The mechanism and the oxidation potential of the dissociative single electron transfer for tetra-n-butylammonium acetate has been investigated via conventional (cyclic voltammetry) and convolution voltammetry. The oxidation potential for tetra-n-butylammonium acetate was determined to be 0.60 ± 0.10 (vs. Ag/ (0.1 M) AgNO₃) in anhydrous acetonitrile. The results also indicated the mechanism of oxidation was concerted dissociative electron transfer (cDET), rather than stepwise as was previously reported. To further investigate the mechanism, a series of aliphatic and aromatic tetra-n butylammonium carboxylates were synthesized and investigated via convolution and conventional methods under anhydrous conditions (propionate, pivalate, phenyl acetate, and benzoate). The reported results showed high reproducibility and consistency with a concerted dissociative electron transfer for aliphatic carboxylates with a systematic shift in the oxidation potentials (0.60 ± 0.09 V for acetate, 0.47 ± 0.05 V for propionate, and 0.40 ± 0.05 V for pivalate) within the series which is expected trend based on radical stabilization energies of the alkyl groups on the aliphatic carboxylates. Hydrogen bonding was investigated as a possible source for the discrepancy between our results and the reported mechanism of the dissociative electron transfer. Because of the extreme hygroscopic nature of carboxylate salts, it was hypothesized that the presence of small amounts of water might alter the reaction mechanism. Deionized water and deuterium oxide additions to anhydrous acetonitrile were performed to test this hypothesis. The mechanism was noted to shift towards a stepwise mechanism as water was added. In addition, the derived oxidation potentials became more positive with increasing concentrations of water. Several explanations are presented with regards to water effects on the shift in the electron transfer mechanism. Indirect electrolysis (homogeneous redox catalysis) was also employed as an alternative and independent approach to quantify the oxidation potentials of carboxylates. A series of substituted ferrocenes were investigated as mediators for the oxidation of tetra-n-butylammonium acetate. Preliminary data showed redox catalysis was feasible for these systems. Further analyses of the electrochemical results suggested a follow-up chemical step (addition to mediator) that competes with the redox catalysis mechanism. As predicted from theoretical working curves, a plateau region in the i_p/i_pd plots (where no meaningful kinetic information could be obtained) was observed. Products mixture analyses verified the consumption of the mediator upon electrolysis, but no further information with regards to the nature of the mechanism was deduced. In a related study the effects of hydrogen bonding and ions on the reactivity of neutral free radicals were examined by laser flash photolysis. The rate of the β-scission of the cumyloxyl radical is influenced by cations (Li⁺ > Mg²⁺ ≈ Na⁺ > ⁿBu₄N⁺) due to stabilizing ion-dipole interactions in the transition state of the developing carbonyl group. Experimental findings are in a good agreement with theoretical work suggesting metal ion complexation can cause radical clocks to run fast with a more significant effect if there is an increase in dipole moment going from the reactant to the transition state. / Ph. D. / Our work focuses on employing electrochemical techniques to investigate single electron transfer processes, which lead to unstable organic species that contain an odd number of electrons called radicals and radical ions. Many essential biological and environmental pathways are found to occur via radicals, i.e. photosynthesis, atmospheric degradation, enzyme catalyzed reactions in biology, autooxidation, DNA mutations, and more. Electrochemical techniques permit us to investigate the scientific fundamentals of radical processes by generating radicals and radical ions in a controlled manner with a higher efficiency. We have combined electrochemical techniques with established physical organic theories of electron transfer to allow us to determine of the rate and mechanism of electron transfer for a selective group of chemical compounds, specifically anions derived from carboxylic acids (carboxylates). A fundamental understanding of single electron transfer processes for carboxylates allows for a prediction of chemical behavior and the future design of novel chemical compounds for alternative chemical functionality. Our findings are the first to report experimental evidence for a so-called concerted dissociative electron transfer mechanism for carboxylates, where the transfer of an electron is accompanied by the simultaneous breakage of a carbon-carbon bond yielding a radical and carbon dioxide. The mechanism has been shown to proceed in a stepwise fashion only in the presence of water. Our work highlights the environmental effects on radical stability such as water and metals ions.

