul Ghania Nait Cherif Nisanthan Ratnam Nicolas Laloi Prof. Eric Léonel Dr. Corinne Gosmini Prof. Erwan Le Gall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(17):4491-4495
The reductive Barbier coupling of aromatic halides and electrophiles has been achieved using a CoBr2/1,10-phenanthroline catalytic system and over stoichiometric amounts of zinc. The reaction displayed a broad scope of substrates, including (hetero)aryl chlorides as pro-nucleophiles and aldehydes or imines as electrophiles, leading to diarylmethanols and diarylmethylamines in moderate to excellent yields, respectively. 相似文献
107.
108.
Dr. Yanhui Wang Dr. Sanghoon Kim Dr. Nicolas Louvain Dr. Johan G. Alauzun Dr. P. Hubert Mutin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4767-4774
An original, halide-free non-hydrolytic sol–gel route to mesoporous anatase TiO2 with hierarchical porosity and high specific surface area is reported. This route is based on the reaction at 200 °C of titanium(IV) isopropoxide with acetic anhydride, in the absence of a catalyst or solvent. NMR spectroscopic studies indicate that this method provides an efficient, truly non-hydrolytic and aprotic route to TiO2. Formation of the oxide involves successive acetoxylation and condensation reactions, both with ester elimination. The resulting TiO2 materials were nanocrystalline, even before calcination. Small (about 10 nm) anatase nanocrystals spontaneously aggregated to form mesoporous micron-sized particles with high specific surface area (240 m2 g−1 before calcination). Evaluation of the lithium storage performances shows a high reversible specific capacity, particularly for the non-calcined sample with the highest specific surface area favouring pseudo-capacitive storage: 253 mAh g−1 at 0.1 C and 218 mAh g−1 at 1 C (C=336 mA g−1). This sample also shows good cyclability (92 % retention after 200 cycles at 336 mA g−1) with a high coulombic efficiency (99.8 %). Synthesis in the presence of a solvent (toluene or squalane) offers the possibility to tune the morphology and texture of the TiO2 nanomaterials. 相似文献
109.
Ting Quan Dr. Nicolas Goubard-Bretesché Dr. Eneli Härk Dr. Zdravko Kochovski Dr. Shilin Mei Prof. Dr. Nicola Pinna Prof. Dr. Matthias Ballauff Prof. Dr. Yan Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4757-4766
MoS2, a typical layered transition-metal dichalcogenide, is promising as an electrode material in supercapacitors. However, its low electrical conductivity could lead to limited capacitance if applied in electrochemical devices. Herein, a new nanostructure composed of hollow carbon–MoS2–carbon was successfully synthesized through an l -cysteine-assisted hydrothermal method by using gibbsite as a template and polydopamine as a carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which were made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS2 flakes, were obtained. The platelets showed excellent dispersibility and stability in water, and good electrical conductivity due to carbon provided by the calcination of polydopamine coatings. The hollow nanoplate morphology of the material provided a high specific surface area of 543 m2 g−1, a total pore volume of 0.677 cm3 g−1, and fairly small mesopores (≈5.3 nm). The material was applied in a symmetric supercapacitor and exhibited a specific capacitance of 248 F g−1 (0.12 F cm−2) at a constant current density of 0.1 A g−1; thus suggesting that hollow carbon–MoS2–carbon nanoplates are promising candidate materials for supercapacitors. 相似文献