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71.
72.
Although compounds undergoing thermally induced spin crossover have been widely studied, their experimental d-orbital populations from single-crystal X-ray diffraction have rarely been reported. Three pairs of structures of iron/manganese coordination compounds were re-evaluated. Least-squares refinements relied on aspherical scattering factors obtained from molecular quantum-mechanical DFT single-point computations of the respective solid-state conformation, initiated by accurate starting structures from preliminary invariom refinements of the ligand environment. Further evaluation concerned d-orbital populations of metal ions from (a) single-point computations projected onto the Hansen-Coppens multipole model and from (b) experimental refinements of the metal atoms only. The latter were successful for good-quality data, independent of temperature, and provided only one spin state was exclusively present in the crystal. Crystals that underwent light-induced excited spin state trapping were not showing the expected d-orbital populations. 相似文献
73.
Singh AP Ghadwal RS Roesky HW Holstein JJ Dittrich B Demers JP Chevelkov V Lange A 《Chemical communications (Cambridge, England)》2012,48(61):7574-7576
An abnormal N-heterocyclic carbene (aNHC) has been used as a Lewis base to initiate dismutation of trichlorosilane. This report presents the reactivity differences of a normal N-heterocyclic carbene (NHC) versus aNHC with heavier group 14 elements. Three novel compounds (NHC)(2)·SiCl(2)H(2) (2), aNHC·SiCl(2)H(2) (3), and aNHC·GeCl(2) (4) have been synthesized and characterized by single crystal X-ray analysis, solid-state NMR and DFT calculations. 相似文献
74.
Bejan I Abd-el-Aal Y Barnes I Benter T Bohn B Wiesen P Kleffmann J 《Physical chemistry chemical physics : PCCP》2006,8(17):2028-2035
Formation of nitrous acid (HONO) in the gas phase has been observed for the first time in a flow tube photoreactor upon irradiation (lambda = 300-500 nm) of 2-nitrophenol and methyl substituted derivatives using a selective and sensitive instrument (LOPAP) for the detection of HONO. Formation of HONO by heterogeneous NO2 photochemistry has been excluded, since production of NO2 under the experimental conditions is negligible. Variation of the surface to volume ratio and the nitrophenol concentration showed that the photolysis occurred in the gas phase indicating that HONO formation is initiated by intramolecular hydrogen transfer from the phenolic OH group to the nitro group. From the measured linear dependence of the HONO formation rate on the reactant's concentration and photolysis light intensity, a non-negligible new HONO source is proposed for the urban atmosphere during the day. Unexpectedly high HONO mixing ratios have been observed recently in several field campaigns during the day. It is proposed that the photolysis of aromatic compounds containing the ortho-nitrophenol entity could help to explain, at least in part, this high contribution of HONO to the oxidation capacity of the urban atmosphere. 相似文献
75.
Due to their poor solubility during IEF membrane proteins cannot be separated and analyzed satisfactorily with classical 2-DE. A more efficient method for such hydrophobic proteins is the benzyldimethyl-n-hexadecylammonium chloride (16-BAC)/SDS-PAGE, but the corresponding protocol is intricate and time-consuming. We now developed an easy-to-handle electrophoresis method in connection with a novel device which enables reproducible separation of ionic solubilized membrane proteins using individually rehydrated plastic sheet gel strips. These strips are suitable for the first dimension in a 2-D 16-BAC/SDS system and can be handled easily; this is demonstrated by the separation of membrane proteins of human embryonic kidney (HEK293) cells. 相似文献
76.
77.
Birger Lange Friederike Fleischhaker Rudolf Zentel 《Macromolecular rapid communications》2007,28(12):1291-1311
Artificial opals are self‐assembled colloidal crystals, which consist of a cubic dense packing (fcc) of hard (not film‐forming) colloids with diameters ranging from 200 to 900 nm. Because of their periodic nanostructure the assemblies are able to reflect light that matches their periodicity, i.e., UV‐ to IR‐radiation depending on the size of the colloids. Thus, they present a subgroup of ‘photonic crystals’. While, originally, the chemistry inside the colloids and the resulting opals was of minor significance, nowadays the chemical variation of opals is becoming more and more important for the preparation of functional and patterned opals. The search for functional opals is, therefore, especially focused on four topics: I) coloring agents, II) incorporation of fluorescent materials, III) replication, and IV) the controlled incorporation of defects.
78.
Mauermann M Long GR Kollmeier B 《The Journal of the Acoustical Society of America》2004,116(2):1066-1080
Hearing thresholds measured with high-frequency resolution show a quasiperiodic change in level called threshold fine structure (or microstructure). The effect of this fine structure on loudness perception over a range of stimulus levels was investigated in 12 subjects. Three different approaches were used. Individual hearing thresholds and equal loudness contours were measured in eight subjects using loudness-matching paradigms. In addition, the loudness growth of sinusoids was observed at frequencies associated with individual minima or maxima in the hearing threshold from five subjects using a loudness-matching paradigm. At low levels, loudness growth depended on the position of the test- or reference-tone frequency within the threshold fine structure. The slope of loudness growth differs by 0.2 dB/dB when an identical test tone is compared with two different reference tones, i.e., a difference in loudness growth of 2 dB per 10-dB change in stimulus. Finally, loudness growth was measured for the same five subjects using categorical loudness scaling as a direct-scaling technique with no reference tone instead of the loudness-matching procedures. Overall, an influence of hearing-threshold fine structure on loudness perception of sinusoids was observable for stimulus levels up to 40 dB SPL--independent of the procedure used. Possible implications of fine structure for loudness measurements and other psychoacoustic experiments, such as different compression within threshold minima and maxima, are discussed. 相似文献
79.
Loudness was measured as a function of signal bandwidth for 10-, 100-, and 1000-ms-long signals. The test and reference signals were bandpass-filtered noise spectrally centered at 2 kHz. The bandwidth of the test signal was varied from 200 to 6400 Hz. The reference signal had a bandwidth of 3200 Hz. The reference levels were 45, 55, and 65 dB SPL. The level to produce equal loudness was measured with an adaptive, two-interval, two-alternative forced-choice procedure. A loudness matching procedure was used, where the tracks for all signal pairs to be compared were interleaved. Mean results for nine normal-hearing subjects showed that the magnitude of spectral loudness summation depends on signal duration. For all reference levels, a 6- to 8-dB larger level difference between equally loud signals with the smallest (delta f = 200 Hz) and largest (delta f = 6400 Hz) bandwidth is found for 10-ms-long signals than for the 1000-ms-long signals. The duration effect slightly decreases with increasing reference loudness. As a consequence, loudness models should include a duration-dependent compression stage. Alternatively, if a fixed loudness ratio between signals of different duration is assumed, this loudness ratio should depend on the signal spectrum. 相似文献
80.
Indole-3-carboxylic acid (as well as indole-3-glyoxylic acid) derivatives are readily prepared from indoles (including oxindoles) and phosgene (oxalyl chloride), respectively. The interaction of these reagents with the indole Grignard reagent afforded several products including the cyclo-tetramers, 21 and 30 . Indolo-fused heterocycles can be readily prepared from the reaction of phosgene (or oxalyl chloride) with suitable reactants. Thus e.g., phosgene and 2-(2-hydroxy-phenyl)-N-methylindole readily gave 5,6-dihydro-11-methyl-6-oxobenzo[a]pyrano[4,3-b] indole ( 33 ). 相似文献