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  • 1.
    Azhdar, Bruska
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Yu, Wenbin
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Reitberger, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Gedde, Ulf
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    A new method for assessing the efficiency of stabilizers in polyolefins exposed to chlorinated water media2009In: Polymer testing, ISSN 0142-9418, E-ISSN 1873-2348, Vol. 28, no 6, p. 661-667Article in journal (Refereed)
    Abstract [en]

    The chlorine used as disinfectant in tap water degrades most materials, including polyethylene. The most adequate (functional) test method, the pressure test, is complicated and expensive because the chlorinated aqueous media (Cl-2 or ClO2 in water) are unstable and they undergo reactions that are dependent on the pH. A new method which assesses the protection efficiency of phenolic antioxidants in polyolefins was developed. The method uses a liquid hydrocarbon analogue, squalane, in which antioxidants are dissolved. The organic phase was dispersed in the aqueous chlorinated phase (containing 10 ppm of either Cl-2 or ClO2; pH=6.8) at 70 degrees C by intense stirring. The depletion of antioxidant (Irganox 1010) was monitored by standard DSC determination of the oxidation induction time. It was shown that 300 min of exposure was sufficient to obtain useful data.

  • 2. Bauer, Georg
    et al.
    Chatgilialoglu, Chryssostomos
    Gebicki, Jerzy L.
    Gebicka, Lidia
    Gescheidt, Georg
    Golding, Bernard T.
    Goldstein, Sara
    Kaizer, Jozsef
    Merenyi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Speier, Gabor
    Wardman, Peter
    Biologically relevant small radicals2008In: Chimia (Basel), ISSN 0009-4293, Vol. 62, no 9, p. 704-712Article in journal (Refereed)
    Abstract [en]

    Biologically relevant small radicals are at the focus of the working group 4 (WG4) of the COST Action CM0603 (Free Radicals in Chemical Biology, CHEMBIORADICAL). This article surveys the areas of research being undertaken by the partners in WG4. The character of the radicals is described together with experimental techniques utilized to follow their structure and reactivity. Specifically, C-, S-, N- and O-centered radicals of small size, and their interaction with different biomolecules are described. Processes at the molecular level exemplifying important biological signaling and damaging pathways are introduced.

  • 3.
    Bergenudd, Helena
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Investigation of the ATRP process through simulations - predicting the limit of controlManuscript (preprint) (Other academic)
    Abstract [en]

    The limit for when a well controlled atom transfer radical polymerization (ATRP) system can be obtained is described based on the results from kinetic simulations where the ATRP equilibrium constant, KATRP, is varied and the rates and degree of control in different ATRP systems are evaluated. The apparent rate constant, kpapp, increases with increasing KATRP, but a maximum is reached where after kpapp decreases as the result of a large degree of initial terminations due to the strong shift of the equilibrium towards the active species. Before the maximum is reached as KATRP is increased, the limit of control is passed, i.e. when KATRP is increased further, apparent first order kinetics and well controlled molecular weights will no longer be obtained. The equilibrium constant at which the limit of control is reached varies linearly with the propagation rate constant. This enables the design of well controlled ATRP systems based on the knowledge of the propagation rate constant and KATRP. The influence of the conversion and chain length dependence of the termination rate constant on the simulation results is also discussed. The kpappKATRP trend shown in the simulations is confirmed by comparing with previous experimental results.

  • 4.
    Bergenudd, Helena
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Understanding the mechanisms behind atom transfer radical polymerization: exploring the limit of control2011Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Atom transfer radical polymerization (ATRP) is one of the most commonly employed techniques for controlled radical polymerization. ATRP has great potential for the development of new materials due to the ability to control molecular weight and polymer architecture. To fully utilize the potential of ATRP as polymerization technique, the mechanism and the dynamics of the ATRP equilibrium must be well understood.

    In this thesis, various aspects of the ATRP process are explored through both laboratory experiments and computer modeling. Solvent effects, the limit of control and the use of iron as the mediator have been investigated. It was shown for copper mediated ATRP that the redox properties of the mediator and the polymerization properties were significantly affected by the solvent. As expected, the apparent rate constant (kpapp) increased with increasing activity of the mediator, but an upper limit was reached, where after kpapp was practically independent of the mediator potential. The degree of control deteriorated as the limit was approached.

    In the simulations, which were based on the thermodynamic properties of the ATRP equilibrium, the same trend of increasing kpapp with increasing mediator activity was seen and a maximum was also reached. The simulation results could be used to describe the limit of control. The maximum equilibrium constant for controlled ATRP was correlated to the propagation rate constant, which enables the design of controlled ATRP systems.

    Using iron compounds instead of copper compounds as mediators in ATRP is attractive from environmental aspects. Two systems with iron were investigated. Firstly, iron/EDTA was investigated as mediator as its redox properties are within a suitable range for controlled ATRP. The polymerization of styrene was heterogeneous, where the rate limiting step is the adsorption of the dormant species to the mediator surface. The polymerizations were not controlled and it is possible that they had some cationic character.

    In the second iron system, the intention was to investigate how different ligands affect the properties of an ATRP system with iron. Due to competitive coordination of the solvent, DMF, the redox and polymeri­zation properties were not significantly affected by the ligands. The differences between normal and reverse ATRP of MMA, such as the degree of control, were the result of different FeIII speciation in the two systems.

  • 5.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Coullerez, Geraldine
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Malmström, Eva E.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Solvent Effects on ATRP of Oligo(ethylene glycol) Methacrylate. Exploring the Limits of Control2009In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 42, no 9, p. 3302-3308Article in journal (Refereed)
    Abstract [en]

    Five copper complexes in combination with six monomer-solvent mixtures have been used to investigate the solvent effects oil ATRP of oligo(ethylene glycol) methacrylate (OEGMA). The redox properties of the copper complexes in OEGMA-solvent mixtures and the apparent rate constants (k(p)(app)) for ATRP of OEGMA were correlated to the degree of control over the polymerizations. Based on this correlation, a general discussion of the limits of control in ATRIP is carried out. One of the key parameters for control in ATRP is the propagation rate constant, making the choice of monomer essential for the design of ail ATRP system. Also, the solvent effects oil the ATRP equilibrium constant (K-ATRP) affect the limit of control (i.e., the apparent rate constant above which control is lost). The choice of copper complex is also more important than the choice of solvent for the design of a well-controlled ATRP system.

