Computational chemistry studies of UV induced processes in human skin

This thesis presents and uses the techniques of computational chemistry to explore two different processes induced in human skin by ultraviolet light. The first is the transformation of urocanic acid into a immunosuppressing agent, and the other is the enzymatic action of the 8-oxoguanine glycosylase enzyme. The photochemistry of urocanic acid is investigated by time-dependent density functional theory. Vertical absorption spectra of the molecule in different forms and environments is assigned and candidate states for the photochemistry at different wavelengths are identified. Molecular dynamics simulations of urocanic acid in gas phase and aqueous solution reveals considerable flexibility under experimental conditions, particularly for for the cis isomer where competition between intra- and inter-molecular interactions increases flexibility. A model to explain the observed gas phase photochemistry of urocanic acid is developed and it is shown that a reinterpretation in terms of a mixture between isomers significantly enhances the agreement between theory and experiment , and resolves several peculiarities in the spectrum. A model for the photochemistry in the aqueous phase of urocanic acid is then developed, in which two excited states governs the efficiency of photoisomerization. The point of entrance into a conical intersection seam is shown to explain the wavelength dependence of photoisomerization quantum yield. Finally some mechanistic aspects of the DNA repair enzyme 8-oxoguanine glycosylase is investigated with density functional theory. It is found that the critical amino acid of the active site can provide catalytic power in several different manners, and that a recent proposal involving a SN1 type of mechanism seems the most efficient one.

Improving Readability of Swedish Electronic Health Records through Lexical Simplification : First Results

This paper describes part of an ongoing effort to improve the readability of Swedish electronic health records (EHRs). An EHR contains systematic documentation of a single patient’s medical history across time, entered by healthcare professionals with the purpose of enabling safe and informed care. Linguistically, medical records exemplify a highly specialised domain, which can be superficially characterised as having telegraphic sentences involving displaced or missing words, abundant abbreviations, spelling variations including misspellings, and terminology. We report results on lexical simplification of Swedish EHRs, by which we mean detecting the unknown, out-ofdictionary words and trying to resolve them either as compounded known words, abbreviations or misspellings.

Bilingual Lexical Access in Reading : Analyzing the Effect of Semantic Context on Non-Selective Access in Bilingual Memory

Recent empirical studies about the neurological executive nature of reading in bilinguals differ in their evaluations of the degree of selective manifestation in lexical access as implicated by data from early and late reading measures in the eye-tracking paradigm. Currently two scenarios are plausible: (1) Lexical access in reading is fundamentally language non-selective and top-down effects from semantic context can influence the degree of selectivity in lexical access; (2) Cross-lingual lexical activation is actuated via bottom-up processes without being affected by top-down effects from sentence context. In an attempt to test these hypotheses empirically, this study analyzed reader-text events arising when cognate facilitation and semantic constraint interact in a 22 factorially designed experiment tracking the eye movements of 26 Swedish-English bilinguals reading in their L2. Stimulus conditions consisted of high- and low-constraint sentences embedded with either a cognate or a non-cognate control word. The results showed clear signs of cognate facilitation in both early and late reading measures and in either sentence conditions. This evidence in favour of the non-selective hypothesis indicates that the manifestation of non-selective lexical access in reading is not constrained by top-down effects from semantic context.