Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

GLOBAL AND LOCAL REACTIVITY DESCRIPTORS FOR PICLORAM HERBICIDE: A THEORETICAL QUANTUM STUDY

In this work, we studied the reactivity of picloram in the aqueous phase at the B3LYP/6-311++G(2d,2p) and MP2/6-311++G(2d,2p) levels of theory through global and local reactivity descriptors. The results obtained at the MP2 level indicate that the cationic form of picloram exhibits the highest hardness while the anionic form is the most nucleophilic. From the Fukui function values, the most reactive site for electrophilic and free radical attacks are on the nitrogen in the pyridine ring. The more reactive sites for nucleophilic attacks are located on the nitrogen atom of the amide group and on the carbon atoms located at positions 2 and 3 in the pyridine ring.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

Antenna Design for Contactless IC Card Applications

Contactless integrated circuit cards are one form of application of radio frequency identification. They are used in applications such as access control, identification, and payment in public transport. The contactless IC cards are passive which means that both the data and the energy are transferred to the card without contact using inductive coupling. Antenna design and optimization of the design for contactless IC cards defined by ISO/IEC14443 is studied. The basic operation principles of contactless system are presented and the structure of contactless IC card is illustrated. The structure was divided between the contactless chip and the antenna. The operation of the antenna was covered in depth and the parameters affecting to the performance of the antenna were presented. Also the different antenna technologies and connection technologies were provided. The antenna design process with the parameters and the design tools isillustrated and optimization of the design is studied. To make the design process more ideal a target of development was discovered, which was the implementation of test application. The optimization of the antenna design was presented based on the optimization criteria defined in this study. The solution for the implementation of these criteria and the effect of each criterion was found. For enhancing the performance of the antenna a focus for future study was proposed.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Studies on the Multifaceted Interaction of Atoms and an Electromagnetic Field

In this Thesis the interaction of an electromagnetic field and matter is studied from various aspects in the general framework of cold atoms. Our subjects cover a wide spectrum of phenomena ranging from semiclassical few-level models to fully quantum mechanical interaction with structured reservoirs leading to non-Markovian open quantum system dynamics. Within closed quantum systems, we propose a selective method to manipulate the motional state of atoms in a time-dependent double-well potential and interpret the method in terms of adiabatic processes. Also, we derive a simple wave-packet model, based on distributions of generalized eigenstates, explaining the finite visibility of interference in overlapping continuous-wave atom lasers. In the context of open quantum systems, we develop an unraveling of non-Markovian dynamics in terms of piecewise deterministic quantum jump processes confined in the Hilbert space of the reduced system - the non-Markovian quantum jump method. As examples, we apply it for simple 2- and 3-level systems interacting with a structured reservoir. Also, in the context of ion-cavity QED we study the entanglement generation based on collective Dicke modes in experimentally realistic conditions including photonic losses and an atomic spontaneous decay.