  • 6.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Investigation of iron complexes in ATRP: Indications of different iron species in normal and reverse ATRP2011In: Journal of Molecular Catalysis A: Chemical, ISSN 1381-1169, E-ISSN 1873-314X, Vol. 346, no 1-2, p. 20-28Article in journal (Refereed)
    Abstract [en]

    In an attempt to correlate the ATRP kinetics and the redox properties of the mediator, eight iron complexes with nitrogen, phosphorous and carboxylic acid containing ligands were investigated by electrochemical measurements and by using them as mediators in normal and reverse ATRP of MMA in DMF. The redox properties of the iron complexes in DMF, measured by cyclic voltammetry, did not differ significantly, which was reflected in the ATRP kinetics as the apparent rate constants were practically the same with all the complexing ligands. The degree of control over the polymerization was, however, much improved in reverse ATRP as compared to normal ATRP. In this ATRP system, the ligand type is not crucial for the redox or polymerization properties. Several observations indicate that the iron species in the two systems were not the same, the Fe(III) species resulting from oxidation of Fe(II) in normal ATRP is different from the starting Fe(III) species in reverse ATRP.

  • 7.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Predicting the Limit of Control in the ATRP Process: Results from Kinetic Simulations2011In: Macromolecular Theory and Simulations, ISSN 1022-1344, E-ISSN 1521-3919, Vol. 20, no 9, p. 814-825Article in journal (Refereed)
    Abstract [en]

    Kinetic simulations are reported, where the ATRP equilibrium constant K(ATRP) is varied and the rates and degree of control in different ATRP systems are evaluated. The apparent rate constant k(app) increases with increasing K(ATRP), but a maximum is reached. The limit of control is passed before the maximum, i.e. when K(ATRP) is increased further, apparent first-order kinetics and well-controlled molecular weights will no longer be obtained. The equilibrium constant at which the limit of control is reached varies linearly with the propagation rate constant. This enables the design of well controlled ATRP systems. The influence of the conversion and chain length dependence of the termination rate constant on the simulation results is discussed.

  • 8.
    Bergenudd, Helena
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Nyström, Daniel
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Heterogeneous iron(II)-chloride mediated radical polymerization of styrene2009In: Journal of Molecular Catalysis A: Chemical, ISSN 1381-1169, E-ISSN 1873-314X, Vol. 306, no 1-2, p. 69-76Article in journal (Refereed)
    Abstract [en]

    In an attempt to perform atom transfer radical polymerization (ATRP) with a more environmentally friendly mediator, polymerization of styrene in the presence of iron(II)-chloride and EDTA was explored from a mechanistic point of view. The presence of EDTA, which normally can form a complex with FeCl2, had no influence on the polymerization results as both the mediator and EDTA were insoluble in the polymerization medium. A mechanism is suggested for the heterogeneous polymerization of styrene mediated by iron (II)-chloride in p-xylene at 50 °C. Varying the mediator amount more than 10-fold revealed that the rate limiting step at low mediator amounts was the adsorption of the initiator or dormant polymer to the mediator surface, whereas at higher mediator amounts, the rate limiting step was instead the activation step in the ATRP equilibrium. The mechanism changed to free radical polymerization in solution at a certain conversion, resulting in lower apparent rate constant and an increased amount of transfer and termination reactions. Chain extension with MMA showed that a significant proportion of the polymer chain ends were active also at high conversions.

  • 9.
    Blomberg, Eva
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
    Lundin, Maria
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Layer-by-Layer Assembly of Biomacromolecules2011In: Encyclopedia of Surface and Colloid Science, SecondEdition / [ed] P. Somasundaran, London: Taylor & Francis, 2011, 1, p. 1-14Chapter in book (Refereed)
    Abstract [en]

    The ability to construct thin films with controlled thickness on almost any type of surface is of great interestin many research fields. For biomedical applications, thin films on medical devices have been found toimprove the biocompatibility, reduce the immunological response, and deliver medical drugs locally. Thelayer structure is closely related to the function and efficiency of such films. During the last decades, it hasbeen shown that the layer-by-layer (LbL) assembly of charged macromolecules has created an inexpensiveroute to the formation of thin multilayer films, and the interest in using biomacromolecules (e.g., polysaccharidesand proteins) has emerged in recent years. The LbL technique offers unique opportunities forcontrolling the physical properties of thin surface layers, such as film thickness, chemical and elasticproperties, and stability. In this entry, we will focus on recent advances in the multilayer film area usingbiomacromolecules. We will discuss how different physicochemical properties of biomacromolecules andof the deposition solution affect the formation and structure of LbL-assembled multilayer. Finally, we willaddress some suggested applications for these biopolymer film coatings.

  • 10.
    Brinck, Tore
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
    Haeberlein, Markus
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    A Computational Analysis of Substituent Effects on the O-H Bond Dissociation Energy in Phenols: Polar Versus Radical Effects1997In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 119, no 18, p. 4239-4244Article in journal (Refereed)
  • 11.
    Brinck, Tore
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
    Lee, Hau-Nan
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Physical Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Quantum Chemical Studies on the Thermochemistry of Alkyl and Peroxyl Radicals.1999In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 103, p. 7094-7104-Article in journal (Refereed)
  • 12.
    Carlsson, Magnus
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    The inter-and intramolecular selectivity of the carbonate radical anion in its reactions with lignin and carbohydrates2005Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    In the present thesis, the effects of the carbonate radical anion on lignin and cellulose were investigated.

    The carbonate radical has a rather high reactivity towards aromatic lignin constituents. It reacts especially fast with phenolates. All these reactions occur by way of electron transfer. Small carbohydrates react with CO3 •- much slower than aromatics. These reactions are hydrogen transfer reactions. However, in very basic media, where the carbohydrates deprotonate to some extent, their anions react with CO3 •- by way of electron transfer and the rates approach those of non-phenolic aromatics. These findings suggest that in neutral or slightly alkaline media CO3 •- might serve as an excellent delignifying agent of pulp down to very low lignin contents. With small carbohydrates possessing one or two glucosidic bonds, CO3 •- abstracts hydrogen predominantly from C1 – H bonds, which results in rupture of the glucosidic linkage. Interestingly, however, the glucosidic bonds in cotton linters are rather resistent towards CO3 •-. This has probably morphological reasons. These results imply that, even at very low lignin contents, where CO3 •- is bound to react with cellulose, the reactions will not lead to substantial decrease in pulp viscosity.

    At present the cheapest and most practical way of producing CO3 •- radicals in the presence of pulp is to mix the latter with peroxynitrite and CO2. We have performed such experiments on pulp with very promising results. The Kappa number decreased substantially, brightness increased, while the viscosity remained high. This confirms the predicted excellent properties of the carbonate radical.

    However, before the peroxynitrite method can be implemented in the pulp industry, a number of technical problems has to be solved. Chief among them is a slow and steady dosage of peroxynitrite to minimise side reactions of the radicals with peroxynitrite and the nitrite impurity. The fate of the NO2 radical, the coproduct of CO3 •-, has also to be assessed. NO2 will probably have to be removed by vigorous degassing in order to block the possible nitration of cellulose.

