Preparation of Industrially Important Hydroxy Acids and Diacids from 2,2-Disubstituted Propane-1,3-Diols and Linear Primary Diols by Green Chemistry Methods

Environmentally benign and economical methods for the preparation of industrially important hydroxy acids and diacids were developed. The carboxylic acids, used in polyesters, alkyd resins, and polyamides, were obtained by the oxidation of the corresponding alcohols with hydrogen peroxide or air catalyzed by sodium tungstate or supported noble metals. These oxidations were carried out using water as a solvent. The alcohols are also a useful alternative to the conventional reactants, hydroxyaldehydes and cycloalkanes. The oxidation of 2,2-disubstituted propane-1,3-diols with hydrogen peroxide catalyzed by sodium tungstate afforded 2,2-disubstituted 3-hydroxypropanoic acids and 1,1-disubstituted ethane-1,2-diols as products. A computational study of the Baeyer-Villiger rearrangement of the intermediate 2,2-disubstituted 3-hydroxypropanals gave in-depth data of the mechanism of the reaction. Linear primary diols having chain length of at least six carbons were easily oxidized with hydrogen peroxide to linear dicarboxylic acids catalyzed by sodium tungstate. The Pt/C catalyzed air oxidation of 2,2-disubstituted propane-1,3-diols and linear primary diols afforded the highest yield of the corresponding hydroxy acids, while the Pt, Bi/C catalyzed oxidation of the diols afforded the highest yield of the corresponding diacids. The mechanism of the promoted oxidation was best described by the ensemble effect, and by the formation of a complex of the hydroxy and the carboxy groups of the hydroxy acids with bismuth atoms. The Pt, Bi/C catalyzed air oxidation of 2-substituted 2-hydroxymethylpropane-1,3-diols gave 2-substituted malonic acids by the decarboxylation of the corresponding triacids. Activated carbon was the best support and bismuth the most efficient promoter in the air oxidation of 2,2-dialkylpropane-1,3-diols to diacids. In oxidations carried out in organic solvents barium sulfate could be a valuable alternative to activated carbon as a non-flammable support. In the Pt/C catalyzed air oxidation of 2,2-disubstituted propane-1,3-diols to 2,2-disubstituted 3-hydroxypropanoic acids the small size of the 2-substituents enhanced the rate of the oxidation. When the potential of platinum of the catalyst was not controlled, the highest yield of the diacids in the Pt, Bi/C catalyzed air oxidation of 2,2-dialkylpropane-1,3-diols was obtained in the regime of mass transfer. The most favorable pH of the reaction mixture of the promoted oxidation was 10. The reaction temperature of 40°C prevented the decarboxylation of the diacids.

Computing the Stochastic Complexity of Simple Probabilistic Graphical Models

Minimum Description Length (MDL) is an information-theoretic principle that can be used for model selection and other statistical inference tasks. There are various ways to use the principle in practice. One theoretically valid way is to use the normalized maximum likelihood (NML) criterion. Due to computational difficulties, this approach has not been used very often. This thesis presents efficient floating-point algorithms that make it possible to compute the NML for multinomial, Naive Bayes and Bayesian forest models. None of the presented algorithms rely on asymptotic analysis and with the first two model classes we also discuss how to compute exact rational number solutions.

Exploring privacy for ubiquitous computing: Tools, methods and experiments

Ubiquitous computing is about making computers and computerized artefacts a pervasive part of our everyday lifes, bringing more and more activities into the realm of information. The computationalization, informationalization of everyday activities increases not only our reach, efficiency and capabilities but also the amount and kinds of data gathered about us and our activities. In this thesis, I explore how information systems can be constructed so that they handle this personal data in a reasonable manner. The thesis provides two kinds of results: on one hand, tools and methods for both the construction as well as the evaluation of ubiquitous and mobile systems---on the other hand an evaluation of the privacy aspects of a ubiquitous social awareness system. The work emphasises real-world experiments as the most important way to study privacy. Additionally, the state of current information systems as regards data protection is studied. The tools and methods in this thesis consist of three distinct contributions. An algorithm for locationing in cellular networks is proposed that does not require the location information to be revealed beyond the user's terminal. A prototyping platform for the creation of context-aware ubiquitous applications called ContextPhone is described and released as open source. Finally, a set of methodological findings for the use of smartphones in social scientific field research is reported. A central contribution of this thesis are the pragmatic tools that allow other researchers to carry out experiments. The evaluation of the ubiquitous social awareness application ContextContacts covers both the usage of the system in general as well as an analysis of privacy implications. The usage of the system is analyzed in the light of how users make inferences of others based on real-time contextual cues mediated by the system, based on several long-term field studies. The analysis of privacy implications draws together the social psychological theory of self-presentation and research in privacy for ubiquitous computing, deriving a set of design guidelines for such systems. The main findings from these studies can be summarized as follows: The fact that ubiquitous computing systems gather more data about users can be used to not only study the use of such systems in an effort to create better systems but in general to study phenomena previously unstudied, such as the dynamic change of social networks. Systems that let people create new ways of presenting themselves to others can be fun for the users---but the self-presentation requires several thoughtful design decisions that allow the manipulation of the image mediated by the system. Finally, the growing amount of computational resources available to the users can be used to allow them to use the data themselves, rather than just being passive subjects of data gathering.