Biochemical Modification of Thermomechanical Pulp Fibers

The first objective of this study was to find out reliable laboratory methods to predict the effect of enzymes on specific energy consumption and fiber properties of TMP pulp. The second one was to find with interactive software called “Knowledge discovery in databases” enzymes or other additives that can be used in finding a solution to reduce energy consumption of TMP pulp. The chemical composition of wood and enzymes, which have activity on main wood components were presented in the literature part of the work. The results of previous research in energy reduction of TMP process with enzymes were also highlighted. The main principles of knowledge discovery have been included in literature part too. The experimental part of the work contains the methods description in which the standard size chip, crushed chip and fiberized spruce chip (fiberized pulp) were used. Different types of enzymatic treatment with different dosages and time were tested during the experiments and showed. Pectinase, endoglucanase and mixture of enzymes were used for evaluation of method reliability. The fines content and fiber length of pulp was measured and used as evidence of enzymes' effect. The refining method with “Bauer” laboratory disc refiner was evaluated as not highly reliable. It was not able to provide high repeatability of results, because of uncontrolled feeding capacity and refining consistency. The refining method with Valley refiner did not have a lot of variables and showed stable and repeatable results in energy saving. The results of experiments showed that efficient enzymes impregnation is probably the main target with enzymes application for energy saving. During the work the fiberized pulp showed high accessibility to enzymatic treatment and liquid penetration without special impregnating equipment. The reason was that fiberized pulp has larger wood surface area and thereby the contact area between the enzymatic solution and wood is also larger. Standard size chip and crushed chip treatment without special impregnator of enzymatic solution was evaluated as not efficient and did not show visible, repeatable results in energy consumption decrease. Thereby it was concluded that using of fiberized pulp and Valley refiner for measurements of enzymes' effectiveness in SEC decrease is more suitable than normal size chip and crushed chip with “Bauer” refiner. Endoglucanase with 5 kg/t dosage showed about 20% energy consumption decrease. Mixture of enzymes with 1.5 kg/t dosage showed about 15% decrease of energy consumption during the refining. Pectinase at different dosages and treatment times did not show significant effect on energy consumption. Results of knowledge discovery in databases showed the xylanase, cellulase and pectinase blend as most promising for energy reduction in TMP process. Surfactants were determined as effective additives for energy saving with enzymes.

Structural studies on enzymes of biotechnological and biomedical interest

Structural studies of proteins aim at elucidating the atomic details of molecular interactions in biological processes of living organisms. These studies are particularly important in understanding structure, function and evolution of proteins and in defining their roles in complex biological settings. Furthermore, structural studies can be used for the development of novel properties in biomolecules of environmental, industrial and medical importance. X-ray crystallography is an invaluable tool to obtain accurate and precise information about the structure of proteins at the atomic level. Glutathione transferases (GSTs) are amongst the most versatile enzymes in nature. They are able to catalyze a wide variety of conjugation reactions between glutathione (GSH) and non-polar components containing an electrophilic carbon, nitrogen or sulphur atom. Plant GSTs from the Tau class (a poorly characterized class) play an important role in the detoxification of xenobiotics and stress tolerance. Structural studies were performed on a Tau class fluorodifen-inducible glutathione transferase from Glycine max (GmGSTU4-4) complexed with GSH (2.7 Å) and a product analogue Nb-GSH (1.7 Å). The three-dimensional structure of the GmGSTU4-4-GSH complex revealed that GSH binds in different conformations in the two subunits of the dimer: in an ionized form in one subunit and a non-ionized form in the second subunit. Only the ionized form of the substrate may lead to the formation of a catalytically competent complex. Structural comparison between the GSH and Nb-GSH bound complexes revealed significant differences with respect to the hydrogen-bonding, electrostatic interaction pattern, the upper part of -helix H4 and the C-terminus of the enzyme. These differences indicate an intrasubunit modulation between the G-and Hsites suggesting an induced-fit mechanism of xenobiotic substrate binding. A novel binding site on the surface of the enzyme was also revealed. Bacterial type-II L-asparaginases are used in the treatment of haematopoietic diseases such as acute lymphoblastic leukaemia (ALL) and lymphomas due to their ability to catalyze the conversion of L-asparagine to L-aspartate and ammonia. Escherichia coli and Erwinia chrysanthemi asparaginases are employed for the treatment of ALL for over 30 years. However, serious side-effects affecting the liver and pancreas have been observed due to the intrinsic glutaminase activity of the administered enzymes. Structural studies on Helicobacter pylori L-asparaginase (HpA) were carried out in an effort to discover novel L-asparaginases with potential chemotherapeutic utility in ALL treatment. Detailed analysis of the active site geometry revealed structurally significant differences between HpA and other Lasparaginases that may be important for the biological activities of the enzyme and could be further exploited in protein engineering efforts.

