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).

Layering the Internet-of-Things with Multicasting in Flow-sensors for Internet-of-services

Development of Internet-of-Services will be hampered by heterogeneous Internet-of-Things infrastructures, such as inconsistency in communicating with participating objects, connectivity between them, topology definition & data transfer, access via cloud computing for data storage etc. Our proposed solutions are applicable to a random topology scenario that allow establishing of multi-operational sensor networks out of single networks and/or single service networks with the participation of multiple networks; thus allowing virtual links to be created and resources to be shared. The designed layers are context-aware, application-oriented, and capable of representing physical objects to a management system, along with discovery of services. The reliability issue is addressed by deploying IETF supported IEEE 802.15.4 network model for low-rate wireless personal networks. Flow- sensor succeeded better results in comparison to the typical - sensor from reachability, throughput, energy consumption and diversity gain viewpoint and through allowing the multicast groups into maximum number, performances can be improved.