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Aromatic sulfonation and some substitution reactions of chlorobenzene show deviations in the selectivity relation. A determination of chlorobenzene sulfonation provided the following rate ratio relative to benzene and partial rate factors: 1.0, [---] of 0.064 , mf 1.7 and pf 4. 2. Our work, Olah's nitration, Ferguson's bromination and Stock's chlorination define a new relation that can be express by adding an entropy term (A) to the selectivity relation. We determined the rate of bromine-cyclohexene addition in dichloro-methane at 0° to provide a basis for a systematic variation of solvents at low temperature. An unusual zero-order reaction was encountered. The reaction was light catalyzed and related to hydrogen bromide concentration. The reaction was independent of bromine, cyclohexene, hydroperoxide and oxygen concentration. The reaction order depended on a steady-state concentration of bromonium ion (Br+). We also observed a novel photo effect with mixtures of oxygen, nitrogen and air. The synthesis of Thorpe's caged triacid, 4-methyltricyclo[1.1.0.02-4] butane-1,2,3-tricarboxylic acid has never been repeated or verified. A key intermediate, 1,1,1-ethanetriacetic,was readily converted to 1,1,1-ethanetriacetyl bromide. This last compound could only be a-brominated in the presence of a trace of ether. This successful a-bromination represents an important breakthrough toward getting Thorpe's caged acid.

The diploma thesis is dedicated to the exploitation of sulphonated polystyrene nanofibres as ion exchange nanomaterial. Ion exchange capacity of these nanomaterials has been determined by titration method and AAS. The effect of sulphonation on photophysical, photooxidative and photocytotoxic properties of sensitizer 5,10,15,20-meso- tetraphenylporphyrin (TPP) encapsulated in polystyrene nanofibres has been studied as well. Properties of TPP have been examined with time-resolved spectroscopy, photooxidation of uric acid as substrate and bactericidal tests on Escherichia coli DH5α with pGEM11Z plasmid. It has been discovered that following the sulphonation of the nanofabrics, the encapsulated sensitizer is partly present even in aggregation form. The polystyrene nanofabrics with encapsulated sensitizer keep its bactericidal efficiency also after sulphonation.

<p>The primary cell wall is a complex multipolymer system whose composite structure has been mostly determined from chemical and biochemical studies. Although the primary cell wall serves a central role, with regard to the connective properties of fibres, knowledge about the interactions among the polymers, when it comes to the mechanical properties, is very limited. The physical properties of the polymers, i.e. their elastic and viscous deformations, as well as the ultrastructure of the polymers, i.e. the interactions among the polymers in the outer fibre wall layers that lead to this behaviour, are still not fully understood.</p><p>The aim of this study was to examine how the different wood polymers, viz. lignin, protein, pectin, xyloglucan and cellulose, interact in the outer fibre wall layers of the spruce wood tracheid. The initial objective was to separate an enriched primary cell wall material from a first stage TMP, by means of screening and centri-cleaning. From this material, consisting of the primary cell wall (P) and outer secondary cell wall (S1) materials, thin sheets were prepared and analysed using a number of different analytical methods. The major measuring technique used was dynamic Fourier transform infra-red (FT-IR) spectroscopy in combination with dynamic 2D FT-IR spectroscopy. This technique is based on the detection of small changes in molecular absorption that occur when a sinusoidally stretched sample undergoes low strain. The molecular groups affected by the stretching respond in a specific way, depending on their environment, while the unaffected molecular groups provide no response to the dynamic spectra, by producing no elastic or viscous signals. Moreover, the dynamic 2D FT-IR spectroscopy provides useful information about various intermolecular and intramolecular interactions, which influence the reorientability of functional groups in a polymer material.</p><p>Measurements of the primary cell wall material, using dynamic FT-IR spectroscopy, indicated that strong interactions exist among lignin, protein and pectin, as well as among cellulose, xyloglucan and pectin in this particular layer. This was in contrast to the secondary cell wall, where interactions of cellulose with glucomannan and of xylan with lignin were dominant. It was also indicated that the most abundant crystalline cellulose in the primary cell wall of spruce wood fibres is the cellulose Iβ allomorph, which was also in contrast to the secondary cell wall, where the cellulose Iα allomorph is more dominant. The presence of strong interactions among the polymers in the primary cell wall and, especially, the relatively high content of pectin and protein, showed that there is a very good possibility of selectively attacking these polymers in the primary cell wall. The first selective reaction chosen was a low degree of sulphonation, applied by an impregnation pretreatment of chips with a very low charge of sodium sulfite (Na2SO3). This selective reaction caused some structural modification of the lignin, a weakening of the interactions between lignin;pectin, lignin;protein and pectin;protein, as well as an increased softening of the sulphonated primary cell wall material, when compared to the unsulphonated primary cell wall material. All this resulted in an increased swelling ability of the material.</p>

The primary cell wall is a complex multipolymer system whose composite structure has been mostly determined from chemical and biochemical studies. Although the primary cell wall serves a central role, with regard to the connective properties of fibres, knowledge about the interactions among the polymers, when it comes to the mechanical properties, is very limited. The physical properties of the polymers, i.e. their elastic and viscous deformations, as well as the ultrastructure of the polymers, i.e. the interactions among the polymers in the outer fibre wall layers that lead to this behaviour, are still not fully understood. The aim of this study was to examine how the different wood polymers, viz. lignin, protein, pectin, xyloglucan and cellulose, interact in the outer fibre wall layers of the spruce wood tracheid. The initial objective was to separate an enriched primary cell wall material from a first stage TMP, by means of screening and centri-cleaning. From this material, consisting of the primary cell wall (P) and outer secondary cell wall (S1) materials, thin sheets were prepared and analysed using a number of different analytical methods. The major measuring technique used was dynamic Fourier transform infra-red (FT-IR) spectroscopy in combination with dynamic 2D FT-IR spectroscopy. This technique is based on the detection of small changes in molecular absorption that occur when a sinusoidally stretched sample undergoes low strain. The molecular groups affected by the stretching respond in a specific way, depending on their environment, while the unaffected molecular groups provide no response to the dynamic spectra, by producing no elastic or viscous signals. Moreover, the dynamic 2D FT-IR spectroscopy provides useful information about various intermolecular and intramolecular interactions, which influence the reorientability of functional groups in a polymer material. Measurements of the primary cell wall material, using dynamic FT-IR spectroscopy, indicated that strong interactions exist among lignin, protein and pectin, as well as among cellulose, xyloglucan and pectin in this particular layer. This was in contrast to the secondary cell wall, where interactions of cellulose with glucomannan and of xylan with lignin were dominant. It was also indicated that the most abundant crystalline cellulose in the primary cell wall of spruce wood fibres is the cellulose Iβ allomorph, which was also in contrast to the secondary cell wall, where the cellulose Iα allomorph is more dominant. The presence of strong interactions among the polymers in the primary cell wall and, especially, the relatively high content of pectin and protein, showed that there is a very good possibility of selectively attacking these polymers in the primary cell wall. The first selective reaction chosen was a low degree of sulphonation, applied by an impregnation pretreatment of chips with a very low charge of sodium sulfite (Na2SO3). This selective reaction caused some structural modification of the lignin, a weakening of the interactions between lignin;pectin, lignin;protein and pectin;protein, as well as an increased softening of the sulphonated primary cell wall material, when compared to the unsulphonated primary cell wall material. All this resulted in an increased swelling ability of the material. / QC 20101123