Bio and chemocatalysis for stereo and regioselective one-pot reaction applications

The development of cost efficient, selective and sustainable chemical processes for production of chiral building blocks is of great importance in synthetic and industrial organic chemistry. One way to reach these objectives is to carry out several reactions steps in one vessel at one time. Furthermore, when this kind of one-pot multi step reactions are catalyzed by heterogeneous chemo- and bio-catalysts, which can be separated from the reaction products by filtration, practical access to chiral small molecules for further utilization can be obtained. The initial reactions studied in this thesis are the two step dynamic kinetic resolution of rac-2-hydroxy-1-indanone and the regioselective hydrogenation of 1,2-indanedione. These reactions are then combined in a new heterogeneously catalyzed one-pot reaction sequence enabling simple recovery of the catalysts by filtration, facilitating simple reaction product isolation. Conclusively, the readily available 1,2-indanedione is by the presented one-pot sequence, utilizing heterogeneous enzyme and transition metal based catalysts, transferred with high regio- and stereoselectivity to a useful chiral vicinal hydroxyl ketone structure. Additional and complementary investigation of homogeneous half-sandwich ruthenium complexes for catalyzing the epimerization of chiral secondary alcohols of five natural products containing additional non-functionalized stereocenters was conducted. In principle, this kind of epimerization reactions of single stereocenters could be utilized for converting inexpensive starting materials, containing other stereogenic centers, into diastereomeric mixtures from which more valuable compounds can be isolated by traditional isolation techniques.

Functionalisation of spruce O-acetyl-galactoglucomannans for barrier and composite applications

The increasing use of energy, food, and materials by the growing population in the world is leading to the situation where alternative solutions from renewable carbon resources are sought after. The growing use of plastics depends on the raw-oil production while oil refining are politically governed and required for the polymer manufacturing is not sustainable in terms of carbon footprint. The amount of packaging is also increasing. Packaging is not only utilising cardboard and paper, but also plastics. The synthetic petroleum-derived plastics and inner-coatings in food packaging can be substituted with polymeric material from the renewable resources. The trees in Finnish forests constitute a huge resource, which ought to be utilised more effectively than it is today. One underutilised component of the forests is the wood-derived hemicelluloses, although Spruce Oacetyl-galactoglucomannans (GGMs) have previously shown high potential for material applications and can be recovered in large scale. Hemicelluloses are hydrophilic in their native state, which restrains the use of them for food packaging as non-dry item. To cope with this challenge, we intended to make GGMs more hydrophobic or amphiphilic by chemical grafting and consequently with the focus of using them for barrier applications. Methods of esterification with anhydrides and cationic etherification with a trimethyl ammonium moiety were established. A method of controlled synthesis to obtain the desired properties by the means of altering temperature, reaction time, the quantity of the reagent, and even the solvent for purification of the products was developed. Numerous analytical tools, such as NMR, FTIR, SEC-MALLS/RI, MALDI-TOF-MS, RP-HPLC and polyelectrolyte titration were used to evaluate the products from different perspectives and to acquire parallel proofs of their chemical structure. Modified GGMs with different degree of substitution and the correlating level of hydrophobicity was applied as coatings on cartonboard and on nanofibrillated cellulose-GGM films to exhibit barrier functionality. The water dispersibility in processing was maintained with GGM esters with low DS. The use of chemically functionalised GGM was evaluated for the use as barriers against water, oxygen and grease for the food packaging purposes. The results show undoubtedly that GGM derivatives exhibit high potential to function as a barrier material in food packaging.

Blue and Uv-Emitting Upconversion Nanoparticles: Synthesis and (Bio) Analytical Applications.

