Chemoenzymatic Synthesis of Chiral Organosulfur Compounds

This thesis is primarily concerned with the enzyme- catalysed synthesis of sulfoxides using reductase and dioxygenase enzymes. Chapter 1 provides an introduction to the topic of redox chemistry with particular emphasis on the application of reductase and dioxygenase enzymes in organosulfur chemistry. Earlier literature methods for the production of enantiopure sulfoxides are reviewed. A brief discussion of the methods used for the determination of enantiomeric excess and absolute configuration is provided. Chapter 2 contains results obtained using a range of whole-cell bacteria each using a dimethyl sulfoxide reductase enzyme. The synthesis of a series of racemic sulfoxides and the development of appropriate CSPHPLC analytical methods is discussed. Kinetic resolutions of a series of sulfoxides have been achieved. Chapter 3 contains a presentation of results using dioxygenase enzymes as biocatalysts for the asymmetric sulfoxidation of dialkyl sulfoxides including thioacetal sulfoxides. A new range of monosulfoxides, cis-dihydrodiols and cis- dihydrodiol sulfoxides have been isolated in enantiopure form. Chapter 4 is focussed on the application of chiral sulfoxides in synthesis. A new chemoenzymatic route to diol sulfoxide enantiomers and the derived enantiopure phenols and catechols is discussed. The application of chemically synthesised sulfoxide enantiomers in the production of hydroxy sulfoxides is reported. Chapter 5 provides a full experimental section where the synthesis of sulfides and racemic sulfoxides is included. The methods used in the isolation and characterisation of bioproducts from the biotransformation are discussed and full experimental details given.

Hintakartelli toistettuna pelinä: teoriasta pääkaupunkiseudun bensiinin vähittäismyyntimarkkinoille

Tutkielman tarkoituksena oli soveltaa toistetun pelin teoria- ja empiriapohjaa suomalaiseen tutkimusaineistoon. Kartellin toimintadynamiikka on mallinnettu peliteorian osa-alueen, toistetun pelin kentäksi. Toistetussa pelissä samaa, kerran pelattua peliä pelataan useita kierroksia. Äärettömästi toistetusta pelistä muodostuu toistetun pelin yleinen teoria (The Folk Theorem), jossa jokaisella pelaajalla on yksilöllisesti rationaalinen käytössykli. Toisen pelaajan kanssa tehty yhteistyö kasvattaa pelaajan käytössykliltä kertyvää kokonaishyötyä. Kartellitutkimuksessa ei voi ohittaa oikeustieteellistä näkökulmaa, joten sekin on tiivistetysti mukana esityksessä. Äänettömässä tai implisiittisessä kartellissa ( tacit collusion ) ei avoimen kartellin tavoin ole osapuolten välistä kommunikointia, mutta sen lopputulos on sama. Tästä syystä äänetön kartelli on yhdenmukaistettuna käytöksenä kielletty. Koska myös tunnusmerkit ovat osin samat, kartellitutkimus on saanut arvokasta mittausaineistoa paljastuneiden kartellien käytöksestä. Pelkkään hintatiedostoonkin perustuvalla tutkimuksella on vankka teoreettinen ja empiirinen pohja. Oikeuskirjallisuudessa ja käytännössä hintayhteneväisyyden on yhdessä muiden tunnusmerkkien kanssa katsottu olevan indisio kartellista. Bensiinin vähittäismyyntimarkkinat ovat rakenteellisesti otollinen kenttä toistetulle pelille. Tutkielman empiirisessä osuudessa kohteena olivat pääkaupunkiseudun bensiinin vähittäismyyntimarkkinat ja tiedosto sisälsi otoksia hinta-aikasarjoista ajalta 1.8.2004 - 30.6.2005 kaikkiaan 116:ltä jakeluasemalta Espoosta, Helsingistä ja Vantaalta. Tutkimusmenetelmänä oli toistettujen mittausten varianssianalyysi post hoc-vertailuin. Tilastollisesti merkitsevä hinnoitteluyhtenevyys lähellä sijaitsevien asemien kesken löytyi 47 asemalta, ja näin ollen näillä asemilla on yksi kartellin tunnusmerkeistä. Hinnoitteluyhtenevyyden omaavat asemat muodostivat liikenneyhteyksien mukaan jaetuilla kilpailualueillaan ryhmittymiä ja kaikkiaan tällaisia yhtenevästi hinnoittelevia ryhmittymiä oli 21. Näistä ryhmittymistä 9 oli ns. sekapareja eli osapuolina olivat kylmäasema ja liikenneasema. Useimmissa tapauksissa oli kyseessä alueensa kalleimmin hinnoitteleva kylmäasema. Tutkielman tärkeimmät lähteet: Abrantes-Metz, Rosa M. – Froeb, Luke M. – Geweke, John F. – Taylor, Cristopher T. (2005): A Variance screen for collusion. Working paper no. 275, Bureau of economics, Federal Trade Commission, Washington DC 20580. Dutta, Prajit K. (1999): Strategies and Games, Theory and Practice. The MIT Press, Cambridge, Massachusetts, London, England. Harrington, Joseph E. (2004): Detecting cartels. Working paper. John Hopkins University. Ivaldi, Marc – Jullien, Bruno – Rey, Patric – Seabright, Paul – Tirole, Jean (2003): The Economics of Tacit Collusion. EU:n komission kilpailun pääosaston julkaisu. Phlips, Louis (1996): On the detection of collusion and predation. European Economic Review 40 (1996), 495–510.

