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We present the results of a study of percent composition for a mixture which has been separated by gas chromatography and analyzed using helium pulsed-discharge photoionization detection (He-PDPID) and flame ionization detection (FID). FID has long been the means by which the percent composition of a hydrocarbon mixture has been determined since it has been previously established as a "carbon counting device". However, in this study we present results which show that He-PDPID is more accurate in determining the percent composition of a hydrocarbon mixture and, because it is a universal detection method and can detect compounds that FID cannot, it is also more effective for determining the percent composition of mixtures containing organic compounds with a variety of other functional groups.

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Laser desorption time-of-flight mass spectrometry (LD/TOF-MS) is evaluated for the determination of stable metal isotope ratios. The isotope ratios of five metal ions (Cu, Ca, Mg, Fe, Zn) in atomic absorption standard solutions and two metal ions (Ca, Mg) in human serum samples are determined. With an existing LD/TOF-MS instrument we show that the technique can overcome the difficulties of the most commonly used methods for measuring metal isotope ratios: (1) all metals are ionizable without surface treatment, thus overcoming the major drawback of thermal ionization mass spectrometry (TIMS); (2) there is no matrix involved to interfere with the metal ion detection, thus overcoming the major disadvantage of inductively coupled plasma mass spectrometry (ICPMS); (3) there is no interference from hydride ions, a major disadvantage of fast atom bombardment secondary ionization mass spectrometry; (4) a mixture of metals can be detected simultaneously using a single laser wavelength, overcoming the major disadvantage of resonance ionization mass spectrometry; (5) accuracy and precision comparable to ICPMS can be achieved with the current instrumentation; (6) precision comparable to TIMS is feasible; and most importantly (7) high precision can be achieved on very small quantities of material because the LD/TOF-MS instrument permits all masses to be monitored simultaneously and very small differences in isotope ratio can be detected.

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An evaluation of five commercial software systems used for immunoassay data analysis revealed numerous deficiencies. Often, the utility of statistical output was compromised by poor documentation. Several data sets were run through each system using a four-parameter calibration function, and the results were compared to those from an independent method. Comparable results between systems were obtained, but often several attempts at analysis were necessary. The evaluation process revealed that it is difficult to monitor the numerous options available on these types of programs, and that incorrect results could easily be obtained if comparison analyses were not used. Recommendations for improved software functionality and for using the four-parameter calibration model are presented.

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The success in utilizing in vivo NMR to identify and/or monitor metabolic abnormalities will be determined in large part on the reliability with which the spectral parameters of the metabolites present can be measured. For these reasons it is clear that there is a need for the development of algorithms with which to obtain quantitatively reliable estimates of the spectral parameters of the peaks present. In this report we describe an adaptation of the simplex algorithm which we have found useful in fitting in vivo spectral data in the frequency domain. This simplex algorithm was implemented on an IBM-PC AT compatible computer. We evaluated the simplex algorithm on three representative kinds of spectral data: a simulated spectrum, 31P spectrum of normal calf muscle, and the 31P spectrum of a pediatric patient with a brain tumor. In each case we generated a set of spectra by adding varying amounts of noise. On the basis of our simulations and the two examples discussed, we conclude that the simplex method generates parameters which are reliable estimates of the areas of the peaks present when the signal-to-noise is above 8:1 for phosphocreatine. We found that the speed of convergence of the algorithm was improved by overestimating the linewidths of the peaks present. We also found that the method converged more rapidly in the presence of a moderate amount of noise. We conclude that the algorithm described here can provide a robust method with which to analyze in vivo spectra in a quantitative manner. Because the method requires little user intervention, it lends itself to implementation in a semi-, or fully, automated fashion.

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Chemometrics is broadly defined as the application of mathematical and statistical methods to chemistry. Because the mathematical and statistical aspects of chemistry require measured values, analytical chemists have been at the forefront of the "chemometric revolution." Using the analysis of variance as a paradigm, I present an overview of chemometrics as it is practiced today. Receiving special emphasis are: the design of experiments to acquire information from the relevant universe of possible measurements; the establishment of relationships among independent and dependent variables; the importance of minimizing purely experimental uncertainty; sequential simplex optimization; analysis of principal components; and cluster analysis.

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We present a unified approach to the use of linear models and matrix least squares with the intention of providing a better understanding of the techniques themselves and of the statistics that arise from these techniques as they are used in clinical chemistry. Emphasis is placed on the importance of appropriate experimental designs and adequately precise measurement processes for efficiently obtaining the desired information.

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A "stopped-flow" method for the kinetic Jaffé determination of creatinine was developed, with the use of a computer-controlled continuous-flow system. Simplex optimization was used to find conditions of hydroxide and picrate giving maximum sensitivity for creatinine. We used a modified central composite experimental design to evaluate creatinine sensitivity and albumin, glucose, and acetone interferences as functions of hydroxide and picrate concentrations. More importantly, this work illustrates that the automated development of clinical chemical methods offers an efficient means of obtaining optimized, well-understood analytical procedures for subsequent routine use in the clinical chemistry laboratory.

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The extraction of iron(II) from water into cyclohexane with hexafluoroacetylacetone (HHFA) and tri-n-butyl phosphate (TBP) was optimized by using a simplex algorithm; pH, [HHFA], [TBP], and mixing time were varied. A central composite design was employed to examine in detail the region of the apparent optimum. Regression analysis of the central composite data demonstrated that in the region of the optimum, the response was essentially unaffected by small variations in the levels of the factors investigated.

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The sequential simplex algorithm, an efficient optimization strategy, rapidly improved reaction yield as a function of time and temperature in the synthesis of pi-C(5)H(5)Mo(CO)(2)CSN(CH(3))(2). The work demonstrates the feasibility and efficiency of the simplex design and suggests its application and usefulness in other syntheses.

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