  • 13.
    Carlsson, Magnus
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Lind, Johan
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Merényi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    A selectivity study of reaction of the carbonate radical anion with methyl beta- D-cellobioside and methyl beta-D-glucoside in oxygenated aqueous solutions2006In: Holzforschung, ISSN 0018-3830, E-ISSN 1437-434X, Vol. 60, no 2, p. 130-136Article in journal (Refereed)
    Abstract [en]

    In the presence of oxygen, radiolytically generated carbonate radical anions, CO3.-, were reacted with methyl beta-D-cellobioside and methyl beta-D-glucoside. From the ensuing product pattern, it was concluded that CO3 center dot- abstracts hydrogen atoms predominantly from glucosidic C1 - H bonds. This high intramolecular selectivity was rationalised mainly in terms of a polar effect on the transition state of the hydrogen abstraction reaction. The present findings are in sharp contrast to the relative inertness of CO3(center dot-) towards glucosidic C1 - H bonds previously observed in cotton linters. The reasons for this discrepancy are discussed in light of a possible future role of CO3 center dot- as a bleaching agent for pulp.

  • 14.
    Carlsson, Magnus
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Oscarson, Stefan
    Kenne, Lennart
    Andersson, Rolf
    Reitberger, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    D-gluco-Hexodialdose in Aqueous Solution: Determination of the Main Forms by NMR spectroscopyManuscript (preprint) (Other academic)
  • 15.
    Carlsson, Magnus
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Stenman, David
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Merényi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Reitberger, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    A comparative study on the degradation of cotton linters induced by carbonate and hydroxyl radicals generated from peroxynitrite2005In: Holzforschung, ISSN 0018-3830, E-ISSN 1437-434X, Vol. 59, no 2, p. 132-142Article in journal (Refereed)
    Abstract [en]

    Carbonate (CO3.(-)) and hydroxyl (HO.) radicals were chemically produced in cotton linter suspensions using peroxynitrite as a radical precursor. Both radicals could degrade cotton linters, as shown by viscosity and GPC-SEC measurements. As evidenced by the viscosity measurements, the presence of oxygen during the cotton linter treatments slightly increased cellulose degradation by both radicals. For the carbonate radical, more than 90% of the viscosity losses could be recovered by reductive NaBH4 treatment before measuring the viscosity, whereas only approximately 40% of the viscosity was recovered after hydroxyl radical degradation and subsequent NaBH4 treatment. This indicates that carbonate radicals mainly abstract H-atoms adjacent to hydroxyl groups, i.e., at C-2, C-3 and C-6. This intramolecular selectivity may reflect a polar effect, whereby hydrogen atom abstractions from these positions are favoured. In addition, abstraction at C-6 would be sterically and statistically favoured.

  • 16.
    Carlsson, Magnus
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Stenman, David
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Merényi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Reitberger, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    The Carbonate Radical as One-Electron Oxidant of Carbohydrates in Alkaline media2005In: Holzforschung, ISSN 0018-3830, E-ISSN 1437-434X, Vol. 59, no 2, p. 143-146Article in journal (Refereed)
    Abstract [en]

    The mechanism by which the carbonate radical anion reacts with D-glucose in alkaline aqueous solutions has been studied by means of gamma-radiolysis. From the product analysis it is concluded that the reaction sequence is initiated by a one-electron transfer between the carbonate radical anion and deprotonated D-glucose. In the presence of molecular oxygen, the major, if not only products of this reaction sequence are formic acid, arabinose and gluconic acid and reaction schemes are proposed to account for the observed formation of these products.

  • 17. Cera, E.
    et al.
    Grivé, M.
    Bruno, J.
    Eriksen, Trygve E.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Modelling experimental results on radiolytic processes at the spent fuel water interface. II. Radionuclides release2006In: Mater Res Soc Symp Proc, 2006, p. 537-546Conference paper (Refereed)
    Abstract [en]

    Experimental and modelling efforts in the last decade in the frame of nuclear waste management field have been focused on studying the role of the UO2 surfaces in poising the redox state of solid/water systems as well as the radionuclides release behaviour. For this purpose, an experimental programme was developed consisting on dissolution experiments with PWR spent fuel fragments in an anoxic environment and by using different solution compositions. Some of the collected data has been previously published [1], specifically those data concerning radiolysis products and dissolution of the matrix. The results and the modelling tasks indicated an overall balance of the generated radiolytic species and that uranium dissolution was controlled by the oxidation of the spent fuel matrix in 10mM bicarbonate solutions while in the tests carried out at lower or without carbonate concentrations uranium in the aqueous phase was governed by the precipitation of schoepite. This paper is the continuation of a series accounting for the data and modelling work related to investigating the release behaviour of minor radionuclides from the spent fuel. Uranium concentrations as a function of time showed an initial increase until reaching a steady stale, indicating a matrix dissolution control. The same behaviour is observed for neptunium, caesium, strontium, technetium and molybdenum indicating a congruent release of these elements with the major component of the fuel matrix. On the other hand, no clear tendency is observed for plutonium data where additional solubility limiting mechanisms may apply. Kinetic modelling of the trace elements: caesium, strontium, technetium and molybdenum is based on the congruent release of these elements with the major component of the fuel matrix. Rate constants have been determined. Kinetic modelling of neptunium data took also into account the. subsequent precipitation as Np(IV) hydroxide. Finally, measured Pu concentrations may be explained by the precipitation of Pu(IV) and/or Pu(III) solid phases.

  • 18.
    Cherkasov, Artem
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Substituent Effects on Thermochemical Properties of C-, N-, O- and S-Centered Radicals. Physical Interpretation of Substituent Effects.1999In: Journal of chemical information and computer sciences, ISSN 0095-2338, E-ISSN 1520-5142, Vol. 39, p. 1057-1063Article in journal (Refereed)
  • 19.
    Cherkasov, Artem
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Substituent Effects on Thermochemical Properties of Free Radicals. New Substituent Scales for C-Centered Radicals1998In: Journal of chemical information and computer sciences, ISSN 0095-2338, E-ISSN 1520-5142, Vol. 38, no 6, p. 1151-1156Article in journal (Refereed)
  • 20.
    Cherkasov, Artem R
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Galkin, Vladimir
    University of Kazan, Russia.
    A Novel Approach to the Analysis of Substituent Effects. Quantitative Description of Ionization Energies and Gas Basicity of Amines.1999In: Journal of Molecular Graphics and Modelling, ISSN 1093-3263, E-ISSN 1873-4243, Vol. 17, no 15, p. 28-42Article in journal (Refereed)
  • 21.
    Claudino, Mauro
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Johansson, Mats K. G.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Thiol-ene coupling of 1,2-disubstituted alkene monomers: The kinetic effect of cis/trans-isomer structures2010In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 46, no 12, p. 2321-2332Article in journal (Refereed)
    Abstract [en]

    The free-radical induced reaction between a tri-functional thiol (2-ethyl-(hydroxymethyl)-1,3-propanediol trimercapto propionate) and two 1,2-disubstituted alkenes (methyl oleate and methyl elaidate) has been investigated under photochemical conditions. The photoreaction was monitored via time-resolved FUR, Raman and NMR spectroscopy to provide insights about the kinetics and efficiency in end-product formation. The information collected was subjected to numerical modelling using the GEPASI software using pre-established literature values for the rate coefficients in order to verify the proposed reaction scheme. The results confirm the thiol-ene reaction mechanism showing a very fast cis/trans-isomerization (<1.0 min) when compared with the total disappearance of unsaturations, indicating that the rate-limiting step controlling the reaction is the hydrogen transfer from the thiol involved in the formation of product. High thiol-ene conversions can be obtained at reasonable rates without major influence of side-reactions when performed in bulk indicating that this reaction is suitable for network forming purposes with mono-unsaturated fatty acid methyl esters derivatives. The kinetic and mechanistic information collected provides a basis for the design of new thiol-ene systems aiming at material and coating applications.