Introduktionen av kärnkraften i Finland

Finlands industri har av tradition varit starkt energikrävande. Träförädlingsindustrin, som fick sin egentliga start i medlet på 1800-talet, använde stora mängder energi liksom metallförädlingsföretagen i ett senare skede. Krigstiden med sin energiransonering visade handgripligen för allmänheten liksom för specialisterna att en tillräcklig tillgång till energi är ett livsvillkor för vår industri och därmed för vårt land. Efterkrigstiden kännetecknades av en allt snabbare utbyggnad av den på vatten- och ångkraft baserade elkraftskapaciteten, en utbyggnad som den inhemska verkstadsindustrin i stor utsträckning deltog i. Men redan på 1950-talet var vattenkraften till stor del utbyggd, varför den privata såväl som den statliga sektorns intresse allt mera inriktade sig på den speciellt i USA favoriserade atomenergin. Efter fördjupade studier i kärnfysik och kärnteknik vid the International School of Nuclear Science and Engineering i USA deltog författaren av dessa rader intensivt (först som Ahlströmanställd och senare som VD för Finnatom) i den utvecklingsverksamhet inom det kärntekniska området som inte bara elproducenterna utan även verkstadsindustrin i vårt land genomförde. Det var därför naturligt för mig att som objekt för min doktorsavhandling välja introduktionen av kärnkraften i Finland med speciell fokus på den inhemska verkstadsindustrins roll. Jag ställde följande forskningsfrågor: a. När och hur skedde introduktionen av kärnkraften i Finland? b. Vilka var orsakerna till och resultatet av denna introduktion? c. Vilken var den inhemska verkstadsindustrins roll? Ett grundligt studium av litteraturen inklusive mötesprotokoll och tidningsreferat samt personligen genomförda intervjuer med ett trettiotal av de verkliga aktörerna i den långa och komplicerade introduktionsprocessen ledde till en teori, vars riktighet jag anser mig ha kunnat bevisa. Den inhemska verkstadsindustrins roll var synnerligen central. Dess representanter lyckades, bl.a. refererande till erfarenheterna från utbyggnaden av vatten- och ångkraften liksom till byggandet av den underkritiska milan YXP samt forskningsreaktorn TRIGA, övertyga beslutsfattarna om att den besatt nödig kompetens för att kompensera den kompetensbrist som kunde iakttas inom vissa områden hos den sovjetiska kärnkraftverksleverantören. De inhemska leveranserna påverkade även driftsresultatet, speciellt i fallet Lovisa, i positiv riktning. Introduktionsprocessen, som omfattade tiden från slutet av 1950-talet till början på 1980-talet, beskrevs, noterande bl.a. J. W. Creswells anvisningar, i detalj i avhandlingen. Introduktionen fick som resultat konkurrenskraftig elkraft, impuls till start av nya företag, exempelvis Nokia Elektronik, liksom en klar höjning av den tekniska nivån hos vår industri, inkluderande kärnteknisk tillverkning i stor skala. Katastrofen i Tjernobyl i slutet av april 1986 innebar emellertid att utvecklingen tog en paus på ett par decennier. Erfarenheterna från introduktionsfasen kan förhoppningsvis utnyttjas till fullo nu, när utbyggnaden av kärnkraften återupptagits i vårt land.

