Over 70% of the Earth s economically recoverable nickel (Ni) resides in laterite ore deposits, however they account for less than half of the current global nickel production. During laterization, nickel and other soluble ions are taken into solution before re-precipitating within iron oxide minerals in the limonite zone, or as serpentines and other phyllosilicates in the layers below this zone. It is these laterite deposits that show the greatest potential for low energy, environmentally conscious processing. The major host of nickel in the limonite zone is the iron-oxyhydroxide mineral goethite, α-FeOOH, where up to 4 mol% Ni has been reported in natural specimens, and even higher levels in synthetic samples (5.5 mol%). The Ni is assumed to be incorporated in the crystal structure of the goethite, but previous characterisation work only demonstrated a weak to moderate correlation of mineral structure change with the nickel content in goethite. Mining companies working on the extraction and recovery of nickel from the limonite zone of lateritic deposits have noticed that the ease with which nickel can be extracted varies greatly; goethite rich ores that appear to have similar mineralogies/geologies can display extreme variation in their leachability. It is not clear why the ores behave in this way, but in order for extraction techniques and subsequent recovery of nickel to be improved, the reasons behind this variability need to be understood. The lateritic ore materials from which nickel is extracted are generally made up of a number of different mineral phases. The multiphase nature of the samples means that characterisation of the goethite-type phases from these materials is challenging. To simplify the system and allow the association of Ni into goethite and/or other iron oxyhydroxide phases to be studied in a controlled environment, a synthetic study was carried out. Ni-bearing goethites have been synthesised at a series of different temperatures and characterised by a range of analytical techniques including PXRD, IR, Raman, TGA, ICP-OES, SEM and TEM. It was found that a second phase, ferrihydrite, co-existed with the goethites, the proportion of which increased at lower synthesis temperatures and with increasing amounts of Ni. Ferrihydrite is known to be a precursor phase in the formation of goethite, but its poorly crystalline nature makes it difficult to identify using standard characterisation techniques such as PXRD. The introduction of Ni to the system increases the stability of the ferrihydrite phase, inhibiting its transformation to goethite. It is believed that some of the Ni thought to be incorporated into goethite could actually reside in an undetected ferrihydrite phase, which could account for the differences observed in the leachability of natural materials. Characterisation techniques were investigated to try and determine a simple way to identify ferrihydrite in these systems, which could ideally be used in the field to identify the presence of ferrihydrite in goethite rich ore materials. Thermal analysis proved to be particularly promising as a technique which could be used to identify ferrihydrite rich deposits before extraction, enabling the most efficient and environmentally conscious metal recovery process for each deposit to be identified. In order to investigate the way in which Ni partitions itself between structural incorporation into goethite and association with a secondary ferrihydrite phase, a new washing technique was developed using EDTA, which is capable of selectively removing the ferrihydrite phase whilst leaving the goethite intact. This investigation suggests that a maximum of ~2.5 mol% of Ni is structurally incorporated into goethite, regardless of how much is added during the synthesis. Any excess nickel, above that which is substituted into the goethite structure, was found to be associated with the poorly crystalline ferrihydrite phase. Despite being considered a metastable phase, the increased stability of ferrihydrite resulting from the presence of Ni suggests that it may persist in laterite deposits within geological systems. If ferrihydrite is indeed present in nickeliferous laterites, it may be a significant host for Ni, and potentially many other critical elements. Based on the methodology developed whilst studying synthetic samples, a characterisation program for materials from lateritic ore deposits was conducted to investigate the presence of ferrihydrite in natural systems. From the research presented and discussed in this thesis, proof of the presence or absence of ferrihydrite in laterite systems, causing variations in the leachability of the ore materials, could not be conclusively established. The thermal analysis technique developed here successfully identified and quantified ferrihydrite in the presence of goethite in synthetic systems, and showed great potential when used to characterise the lateritic goethite samples, certainly suggesting that ferrihydrite could be present in these natural ore materials. With further refinement of the methodology, to enable a larger range of sample types to be accurately analysed, TGA is a technique which could be used as a screening tool for laterite ores.