  • 22.
    Claudino, Mauro
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    van der Meulen, Inge
    Eindhoven University of Technology, Laboratory of Polymer Chemistry, Eindhoven, The Netherlands.
    Trey, Stacy
    SP Trätek, SP Technical Research Institute of Sweden, Stockholm.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Heise, Andreas
    Eindhoven University of Technology, Laboratory of Polymer Chemistry, Eindhoven, The Netherlands.
    Johansson, Mats K. G.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
    Photoinduced thiol-ene cross-linking of globalide/ε-caprolactone copolymers: curing performance and resulting thermoset properties2012In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 50, no 1, p. 16-24Article in journal (Refereed)
    Abstract [en]

    The increasing demand for bioderived polymers led us to investigate the potential use of the macrolactone globalide in thermoset synthesis via the photoinduced thiolene reaction. A series of six lipase-catalyzed poly(globalide-caprolactone) copolyesters bearing internal main-chain unsaturations ranging from 10 to 50 and 100 mol % were successfully crosslinked in the melt with equal amounts of thiol groups from trimethylolpropane-trimercapto propionate affording fully transparent amorphous elastomeric materials with different thermal and viscoelastic properties. Three major conclusions can be drawn from this study: (i) high thiol-ene conversions (> 80%) were easily attained for all cases, while maintaining the cure behavior, and irrespective of functionality at reasonable reaction rates; (ii) parallel chain-growth homopropagation of the ene monomer is insignificant when compared with the main thiolene coupling route; and (iii) high ene-density copolymers result in much lower extracted sol fractions and high T(g) values as a result of a more dense and homogeneous crosslinked network. The thiol-ene system evaluated in this contribution serve as model example for the sustainable use of naturally occurring 1,2-disubstituted alkenes in making semisynthetic polymeric materials in high conversions with a range of properties.

  • 23.
    Coullerez, Geraldine
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry. KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Solvent effects on the redox properties of Cu complexes used as mediators in atom transfer radical polymerization2006In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 110, no 34, p. 10355-10360Article in journal (Refereed)
    Abstract [en]

    Solvent effects on the redox properties of six Cu(I) complexes used as mediators in atom transfer radical polymerization (ATRP) have been studied using cyclic voltammetry. The six ligands used were tris[2(dimethylamino) ethyl] amine, N-(n-propyl)-2-pyridylmethanimine, N, N, N', N', N'-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyl-triethylenetetramine, 2,2'-bipyridine, and 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecan. The solvents used were DMSO, DMF, MeCN, MeOH, IP, and BuOH. Significant solvent effects were observed and quantitatively analyzed in terms of Kamlet-Taft relationships. The resulting Kamlet-Taft equations were found to successfully describe the solvent effects and could thus be used as tools for the design of ATRP in new solvents. The solvent sensitivity of the different ligands and the nature of the solvent effects are also discussed to some extent.

  • 24. Degueldre, C.
    et al.
    Favarger, P. Y.
    Rosse, R.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Uranium colloid analysis by single particle inductively coupled plasma-mass spectrometry2006In: Talanta: The International Journal of Pure and Applied Analytical Chemistry, ISSN 0039-9140, E-ISSN 1873-3573, Vol. 68, no 3, p. 623-628Article in journal (Refereed)
    Abstract [en]

    Uranium single particle analysis has been performed by inductively coupled plasma-mass spectrometry (ICP-MS) and the performances are compared with that provided by scanning electron microsopy and single particle counting. The transient signal induced by the flash of ions due to the ionisation of all titanium Colloidal particle in the plasma torch can be detected and measured for selected uranium ion masses (U-238(+), U-235(+) or 254[(UO)-U-238-O-16](+)) by the mass spectrometer. The signals recorded via time scanning are analysed as a function of particle size or fraction of the studied element or isotope in the colloid phase. The frequency of the flashes is directly proportional to the concentration of particles in the colloidal suspension. The feasibility tests were performed on uranium dioxide particles. The study also describes the experimental conditions and the choice of mass to detect uranium colloids in a single particle analysis mode.

  • 25. Degueldre, C.
    et al.
    Favarger, P. Y.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Gold colloid analysis by inductively coupled plasma-mass spectrometry in a single particle mode2006In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 555, no 2, p. 263-268Article in journal (Refereed)
    Abstract [en]

    Analysis in a single particle mode of gold colloids in water has been performed by inductively coupled plasma-mass spectrometry (ICP-MS). The signal induced by the flash of ions due to the ionization of a colloid in the plasma torch can be measured for the ions (197)An(+) by the mass spectrometer without interferences. The intensity of the MS signal is recorded in time scan. The recorded peak distributions were analysed as a function of the colloid size for five monodisperse colloids (80-250 nm). This study describes the experimental conditions to analyse gold colloids in a single particle mode. The size detection limit is around 25 nm corresponding to 0.15 fg colloids and one particle per ml may be detected during a 1 min time scan within standard procedure.

  • 26. Degueldre, C.
    et al.
    Raabe, J.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Investigations of clay colloid aggregates by scanning transmission X-ray microspectroscopy of suspensions2009In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 24, no 10, p. 2015-2018Article in journal (Refereed)
    Abstract [en]

    The environmental behaviour of colloidal clay in aquatic systems is linked to the properties of their aggregates. Earlier investigations of clay colloids were performed with electron microscope techniques which caused de-hydration of the particles. Information on the structure of colloid aggregates is needed for understanding their sedimentation behaviour, as well as colloid contaminant transport properties in natural systems. Scanning transmission X-ray microspectroscopy successfully produced images of montmorillonite colloid aggregates in a pseudo-equilibrium state in 1 mM NaCl suspensions equilibrated for more than a year. These clay aggregates were revealed at photon energies below the O absorption edges of clay and water. They were spherical or ellipsoidal with diameters of the order of 100-800 nm. The aggregates are porous and gel like with lower densities than the clay mineral. These investigations are important for modelling the occurrence of clay aggregates in aqueous environments.