Σκοπός της μελέτης ήταν ο ποσοτικός προσδιορισμός των ιχνοστοιχείων βαρέων μετάλλων του ψευδαργύρου, καδμίου και χαλκού στο υδατοειδές υγρό ασθενών με ψευδοαποφολίδωση και η μέτρηση του δυναμικού οξειδοαναγωγής στο υδατοειδές αυτών των ασθενών. Υλικό και μέθοδοι: Δείγματα υδατοειδούς υγρού ελήφθησαν κατά την εγχείρηση καταρράκτη από 14 ασθενείς με PEX σύνδρομο (7 άνδρες και 7 γυναίκες) και 21 ασθενείς με καταρράκτη αλλά χωρίς PEX (9 άνδρες και 12 γυναίκες). Τα δείγματα διατηρήθηκαν στους -24C μέχρι την ανάλυση. Τα επίπεδα των τριών μετάλλων και στις δύο ομάδες προσδιορίστηκαν, για πρώτη φορά στην Οφθαλμολογία, με τη μέθοδο της βολταμετρίας με χρήση ηλεκτροδίων υαλώδους γραφίτη με υμένιο υδραργύρου, ενδεικτικού ηλεκτροδίου λευκόχρυσου και αναφοράς Ag/AgCl. Εφαρμόσθηκε η τεχνική της ανοδικής βολταμετρίας απογύμνωσης με τετραγωνικούς παλμούς και έγινε σύγκριση των τιμών ανάμεσα στις δύο ομάδες. Η στατιστική επεξεργασία των αποτελεσμάτων έγινε με το Mann-Whitney test (p<0.05) Στη συνέχεια, κατά τον ίδιο τρόπο, δείγματα υδατοειδούς ελήφθησαν από 13 ασθενείς με PEX (7 άνδρες/6 γυναίκες) και 22 ασθενείς χωρίς PEX (7 άνδρες/15 γυναίκες). Η μέτρηση του δυναμικού οξειδοαναγωγής γινόταν αμέσως μετά την απόκτηση του κάθε δείγματος και για το σκοπό αυτό χρησιμοποιήθηκε για πρώτη φορά στην Οφθαλμολογία, ένα μικροηλεκτρόδιο λευκοχρύσου μαζί με ένα ενσωματωμένο ηλεκτρόδιο αναφοράς Ag/AgCl/KCl. Η στατιστική ανάλυση των αποτελεσμάτων έγινε με το t-test για ανεξάρτητα δείγματα (p<0.05). Αποτελέσματα: O Cu βρέθηκε στατιστικά σημαντικά χαμηλότερος στην PEX ομάδα σε σχέση με τη φυσιολογική ομάδα (p<0.05), ενώ ο Zn και το Cd δεν παρουσίασαν καμία συσχέτιση στο υδατοειδές υγρό ασθενών με ψευδοαποφολίδωση. Το δυναμικό οξειδοαναγωγής ήταν στατιστικά σημαντικά υψηλότερο στο υδατοειδές των ασθενών με PEX σύνδρομο. Συμπεράσματα: Στην παρούσα εργασία εφαρμόζεται για πρώτη φορά, η ανοδική βολταμετρία απογύμνωσης για τον προσδιορισμό στο υδατοειδές υγρό του Zn, Cd και Cu και η μέτρηση του δυναμικού οξειδοαναγωγής στο υδατοειδές. Τόσο τα στατιστικώς σημαντικά χαμηλότερα επίπεδα Cu στο υδατοειδές ασθενών με PEX, όσο και το υψηλότερο δυναμικό οξειδοαναγωγής στο υδατοειδές αυτών των ασθενών ενισχύουν την παθογενετική θεωρία του οξειδωτικού στρες του PEX συνδρόμου. / To determine the Zn, Cd and Cu concentrations in aqueous humor of patients with PEX syndrome and to evaluate the overall oxidative status of the aqueous in this group by measuring the reduction-oxidation (redox) potential in the aqueous samples. Material and methods: Samples from aqueous humor were collected during cataract extraction from 14 patients with PEX syndrome (7 male/7 female) and 21 patients without PEX (9 male/12 female). All samples were stored in -24C until analyzed. The levels of selected trace elements in both groups were assayed for the first time in the field of Ophthalmology, with anodic stripping voltammetry, using the square wave differential pulse technique. In this analytical procedure a glassy carbon mercury film electrode, a platinum indicator and a reference Ag/AgCl electrode were used. Finally the metal levels in all samples were compared between the two groups using the Mann-Whitney test (p<0.05). Similarly, samples were collected during cataract extraction from 13 patients (7 male/6 female) with PEX syndrome and 22 normal patients (7 male/15 female). A platinum electrode together with a reference electrode Ag/AgCl/KCl was used for the first time in Ophthalmology, for the measurement of the apparent redox potential in the aqueous humor. The independent samples t-test was used to compare aqueous redox potential between the study and control group. Statistical significance was set at 0.05. Results: Cu was found significantly lower in the PEX than in the control group (p<0.05), whereas Zn and Cd had no statistical differences between the two groups. The redox potential was found significantly higher in patients with PEX syndrome than in normal patients (p<0.05). Conclusions: In the present study we represent the first successful application of ASV in eye research for the determination of aqueous Zn, Cd and Cu concentrations and the meauserment of aqueous redox potential. The significantly lower Cu concentrations and the higher redox potential in aqeous humor of PEX syndrome support the role of increased oxidative stress in the development of PEX.

While Aluminium has lots of unique properties and is seen as a material of the future, its production and manufacturing has significant environmental impacts. For complex and dimensional shapes casting remains the main manufacturing method and in this study the environmental pressure of different casting techniques is compared. A screening LCA is conducted to determine the environmental impacts of plaster mould castings in a case study at the Ventana Hackås AB foundry in Mid Sweden. The findings are compared to models of sand, pressure die and lost wax castings, based on literature datasets. The most relevant factors for the environmental performance are identified as the production of the aluminium alloy and the amount and source of energy. For plaster mould castings additionally the plaster consumption is significant, while lost wax castings are dominated by the mould production and general processes. Under similar circumstances a relatively similar performance was found for all casting techniques except the lost wax process, which is at least 3 times more emission intensive. Of the remaining techniques pressure die castings performed the best and plaster mould castings the worst, but different sources of uncertainties have been identified in this comparison. In addition a carbon footprint interface is created based on these findings, to enable specific comparisons of different casting method setups. Customizable variables allow the adaptation of three scenarios to real world conditions. As the main influencing factors the aluminium alloy, source of electricity and casting technique have been identified. / <p>2018-10-10</p>