Zusammenfassung Malonsäure und monosubstit. Malonsäuren reagieren in Acetanhydrid mit Cyclanon-anilen in guter Ausbeute zu Spiro-1,3-oxazinen (3–6 bzw.9–13). Diese labilen Verbindungen lassen sich mit POCl3 leicht in 4-Hydroxy-5,6-polymethylen-pyridone-(2) umwandeln. Analog verhält sich Acetophenonanil.
Malonic acid and monosubstituted malonic acids react in acetic anhydride with cyclanon-aniles yielding the spiro-1.3-oxazines3–6 and9–13. These compounds are readily converted with POCl3 to 4-hydroxy-5.6-polymethylene-pyrid-2-ones. Acetophenon-anil reacts in the same manner.
Herrn Prof. Dr.F. Wessely, Universität Wien, mit den besten Wünschen zum 70. Geburtstag gewidmet. 相似文献
Homogeneity and structure of organically modified polysiloxane networks prepared by sol-gel co-condensation, as well as location and nature of water molecules and silanol groups were studied by 1D and 2D solid-state NMR. 1H–29Si and 1H–1H interatomic distances were estimated from variable contact-time CP/MAS experiments, 1H NMR chemical shifts and off-resonance WISE NMR. A structure model of these networks is proposed and discussed. The fraction of proton-inaccessible units Q4 in the networks decreases with increasing amounts of dimethylsiloxane (D) and methylsiloxane (T) units. In contrast to systems prepared by co-condensation of tetraethoxysilane (TEOS) with dimethyl(diethoxy)silane (DMDEOS), proton-inaccessible units form essential fraction in networks prepared by co-condensation of TEOS with methyl(triethoxy)silane (MTEOS). The proton-accessible part of the networks with high O/Si ratios is nano-heterogeneous phase, which is composed of water containing Qi particles separated by copolymer domains. The overall homogeneity and uniformity of binding sites around silanol groups increases by co-condensation TEOS with DMDEOS or MTEOS, while the amount of physisorbed water as well as the hydrogen bond strength decreases, as compared with neat silica gel prepared by polycondensation of TEOS. 相似文献
We report the existence of broad and weakly asymmetric features in the high-energy (G) Raman modes of freely suspended metallic carbon nanotubes of defined chiral index. A significant variation in peak width (from 12 cm(-1) to 110 cm(-1)) is observed as a function of the nanotube's chiral structure. When the nanotubes are electrostatically gated, the peak widths decrease. The broadness of the Raman features is understood as the consequence of coupling of the phonon to electron-hole pairs, the strength of which varies with the nanotube chiral index and the position of the Fermi energy. 相似文献
The eggshell of the hen is an important structure which provides protection for the developing chick, and also a container for the egg in the food industry. Egg breakage can reach up to 10% of total egg production, causing considerable economic losses. The eggshell consists of membranes, composed mainly of proteins, and the mineral shell composed mainly of the calcite polymorph of CaCO3. The average CaCO3 content of a chicken eggshell is between 93 and 97%, depending on animal genotype, age, housing system of laying hens and mineral nutrition. In the present study, eggs of the same breed and approximately same age were collected from four different production systems: organic farming, free-range production, deep litter system and battery cage system. The CaCO3 content was determined by the standard titration method and by atomic absorption spectroscopy. Thermal properties of dried eggshell powder were measured by thermogravimetric measurements between 30 and 900 °C in air, showing a significant mass loss of?≈?43% between 600 and 850 °C corresponding to the decomposition of CaCO3 to CaO and CO2. The relations between the thermal mass loss and CaCO3 content determined by the titration method/atomic absorption spectroscopy were studied using predictive models fitted by the linear regression method. A good prediction ability with an average prediction error of 0.01% was obtained between CaCO3 determined by titration and the thermal mass loss, indicating that TG could provide a reliable method for evaluation of CaCO3 content in eggshells.
This is a review and analysis of the optical properties of quantum crystallites, with principal emphasis on the electro-optic Stark effect and all optical third order nonlinearity. There are also introductory discussions on physical size regimes, crystallite synthesis, quantum confinement theory, and linear optical properties. The experiments describe CdSe crystallites, exhibiting strong confinement of electrons and holes, and CuCl crystallites, exhibiting weak confinement of the exciton center of mass. In the CdSe system, neither the Stark effect nor the third order nonlinearity is well understood. The Stark shifts appear to be smaller than calculated, and field inducted broadening also occurs. The third order nonlinearity is only modestly stronger than in bulk material, despite theoretical prediction. Unexpectedly large homogeneous widths, due to surface carrier trapping, in the nominally discrete crystallite excited states appear to be involved. The CuCl system shows far narrower spectroscopic homogeneous widths, and corresponds more closely to an ideal quantum dot in the weak confinement limit. CuCl also exhibits exciton superradiance at low temperature. Surface chemistry and crystallite encapsulation are critical in achieving the predicted large Stark and third order optical effects in II-VI and III-V crystallites. 相似文献
Zeolites are highly important heterogeneous catalysts. Besides Brønsted SiOHAl acid sites, also framework AlFR Lewis acid sites are often found in their H‐forms. The formation of AlFR Lewis sites in zeolites is a key issue regarding their selectivity in acid‐catalyzed reactions. The local structures of AlFR Lewis sites in dehydrated zeolites and their precursors—“perturbed” AlFR atoms in hydrated zeolites—were studied by high‐resolution MAS NMR and FTIR spectroscopy and DFT/MM calculations. Perturbed framework Al atoms correspond to (SiO)3AlOH groups and are characterized by a broad 27Al NMR resonance (δi=59–62 ppm, CQ=5 MHz, and η=0.3–0.4) with a shoulder at 40 ppm in the 27Al MAS NMR spectrum. Dehydroxylation of (SiO)3AlOH occurs at mild temperatures and leads to the formation of AlFR Lewis sites tricoordinated to the zeolite framework. Al atoms of these (SiO)3Al Lewis sites exhibit an extremely broad 27Al NMR resonance (δi≈67 ppm, CQ≈20 MHz, and η≈0.1). 相似文献
Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs2AgInCl6 as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs2AgIn1−xFexCl6 (x = 0–1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions (e.g. Fe3+ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe3+ replaces diamagnetic In3+ in the Cs2AgInCl6 lattice with the formation of [FeCl6]3−·[AgCl6]5− domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices.Through Fe3+-alloying, the bandgap of benchmark double perovskite Cs2AgInCl6 can be tuned from 2.8 eV to 1.6 eV. The atomic-level structure of Cs2AgIn1−xFexCl6 was revealed by solid-state nuclear magnetic resonance (ssNMR).相似文献