Regioselective modification of galactose-containing polysaccharides in aqueous media

Biorefining is defined as sustainable conversion of biomass into marketable products and energy. Forests cover almost one third of earth’s land area, and account for approximately 40% of the total annual biomass production. In forest biorefining, the wood components are, in addition to the traditional paper and board products, converted into chemicals and biofuels. The major components in wood are cellulose, hemicelluloses, and lignin. The main hemicellulose in softwoods, which are of interest especially for the Nordic forest industry, is O-acetyl galactoglucomannan (GGM). GGM can be isolated in industrial scale from the waste waters of the mechanical pulping process, but is not yet today industrially utilized. In order to attain desired properties of GGM for specific end-uses, chemical and enzymatic modifications can be performed. Regioselective modifications of GGM, and other galactose-containing polysaccharides were done by oxidations, and by combining oxidations with subsequent derivatizations of the formed carbonyl or carboxyl groups. Two different pathways were investigated: activation of the C-6 positions in different sugar units by TEMPO-mediated oxidation, and activation of C-6 position in only galactose-units by oxidation catalyzed by the enzyme galactose oxidase. The activated sites were further selectively derivatized; TEMPO-oxidized GGM by a carbodiimide-mediated reaction forming amides, and GO-oxidized GGM by indium-mediated allylation introducing double or triple bonds to the molecule. In order to better understand the reaction, and to develop a MALDI-TOF-MS method for characterization of regioselectively allylated GGM, α-D-galactopyranoside and raffinose were used as model compounds. All reactions were done in aqueous media. To investigate the applicability of the modified polysaccharides for, e.g., cellulose surface functionalization, their sorption onto pulp fibres was studied. Carboxylation affects the sorption tendency significantly; a higher degree of oxidation leads to lower sorption. By controlling the degree of oxidation of the polysaccharides and the ionic strength of the sorption media, high degrees of sorption of carboxylated polysaccharides onto cellulose could, however, be obtained. Anionic polysaccharides were used as templates during laccase-catalyzed polymerization of aniline, offering a green, chemo-enzymatic route for synthesis of conducting polyaniline (PANI) composite materials. Different polysaccharide templates, such as, native GGM, TEMPO-oxidized GGM, naturally anionic κ-carrageenan, and nanofibrillated cellulose produced by TEMPO-oxidation, were assessed. The conductivity of the synthesized polysaccharide/PANI biocomposites varies depending on the polysaccharide template; κ-CGN, the anionic polysaccharide with the lowest pKa value, produces the polysaccharide/PANI biocomposites with the highest conductivity. The presented derivatization, sorption, and polymerization procedures open new application windows for polysaccharides, such as spruce GGM. The modified polysaccharides and the conducting biocomposites produced provide potential applications in biosensors, electronic devices, and tissue engineering.

Integration of Electronic Commerce and Enterprise Systems

The necessity of EC (Electronic Commerce) and enterprise systems integration is perceived from the integrated nature of enterprise systems. The proven benefits of EC to provide competitive advantages to the organizations force enterprises to adopt and integrate EC with their enterprise systems. Integration is a complex task to facilitate seamless flow of information and data between different systems within and across enterprises. Different systems have different platforms, thus to integrate systems with different platforms and infrastructures, integration technologies, such as middleware, SOA (Service-Oriented Architecture), ESB (Enterprise Service Bus), JCA (J2EE Connector Architecture), and B2B (Business-to-Business) integration standards are required. Huge software vendors, such as Oracle, IBM, Microsoft, and SAP suggest various solutions to address EC and enterprise systems integration problems. There are limited numbers of literature about the integration of EC and enterprise systems in detail. Most of the studies in this area have focused on the factors which influence the adoption of EC by enterprise or other studies provide limited information about a specific platform or integration methodology in general. Therefore, this thesis is conducted to cover the technical details of EC and enterprise systems integration and covers both the adoption factors and integration solutions. In this study, many literature was reviewed and different solutions were investigated. Different enterprise integration approaches as well as most popular integration technologies were investigated. Moreover, various methodologies of integrating EC and enterprise systems were studied in detail and different solutions were examined. In this study, the influential factors to adopt EC in enterprises were studied based on previous literature and categorized to technical, social, managerial, financial, and human resource factors. Moreover, integration technologies were categorized based on three levels of integration, which are data, application, and process. In addition, different integration approaches were identified and categorized based on their communication and platform. Also, different EC integration solutions were investigated and categorized based on the identified integration approaches. By considering different aspects of integration, this study is a great asset to the architectures, developers, and system integrators in order to integrate and adopt EC with enterprise systems.

