Study of the selectivity of reversed-phase columns for the separation of polycarboxylic acids and polyphenol compounds

A systematic investigation was undertaken into the relative separation performance of five reversed-phase chromatography columns including some commercially new hybrid packed columns for a series of polycarboxylic acids and polyphenol compounds. Information theory (IT) and factor analysis (FA), together with a basic evaluation of retention information (band shape, retention factor and elution order) were used to compare four columns to a conventional C18 column. The results revealed very little difference in retention behaviour between the Phenomenex Aqua C18 column, the Waters XTerra RP C18 column, and the conventional Phenomenex Luna C18 column. However, there were notable differences in the retention processes between the Phenomenex Synergi polar-RP column, which is an ether-linked phenyl base with polar endcapping, and the Luna C18 column. The most significant differences were observed between the Luna C18 column and a Phenomenex Luna Cyano column. However, the limited degree of retention of the polycarboxylic acids and polyphenol compounds on the Luna Cyano column permits only limited use for the separation of these types of compounds. Overall, the Phenomenex Synergi polar-RP column exhibited the best performance for the separation of the test solutes compared to that of the conventional C18 column, with IT yielding an Informational Similarity of 0.99 and FA a moderate correlation coefficient of 0.70. The Phenomenex Synergi polar-RP column gave the best peak shape and offered substantial selectivity differences thereby providing a good alternative over the conventional C18 column for separating polycarboxylic acids and polyphenols.     

New differential techniques for evaluating rate constants and ratios of rate constants. The behaviors of irreversible first-and pseudo-first-order reactions

A record of the time dependence of the difference between two signals, one proportional to the concentration of a reactant or product in one reaction mixture and the other proportional to the concentration of the same or a corresponding substance in another mixture in which the reaction is initiated at the same time as the first, makes it possible to obtain not only the ratio, but also the individual values, of the rate constants for the two reactions. The effects of the experimental variables on a number of measurable parameters are examined, the errors associated with a number of different ways of evaluating the rate constants and their ratio are discussed, and it is shown how conditions can be selected that should provide values whose precisions compare favorably with those attainable by other techniques.     

A micro-sampling method for the determination of blood lead

The analytical micromethod discussed here has been found to be very rapid, accurate, and relatively inexpensive for the determination of blood and urine leads. It has the distinct advantage in that a determination can be repeated. The sensitivity of the method is 1.37 × 10^?10 g per 1% absorption at 283.3 nm. Our laboratories have analyzed 7353 specimens in duplicate or more from March 17, 1971 to April 30, 1972.Considering the many possible sources of contamination (the mobile unit being more so than a clinic) it is the Division of Chemistry's conclusion that an agreement of 84% is good and that a finger-stick method is feasible, and therefore, a complete micro-screening for blood lead is possible.     

Equicompact sets of operators defined on Banach spaces

Let and be Banach spaces. We say that a set denotes the space of all compact operators from into ) is equicompact if there exists a null sequence in such that for all and all . It is easy to show that collectively compactness and equicompactness are dual concepts in the following sense: is equicompact iff is collectively compact. We study some properties of equicompact sets and, among other results, we prove: 1) a set is equicompact iff each bounded sequence in has a subsequence such that is a converging sequence uniformly for ; 2) if does not have finite cotype and is a maximal equicompact set, then, given and a finite set in , there is an operator such that for and all .

     

Signatures of short-range many-body effects in the dielectric function of silicon for finite momentum transfer

We present an investigation of the dynamic structure factor and of the dielectric function epsilonM(Q,omega) of the prototypical semiconductor silicon for finite momentum transfer, combining inelastic x-ray scattering experiments and ab initio calculations. In contrast with optical spectra, for finite momentum transfer time-dependent density-functional theory in the adiabatic local-density approximation together with lifetime broadening describes the physics of valence excitations correctly. Major structures in the spectra, governed by short-range crystal and exchange-correlation local-field effects, are strongly influenced by a mixing of transitions of positive and negative energies, in striking difference to spectra for vanishing momentum transfer. This mixing gives rise to a pronounced Fano asymmetry.     

Percolation and epidemic thresholds in clustered networks

We develop a theoretical approach to percolation in random clustered networks. We find that, although clustering in scale-free networks can strongly affect some percolation properties, such as the size and the resilience of the giant connected component, it cannot restore a finite percolation threshold. In turn, this implies the absence of an epidemic threshold in this class of networks, thus extending this result to a wide variety of real scale-free networks which shows a high level of transitivity. Our findings are in good agreement with numerical simulations.     

VUV photon induced fluorescence study of SF5CF3

The interaction of SF(5)CF(3) with vacuum-UV radiation has been investigated by photon induced fluorescence spectroscopy. Total fluorescence yield and dispersed fluorescence spectra of SF(5)CF(3) were recorded in the 200-1000 nm fluorescence window. In all cases, the fluorescence spectra resemble those of CF(3)X (X = H, F, Cl, and Br) molecules. At photon energies below 20 eV, the emission is attributed to the excited CF(3) and CF(2) fragments. The threshold for the CF(3) emission is 10.2 +/- 0.2 eV, giving an upper limit estimate for the SF(5)-CF(3) bond dissociation energy of 3.9 +/- 0.3 eV. The excitation functions of the CF(3) and CF(2) emissions were measured in the photon energy range 13.6-27.0 eV. The resonant structures observed in SF(5)CF(3) are attributed to electronic transitions from valence to Rydberg orbitals, following similar assignments in CF(3)X molecules. The photoabsorption spectrum of SF(5)CF(3) shows features at the same energies, indicating a strong contribution from Rydberg excitations.