Tekopohjavesi ja sen valmistamista haittaava suodatinaineksen tukkeutuminen

Artificial recharge and clogging process.

Kinetics of propellant decomposition

Equations for solid-state decompositions which are controlled by the phase-boundary movement and nucleation have been examined using ammonium perchlorate/polystyrene propellant decomposition at 503 K and 533 K. It was found that 3 different equations governed by the nucleation process show a good fit of data at these temperatures. However, the best fit was obtained for the following Avrami-Erofeev equation, [-In (1 - α]1/4=kt.

Removal of hexavalent chromium using coffee husk

The potential to remove chromium(VI) from aqueous solutions through biosorption using coffee husk was investigated. The effects of pH, contact time, initial concentration and adsorbent dosage on the adsorption of Cr(VI) were studied. The data obeyed Langmuir and Freundlich adsorption isotherms. The Langmuir adsorption capacity was found to be 44.95 mg/g. The Freundlich constants K-f and n were 1.027 mg/g (litre/mg)(n)] and 1.493, respectively. Desorption studies indicated the removal of 60% of the hexavalent chromium. Infrared spectral studies revealed the presence of functional groups, such as hydroxyl and carboxyl groups, on the surface of the biomass, which facilitates biosorption of Cr(VI).

Frequency-comb-referenced molecular spectroscopy in the mid-infrared region

A simple method for absolute frequency measurements of molecular transitions in the mid-infrared region is reported. The method is based on a cw singly-resonant optical parametric oscillator (SRO), which is tunable from 3.2 to 3.45 µm. The mid- infrared frequency of the SRO is referenced to an optical frequency comb through its pump and signal beams. Sub-Doppler spectroscopy and absolute frequency measurement of the P(7) transition of the ν3 band of CH4 are demonstrated.

Analysis of Compressibility of Sensitive Soils

Sensitive soils, in general, are prone to mechanical disturbances while sampling, handling, and testing. This necessitates the prediction of true field behavior. The compressibility response of such soils is typical of having three zones, mechanistically explained as nonparticulate, transitional, and particulate. Such zoning has enabled the development of a simple method to predict the field compressibility response of the sample. The field compression curve with sigmact act as the most probable yield stress is considered to reflect 0% disturbance. By a comparison of experimentally determined sigmac and sigmact, it is possible to estimate the degree of sample disturbance. When the value of sigmac is closer to sigmact, the sampling disturbance approaches zero. As the value of sigmac reduces, the degree of sampling disturbance increases. The possibility of using this degree of sample disturbance from compressibility data to obtain other true properties from laboratory results of the sampled specimens has been examined.

Ultimate Strength of RC Wall Panels with Openings

Test results of 12 reinforced concrete (RC) wall panels with openings are presented. The panels have been subjected to in-plane vertical loads applied at an eccentricity to represent possible accidental eccentricity that occurs in practice due to constructional imperfections. The 12 specimens consist of two identical groups of six panels each. One group of panels is tested in one-way in-plane action (i.e., supported at top and bottom edges against lateral displacement). The second group of panels is tested in two-way in-plane action (i.e., supported on all the four edges against lateral displacement). Openings in the panels represent typical door and window openings. Cracking loads, ultimate loads, crack patterns, and lateral deflections of the panels are studied. Empirical methods have been developed for the prediction of ultimate load. Also, lateral deflections, cracking loads, and ultimate loads of identical loads tested under one-way and two-way action are compared.