The Finnish Electronic Library - Basic Research Infrastructure

Kristiina Hormia-Poutasen esitys KRE-konferenssissa 2013.

It’s a workflow engine. It’s working with linked data. It’s repository! – Supporting electronic thesis related processes in University of Helsinki library

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

A DNS Bases Approach To Electronic Persistance, or "If Your Pants Fit, Why Use Suspenders?"

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Printed platforms for paper-based analytical applications

Paper-based analytical technologies enable quantitative and rapid analysis of analytes from various application areas including healthcare, environmental monitoring and food safety. Because paper is a planar, flexible and light weight substrate, the devices can be transported and disposed easily. Diagnostic devices are especially valuable in resourcelimited environments where diagnosis as well as monitoring of therapy can be made even without electricity by using e.g. colorimetric assays. On the other hand, platforms including printed electrodes can be coupled with hand-held readers. They enable electrochemical detection with improved reliability, sensitivity and selectivity compared with colorimetric assays. In this thesis, different roll-to-roll compatible printing technologies were utilized for the fabrication of low-cost paper-based sensor platforms. The platforms intended for colorimetric assays and microfluidics were fabricated by patterning the paper substrates with hydrophobic vinyl substituted polydimethylsiloxane (PDMS) -based ink. Depending on the barrier properties of the substrate, the ink either penetrates into the paper structure creating e.g. microfluidic channel structures or remains on the surface creating a 2D analog of a microplate. The printed PDMS can be cured by a roll-ro-roll compatible infrared (IR) sintering method. The performance of these platforms was studied by printing glucose oxidase-based ink on the PDMS-free reaction areas. The subsequent application of the glucose analyte changed the colour of the white reaction area to purple with the colour density and intensity depending on the concentration of the glucose solution. Printed electrochemical cell platforms were fabricated on paper substrates with appropriate barrier properties by inkjet-printing metal nanoparticle based inks and by IR sintering them into conducting electrodes. Printed PDMS arrays were used for directing the liquid analyte onto the predetermined spots on the electrodes. Various electrochemical measurements were carried out both with the bare electrodes and electrodes functionalized with e.g. self assembled monolayers. Electrochemical glucose sensor was selected as a proof-of-concept device to demonstrate the potential of the printed electronic platforms.

