A Statistically Rigorous Test for the Identification of Parent−Fragment Pairs in LC-MS Datasets

Untargeted global metabolic profiling by liquid chromato-graphy−mass spectrometry generates numerous signals that are due to unknown compounds and whose identification forms an important challenge. The analysis of metabolite fragmentation patterns, following collision-induced dissociation, provides a valuable tool for identification, but can be severely impeded by close chromatographic coelution of distinct metabolites. We propose a new algorithm for identifying related parent−fragment pairs and for distinguishing these from signals due to unrelated compounds. Unlike existing methods, our approach addresses the problem by means of a hypothesis test that is based on the distribution of the recorded ion counts, and thereby provides a statistically rigorous measure of the uncertainty involved in the classification problem. Because of technological constraints, the test is of primary use at low and intermediate ion counts, above which detector saturation causes substantial bias to the recorded ion count. The validity of the test is demonstrated through its application to pairs of coeluting isotopologues and to known parent−fragment pairs, which results in test statistics consistent with the null distribution. The performance of the test is compared with a commonly used Pearson correlation approach and found to be considerably better (e.g., false positive rate of 6.25%, compared with a value of 50% for the correlation for perfectly coeluting ions). Because the algorithm may be used for the analysis of high-mass compounds in addition to metabolic data, we expect it to facilitate the analysis of fragmentation patterns for a wide range of analytical problems

Role Playing and the Study of Jury Behavior

Widespread use of simulated trials and mock juries to study jury behavior has stimulated concern for the external validity ofsuch simulations. A study is reported which examined the role-playing nature of mock jury deliberation. Subjects were either given typical role-playing instructions, or were led to believe that they were deciding an actual student discipline case. The two conditions did not differ significantly on their group or individual verdicts, sentence recommendations, deliberation time, or estimated social decision schemes. The significance and limitations of these results for the study of jury behavior are discussed

Small-sample comparisons for the Rukhin goodness-of-fit-statistics

Rukhin's statistic family for goodness-of-fit, under the null hypothesis, has asymptotic chi-squared distribution; however, for small samples the chi-squared approximation in some cases does not well agree with the exact distribution. In this paper we consider this approximation and other three to get appropriate test levels in comparison with the exact level. Moreover, exact power comparisons for several values of the parameter under specified alternatives provide that the classical Pearson's statistic, obtained as a particular case of Rukhin statistic, can be improved by choosing other statistics from the family. An explanation is proposed in terms of the effects of individual cell frequencies on the Rukhin statistic