Η υδροχλωρική δονεπεζίλη (Donepezil.HCl, DPZ) είναι ένα φάρμακο που λαμβάνεται για τη θεραπεία της νόσου Altzheimer. Δρα ως ανασολέας της ακετυλοχοληστερινάσης, ενός ενζύμου υπεύθυνου για την καταστροφή του νευροδιαβιβαστή ακετυλοχολίνη, αυξάνοντας το ποσό της ακετυλοχολίνης στον εγκέφαλο. Παρουσιάζει διάφορες κρυσταλλικές μορφές, συμπεριλαμβανομένων δύο ένυδρων, καθώς και μια άμορφη φάση. Τα δισκία Υδροχλωρικής Δονεπεζίλης λαμβάνονται από το στόμα και μπορεί να αποθηκευθούν για κάποιο χρονικό διάστημα πριν χρησιμοποιηθούν. Τα δισκία DPZ ισχύος 10 mg περιέχουν 3.6 % API, ενώ στις περιπτώσεις όπου λαμβάνει χώρα πολυμορφική μετατροπή, η επιμέρους περιεκτικότητα κάθε πολυμόρφου είναι ακόμα μικρότερη. Η ταυτοποίηση και ποσοτική ανάλυση των πολυμόρφων ή ένυδρων μορφών είναι δυνατή μόνο με τη χρήση περίθλασης ακτίνων Χ και δονητικών φασματοσκοπικών τεχνικών. Λόγω του μικρού ποσοστού της δραστικής ουσίας στα δισκία και της πιθανής παρουσίας περισσοτέρων του ενός πολυμόρφου αλλά και του μεγάλου σχετικά ορίου ανίχνευσης αυτών των τεχνικών η ταυτοποίηση και ποσοτική ανάλυση είναι μια αναλυτική πρόκληση. Στην παρούσα εργασία έγινε προσπάθεια ταυτοποίησης των κρυσταλλικών μορφών του DPZ σε δισκία και έλεγχος της σταθερότητάς τους μετά από διάφορες διαδικασίες παρασκευής των δισκίων, καθώς και μετά από αποθήκευση σε διάφορες συνθήκες υγρασίας και θερμοκρασίας, χρησιμοποιώντας τις πειραματικές τεχνικές XRD, FT-IR και FT-Raman. Παρατηρήθηκε ότι η προέλευση του API, οι συνθήκες αποθήκευσης και κυρίως η μέθοδος παρασκευής των δισκίων επηρεάζουν τη σταθερότητα των φαρμακευτικών σκευασμάτων. Με στόχο τη διερεύνηση της δυνατότητας ανάπτυξης ποσοτικών αναλυτικών μεθόδων προσδιορισμού των πολυμόρφων Ι και ΙΙΙ του DPZ σε δισκία, οι παραπάνω τεχνικές χρησιμοποιήθηκαν για τον υπολογισμό των ορίων ανίχνευσης των δύο πολυμόρφων (0.35% κ.β. για το πολύμορφο Ι και 0.44 % κ.β. για το πολύμορφο ΙΙΙ με την τεχνική Raman, 0.95% κ.β. για το πολύμορφο Ι και 1.3 % κ.β. για το πολύμορφο ΙΙΙ με την τεχνική XRD, 1.2% κ.β. για τη μορφή Ι και 1.0 % κ.β. για τη μορφή ΙΙΙ με την τεχνική IR, όπως προέκυψαν μετά από στατιστική επεξεργασία των πειραματικών δεδομένων των διαφόρων τεχνικών), καθώς και για τον ποσοτικό τους προσδιορισμό. Η τεχνική Raman φαίνεται να μπορεί χρησιμοποιηθεί για ποσοτική ανάλυση των πολυμόρφων Ι και ΙΙΙ του DPZ σε δισκία, ενώ επιπλέον η ποσοτική μέθοδος που παρουσιάσθηκε εδώ είναι απλή και μη καταστροφική για τα δείγματα. Η μέθοδος XRD μπορεί πιθανόν να χρησιμοποιηθεί για την ποσοτική ανάλυση δισκίων DPZ, με μεγαλύτερο όμως σφάλμα σε σύγκριση με την τεχνική Raman, ενώ η μέθοδος FT-IR ATR, παρέχει τα λιγότερο καλά ποσοτικά αποτελέσματα, ακόμα και στην περίπτωση που το δισκίο περιέχει αποκλειστικά το ένα από τα δύο πολύμορφα. Τέλος, με στόχο την ερμηνεία των φασμάτων δόνησης που καταγράφησαν στην παρούσα εργασία, υπολογίστηκαν η σταθερή δομή του μορίου της Δονεπεζίλης και της ένυδρης Δονεπεζίλης (με ένα μόριο νερού ανά μόριο Δονεπεζίλης) και τα φάσματα δόνησης (IR και Raman) με τις μεθόδους Hartree-Fock