  • 27.
    Ekeroth, Ella
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Radiation Induced Oxidative Dissolution of UO22006Doctoral thesis, comprehensive summary (Other scientific)
    Abstract [en]

    This doctoral thesis is focused on oxidative dissolution of UO2 (as a model for spent nuclear fuel) induced by radiolysis of water and the effect of H2 on this process.

    Rate constants for oxidation of UO2 powder by different oxidants such as H2O2 in aqueous suspensions have been experimentally determined. The logarithm of the second order rate constant, ln k, for UO2 oxidation appears to be linearly dependent on the one-electron reduction potential, E0, of the oxidant. This indicates that the rate limiting step in oxidation of UO2 is one-electron transfer. The rate of UO2 oxidation by OH and CO3•- is estimated to be diffusion controlled, k = 10-3 m/min.

    The effect of carbonate on the oxidation kinetics using H2O2 in UO2 powder suspensions has been studied. The second order rate constant for the pure oxidation reaction between UO2 and H2O2 was determined to 4.4 x 10-6 m/min. The carbonate facilitated dissolution rate is found to be limited by diffusion and the rate constant for non-carbonate mediated UO22+ dissolution was determined to (7 ± 1) x 10-8 mol m-2 s-1.

    Furthermore, the relative efficiency (per electron) of one- and two-electron oxidants in causing dissolution of UO2 has been studied. The dissolution yields of one-electron oxidants are strongly dependent on the amount of oxidant (especially at low amounts).

    The reduction of UO22+ in carbonate solutions by H2 (p = 40 bar) at different temperatures has been studied as a function of time. The rate constant and the activation energy were determined, k298 =3.6 x 10 -9 M-1 s-1 and Ea = 130 ± 24 kJ/mol, respectively. The reduction of UO22+ to UO2 occurs in the absence of a catalyst.

    The relative impact of radiolysis products on oxidative dissolution of UO2 has been elucidated. The amount of dissolved UO22+ was measured as a function of time in γ -irradiated aqueous carbonate solutions saturated with various gases containing a UO2-pellet. The simulated dissolution rates were calculated from the surface area, oxidant concentrations and rate constants obtained from the linear relationship mentioned above. The simulated dissolution rates were compared with the experimental dissolution rates and the correlation was fairly good. Thus, the impact of each oxidant in the system studied can be estimated from the simulations. Only the molecular oxidants are of importance in systems of relevance for safety analysis of a deep repository.

  • 28.
    Ekeroth, Ella
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Roth, Olivia
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    The relative impact of radiolysis products in radiation induced oxidative dissolution of UO22006In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 355, no 1-3, p. 38-46Article in journal (Refereed)
    Abstract [en]

    The relative impact of radiolysis products in radiation induced oxidative dissolution Of UO2 has been studied experimentally. The experiments were performed by y-irradiating an aqueous solution containing HCO3 and a UO2-pellet. The U(VI) concentration in the solution was measured as a function of irradiation time. The aqueous solution was saturated with Ar, N2O, N2O/O-2 (80/20), air and O-2 in order to vary the conditions and the initial oxidant yields. The measured rate of oxidation was significantly higher for the O-2- and air saturated systems compared to the other systems. Using oxidant concentrations derived from numerical simulations of the corresponding homogeneous systems and previously determined rate constants for oxidation Of UO2, the relative trend in rate of oxidation in the different systems was reproduced. The results from the simulations were also used to estimate the relative impact of the oxidative radiolysis products as a function of irradiation time, both for gamma- and alpha-irradiated systems. For 7-irradiated systems saturated with Ar, air or 02, the most important oxidant is H2O2 while for N2O- and N2O/O-2-saturated systems the most important oxidant is CO3.-. For a-irradiated systems the most important oxidant was found to be H2O2.

  • 29. Eriksen, Trygve E.
    et al.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Merino, Juan
    Modelling of time resolved and long contact time dissolution studies of spent nuclear fuel in 10 mM carbonate solution - A comparison between two different models and experimental data2008In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 375, no 3, p. 331-339Article in journal (Refereed)
  • 30.
    Eriksen, Trygve E.
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Shoesmith, David W.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Radiation induced dissolution of UO2 based nuclear fuel - A critical review of predictive modelling approaches2012In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 420, no 1-3, p. 409-423Article, review/survey (Refereed)
    Abstract [en]

    Radiation induced dissolution of uranium dioxide (UO2) nuclear fuel and the consequent release of radionuclides to intruding groundwater are key-processes in the safety analysis of future deep geological repositories for spent nuclear fuel. For several decades, these processes have been studied experimentally using both spent fuel and various types of simulated spent fuels. The latter have been employed since it is difficult to draw mechanistic conclusions from real spent nuclear fuel experiments. Several predictive modelling approaches have been developed over the last two decades. These models are largely based on experimental observations. In this work we have performed a critical review of the modelling approaches developed based on the large body of chemical and electrochemical experimental data. The main conclusions are: (1) the use of measured interfacial rate constants give results in generally good agreement with experimental results compared to simulations where homogeneous rate constants are used; (2) the use of spatial dose rate distributions is particularly important when simulating the behaviour over short time periods; and (3) the steady-state approach (the rate of oxidant consumption is equal to the rate of oxidant production) provides a simple but fairly accurate alternative, but errors in the reaction mechanism and in the kinetic parameters used may not be revealed by simple benchmarking. It is essential to use experimentally determined rate constants and verified reaction mechanisms, irrespective of whether the approach is chemical or electrochemical.

  • 31. Eriksson, M.
    et al.
    Fischer, Andreas
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
    Lind, Johan
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Zazzi, A.
    2R, 3S)-2,3-dibromosuccinic acid2006In: Acta Crystallographica Section E: Structure Reports Online, ISSN 1600-5368, E-ISSN 1600-5368, Vol. 62, p. O200-O201Article in journal (Refereed)
    Abstract [en]

    Crystals of the title compound, C4H4Br2O4, were grown from an aqueous solution. The structure features centrosymmetric molecules, each of which forms hydrogen bonds with two adjacent acid molecules, yielding long chains.

  • 32. Eriksson, P.
    et al.
    Engman, L.
    Lind, Johan
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Merenyi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Aqueous phase one-electron reduction of sulfonium, selenonium and telluronium salts2005In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 4, p. 701-705Article in journal (Refereed)
    Abstract [en]

    Triorganylsulfonium, -selenonium and -telluronium salts were reduced by carbon dioxide radical anions/solvated electrons produced in aqueous solution by radiolysis. The radical expulsion accompanying reduction occurred with the expected leaving group propensities (benzyl > secondary alkyl > primary alkyl > methyl > phenyl), although greater than expected loss of the phenyl group was often observed. Diorganyl chalcogenides formed in the reductions were conveniently isolated by extraction with an organic solvent. Product yields based on the amount of reducing radicals obtained from the T-source were often higher than stoichiometric (up to 1800 %) in the reduction of selenonium and telluronium compounds; it is likely that this result can be accounted for in terms of a chain reaction with carbon-centred radicals/formate serving as the chain transfer agent. The product distribution was essentially independent of the reducing species for diphenyl alkyl telluronium salts, whereas significant variations were seen for some of the corresponding selenonium salts. This would suggest the intermediacy of telluranyl radicals in the one-electron reduction of telluronium salts. However, pulse radiolysis experiments indicated that the lifetimes of such a species (the triphenyltelluranyl radical) would have to be less than 1 mus.