Vaihtosuuntaajan reaaliaikainen lämpömalli

Vaihtosuuntaajan IGBT-moduulin liitosten lämpötiloja ei voida suoraan mitata, joten niiden arviointiin tarvitaan reaaliaikainen lämpömalli. Tässä työssä on tavoitteena kehittää tähän tarkoitukseen C-kielellä implementoitu ratkaisu, joka on riittävän tarkka ja samalla mahdollisimman laskennallisesti tehokas. Ohjelmallisen toteutuksen täytyy myös sopia erilaisille moduulityypeille ja sen on tarvittaessa otettava huomioon saman moduulin muiden sirujen lämmittävä vaikutus toisiinsa. Kirjallisuuskatsauksen perusteella valitaan olemassa olevista lämpömalleista käytännön toteutuksen pohjaksi lämpöimpedanssimatriisiin perustuva malli. Lämpöimpedanssimatriisista tehdään Simulink-ohjelmalla s-tason simulointimalli, jota käytetään referenssinä muun muassa implementoinnin tarkkuuden verifiointiin. Lämpömalli tarvitsee tiedon vaihtosuuntaajan häviöistä, joten työssä on selvitetty eri vaihtoehtoja häviölaskentaan. Lämpömallin kehittäminen s-tason mallista valmiiksi C-kieliseksi koodiksi on kuvattu tarkasti. Ensin s-tason malli diskretoidaan z-tasoon. Z-tason siirtofunktiot muutetaan puolestaan ensimmäisen kertaluvun differenssiyhtälöiksi. Työssä kehitetty monen aikatason lämpömalli saadaan jakamalla ensimmäisen kertaluvun differenssiyhtälöt eri aikatasoille suoritettavaksi sen mukaan, mikä niiden kuvaileman termin vaatima päivitysnopeus on. Tällainen toteutus voi parhaimmillaan kuluttaa alle viidesosan kellojaksoja verrattuna suoraviivaiseen yhden aikatason toteutukseen. Implementoinnin tarkkuus on hyvä. Implementoinnin vaatimia suoritusaikoja testattiin Texas Instrumentsin TMS320C6727- prosessorilla (300 MHz). Esimerkkimallin laskemisen määritettiin kuluttavan vaihtosuuntaajan toimiessa 5 kHz kytkentätaajuudella vain 0,4 % prosessorin kellojaksoista. Toteutuksen tarkkuus ja laskentakapasiteetin vähäinen vaatimus mahdollistavat lämpömallin käyttämisen lämpösuojaukseen ja lisäämisen osaksi muuta jo prosessorilla olemassa olevaa systeemiä.

ZigBee-verkot ja evaluointilaitteen suunnittelu

In this thesis a closer look at ZigBee wireless network protocol was made and a ZigBee evaluation device was designed and built for testing it. ZigBee is a digital wireless network technology published in 2004, which was developed for wireless control and automation systems. It is based on the IEEE 802.15.4-2003 standard, and its aim was to create a reliable wireless networking protocol with secure data transmissions, low power consumption and low manufacturing costs. The low power consumption requirement has also led to a slow data rate and a short range, but in a ZigBee network individual network devices can route messages to each other, so short range is not a problem. In automation and control systems a fast data rate is not usually an important requirement either. ZigBee network can form automatically and one ZigBee network can theoretically include thousands of devices, all of which can communicate with each other. ZigBee network is also self-healing, so an individual device dropping out of the network, like breaking down, does not affect functionality of the network. Evaluation device was designed and implemented in four different versions, which were tested with six different antenna designs. All antennas were tested at a range of 100 meters in an open terrain using two different frequencies and transmission powers. Also a range test was performed for selected antennas using transmission power of 4,5 dBm, which was maximum power of the ZigBee chip used in the evaluation device. Range test resulted in a measured range of several hundred meters, which can be considered as a good result for a short-range technology.

Metsähakkeeseen liittyvä liiketoiminta Keski-Suomessa

Tämän työn ensisijaisena tavoitteena on keskisuomalaisen metsähakeliiketoiminnan arvoverkon kuvaaminen, sisältäen keskeiset toimijat ja toiminnot sekä näkemyksiä innovaatiokyvykkyydestä ja informaatiosta. Toinen tavoite on uusien liiketoimintamallien esittäminen. Työ jakautuu teoreettiseen ja empiiriseen osaan. Teoreettisessa osiossa esitetään Porterin (1984) arvojärjestelmä ja Parolinin (1999) arvoverkko. Näiden avulla kuvaillaan empiirisessä osiossa selvitettyjä arvoverkon keskeisiä ominaisuuksia. Innovaatioon liittyvä teoria pohjautuu pääosin innovaatiojärjestelmän, avoimen innovaation ja käytäntölähtöisen innovaatioteorian pohjalle (Harmaakorpi ja Melkas 2008). Liiketoimintamahdollisuuksien tarkastelu perustuu usean erillisen teoreettisen viitekehyksen yhdistelmään. Empiirisen osuuden materiaali on kerätty yritys- ja asiantuntijahaastattelut. Haastattelut on suoritettu kvalitatiivisen tapaustutkimuksen tyyliin, teemahaastatteluin. Laadullisesta materiaalista rakennetut kuvaukset nojaavat vankasti työn teoreettiseen osuuteen.

