This paper focuses on the classification or differentiation of RP-HPLC columns based on measured chromatographic properties. A chemometric study has been conducted on a published data set consisting of 85 RP-HPLC columns and on a data set consisting of 47 self-tested columns. Principal component analysis enables determination of the number of parameters necessary for a rational differentiation. The results show that reducing the number of parameters for such differentiation still allows classification of the columns just as a higher number did. It is shown that three test parameters produce a classification similar to that obtained with five parameters. 相似文献
Time-resolved fluorescence resonance energy transfer (FRET) measurements were used to measure distance distributions and intramolecular dynamics (site-to-site diffusion) of a 28-residue single-domain zinc finger peptide in the absence and presence of zinc ion. Energy transfer was measured between TRP14 and a N-terminal DNS group. As expected, the TRP-to-DNS distance distribution for zinc-bound peptide is shorter and narrower (Rav=11.2 Å,hw=2.8 Å) than the metal-free peptide (Rav=20.1 Å,hw=14.5 Å). The degree of mutual donor-to-acceptor diffusion (D) was also determined for these distributions. For zinc-bound peptide there is no detectible diffusion (D0.2 Å2/ns), whereas for metal-free peptide a considerable amount of motion is occurring between the donor and the acceptor (D=12 Å2/ns). These results indicate that the zinc-bound peptide folds into a unique, well-defined conformation, whereas the metal-free conformation is flexible and rapidly changing. The absence of detectible mutual site-to-site diffusion between the donor and the acceptor in the metal-bound zinc finger peptide indicates that intramolecular motion is essentially frozen out, on the FRET time scale, as a consequence of zinc coordination.Dedicated to the memory of Barbara D. Wells. 相似文献
We report a thermal analysis study of the effect of molecular weight on the amorphous phase structure of poly(phenylene sulfide), PPS, crystallized at temperatures just above the glass transition temperature. Thermal properties of Fortron PPS, having viscosity average molecular weights of 30000 to 91000, were characterized using temperature modulated differential scanning calorimetry (MDSC). We find that while crystallinity varies little with molecular weight, the heat capacity increment at the glass transition decreases as molecular weight decreases. This leads to a smaller liquid-like amorphous phase, and a larger rigid amorphous fraction, in the lower molecular weight PPS. For all molecular weights, constrained fraction decreases as the scan rate decreases.This research is supported by the U. S. Army Research Office through contract DAAH04-96-1-0009. The authors thank Hoechst Celanese for providing different molecular weight Fortron samples and Dr. George Collins for providing sample information. The authors acknowledge the assistance of Elizabeth Oyebode and Leonardo Grimaldi with sample preparation and MDSC work. 相似文献
Although , (Fp η-C5H5Fe(CO)2) (I) is stable and characterizable, the lower homologue FpCH2CH(CO2CH3)2 (II) is not; this we attribute to a facile elimination reaction resulting from the relatively acidic β-hydrogen of II. Formation of I from Fp? and XCH2CE2CH3 (X Br, Cl; E CO2CH2CH3) and cleavage of its FeC bonds (using H+, Br2, CeIV and HgII) occur without major amounts of ester group migrations, even though ·CH2CE2CH3 radicals are involved in some of these reactions. 相似文献
A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (χc, χMA, χRA, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared
by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110°C, then briefly
heated to 136°C, then re-annealed at 110°C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow
the devitrification of the rigid amorphous fraction to be examined.
We observe a lower endotherm, termed the ‘annealing’ peak in the non-reversing heat flow after annealing at 110°C. By brief
heating above this lower endotherm and immediately quenching in LN2-cooled glass beads, the glass transition temperature and χRA decrease substantially, χMA increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification
of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110°C causes the glass transition and χRA to increase, and χMA to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal
reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid
amorphous fraction.
Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid
amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show
the homogeneous stack model is the correct one for Nylon-6. The cooperativity length (ξA) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of
some of the RAF leads to the broadening of the glass transition region and shift of Tg. 相似文献
The first synthesis of the polycyclic ring systems of artocarpol A and D has been accomplished. These natural products were isolated recently from the root bark of Artocarpus rigida, and artocarpol A has been shown to have potent antiinflammatory properties. The synthesis of an artocarpol D analogue was achieved on condensation of 11H-dibenzo[b,f]oxepin-10-one with senecialdehyde. The reaction of this oxepinone with citral afforded a 2H-pyran that on subsequent irradiation afforded an analogue of artocarpol A. [reaction: see text] 相似文献