Imbuing airborne electronic warfare self-protection : possibilities to disguise

Tutkielman nimi käännettynä suomeksi on Lentokoneiden omasuojajärjestelmien kyllästäminen – mahdollisuuksia kätkeytymiseen. Siinä keskitytään etsimään aktiivisia, ilmauhkaa kohti säteileviä keinoja ilmahyökkääjän, lentokoneen tai helikopterin, omasuojajärjestelmän harhauttamiseksi. Järjestelmät pyrkivät varoittamaan lentäjää laser- ja tutkasäteilyhavainnoista sekä ohjuksen laukaisusta ja lähestymisestä. Omasuojajärjestelmiin kuuluviin vastakeinoihin tutkimus ei keskity. Tavoitteena harhauttamisella on ilmapuolustuksen todellisen määrän ja sijainnin suojaaminen. Epätietoisuus voi saada lentäjän tekemään vääriä johtopäätöksiä. Työ ei fokusoi harhauttamisen taktiseen kehykseen työn kannalta tarpeellista määrää enempää. Tietosuojasyistä tutkimus ei käsittele käytössä olevien omasuojajärjestelmien operatiivisia ominaisuuksia vaan käsittelee teoriaa niiden taustalla. Tutkimus tehtiin käyttäen taustatutkimukselle enemmän tyypillistä kirjallisuustutkimusta. Jo tutki-muksen alkuvaiheessa oli oletettavaa, että elektronisiin sensoreihin perustuvaa omasuojajärjestelmää pystytään harhauttamaan. Systeemianalysoinnilla pyrittiin löytämään vastauksia tähän olettamukseen. Omasuojajärjestelmästä muodostettiin jo tutkimuksen varhaisessa vaiheessa malli. Tieteellistä kirjallisuutta omasuojajärjestelmistä on olemassa jonkin verran, ja niistä löydettyä tietoa omasuojajärjestelmien ominaisuuksista ja sensoreista yhdistettiin malliin niin, että siitä saatiin mahdollisimman tarkka systeemin kuvaus todellisesta omasuojajärjestelmästä. Analyysin tavoitteena oli löytää niitä kriteereitä, joilla omasuojajärjestelmä saataisiin kohtuullisen tehokkaasti uskomaan harhautusta oikeaksi hälytykseksi. Ohjuksen laukaisusta varoittava sensori perustuu ohjuksen moottorin muodostaman pilven lämpö-säteilyyn. Säteily kuitenkin muuttuu lennon eri vaiheissa, mikä tuottaa haasteita järjestelmälle. Millimetrialueen tutkan käyttö varoittimen sensorina on myös yksi vaihtoehto. Laser-varoittimet toimivat koko sillä taajuusalueella, mitä sotilaskäytössä tulenjohtamiseen ja ohjusten ohjaamiseen käytetään. Tutkavaroittimen tutkimus on vielä kesken. Löydettyjä tuloksia analysoimalla tulen tässä vaiheessa hieman ristiriitaisiin tuloksiin. Lämpösäteilyn käytön suurin haaste on sen eteneminen ilmakehässä. Varoittimen tavoitekaan ei ole toimia kymmentä kilometriä pidemmälle. Yksi mahdollinen ratkaisu on suunnitella ja toteuttaa raketti, jonka tuottaa lämpösäteilyä kuten tietty puolustavan joukon käytössä oleva ohjus. Jos koneessa on kuitenkin myös millimetrialueen tutka tukemassa varoitusjärjestelmää, hankaloituu rakettiharhautus merkittävästi, koska sen pitäisi oletettavasti olla lentokoneen kanssa melko tarkasti kohtaavalla reitillä. Laser-varoitin on ilmeisesti herkin järjestelmistä, koska se voi tietyissä olosuhteissa ja varsinkin matalalla lentokorkeudella aiheuttaa paljon vääriä hälytyksiä ilman tarkoituksellista harhauttamista. Laserin käyttö yhdistettynä raketin laukaisuun saattaisi tuottaa halutun tuloksen. Tutkavaroittimen harhautus onnistuu, jos valelaitteen signaali on uskottavan tarkka.

Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Value creation through sponsorship in electronic sports

The objective of this thesis was to study value creation through sponsor-ship in a new emerging electronic sports environment. Sub-questions were formulated which helped in finding answers to the main research question. Theory of traditional sports and practice of electronic sports were compared with each other in order to find out how theories of tradi-tional sports fare in the new environment. B2B-relationship model of Actors, resources and activities is used in this thesis to help in clarifying the different variables used in electronic sports sponsorship environment. The empirical research was conducted via interviews with the managers working in electronic sports environment. One of the main conclusions is that relationship management is really important.. Actors in electronic sports need to find and create win-win-win situations. This means that they need to benefit the actors in sponsoring relationship and also the community.

First-principles study on electronic and structural properties of Cu(In/Ga)Se alloys for solar cells

Thin-film photovoltaic solar cells based on the Cu(In1−xGax)Se2 (CIGS) alloys have attracted more and more attention due to their large optical absorption coefficient, long term stability, low cost, and high efficiency. Modern theoretical studies of this material with first-principles calculations can provide accurate description of the electronic structure and yield results in close agreement with experimental values, but takes a large amount of calculation time. In this work, we use first-principles calculations based on the computationally affordable meta- generalized gradient approximation of the density-functional theory to investigate electronic and structural properties of the CIGS alloys. We report on the simulation of the lattice parameters and band gaps, as a function of chemical composition. The obtained results were found to be in a good agreement with the available experimental data.