Videolaparoscopia no trauma abdominal

Despite the use of laparoscopy in abdominal trauma for several decades, it was only after the advent of video chip camera that an explosion of interest ocurred, giving rise to possibilities and perspectives not only in diagnosis but also in therapeutics. In trauma, its use has been gradually defined and experience has shown the benefits of the method in early diagnosis of visceral injuries as well as avoiding unnecessary laparotomies. Trauma laparoscopy is a safe method, can reduce negative and nontherapeutic laparotomies. The worrisome failure of laparoscopy to detect gastrintestinal injuries, specially small bowel lesions can be avoided with a mandatory and apropriated "run bowel" exploration. We believe that in hemodinamically stable patients, video laparoscopy is safely indicated in some situations in trauma, such as evaluation of diaphragmatic injuries in thoraco abdominal stab wounds and tangential gunshot wounds of anterior abdominal wall.

Improving strategic decision-making with simulation based decision support systems

Combating climate change is one of the key tasks of humanity in the 21st century. One of the leading causes is carbon dioxide emissions due to usage of fossil fuels. Renewable energy sources should be used instead of relying on oil, gas, and coal. In Finland a significant amount of energy is produced using wood. The usage of wood chips is expected to increase in the future significantly, over 60 %. The aim of this research is to improve understanding over the costs of wood chip supply chains. This is conducted by utilizing simulation as the main research method. The simulation model utilizes both agent-based modelling and discrete event simulation to imitate the wood chip supply chain. This thesis concentrates on the usage of simulation based decision support systems in strategic decision-making. The simulation model is part of a decision support system, which connects the simulation model to databases but also provides a graphical user interface for the decisionmaker. The main analysis conducted with the decision support system concentrates on comparing a traditional supply chain to a supply chain utilizing specialized containers. According to the analysis, the container supply chain is able to have smaller costs than the traditional supply chain. Also, a container supply chain can be more easily scaled up due to faster emptying operations. Initially the container operations would only supply part of the fuel needs of a power plant and it would complement the current supply chain. The model can be expanded to include intermodal supply chains as due to increased demand in the future there is not enough wood chips located close to current and future power plants.

Exploration and Design of Power-Efficient Networked Many-Core Systems

Multiprocessing is a promising solution to meet the requirements of near future applications. To get full benefit from parallel processing, a manycore system needs efficient, on-chip communication architecture. Networkon- Chip (NoC) is a general purpose communication concept that offers highthroughput, reduced power consumption, and keeps complexity in check by a regular composition of basic building blocks. This thesis presents power efficient communication approaches for networked many-core systems. We address a range of issues being important for designing power-efficient manycore systems at two different levels: the network-level and the router-level. From the network-level point of view, exploiting state-of-the-art concepts such as Globally Asynchronous Locally Synchronous (GALS), Voltage/ Frequency Island (VFI), and 3D Networks-on-Chip approaches may be a solution to the excessive power consumption demanded by today’s and future many-core systems. To this end, a low-cost 3D NoC architecture, based on high-speed GALS-based vertical channels, is proposed to mitigate high peak temperatures, power densities, and area footprints of vertical interconnects in 3D ICs. To further exploit the beneficial feature of a negligible inter-layer distance of 3D ICs, we propose a novel hybridization scheme for inter-layer communication. In addition, an efficient adaptive routing algorithm is presented which enables congestion-aware and reliable communication for the hybridized NoC architecture. An integrated monitoring and management platform on top of this architecture is also developed in order to implement more scalable power optimization techniques. From the router-level perspective, four design styles for implementing power-efficient reconfigurable interfaces in VFI-based NoC systems are proposed. To enhance the utilization of virtual channel buffers and to manage their power consumption, a partial virtual channel sharing method for NoC routers is devised and implemented. Extensive experiments with synthetic and real benchmarks show significant power savings and mitigated hotspots with similar performance compared to latest NoC architectures. The thesis concludes that careful codesigned elements from different network levels enable considerable power savings for many-core systems.