Variance Reduction in Analytical Chemistry : New Numerical Methods in Chemometrics and Molecular Simulation

This thesis is based on five papers addressing variance reduction in different ways. The papers have in common that they all present new numerical methods. Paper I investigates quantitative structure-retention relationships from an image processing perspective, using an artificial neural network to preprocess three-dimensional structural descriptions of the studied steroid molecules. Paper II presents a new method for computing free energies. Free energy is the quantity that determines chemical equilibria and partition coefficients. The proposed method may be used for estimating, e.g., chromatographic retention without performing experiments. Two papers (III and IV) deal with correcting deviations from bilinearity by so-called peak alignment. Bilinearity is a theoretical assumption about the distribution of instrumental data that is often violated by measured data. Deviations from bilinearity lead to increased variance, both in the data and in inferences from the data, unless invariance to the deviations is built into the model, e.g., by the use of the method proposed in paper III and extended in paper IV. Paper V addresses a generic problem in classification; namely, how to measure the goodness of different data representations, so that the best classifier may be constructed. Variance reduction is one of the pillars on which analytical chemistry rests. This thesis considers two aspects on variance reduction: before and after experiments are performed. Before experimenting, theoretical predictions of experimental outcomes may be used to direct which experiments to perform, and how to perform them (papers I and II). After experiments are performed, the variance of inferences from the measured data are affected by the method of data analysis (papers III-V).

Deictic Demonstratives in Japanese, Finnish and Swedish : First and Third Language Perspectives

The goal of this thesis is twofold. Firstly, it investigates the actual, native use of spatial-deictic demonstratives in Japanese, Finnish and Swedish. Secondly, it investigates and elucidates the interlanguage of Finnish-speaking and Swedish-speaking learners of Japanese regarding their use of Japanese spatial-deictic demonstratives in the light of respective native use and, in comparison to the descriptions of demonstratives in the teaching materials used. Thus, the present study deals with analyses of two sets of empirical data: data produced by native-speaking informants (L1 data) and data produced by language learners (L2 data). These were elicited by Discourse Completion Tasks (DCTs) designed, collected and analyzed using both quantitative and qualitative methods by the author. The results showed that the actual use of demonstratives by the native informants was not always in accordance with the way described in grammars. The typological similarities between Japanese and Finnish were in this study not reflected in the native use of demonstratives, and some uses were not solely based on the spatial relations between the referent, the speaker and the addressee, but rather on social-interactional factors. The main findings regarding the learner data revealed some differences in the usage rate of the demonstratives between the two Finnish-speaking groups and the one Swedish-speaking learner group studied. There were, however, no particular differences found between them regarding the type of demonstrative used. It is suggested that these differences are first and foremost connected both with the teaching materials used and the more or less heterogeneous linguistic environment in which the learners reside, and only thereafter with the typological similarities or differences between their respective native languages, Finnish and Swedish, and the target language, Japanese. It is further argued that the learners’ use of the different Japanese demonstratives, that is the type of demonstrative used, could be explained in terms of familiarity with the grammar. That is, when the situations used in the DCTs were exemplified in teaching materials and were familiar to them, the learners seemed to use Japanese demonstratives as they are described in the teaching materials and as the native Japanese speakers use them. When the situations used in the DCTs were not exemplified in the teaching materials, the learners seem to rely more on their native language. The results, thus, suggest that the learners’ interlanguage is influenced by the grammar of the target language known to the learners, but also by the number of languages (or varieties) that the learners have contact with at the time of learning. The results of the present study have implications for the teaching of Japanese in at least two ways. Firstly, the importance of grammar instruction must be emphasized since its effect on the learners’ language is apparent. Secondly, the contents of teaching materials should be revised on the basis of the native speakers’ actual use of the grammar.