ab-initio και DFT (Density Functional Theory) και χρήση του υπολογιστικού πακέτου Gaussian09. / Donepezil hydrochloride (DPZ) is a medication used to treat Altzheimer’s disease. It acts as an inhibitor of acetylcholisterinase, an enzyme responsible for the destruction of the neurotransmitter acetylcholine, thus increasing the level of acetylcholine in the brain. As most of the pharmaceutical solids, DPZ exhibits polymorphism. Donepezil hydrochloride has different crystalline forms, including two hydrates, as well as an amorphous phase. DPZ is available for oral administration in tablets which can be stored for some time before use. In the present study, an effort was made to identify the crystal form of DPZ in tablets, as well as to test its stability against time, temperature and humidity, after various manufacturing processes, using XRD, FT-IR and FT-Raman techniques. The data showed that the origin of the API, the storing conditions and mainly the manufacturing process of the tablets affect the stability of the API. Quantitative determination of polymorphs I and III of DPZ in tablets was also attempted using the above experimental methods. Calibration models were constructed and applied in DPZ tablets. The detection limits of polymorphs I and III of DPZ for each technique, derived after statistical treatment of the experimental data, were calculated. Raman spectroscopy exhibited the lower detection limit (0.35 weigh % for polymorph Ι and 0.44 % weigh % for polymorph ΙΙΙ) compared with XRD (0.95% weigh % for polymorph Ι and 1.3 % weigh % for polymorph ΙΙΙ) and IR spectroscopy (1.2% weigh % for polymorph Ι and 1.0 % weigh % for polymorph ΙΙΙ). The data suggest that Raman spectroscopy could be applied to quantify polymorphs I and III in DPZ tablets; moreover, the Raman quantitative method presented in this work is simple and non-destructive for the tablets. The application of the X ray diffraction method for the quantitative analysis of polymorphs I and III in tablets yielded larger errors compared with Raman spectroscopy, while the FT-IR ATR technique yielded poor quantitative results, even in the case that only one polymorph was present in DPZ tablets. Finaly, in order to facilitate the assignment of the vibrational spectra recorded in this study, the optimized structure and the vibrational spectra (IR and Raman) of Donepezil and Donepezil hydrate (Donepezil:H20 = 1:1) molecules were calculated at the Hartree-Fock and DFT (Density Functional Theory) level of theory using the Gaussian 09 program package. The weigh % of the API in the tablets containing 10 mg of DPZ is 3.6 %. In cases where two or more polymorphs are present, the weigh % of each polymorphic form is lower. The difficulty in the identification and quantification of the crystal phase of DPZ is stemming from the small percentage of the API in the tablets, the considerable overlapping of DPZ XRPD patterns and IR and Raman spectra of the polymorphs and the excipients and the availability of various polymorphs.