Rare-earth based upconverting nanoparticles (UCNPs) have attracted much attention due to their unique luminescent properties. The ability to convert multiple photons of lower energy to ones with higher energy through an upconversion (UC) process offers a wide range of applications for UCNPs. The emission intensities and wavelengths of UCNPs are important performance characteristics, which determine the appropriate applications. However, insufficient intensities still limit the use of UCNPs; especially the efficient emission of blue and ultraviolet (UV) light via upconversion remains challenging, as these events require three or more near-infrared (NIR) photons. The aim of the study was to enhance the blue and UV upconversion emission intensities of Tm3+ doped NaYF4 nanoparticles and to demonstrate their utility in in vitro diagnostics. As the distance between the sensitizer and the activator significantly affect the energy transfer efficiency, different strategies were explored to change the local symmetry around the doped lanthanides. One important strategy is the intentional co-doping of active (participate in energy transfer) or passive (do not participate in energy transfer) impurities into the host matrix. The roles of doped passive impurities (K+ and Sc3+) in enhancing the blue and UV upconversions, as well as in influencing the intense UV upconversion emission through excess sensitization (active impurity) were studied. Additionally, the effects of both active and passive impurity doping on the morphological and optical performance of UCNPs were investigated. The applicability of UV emitting UCNPs as an internal light source for glucose sensing in a dry chemistry test strip was demonstrated. The measurements were in agreement with the traditional method based on reflectance measurements using an external UV light source. The use of UCNPs in the glucose test strip offers an alternative detection method with advantages such as control signals for minimizing errors and high penetration of the NIR excitation through the blood sample, which gives more freedom for designing the optical setup. In bioimaging, the excitation of the UCNPs in the transparent IR region of the tissue permits measurements, which are free of background fluorescence and have a high signal-to-background ratio. In addition, the narrow emission bandwidth of the UCNPs enables multiplexed detections. An array-in-well immunoassay was developed using two different UC emission colours. The differentiation between different viral infections and the classification of antibody responses were achieved based on both the position and colour of the signal. The study demonstrates the potential of spectral and spatial multiplexing in the imaging based array-in-well assays.

Hardware design of a multiconverter for hybrid vehicle applications

Hybridiajoneuvosovellukset vaativat usein sekä korkea- että matalajännitejärjestelmän. Korkeajännitejärjestelmä sisältää yleensä energiavaraston, joka on joko superkondansaattori tai korkeajänniteakusto, dieselgeneraattorin tai range extenderin ja ajokäytön. Korkeajännitejärjestelmään liitetään usein myös erilaisia apukäyttöjä kuten kompressoreita ja hydraulipumppuja. Matalajännitejärjelmä koostuu yleensä ohjausyksiköistä, ajovaloista, yms. laitteista. Perinteisesti matalajännitejärjestelmää on syötetty dieselmoottorin laturista, mutta korkeajännitejärjestelmien myötä DC/DC-hakkurin käyttäminen korkea- ja matalajännitejärjestelmien välillä on herättänyt kiinnostusta, koska tällöin laturin voisi poistaa ja matalajänniteakustoa pienentää. Tässä työssä kuvatun monilähöisen tehonmuokkaimen invertterisilta soveltuu apukäyttöjen ajamiseen, ja erotettu DC/DC-hakkuri matalajännitejärjestelmän syöttämiseen. Tässä työssä käydään läpi edellä mainitun tehonmuokkaimen suunnittelu, keskittyen eritoten laitteen korkeajänniteosien mitoitukseen ja termiseen suunniteluun. DC/DC-hakkurin osalta perinteisiä piistä valmistettuja IGBT transistoreja vertaillaan piikarbidi MOSFET transistoreihin. Lämpömallilaskujen paikkaansapitävyyttä tutkitaan suorittamalla prototyyppilaitteelle hyötysuhdemittaus, jonka tuloksia verrataan laskettuihin tuloksiin. Lämpömallin parannusmahdollisuuksia käsitellään myös hyötysuhdemittauksen tulosten perusteella.

Adopting the Vaadin Java framework to rebuild VTT’s Web Interfaces and Database Applications

With the growth in new technologies, using online tools have become an everyday lifestyle. It has a greater impact on researchers as the data obtained from various experiments needs to be analyzed and knowledge of programming has become mandatory even for pure biologists. Hence, VTT came up with a new tool, R Executables (REX) which is a web application designed to provide a graphical interface for biological data functions like Image analysis, Gene expression data analysis, plotting, disease and control studies etc., which employs R functions to provide results. REX provides a user interactive application for the biologists to directly enter the values and run the required analysis with a single click. The program processes the given data in the background and prints results rapidly. Due to growth of data and load on server, the interface has gained problems concerning time consumption, poor GUI, data storage issues, security, minimal user interactive experience and crashes with large amount of data. This thesis handles the methods by which these problems were resolved and made REX a better application for the future. The old REX was developed using Python Django and now, a new programming language, Vaadin has been implemented. Vaadin is a Java framework for developing web applications and the programming language is extremely similar to Java with new rich components. Vaadin provides better security, better speed, good and interactive interface. In this thesis, subset functionalities of REX was selected which includes IST bulk plotting and image segmentation and implemented those using Vaadin. A code of 662 lines was programmed by me which included Vaadin as the front-end handler while R language was used for back-end data retrieval, computing and plotting. The application is optimized to allow further functionalities to be migrated with ease from old REX. Future development is focused on including Hight throughput screening functions along with gene expression database handling

Social-business tensions and their management in social enterprise: evidence from Finland.