Ultimate Strength of R.C. Wall Panels in Two-Way In-Plane Action

Test results of 24 reinforced concrete wall panels in two-way action (i.e., supported on all the four sides) and subjected to in-plane vertical load are presented. The load is applied at an eccentricity to represent possible accidental eccentricity that occurs in practice due to constructional imperfections. Influences of aspect ratio, thinness ratio, slendemess ratio, vertical steel, and horizontal steel on the ultimate load are studied. Two equations are proposed to predict the ultimate load carried by the panels. The first equation is empirical and is arrived at from trial and error fitting with test data. The second equation is semi-empirical and is developed from a modification of the buckling strength of thin rectangular plates. Both the equations are formulated so as to give a safe prediction of a large portion of ultimate strength test results. Also, ultimate load cracking load and lateral deflections of identical panels in two-way action (all four sides supported) and oneway action (top and bottom sides only supported) are compared.

Stiffness Coefficients of Layered Soil Systems

One of the most important dynamic properties required in the design of machine foundations is the stiffness or spring constant of the supporting soil. For a layered soil system, the stiffness obtained from an idealization of soils underneath as springs in series gives the same value of stiffness regardless of the location and extent of individual soil layers with respect to the base of the foundation. This paper aims to develop the importance of the relative positioning of soil layers and their thickness beneath the foundation. A simple and approximate procedure called the weighted average method has been proposed to obtain the equivalent stiffness of a layered soil system knowing the individual values of the layers, their relative position with respect to foundation base, and their thicknesses. The theoretically estimated values from the weighted average method are compared with those obtained by conducting field vibration tests using a square footing over different two- and three-layered systems and are found to be very good. The tests were conducted over a range of static and dynamic loads using three different materials. The results are also compared with the existing methods available in the literature.

Improved Inverted V-Notch or Chimney Weir

This paper is devoted to the improvement of the measuring range of inverted V-notch (IVN) weir, a practical linear sharp-crested weir, designed earlier by the writers. The range of linearity of IVN can be considerably enhanced (by more than 200%) by the addition of a retangular weir of width 0.265W (W = half crest width) at a depth of 0.735d (d = altitude of IVN), above the crest of the weir, which is equivalent to providing at this depth two vertical straight lines to the IVN, resulting in a chimney-shaped profile; hence, the modified weir is named chimney weir. The design parameters of the weir, that is, the linearity range, base flow depth, and datum constant, which fixes the reference plane of the weir, are estimated by solving the nonlinear programming problem using a numerical optimization procedure. For flows through this weir above a depth of 0.22d, the discharges are proportional to the depth of flow measured above a reference plane situated at 0.08d above the weir crest for all heads in the range 0.22d <= h <= 2.43d, within a maximum percentage deviation of ±1.5 from the theoretical discharge. A significant result of the analysis is that the same linear head-discharge relationship governing the flow through the IVN is also valid for the extended chimney weir. Experiments with three different chimney weirs show excellent agreement with the theory by giving a constant average coefficient of discharge for each weir.

Critical Reappraisal of Colloidal Activity of Clays

Soil properties and their behavior, apart from stress history, are influence markedly by physicochemical characteristics of the constituent clay and nonclay minerals and their relative proportions. Atterberg limits and Skempton's colloidal activity, which are simple quantitative parameters, reflect the composite effects of the soil constituents and their interactions with pore fluid. Micromechanistic interpretations of these parameters have been provided in this paper. It has been shown that, in general, the liquid limit of fine-grained soils reflects the physicochemical potential and that each of the factors of Skempton's colloidal activity are interdependent. It has been illustrated that property correlations with colloidal activity, as well as with Atterberg limits, result in involved interrelationships due to the interdependence of the parameters.

Nature of chemistry in the national frame curricula for upper secondary education in Finland, Norway and Sweden

The aim of this study was to discover how current chemistry syllabi in the frame curricula for up- per secondary education in three Nordic countries (Finland, Norway, and Sweden) take into account topics related to the nature of chemistry. By qualitative content analysis, the statements related to the nature of chemistry were divided into categories. Conclusions and implications for improving the frame curricula under study were made by comparing results with research into the nature of science. Chemistry syllabi from the Nordic frame curricula analyzed take into account the aims related to the nature of chemistry in a very similar manner. The ideas that should be made more explicit in all of the analyzed curricula are: i) the limits of the chemical models and theories, ii) the relationship between chemistry and other natural sciences, iii) the importance of creativity in chemical research, iv) the concepts of evidence in science texts, v) the social nature of chemical research, and vi) chemistry as a technological practice.