De nos jours, la modification de surface fait l'objet d'attentions particulières en raison de sa variété d'applications dans divers domaines. Dans ce contexte, l'objectif de cette thèse a été de traiter de la modification localisée de surfaces dans des conditions douces en utilisant le microscope électrochimique à balayage (SECM). En tant que preuve de concept pour l'écriture directe, différentes stratégies ont été menées pour la modification de surface par gravure de matériaux, greffage de couche organique et modification de la structure chimique surfacique. Des surfaces de verre et d'or ont été les principaux substrats qui ont été modifiés du fait de leur large utilisation notamment dans les nanotechnologies. Cette thèse est présentée sous forme de quatre chapitres et le premier est consacré à la technique SECM ainsi qu'à la modification de surface en général. Les trois autres parties concernent le travail effectué pour valider le concept d'écriture directe. Dans la première partie, une matrice de silice synthétisée par voie sol-gel et dopée avec un ion métallique (cuivre ou or) est utilisée comme matériau d'écriture à l'aide d'une sonde locale (ultramicroéléctrode). Le SECM est utilisé en mode de rétroaction avec des médiateurs tels que viologène de méthyle et le p-benzoquinone. Le diamètre de l'ultramicroélectrode (UME) et la durée d'hydrolyse ont été des facteurs pris en compte pour étudier l'effet sur la taille des plots métalliques électrogénérés. Dans la deuxième partie, la gravure par voie humide localisée de la surface de l'or a été réalisée en utilisant le SECM opérant dans un électrolyte à base de diméthylsulfoxide chargé avec de l'iode. Dans cette méthode, une UME est positionnée (à une distance connue) à proximité de la surface d'or pour générer électrochimiquement l'ion triiodure à la pointe de l'UME de platine, agissant comme oxydant à la surface d'or. La troisième partie comprend deux travaux expérimentaux différents mais complémentaires. Le premier porte sur la réduction électrochimique sur électrode d'or d'un sel de diazonium préparé à partir de l'éthylènediamine, une molécule aliphatique. Pour la première fois, la fonctionnalisation covalente sur or d'un sel de diazonium est démontrée via la diazotation d'un groupe amino de l'éthylènediamine. Dans la seconde partie, un substrat de verre a été greffé par un film à base de 3-aminopropyle silane qui a été réalisée par un procédé sol-gel. Ensuite, la lame de verre modifiée a été fonctionnalisée avec du glutaraldéhyde pour greffer la tyrosinase. Enfin, le mode de réaction du SECM a également été utilisé pour vérifier l’activité catalytique de cette enzyme. La pointe de l’UME est positionnée à proximité de la surface modifiée par l’enzyme afin de réaliser une mesure de courant de l’activité enzymatique à partir d’un balayage horizontal dans le plan x-y. / Nowadays, the modification of surfaces has drawn more attention due to its variety of applications in various domains. Therefore, the purpose of this thesis deals with the localized modification of surfaces in mild condition by using the scanning electrochemical microscope (SECM) instrument. As a proof of concept for direct writing, different strategies have been used for surface modifications through removing surface materials, grafted organic layer and changing the chemical structure of the surface. Gold wafer and glass surfaces were the main substrates which have been modified since these materials are very used especially in nanotechnologies. This dissertation is conducted in four chapters and the first one focuses on SECM technique and surface modifications in general. The three other parts concern the work performed to validate the concept of direct writing. In the first part, metal ion (copper and gold)-doped silica matrices have been prepared by the well-known sol-gel method. Copper and gold metallic particles are produced locally by using the SECM in feedback mode with mediators such as methyl viologen and p-benzoquinone. The diameter of ultramicroelectrode (UME) tip and hydrolysis period were factors taken into account to study the effect on the size of electrogenerated metallic spots. In the second part, the localized wet etching of gold surface has been achieved by using SECM where a dimethylsulfoxide-based electrolyte charged with iodine is used. In this method an UME probe is positioned (at a known distance) close to the gold surface. Friendly environment method was used as etching process to generate electrochemically triiodide ion at the platinum UME tip, acting as an oxidant for gold surface. he third part includes two different experimental works. The first one covers the electrochemical reduction on gold electrode of diazonium salt prepared from ethylenediamine, an aliphatic diamine molecule. For the first time, the covalent functionalization on gold of a diazonium salt is demonstrated, and required diazotization of one amine group from ethylenediamine. In the second work, glass substrate was grafted by 3-aminopropyl silane film which was performed by sol-gel method. Then the modified-glass slide was functionalized by glutaraldehyde solution in order to immobilize tyrosinase molecules. Finally, the feedback mode of SECM has also been used to monitor the catalytic activity of tyrosinase. The tip of ultramicroelectrode was positioned close to the enzyme-modified surface and was scanned horizontally in x-y plane while measuring current from re-generated mediator molecules was carried out.

