ABSTRACT
Differences in tax levels for diesel oil stimulate the illegal removal of characteristic diazo compounds purposely added to designate its possible usage. In order to reduce the losses in the national income, there is a strong need to develop a sensitive and cost-effective analytical procedure for the detection of this illegal action. In this study, we describe a novel analytical approach for a qualitative and quantitative determination of two diazo compounds (Solvent Yellow 124 and Solvent Red 19) that are usually added to diesel oil. The methodology proposed combines the use of excitation-emission matrix fluorescence spectroscopy as an analytical technique and partial least squares regression as a multiple modeling tool. With this new methodology, relatively low root mean square errors of prediction (for independent set of test samples) that are equal to 0.223 for Solvent Red 19 and 0.263 for Solvent Yellow 124, were obtained and the results were stable, which were indicated by an analysis performed after 48 and 96 h. The methodology is also nondestructive and allows for (i) simultaneous detection of diesel oil additives, (ii) determination of satisfactory limits of detection (0.048 and 0.042 mg L(-1) for Solvent Red 19 and Solvent Yellow 124, respectively), and (iii) obtaining of considerably low relative standard deviations of 2.33% for Solvent Yellow 124 and of 3.23% for Solvent Red 19 in comparison with the existing norm level.
ABSTRACT
The problem of linking the dynamic electron correlation effects defined in traditional ab initio methods [or wave function theories (WFTs)] with the structure of the individual density functional theory (DFT) exchange and correlation functionals has been analyzed for the Ne atom, for which nondynamic correlation effects play a negligible role. A density-based approach directly hinged on difference radial-density (DRD) distributions defined with respect the Hartree-Fock radial density has been employed for analyzing the impact of dynamic correlation effects on the density. Attention has been paid to the elimination of basis-set incompleteness errors. The DRD distributions calculated by several ab initio methods have been compared to their DFT counterparts generated for representatives of several generations of broadly used exchange-correlation functionals and for the recently developed orbital-dependent OEP2 exchange-correlation functional [Bartlett et al., J. Chem. Phys. 122, 034104 (2005)]. For the local, generalized-gradient, and hybrid functionals it has been found that the dynamic correlation effects are to a large extend accounted for by densities resulting from exchange-only calculations. Additional calculations with self-interaction corrected exchange potentials indicate that this finding cannot be explained as an artifact caused by the self-interaction error. It has been demonstrated that the VWN5 and LYP correlation functionals do not represent any substantial dynamical correlation effects on the electron density, whereas these effects are well represented by the orbital-dependent OEP2 correlation functional. Critical comparison of the present results with their counterparts reported in literature has been made. Some attention has been paid to demonstrating the differences between the energy- and density-based perspectives. They indicate the usefulness of density-based criteria for developing new exchange-correlation functionals.
ABSTRACT
The evolution of a technique of inguinal hernia repair, progressively incorporating more modern materials and concepts, is described and evaluated. Anatomic precepts of hernia anatomy put forth by Condon form the foundation of this technique. The Shouldice methodology dominates the original plan of patient management but more modern suture materials and local anesthetics afford even greater ease and efficiency to this hernia repair plan. The results of 421 herniorrhaphies done by the primary author over ten years are reported with three patients lost during follow-up (0.7%). No cases are included unless a minimum of three years since surgery has elapsed. The unselected recurrence rate is 2.77 per cent. All ten recurrences are studied and related to changes in surgical technique. Cost effectiveness goals such as early discharge and same-day surgery are also discussed as they apply to this approach.