  • 33.
    García García, Sandra
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Temperature effect on the stability of bentonite colloids in water2006In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 298, no 2, p. 694-705Article in journal (Refereed)
    Abstract [en]

    The stability of natural bentonite suspensions has been investigated as a function of temperature at pH 9 and ionic strength 10-3 M. The sedimentation rate of the particles is directly related to their stability. The sedimentation kinetics was determined by examining the variation of particle concentration in solution with time. The observed kinetics for sedimentation is discussed quantitatively in terms of the potential energy between particles. The ζ-potential of the particles was measured and the DLVO theory was used to calculate attractive and repulsive potentials. Experimental observations are consistent with DLVO model predictions and show that the stability of bentonite colloids increases with temperature. Differences with other colloidal systems can be attributed to the temperature dependence of the surface charge of bentonite particles.

  • 34.
    García García, Sandra
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Kinetic determination of critical coagulation concentrations for sodium- and calcium-montmorillonite colloids in NaCl and CaCl2 aqueous solutions2007In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 315, no 2, p. 512-519Article in journal (Refereed)
    Abstract [en]

    The stability of the sodium and calcium forms of montmorillonite was studied at different NaCl and CaCl2 concentrations. The aggregation kinetics was determined from the decrease in particle concentration with time at different electrolyte concentrations. The DLVO theory defines the critical coagulation concentration (CCC) value as the electrolyte concentration that balances the attractive and repulsive potential energies between the particles, making aggregation diffusion-controlled. Therefore CCC values were obtained by extrapolation of the aggregation rate constants measured as a function of ionic strength to conditions where the rate constant value is determined by diffusion only. When the electrolyte was CaCl2, the CCC value was found to be approximately two orders of magnitude lower than the CCC values obtained using NaCl as electrolyte.

  • 35.
    GIERER, J
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    YANG, EQ
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    REITBERGER, T
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    ON THE IMPORTANCE OF SUPEROXIDE RADICAL-ANIONS IN OXYGEN BLEACHING OF PULP1993In: Abstracts of Papers of the American Chemical Society, Vol. 205Article in journal (Refereed)
  • 36. Goldstein, S.
    et al.
    Lind, Johan
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Merenyi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Chemistry of peroxynitrites as compared to peroxynitrates2005In: Chemical Reviews, ISSN 0009-2665, E-ISSN 1520-6890, Vol. 105, no 6, p. 2457-2470Article, review/survey (Refereed)
  • 37. Goldstein, S.
    et al.
    Samuni, A.
    Hideg, K.
    Merenyi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Structure-activity relationship of cyclic nitroxides as SOD mimics and scavengers of nitrogen dioxide and carbonate radicals2006In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 110, no 10, p. 3679-3685Article in journal (Refereed)
    Abstract [en]

    Synthetic nitroxide antioxidants attenuate oxidative damage in various experimental models. Their protective effect reportedly depends on ring size and ring substituents and is greater for nitroxides having lower oxidation potential. The present study focuses on the kinetics and mechanisms of the reactions of piperidine, pyrrolidine and oxazolidine nitroxides with HO2 center dot/O-2(center dot-), (NO2)-N-center dot and CO3 center dot- radicals, which are key intermediates in many inflammatory and degenerative diseases. It is demonstrated that nitroxides are the most efficient scavengers of (NO2)-N-center dot at physiological pH (k = (3-9) x 10(8) M-1 s(-1)) and among the most effective metal-independent scavengers Of CO3 center dot- radicals (k = (2 - 6) x 10(8) M-1 s(-1)). Their reactivity toward HO2 center dot, though not toward center dot NO2 and CO3 center dot-, depends on the nature of the ring side-chain and particularly on the ring-size. All nitroxide derivatives react slowly with O-2(center dot-) and are relatively inefficient SOD mimics at physiological pH. Even piperidine nitroxides, having the highest SOD-like activity, demonstrate a catalytic activity of about 1000-fold lower than that of native SOD at pH 7.4. The present results do not indicate any correlation between the kinetics of HO2 center dot/O-2(center dot-), (NO2)-N-center dot, and CO3 center dot- removal by nitroxides and their protective activity against biological oxidative stress and emphasize the importance of target-oriented nitroxides, i.e., interaction between the biological target and specific nitroxides.

  • 38. Goldstein, Sara
    et al.
    Samuni, Amram
    Merenyi, Gabor
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Kinetics of the reaction between nitroxide and thiyl radicals: Nitroxides as antioxidants in the presence of thiols2008In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, no 37, p. 8600-8605Article in journal (Refereed)
    Abstract [en]

    Cyclic nitroxides effectively protect cells, tissues, isolated organs, and laboratory animals from radical-induced damage. The present study focuses on the kinetics and mechanisms of the reactions of piperidine and pyrrolidine nitroxides with thiyl radicals, which are involved in free radical "repair" equilibria, but being strong oxidants can also produce cell damage. Thiyl radicals derived from glutathione, cysteine, and penicillamine were generated in water by pulse radiolysis, and the rate constants of their reactions with 2,2,6,6-tetramethylpiperidine-1-oxyl (TPO), 4-OH-TPO, and 3-carbamoyl-proxyl were determined to be (5-7) x 10(8) M-1 s(-1) at pH 5-7, independent of the structure of the nitroxide and the thiyl radical. It is suggested that the reaction of nitroxide (>NO center dot) with thiyl radical (RS center dot) yields an unstable adduct (>NOSR). The deprotonated form of this adduct decomposes via heterolysis of the N-O bond, yielding the respective amine (>NH) and sulfinic acid (RS(O)OH). The protonated form of the adduct decomposes via homolysis of the N-O bond, forming the aminium radical (>NH center dot+) and sulfinyl radical (RSO center dot), which by subsequent reactions involving thiol and nitroxide produce the respective amine and sulfonic acid (RS(O)(2)OH). Nitroxides that are oxidized to the respective oxoammonium cations (>N+=O) are recovered in the presence of NADH but not in the presence of thiols. This suggests that the reaction of >N+=O with thiols yields the respective amine. Two alternative mechanisms are suggested, where >N+=O reacts with thiolate (RS-) directly generating the adduct >NOSR or indirectly forming >NO center dot and RS center dot, which subsequently together yield the adduct >NOSR. Under physiological conditions the adduct is mainly deprotonated, and therefore nitroxides can detoxify thiyl radicals. The proposed mechanism can account for the protective effect of nitroxides against reactive oxygen- and nitrogen-derived species in the presence of thiols.

