Evaluation of sample processing and sub-sampling performance

A methodology for the estimation of sample processing and sub-sampling performance based on the comparison of the global method experimental dispersion of results with the uncertainty estimated from developed models for the subsequent analytical steps is presented. This approach is a valuable alternative to the evaluation of adequate experimental information using a classical ANOVA, since the significance of the sample processing and sub-sampling is evaluated with a higher number of degrees of freedom for the same number of experimental assays, due to the high number of degrees of freedom associated with the uncertainty estimated for the subsequent analytical steps from the combination of the involved sources of uncertainty.Considering the construction of a model to describe the performance of the analytical steps following sample processing and sub-sampling over a broad concentration range, the experimental assays involved at the evaluation of the sample processing and sub-sampling can be performed at any concentration meeting the previously validated range and several months after the development of that model once its adequacy has been proven over time.This approach, which also allows the construction of a detailed performance model for the global analytical method over a broad concentration range, was applied to the determination of pesticide residues in apples by gas-chromatography with electron capture detector.Considering that no information was available regarding the samples heterogeneity, sub-sampling performance was evaluated considering a sample representing the worst expectable homogeneity. This was accomplished by spiking just one out of the 10 halves of apples processed in each sample.The developed model for the performance of the analytical method was successfully and easily applied to routine analysis through an automated link between the information generated by the chromatograph software with a file containing the model.     

Sources and Sinks in Comparability Graphs

We prove that a subset S of vertices of a comparability graph G is a source set if and only if each vertex of S is a source and there is no odd induced path in G between two vertices of S. We also characterize pairs of subsets corresponding to sources and sinks, respectively. Finally, an application to interval graphs is obtained.     

LM-g splines

As an extension of the notion of an L-g spline, three mathematical structures called LM-g splines of types I, II, and III are introduced. Each is defined in terms of two differential operators the coefficients a_j, J = 0,…, n − 1, and b_i, I = 0,…, m, are sufficiently smooth; and b_m is bounded away from zero on [0, T]. Each of the above types of splines is the solution of an optimization problem more general than the one used in the definition of the L-g spline and hence it is recognized as an entity which is distinct from and more general mathematically than the L-g spline. The LM-g splines introduced here reduce to an L-g spline in the special case in which m = 0 and b₀ = constant ≠ 0. After the existence and uniqueness conditions, characterization, and best approximation properties for the proposed splines are obtained in an appropriate reproducing kernel Hilbert space framework, their usefulness in extending the range of applicability of spline theory to problems in estimation, optimal control, and digital signal processing are indicated. Also, as an extension of recent results in the generalized spline literature, state variable models for the LM-g splines introduced here are exhibited, based on which existing least squares algorithms can be used for the recursive calculation of these splines from the data.     

Application of the radioreagent method for trace determination of lead

A radioreagent method of analysis was developed and applied to the determination of trace quantities of lead in several types of samples. The method is based on the extraction of radioactive cobalt, displaced by lead from the cobalt chelate of ethylenediaminetetraacetate labelled with⁶⁰Co, into a tetracycline-benzyl alcohol solution. The radioactivity of the released cobalt, extracted into the organic phase, is proportional to the lead concentration. Interference caused by some elements was eliminated by means of a previous separation of lead using dithizone. The method was applied for lead determination in aerosol samples, gasoline and samples from the International Atomic Energy Agency, namely: simulated-air filter (Air-3), fresh water (W-3), dried animal whole blood (A-2) and calcined animal bone (A-3/1). The sensitivity, accuracy and precision of the method were also studied.Part of this material was submitted to the University of São Paulo in partial fulfilment for a Doctor of Science's Degree of A. M. G. FIGUEIREDO.     

Carbocations in action. Design, synthesis, and evaluation of a highly acid-sensitive naphthalene-based backbone amide linker for solid-phase synthesis

The design, synthesis, and properties of an extremely acid-labile backbone amide linker based on a regiospecifically substituted tetraalkoxy naphthaldehyde core are presented. This handle enables cleavage of peptide backbone amides (secondary amides) off a solid support using as little as 0.5% TFA in CH2Cl2. This proceeds without cleavage of tert-butyl ethers and tert-butyl esters. The design is based on a DFT study that predicted the most stabile alkoxy-substituted methyl naphthyl carbocation. [structure: see text]