This thesis aims to provide insight into the social-business tensions the social enterprises face in their operation and how they manage them. The social-business tensions are examined from four theoretical perspectives using triangulation approach. The theoretical lenses chosen are organizational identity, stakeholder theory, paradox theory and institutional theory. The theories aim to clarify, how the tensions are formed, how they appear and how they are managed in social enterprises. One viewpoint of this thesis is to examine the competence of these theories in explaining the social-business tensions in practise. The qualitative data was collected by interviewing persons from the management of two social enterprises. The empirical evidence of this thesis suggests that the appearing of social-business tensions varies between the social enterprises and they can be seen both as an advantage and as a challenge. Most of the social-business tensions arise from the enterprise’s multiple incoherent objectives, their stakeholders’ various demands and the differing understanding of the company’s central operation among the members of the organization. According to this thesis, the theories of organizational identity, stakeholder, paradox and institution are all able to provide unique insight into the identification and management of the social-business tensions. However, the paradox theory turned out to be the most abstract of the theories and thus being the farthest from the practise.

Mobile applications, solution for sustainable agriculture? - Study of mAgriculture services in Kenya

During the recent years, mobile services have spread to many different sectors, including education, health and agriculture, while changing the practices in those fields. Agriculture sector is under pressure to fill the ever-crowing food demand, while suffering from lack of agriculture resources (such as water and soil) and climate change, as well as figuring how to involve young people in the agriculture sector, in order to replace aging farmers. These issues create a need to bring new sustainable solutions to the agriculture sector. This is the demand, which mobile agriculture, mAgriculture, services are trying to answer. This thesis will examine the mAgriculture services in the Kenyan market. The thesis will provide an overview of the currently available mAgriculture services, their outcome and issues with which they are struggling. The thesis will also present recommendations on how to improve currently existing services and processes behind them. Secondly, thesis will provide four ideas for new services, which would answer for the needs of the farmers. Suitable business models, regarding the new services, are also covered. The thesis focuses with the young farmers as a target group, but findings are also applicable with other potential target groups as well.

Acquisition Failure: The case of a multinational enterprise from an emerging market failing in Indonesia.

The escalation in the number of mergers and acquisition transactions involving emerging market firms is a relatively recent phenomenon; as a consequence academic research in such topic is rather limited. The purpose of this research study was to discuss the possible reasons that led the acquisition failure of an emerging multinational firm and an Indonesian player. Extensive theoretical research was performed and it had been achieved, based on this, the finding of a framework that facilitated to understand the way in which the concepts of cultural distances and relate liabilities of foreignness in the process of acquisitions of foreign companies in emerging markets. The theoretical background collects literature related to acquisitions, models of cultural studies between nations and liabilities of foreignness. It has been generated a variety of frameworks that aid to understand the way that the institutional distance and cultural factors together with the concept of liabilities of foreignness can affect the process of market entry of an emerging multinational company to the extent that the best way to stop losing money is to abandon the project. The empirical research consisted of selective semi-structured interviews and an extensive research in available public data on the chosen study case of this research. There were several factors that were identified as the cause of the failure in the market entry of a Mexican multinational firm in Indonesia. The weakness shown by the local government authorities was used by the local community leaders who rioted because of discomfort. These groups were the ones who made the government submit to the extent that the agreements reached at the beginning of the deal were either canceled or modified in a way that favored always the local community. The contributions of this study fall into the knowledge field of emerging multinational firms and market entry process.

Perception of privacy in smartphone applications: profiling users based on personality types.

This document is focused on studying privacy perception and personality traits of users in the context of smartphone application privacy. It is divided into two parts. The first part presents an in depth systematic literature review of the existing academic writings available on the topic of relation between privacy perception and personality traits. Demographics, methodologies and other useful insight is extracted and the available literature is divided into broader group of topics bringing the five main areas of research to light and highlighting the current research trends in the field along with pinpointing the research gap of interest to the author. The second part of the thesis uses the results from the literature review to administer an empirical study to investigate the current privacy perception of users and the correlation between personality traits and privacy perception in smartphone applications. Big five personality test is used as the measure for personality traits whereas three sub-variables are used to measure privacy perception i.e. perceived privacy awareness, perceived threat to privacy and willingness to trade privacy. According to the study openness to experience is the most dominant trait having a strong correlation with two privacy sub-variables whereas emotional stability doesn’t show any correlation with privacy perception. Empirical study also explores other findings as preferred privacy sources and application installation preferences that provide further insight about users and might be useful in future.