A Hub System for Cloud-Computing Based Business-Collaboration: Automating Ontology-Enabled Electronic Business-Service Discovery

The management and coordination of business-process collaboration experiences changes because of globalization, specialization, and innovation. Service-oriented computing (SOC) is a means towards businessprocess automation and recently, many industry standards emerged to become part of the service-oriented architecture (SOA) stack. In a globalized world, organizations face new challenges for setting up and carrying out collaborations in semi-automating ecosystems for business services. For being efficient and effective, many companies express their services electronically in what we term business-process as a service (BPaaS). Companies then source BPaaS on the fly from third parties if they are not able to create all service-value inhouse because of reasons such as lack of reasoures, lack of know-how, cost- and time-reduction needs. Thus, a need emerges for BPaaS-HUBs that not only store service offers and requests together with information about their issuing organizations and assigned owners, but that also allow an evaluation of trust and reputation in an anonymized electronic service marketplace. In this paper, we analyze the requirements, design architecture and system behavior of such a BPaaS-HUB to enable a fast setup and enactment of business-process collaboration. Moving into a cloud-computing setting, the results of this paper allow system designers to quickly evaluate which services they need for instantiationg the BPaaS-HUB architecture. Furthermore, the results also show what the protocol of a backbone service bus is that allows a communication between services that implement the BPaaS-HUB. Finally, the paper analyzes where an instantiation must assign additional computing resources vor the avoidance of performance bottlenecks.

Seasonal fluctuations in blue-green algae, especially in heterocystous species in polluted coastal waters off Helsinki city, in the northern part of the Gulf of Finland

Tiivistelmä

Victims of the White War or Rebellions of the Green Revolution? Bolivian Indigenous Women Prisoners' Position in the "War on Drugs" Explored through a Criminological Gaze

Tässä tutkielmassa tarkastellaan Bolivialaisten naisvankien (alkuperäisväestön) ja globaalin huumesodan ("War on Drugs") välistä yhteyttä. Keskustelu sijoitetaan laajemmin kokan viljelyn politiikkaan ja alkuperäisväestön kulttuuriin. Kokaa viljeleviä köyhiä maalaisia, joista huomattava osa on naisia, on vangittu Boliviassa kiihtyvää tahtia viime vuosikymmeninä. Moni naisista on kokan tuotannossa ja kaupassa mukana, sillä se on monesti ainoa keino taloudelliseen selviämiseen. Yleisesti ottaen naisvangit ja naisrikolliset ovat marginaalinen ilmiö. Kansainvälisesti tarkasteltuna naisvankien suhteellinen osuus koko vankilaväestöstä on noin 5,2 % (keskiarvo). Boliviassa osuus on vaihdellut 6,1 %:n ja 17,1 %:n välillä vuosina 2000-2008. Naisvankien määrä yleisesti ottaen on ollut rajussa kasvussa, suurin syy naisten vangitsemiseen on huumausaineisiin liittyvät rikokset. Näyttää myös siltä että vähemmistöt ja etnisen taustan omaavat henkilöt ovat yliedustettuina vankilaväestössä. Bolivia seuraa tätä kansainvälistä trendiä. Tämä tutkielma on rajattu kysymyksiin Bolivian intiaaniperäisten naisten osuudesta maan huumerikollisuudessa, sekä heidän suhteellisen korkeaa vangitsemisastetta selittäviin yhteiskunnallisiin tekijöihin. Kysymykset sukupuolesta, etnisyydestä ja kokan viljelyn politiikasta ovat keskiössä. Yleisiä kriminologisia teorioita peilataan kriittisesti suhteessa aineistoon ja Bolivian kontekstiin. Huumesodan ja Bolivian ankaran huumelainsäädännön seurauksista keskustellaan kriittisesti, sekä pohditaan köyhän alkuperäisväestön massavangitsemisen tarpeellisuutta. Tutkimuskysymykseni ovat: mitkä tekijät selittävät kohtuullisen korkean intiaaniperäisten naisvankien määrän Boliviassa, ja mikä on heidän asemansa globaalissa huumesodassa? Tutkielmassa on analysoitu kvantitatiivista ja kvalitatiivista aineistoa. Päälähteenä on ollut Bolivian tilastokeskuksen tuottamat rikostilastot. Tutkielman tärkeimpänä löydöksenä voidaan pitää havaintoa, että vastoin tiettyjä olettamuksia, intiaaniperäiset naiset ovat hyvinkin aktiivisia perinteisesti miehisiksi käsitetyillä aloilla kuten rikollisuudessa ja politiikassa. Tutkielmassa osoitetaan myös, että pidätysten määrät ovat moninkertaistuneet muutamassa vuosikymmenessä. Koska kokan viljelyssä on kyse pääasiallisesti taloudellisesta toimeentulosta, tämä tutkielma kysyy, onko hengissä pysyminen rikos?