Neste trabalho foram sintetizados a poli-2-etinilpiridina (P2EP), poli-4etinilpiridina (P4EP), o iodeto de poli(2-N-t-butilpiridiniumilacetileno) (P2EPtBu) e a poli-β-etinilnaftaleno (P&#946:EN), os quais são poliacetilenos substituídos. Estes polímeros, juntamente com o cloreto de poli(2-piridínio-2-piridilacetileno) (P2EPH), foram caracterizados por espectroscopia vibracional no infravermelho e Raman. Estes polímeros apresentaram variação na posição das bandas Raman com a energia da radiação excitante - chamada dispersão Raman ou fotosseletividade - da ordem de 10 cm-1, bem inferior ao apresentado pelo poliacetileno (cerca de 60 cm-1). Este deslocamento foi interpretado utilizando-se dois dos modelos existentes para descrever este fenômeno: o Modelo de Modo de Amplitude (AMM) e o Modelo de Coordenada de Conjugação Efetiva (ECCM), os quais fornecem informações sobre a estrutura polimérica e sobre seus níveis eletrônicos. Utilizando-se o AMM foi possível obter informações sobre os níveis eletrônicos excitados de mesma simetria que o estado eletrônico fundamental. Por outro lado, o ECCM, com a ajuda de cálculos DFT, mostrou diferenças na extensão da conjugação e no grau de dimerização entre o P2EP na forma cis e trans e indicou que este polímero apresentava, predominantemente, a estrutura cis, fato este confirmado pelos espectros no infravermelho. A dopagem com I2 provocou efeitos diferentes na estrutura dos polímeros. Os espectros no infravermelho dos polímeros dopados indicaram que o P2EP e o P2EPH apresentaram aumento na quantidade de segmentos cis enquanto o P2EPtBu apresentou diminuição na quantidade desses segmentos. Os espectros Raman dos polímeros dopados confirmaram os dados dos espectros no infravermelho. Esta diferença foi interpretada como sendo devida à diferença no volume do substituinte, pois grupos volumosos favorecem o isômero trans-cisóide onde a distância entre os substituintes é maior. A dopagem também levou a um aumento na condutividade dos polímeros, porém os valores de condutividade obtidos foram bem inferiores que os apresentados pelo poliacetileno dopado (10-5 a 10-7 contra 102 S cm-1, tipicamente). / In this work poly-2-ethynylpyridine (P2EP), poly-4-ethynylpyridine (P2EP), poly(2-N-t-butylpyridiniumylacetylene) iodide (P2EPtBu) and poly-β-pethynylnaphthalene (PβEN) were synthesized. These polymers, which are polyacetylenes derivatives, and poly(2-pyridinium-2-pyridylacetylene) chloride (P2EPH) were analyzed by vibrational techniques. It was observed that some Raman band positions shifted when excitation energy was changed, however this shift (ca. 10 cm-1) was substantially smaller than the presented by polyacetylene (ca. 60 cm-1). This phenomenon called Raman dispersion or photoselectivity - was examinated using Amplitude Mode Model (AMM) and Effective Conjugation Coordinate Model (ECCM) and gave us important information about polymer structure and its electronic energies levels. Using AMM it was possible to infere information about electronic excited states with the same symmetry of the electronic ground state. ECCM gave us evidences about differences in conjugation extension and dimerization degree between cis and trans structures. Besides this, ECCM was successful in indicating cis structure to P2EP. Infrared spectrum confirmed that this polymer is mainly cis. I2 doping of P2EP, P2EPH and P2EPtBu provoked differents perturbations in these systems. P2EP and P2EPH increased their cis segments amount, as showed by infrared spectra. On the other hand, this doping induced the decrease of cis segments in P2EPtBu. Raman spectroscopy supported these conclusions too. This difference was interpretated as due to the side group volume, which could favour one or another isomerization. Electronic conductivity increased by doping for all these three polymers, however the conductivity is considerably lower than the presented by polyacetylene (from 10-5 to 10-7 S cm-1 for these substituted polyacetylenes against typically 10-2 S cm-1 for polyacetylene).

