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71.
An upper limit of the barrier to internal rotation around the phenyl-carbonyl bond in pentalfluorobenzaldehyde dissolved in a freon mixture has been estimated from low temperature 19F NMR study. Protonation of this compound increases drastically the free energy of activation ΔG≠. Complete lineshape analysis leads to ΔG≠ (273 K) = 60.4 kJ/mol, comparable to the value obtained for protonated benzaldehyde. This result, as well as those obtained by CNDO/2 calculations support the conclusions that protonated pentafluorobenzaldehyde is planar in the ground state. This is not the case for protonated pentafluoroacetophenone in which the lower barrier height when compared to protonated acetophenon has been related to the steric strain and dipole repulsion.  相似文献   
72.
73.
In measuring inter-phase distribution coefficients (k111)it is often convenient, and sometimes necessary, to obtain all of the analytical data from one phase. A rigorous formula, applicable to both low and high k111 values has been derived; measurements of the distribution of mercury, methylmercury and 67Cu2+ between various pairs of phases with this formula gave k111 values similar to those obtained from other approaches.  相似文献   
74.
The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.  相似文献   
75.
Matrix-assisted laser-desorption ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize two different sulfated beta-cyclodextrins (HS-beta-CD). It was found that the HS-beta-CDs have broad heterogeneity in terms of sulfation degree. The average sulfate contents were in the range of 6 to 8 per CD molecule. Furthermore the sugar moieties of both HS-beta-CDs were sulfated either at position 6 or at positions 2 and 6, but not at position 3. Enantiomeric separation by capillary zone electrophoresis (CZE) using the HS-beta-CDs as chiral selectors showed that these CDs exhibited similar chiral selectivity and resolution of the ephedrine enantiomers. One of the CDs was employed for the enantiomeric purity evaluation of (1R,2S)-ephedrine (or (-)-ephedrine) by capillary zone electrophoresis. Quantification was done by comparison between the corrected peak areas of the minor enantiomer and (-)-ephedrine.  相似文献   
76.
Torbjörn Tambour 《代数通讯》2013,41(11):5353-5361
We compute the number of solutions to some equations in finite groups and use these computations to give a new proof of Itô's theorem on the degrees of the irreducible characters.  相似文献   
77.
Certified reference materials (CRMs) have now been in regular use for several decades. Their production and certification are regulated by international standards. But, even today there are no agreements on procedures for evaluating results obtained by the users. As a consequence, the way CRM results are treated in the literature leaves a lot to be desired. A statistical evaluation is rarely, if ever, described in published reports. The most common approach is to compare the found mean and/or range with the certified range and then state if the mean falls within the certified range, or if the two ranges overlap. If this happens, the analyst is usually satisfied. In addition, usually no regard is paid to the fact that the certified interval is based on a 95% confidence interval (CI) and the found interval on standard deviation and that this evaluation has little, if any, statistical relevance. Long-term evaluation of a CRM often consists in nothing more than producing a control chart, which relates the found results to the certified mean and CI. This paper is an attempt to improve the situation by providing a set of easy-to-use guidelines for evaluating results from CRMs. During the process we have identified different areas in which there is a need for such guidelines: 1.?short-term evaluation of a single, or multiple, determination at one or several specific times; 2.?identification of systematic and random errors; 3.?evaluation of CRMs when used in a collaborative trial of a method; and 4.?long-term evaluation for monitoring an analytical process over extended periods of time. It is important that the guidelines do not require expert competence in statistics from the analyst. Such obstacles would probably render most guidelines unused.  相似文献   
78.
Using shaped laser pulses, we increase the yield of ultrafast electron injection from the sensitizer to TiO2 nanocrystals in the core part of a dye-sensitized solar cell. The temporal structure of the optimized excitation pulse is in clear correlation with nuclear oscillations in the impulsively excited dye molecule. From DFT structure optimization and normal mode analyses we identified the modes which are responsible for the oscillations. The best pulse shape suggests Impulsive Stimulated (anti-Stokes) Raman scattering as a key process of optimization.  相似文献   
79.
Employing the colloidal probe AFM technique we have investigated normal and friction forces between flat mica surfaces and silica particles coated with mucin and combined mucin-chitosan layers in presence and absence of anionic surfactant, SDS, in 30 mM NaCl solution. We have shown that the normal interactions between mucin coated mica and silica surfaces are dominated by long-range steric repulsion on both compression and decompression. Friction forces between such mucin layers are characterized by a low effective friction coefficient, mu(eff)=0.03+/-0.02, which is lower than the value of 0.13+/-0.02 observed when chitosan layers were adsorbed. Forces between combined mucin-chitosan layers have also been measured. Adsorption of chitosan on mucin results in considerable compaction of the layer, and development of attractive forces detectable on separation. Friction between mucin-chitosan layers in 30 mM NaCl solution is high, with mu(eff) approximately 0.4. Adsorption of additional mucin to this layer results in no improvement with respect to lubrication as compared to the mucin-chitosan layer, and mu(eff) approximately 0.4 is observed. We argue that the layers containing both mucin and chitosan are not strictly layered but rather strongly entangled. As a result attractive interactions between oppositely charged moieties of sialic acid residues from mucin and amine groups from chitosan residing on the opposing surfaces contribute to the increased friction. The effects of SDS on normal and friction forces between combined mucin-chitosan layers were also investigated. The relation between surface interactions and friction properties is discussed.  相似文献   
80.
The new Ru complex 8 containing the bio-inspired ligand 7 was successfully synthesized and characterized. Complex 8 efficiently catalyzes water oxidation using Ce(IV) and Ru(III) as chemical oxidants. More importantly, this complex has a sufficiently low overpotential to utilize ruthenium polypyridyl-type complexes as photosensitizers.  相似文献   
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