  • 39.
    Hansson, Susanne
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Antoni, Per
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Bergenudd, Helena
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Malmström, Eva
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
    Selective cleavage of polymer grafts from solid surfaces: assessment of initiator content and polymer characteristics2011In: POLYM CHEM, ISSN 1759-9954, Vol. 2, no 3, p. 556-558Article in journal (Refereed)
    Abstract [en]

    A novel initiator for atom transfer radical polymerization, also allowing for selective cleavage of polymer grafts, was designed and immobilized on a solid substrate. After cleavage, the initiator content was determined by utilizing Ellman's reagent and the cleaved polymer grafts were isolated and characterized by size exclusion chromatography.

  • 40.
    Holmboe, Michael
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    The Bentonite Barrier: Microstructural properties and the influence of γ-radiation2011Doctoral thesis, comprehensive summary (Other academic)
  • 41.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Influence of γ-radiation on the reactivity of Montmorillonite towards H2O22012In: Radiation Physics and Chemistry, ISSN 0969-806X, E-ISSN 1879-0895, Vol. 81, no 2, p. 190-194Article in journal (Refereed)
    Abstract [en]

    Compacted and water saturated bentonite will be used as an engineered barrier in deep geological repositories for radioactive waste in many countries. Due to the high dose rate of ionizing radiation outside the canisters holding the nuclear waste, radiolysis of the interlayer and pore water in the compacted bentonite is unavoidable. Upon reaction with the oxidizing and reducing species formed by water radiolysis (OH•, e-(aq), H•, H202, H2, H02•, H30+), the overall redox properties in the bentonite barrier may change. In this study the influence of γ-radiation on the structural Fe(II)/Fe(III) content in montmorillonite and its reactivity towards hydrogen peroxide (H2O2) was investigated in parallel experiments. The results show that under anoxic conditions the structural Fe(II)/FeTot ratio of dispersed montmorillonite are increased from ≤ 3 to 25-30% after γ-doses comparable to repository conditions. Furthermore, a strong correlation between the structural Fe(II)/FeTot ratio and the H2O2 decomposition rate in montmorillonite dispersions was found. This correlation was further verified in experiments with consecutive H2O2 additions, since the structural Fe(II)/FeTot ratio was seen to decrease concordantly. This work shows that the structural iron in montmorillonite could be a sink for one of the major oxidants formed upon water radiolysis in the bentonite barrier, H2O2.

  • 42.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Norrfors, Karin
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry (closed 20110630).
    Effect of γ-radiation on Radionuclide Retention in Compacted Bentonite2011In: Radiation Physics and Chemistry, ISSN 0969-806X, E-ISSN 1879-0895, Vol. 80, no 12, p. 1371-1377Article in journal (Refereed)
    Abstract [en]

    Compacted bentonite is proposed as an engineered barrier in many concepts for disposal of high level nuclear waste. After the initial deposition however, the bentonite barrier will inevitably be exposed to ionizing radiation (mainly gamma) under anoxic conditions. Because of this, the effects of gamma-radiation on the apparent diffusivity values and sorption coefficients in bentonite for Cs(+) and Co(2+) were tested under different experimental conditions. Radiation induced effects on sorption were in general more noticeable for Co(2+) than for Cs(+), which generally showed no significant differences between irradiated and unirradiated clay samples. For Co(2+) however, the sorption to irradiated MX80 was significantly lower than to the unirradiated clay samples regardless of the experimental conditions. This implies that gamma-radiation may alter the surface characteristics contributing to surface complexation of Co(2+). With the experimental conditions used, however, the effect of decreasing sorption was not large enough to be reflected on the obtained D. values.

  • 43.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Colloid diffusion in compacted bentonite: microstructural constraints2010In: Clays and clay minerals, ISSN 0009-8604, E-ISSN 1552-8367, Vol. 58, no 4, p. 532-541Article in journal (Refereed)
    Abstract [en]

    In Sweden and in many other countries, a bentonite barrier will be used in the repository for spent nuclear fuel. In the event of canister failure, colloidal diffusion is a potential, but scarcely studied mechanism of radionuclide migration through the bentonite barrier. Column and in situ experiments are vital in understanding colloid diffusion and in providing information about the microstructure of compacted bentonite and identifying cut-off limits for colloid filtration. This study examined diffusion of negatively charged 2-, 5-, and 15-nm gold colloids in 4-month diffusion experiments using MX-80 Wyoming bentonite compacted to dry densities of 0.6–2.0 g/cm3. Breakthrough of gold colloids was not observed in any of the three diffusion experiments. In a gold-concentration profile analysis, colloid diffusion was only observed for the smallest gold colloids at the lowest dry density used (estimated apparent diffusivity Da 5x10–13 m2/s). The results from a microstructure investigation using low-angle X-ray diffraction suggest that at the lowest dry density used, interlayer transport of the smallest colloids cannot be ruled out as a potential diffusion pathway, in addition to the expected interparticle transport. In all other cases, with either greater dry densities or larger gold colloids, compacted bentonite will effectively prevent diffusion of negatively charged colloids due to filtration.

  • 44.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Free porosity investigation of compacted Bentonite using XRDIn: Applied Clay Science, ISSN 0169-1317, E-ISSN 1872-9053Article in journal (Other academic)
    Abstract [en]

    Many countries intend to use compacted bentonite as abarrier in their deep geological repositories for nuclearwaste. In order to describe and predict hydraulicconductivity or radionuclide transport through thebentonite barrier, fundamental understanding of themicrostructure of compacted bentonite is needed. Thisstudy examined the interlayer swelling and overallmicrostructure of Wyoming Bentonite MX-80 and thecorresponding homo-ionic Na+ and Ca2+ forms, usingXRD with samples saturated under confined swellingconditions and free swelling conditions. For thesamples saturated under confined conditions, theinterparticle, or so-called free porosity was estimatedby comparing the experimental interlayer distancesobtained from one-dimensional XRD profile fittingagainst the maximum interlayer distances possible forthe corresponding water content. The results showedthat interlayer porosity dominated total porosity,irrespective of water content, and that free porositywas lower than previously reported in the literature. Atcompactions relevant for the saturated bentonitebarrier (1.4-1.8 g/cm3), the free porosity was estimatedto ≤ 3%.