Εξαιτίας των πολλών εφαρμογών του καδμίου στη βιομηχανία αλλά και των ταυτόχρονα τοξικών ιδιοτήτων του στα έμβια όντα, η απομάκρυνση του Cd(II) από υδατικά απόβλητα είναι σήμερα ένα ενδιαφέρον θέμα έρευνας στην Περιβαλλοντική Χημεία. Η υγρή εκχύλιση (εκχύλιση με διαλύτη) είναι μια αποτελεσματική μέθοδος για την απομάκρυνση του Cd(II) από διαλύματα που περιέχουν ιόντα χλωριδίων, θειικά ή φωσφορικά διαλύματα. Κατά την υγρή εκχύλιση το μεταλλοϊόν συμπλοκοποιείται με έναν οργανικό υποκαταστάτη σχηματίζοντας ένα χημικό είδος που μεταφέρεται από την υδατική στην οργανική φάση σε ένα διφασικό σύστημα. Αναφέρθηκε πρόσφατα ότι το κάδμιο(II) μπορεί να εκχυλιστεί από μέσα που περιέχουν ιόντα χλωριδίων ή ιόντα χλωριδίων/νιτρικών χρησιμοποιώντας δύο 2-πυρίδυλο κετονοξίμες, και συγκεκριμένα την 1-(2-πυριδυλο)-δεκατρια-1-όνη οξίμη (2PC12) και την 1-(2-πυριδυλο)-δεκαπεντε-1-όνη (2PC14), ως μέσα εκχύλισης. Ο στόχος αυτής της εργασίας είναι να μοντελοποιήσει την φύση των χημικών ειδών που σχηματίζονται κατα την διαδικασία της υγρής εκχύλισης του Cd(II) χρησιμοποιώντας 2-πυρίδυλο κετονοξίμες ως μέσα εκχύλισης. Έτσι μελετήσαμε τις αντιδράσεις διαφόρων πηγών Cd(II) με 2-πυρίδυλο οξίμες ως υποκαταστάτες (Σχήμα I). Οι υποκαταστάτες που χρησιμοποιήθηκαν ήταν οι 2-πυριδίνη αλδοξίμη (paoH), μέθυλο 2-πυρίδυλο κετονοξίμη (mepaoH), φαίνυλο 2-πυρίδυλο κετονοξίμη (phpaoH) και πυριδινη-2-αμιδοξίμη (ampaoH). Η συστηματική συνθετική μας διερεύνηση οδήγησε στα προϊόντα [CdI2(paoH)2] (1), [Cd(NO3)2(paoH)2] (2), [Cd(NO3)(H2O)(paoH)2](NO3) (3), [Cd(paoH)3](ClO4)2 (4), [Cd(pao)2(paoH)2] (5), [CdI2(mepaoH)2] (6), [Cd(NO3)2(mepaoH)2] (7), [Cd(O2CMe)2(mepaoH)2] (8), [CdCl2(phpaoH)2] (9), [Cd4Br8(phpaoH)4]n (10), [CdI2(phpaoH)2] (11), [Cd(NO3)2(phpaoH)2] (12), [Cd2(Ο2CMe)4(phpaoH)2]n (13), [CdCl2(ampaoH)2] (14), [CdBr2(ampaoH)2] (15), [CdI2(ampaoH)2] (16) και [Cd(NO3)2(ampaoH)2] (17). Οι μοριακές και κρυσταλλικές δομές των συμπλόκων προσδιορίστηκαν με κρυσταλλογραφία ακτίνων Χ επί μονοκρυστάλλων των ενώσεων (Σχήμα II). Τα σύμπλοκα χαρακτηρίσθηκαν με στοιχειακές αναλύσεις και διάφορες φασματοσκοπικές μεθόδους (IR, Raman, NMR, Φωτοφωταύγεια). Τα φασματοσκοπικά δεδομένα μελετήθηκαν σε σχέση με τις γνωστές δομές των ενώσεων. Tα περισσότερα σύμπλοκα είναι μονοπυρηνικά. Οι ενώσεις 10 και 13 είναι 1D πολυμερή ένταξης. Τα μόρια paoH, mepaoH, phpaoH και ampaoH συμπεριφέρονται ως Ν(πυρίδυλο), Ν(οξιμικό)-διδοντικοί χηλικοί υποκαταστάτες. Τα ιόντα CdII στα σύμπλοκα είναι 6-, 7- και 8-ενταγμένα. Οι κρυσταλλικές δομές των περισσοτέρων συμπλόκων σταθεροποιούνται από δεσμούς Η. Τα περισσότερα σύμπλοκα διασπώνται στο DMSO, όπως προκύπτει από τα 1Η ΝΜR φάσματά τους. Τα σύμπλοκα 9, 14 και 12, 17 μοντελοποιούν τα χημικά είδη [CdCl2(μέσο εκχύλισης)2] και [Cd(NO3)2(μέσο εκχύλισης)2] που έχει προταθεί ότι σχηματίζονται κατά τη διαδικασία της υγρής εκχύλισης του Cd(II) με τη χρησιμοποίηση των 2PC12 και 2PC14 σε διαλύματα χλωριδίων και χλωριδίων/νιτρικών, αντίστοιχα. Με επιφύλαξη προτείνουμε ότι η ικανότητα των 2-πυρίδυλο κετοξιμών να απομακρύνουν Cd(II) από υδατικά απόβλητα οφείλεται στην ισχυρά χηλική φύση των μέσων εκχύλισης. / Because of the wide application of cadmium in various industrial facilities and its simultaneous toxic properties for organisms, the removal of Cd(II) from wastewater is a currently hot topic in environmental chemistry. Solvent extraction is an efficient method from the removal of Cd(II) from chloride, sulfate or phosphate solutions. Solvent extraction occurs when a metal ion is coordinated to an organic ligand to form a species that is transferred from the aqueous to the organic phase in a two-phase system. It has recently been reported that cadmium(II) can be extracted from chloride or chloride/nitrate media using two 2-pyridyl ketoximes, namely 1-(2-pyridyl)-trideca-1-one oxime (2PC12) and 1-(2-pyridyl)-pentadeca-one oxime (2PC14), as extractants and chloroform or hydracarbons as organic solvents [A. Parus, K. Wieszczycka, A. Olszanowski (2011) Hydrometallurgy, 105, 284]. The goal of this work is to model the nature of the chemical species that are formed during the solvent extraction of Cd(II) using 2-pyridyl ketoximes as extractants. Thus, we studied the reactions of various Cd(II) sources with 2-pyridyl oximes as ligands (Scheme I). The ligands used were 2-pyridine aldoxime (paoH), methyl 2-pyridyl ketoxime (mepaoH), phenyl 2-pyridyl ketoxime (phpaoH) and pyridine-2-amidoxime (ampaoH). Our systematic investigations gave the products [CdI2(paoH)2] (1), [Cd(NO3)2(paoH)2] (2), [Cd(NO3)(H2O)(paoH)2](NO3) (3), [Cd(paoH)3](ClO4)2 (4), [Cd(pao)2(paoH)2] (5), [CdI2(mepaoH)2] (6), [Cd(NO3)2(mepaoH)2] (7), [Cd(O2CMe)2(mepaoH)2] (8), [CdCl2(phpaoH)2] (9), [Cd4Br8(phpaoH)4]n (10), [CdI2(phpaoH)2] (11), [Cd(NO3)2(phpaoH)2] (12), [Cd2(Ο2CMe)4(phpaoH)2]n (13), [CdCl2(ampaoH)2] (14), [CdBr2(ampaoH)2] (15), [CdI2(ampaoH)2] (16) and [Cd(NO3)2(ampaoH)2] (17). The molecular and crystal structures of the complexes have been determined by single-crystal, X-ray crystallography (Scheme II). The complexes have been characterized by elemental analyses and various spectroscopic techniques (IR, Raman, NMR, Photoluminescence). The spectroscopic data are discussed in terms of the known structures. Most complexes are mononuclear. Compounds 10 and 13 are 1D coordination polymers. The paoH, mepaoH, phpaoH and ampaoH molecules behave as N(pyridyl), N(oxime)–bidentate chelating ligands. The CdII ions in the complexes are 6-, 7- and 8-coordinate. The crystal structures of most complexes are stabilized by H bonds. Most of the complexes decompose in DMSO, as evidenced by 1H NMR spectroscopy. Complexes 9, 14 and 12, 17 model the chemical species [CdCl2(extractant)2] and [Cd(NO3)2(extractant)2] that have been proposed to form during the solvent extraction of Cd(II) using 2PC12 and 2PC14 in chloride and dilute chloride/concentrated nitrate solutions, respectively. We tentatively propose that the ability of 2-pyridyl ketoximes to remove Cd(II) from wastewater is due to the strongly chelating nature of the extractants.