  • 45.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Free Porosity of Compacted Saturated MX-80 Bentonite and Na-montmorillonite as a Function of Dry Density2009Article in journal (Refereed)
  • 46.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Porosity investigation of compacted bentonite using XRD profile modeling2012In: Journal of Contaminant Hydrology, ISSN 0169-7722, E-ISSN 1873-6009, Vol. 128, no 1-4, p. 19-32Article in journal (Refereed)
    Abstract [en]

    Many countries intend to use compacted bentonite as a barrier in their deep geological repositories for nuclear waste. In order to describe and predict hydraulic conductivity or radionuclide transport through the bentonite barrier, fundamental understanding of the microstructure of compacted bentonite is needed. This study examined the interlayer swelling and overall microstructure of Wyoming Bentonite MX-80 and the corresponding homo-ionic Na+ and Ca2+ forms, using XRD with samples saturated under confined swelling conditions and free swelling conditions. For the samples saturated under confined conditions, the interparticle, or so-called free or external porosity was estimated by comparing the experimental interlayer distances obtained from one-dimensional XRD profile fitting against the maximum interlayer distances possible for the corresponding water content. The results showed that interlayer porosity dominated total porosity, irrespective of water content, and that the interparticle porosity was lower than previously reported in the literature. At compactions relevant for the saturated bentonite barrier (1.4-1.8 g/cm(3)), the interparticle porosity was estimated to <= 3%.

  • 47.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    García García, Sandra
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Effects of gamma-irradiation on the stability of colloidal Na+-Montmorillonite dispersions2009In: Applied Clay Science, ISSN 0169-1317, E-ISSN 1872-9053, Vol. 43, no 1, p. 86-90Article in journal (Refereed)
    Abstract [en]

    In many concepts for final storage of spent nuclear fuel bentonite will be used as an engineered barrier, mainly due to its inertness, plasticity and ability to retard transport of radionuclides by adsorption. In the event of water-bearing fractures making contact with the bentonite barrier, generation and transport of colloidal particles will strongly depend on groundwater composition and the surface properties of the colloidal particles. The bentonite barrier will unavoidably be exposed to ionizing radiation from the spent nuclear fuel but very little is known about effects of ionizing radiation on bentonite concerning colloidal stability. In this work we have studied the effect of gamma-radiation on the stability of dilute colloidal Na+-montmorillonite dispersions using a Cs-137 gamma-source (doses of 0-53.2 kGy). Aggregation kinetics and sedimentation experiments revealed significant radiation effects, evident as increased colloid stability. The only rationale for this is a gamma-radiation induced increase in surface potential. The effects appeared to depend on the Na+-montmorillonite concentration in the irradiated dispersions, indicating that the change in surface potential is induced by aqueous radiolysis products.

  • 48.
    Holmboe, Michael
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Wold, Susanna
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Petterson, Torbjörn
    KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
    Effects of the injection grout Silica sol on Bentonite2011In: Physics and Chemistry of the Earth, ISSN 1474-7065, E-ISSN 1873-5193, Vol. 36, no 17/18, p. 1580-1589Article in journal (Refereed)
    Abstract [en]

    Silica sol, i.e., colloidal SiO2, may be used as a low-pH injection grout for very fine fractures in the construction of deep geological repositories for radioactive waste in Sweden and in Finland. If the bentonite barrier encounters SiO2-colloid particles under conditions favorable for aggregation, there is concern that it will modify the bentonite barrier at the bentonite/bedrock interface. In this study qualitative experiments were performed with mixed dispersions of SiO2-colloids and bentonite or homo-ionic Na/Ca-montmorillonite. Samples were prepared at different colloid concentrations and treated under various conditions such as low and high ionic strength (0.3 M NaCl), as well as dehydration and redispersing. Free swelling and settling experiments were performed in order to qualitatively compare the conditions in which SiO2-colloids affect the bulk/macro properties of bentonite. In order to study specific SiO2-colloid/montmorillonite interactions and preferred type of initial aggregation, dilute dispersions of homo-ionic montmorillonite dispersions mixed with varying concentrations of SiO2-colloids were prepared and selected samples were characterized by PCS, SEM/EDS, AFM and PXRD. The results from this study show that bentonite and montmorillonite particles can be modified by SiO2-colloids when mixed in comparable amounts, due to dehydration or high ionic strength. Some indications for increased colloidal stability for the SiO2-colloid modified clay particles were also found. From the AFM investigation it was found that initial attachment of the SiO2-colloids in Na+ dominated samples seemed to occur on the edges of the montmorillonite layers. In Ca2+ dominated samples not subjected to excess NaCl, SiO2-colloid sorption onto the faces of the montmorillonite layers was also found. In all, contact between the bentonite barrier and ungelled Silica sol should preferably be avoided.

  • 49.
    Hossain, Mohammad Mohsin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jönsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Effects of ionic strength on the kinetics for UO2 oxidation2008In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 373, no 1-3, p. 190-193Article in journal (Refereed)
    Abstract [en]

    The effect of ionic strength on the kinetics of UO2 oxidation by H2O2 in aqueous solution has been studied using powder suspensions, where the concentration of H2O2 was monitored as a function of time. Experiments were performed at 0 and 10 mM HCO3-. NaCl and Na2SO4 were used to adjust the ionic strength. At 0 mM HCO3- (where the kinetics is influenced by both oxidation and dissolution) the rate constant for the reaction increases with increasing ionic strength while at 10 mM HCO3- (where the kinetics is independent of the dissolution of oxidized UO2) the rate constant is virtually independent of ionic strength. This implies that dissolution of oxidized UO2 in the absence of HCO3- is ionic strength dependent. As expected, the reaction between H2O2 and UO2 is not affected by ionic strength since H2O2 has no charge. This finding also implies that peroxymonocarbonate (HCO4-) cannot be an important oxidant under the present conditions.

  • 50.
    Hossain, Mohammad Moshin
    et al.
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Ekeroth, Ella
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Jonsson, Mats
    KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
    Effects of HCO3- on the kinetics of UO2 oxidation by H2O22006In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 358, no 2-3, p. 202-208Article in journal (Refereed)
    Abstract [en]

    The effect of HCO3- on the kinetics of UO2 oxidation by H2O2 in aqueous solution has been studied using powder suspensions where the concentration of H2O2 was monitored as a function of time. By varying the UO2 surface to solution volume ratio second order rate constants were obtained for HCO3- concentrations ranging from 0 to 100 mM. The second order rate constant increases linearly with HCO3- concentration from 0 to approximately 1 mM. Above 1 mM HCO3- the rate constant is 4.4 × 10-6 m min-1 independent of [HCO3-]. This indicates that the kinetics of the reaction depends on both oxidation and dissolution below 1 mM HCO3- while at higher concentrations it is solely governed by oxidation. Hence, the rate constant obtained at HCO3- concentrations above 1 mM is the true rate constant for oxidation of UO2 by H2O2. The results also imply that the reaction between HCO3- and oxidized UO2 on the UO2 surface (i.e. HCO3- facilitated dissolution) is limited by diffusion (ca 10-3 m min-1 in the present system). Furthermore, the experimental results were used to estimate the oxidation site density of the powder used (126 sites nm-1) and the rate constant for dissolution of UO22 + from the UO2 surface (7 × 10-8 mol m-2 s-1).

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