Neste trabalho foram sintetizados a poli-2-etinilpiridina (P2EP), poli-4etinilpiridina (P4EP), o iodeto de poli(2-N-t-butilpiridiniumilacetileno) (P2EPtBu) e a poli-β-etinilnaftaleno (P&#946:EN), os quais são poliacetilenos substituídos. Estes polímeros, juntamente com o cloreto de poli(2-piridínio-2-piridilacetileno) (P2EPH), foram caracterizados por espectroscopia vibracional no infravermelho e Raman. Estes polímeros apresentaram variação na posição das bandas Raman com a energia da radiação excitante - chamada dispersão Raman ou fotosseletividade - da ordem de 10 cm-1, bem inferior ao apresentado pelo poliacetileno (cerca de 60 cm-1). Este deslocamento foi interpretado utilizando-se dois dos modelos existentes para descrever este fenômeno: o Modelo de Modo de Amplitude (AMM) e o Modelo de Coordenada de Conjugação Efetiva (ECCM), os quais fornecem informações sobre a estrutura polimérica e sobre seus níveis eletrônicos. Utilizando-se o AMM foi possível obter informações sobre os níveis eletrônicos excitados de mesma simetria que o estado eletrônico fundamental. Por outro lado, o ECCM, com a ajuda de cálculos DFT, mostrou diferenças na extensão da conjugação e no grau de dimerização entre o P2EP na forma cis e trans e indicou que este polímero apresentava, predominantemente, a estrutura cis, fato este confirmado pelos espectros no infravermelho. A dopagem com I2 provocou efeitos diferentes na estrutura dos polímeros. Os espectros no infravermelho dos polímeros dopados indicaram que o P2EP e o P2EPH apresentaram aumento na quantidade de segmentos cis enquanto o P2EPtBu apresentou diminuição na quantidade desses segmentos. Os espectros Raman dos polímeros dopados confirmaram os dados dos espectros no infravermelho. Esta diferença foi interpretada como sendo devida à diferença no volume do substituinte, pois grupos volumosos favorecem o isômero trans-cisóide onde a distância entre os substituintes é maior. A dopagem também levou a um aumento na condutividade dos polímeros, porém os valores de condutividade obtidos foram bem inferiores que os apresentados pelo poliacetileno dopado (10-5 a 10-7 contra 102 S cm-1, tipicamente). / In this work poly-2-ethynylpyridine (P2EP), poly-4-ethynylpyridine (P2EP), poly(2-N-t-butylpyridiniumylacetylene) iodide (P2EPtBu) and poly-β-pethynylnaphthalene (PβEN) were synthesized. These polymers, which are polyacetylenes derivatives, and poly(2-pyridinium-2-pyridylacetylene) chloride (P2EPH) were analyzed by vibrational techniques. It was observed that some Raman band positions shifted when excitation energy was changed, however this shift (ca. 10 cm-1) was substantially smaller than the presented by polyacetylene (ca. 60 cm-1). This phenomenon called Raman dispersion or photoselectivity - was examinated using Amplitude Mode Model (AMM) and Effective Conjugation Coordinate Model (ECCM) and gave us important information about polymer structure and its electronic energies levels. Using AMM it was possible to infere information about electronic excited states with the same symmetry of the electronic ground state. ECCM gave us evidences about differences in conjugation extension and dimerization degree between cis and trans structures. Besides this, ECCM was successful in indicating cis structure to P2EP. Infrared spectrum confirmed that this polymer is mainly cis. I2 doping of P2EP, P2EPH and P2EPtBu provoked differents perturbations in these systems. P2EP and P2EPH increased their cis segments amount, as showed by infrared spectra. On the other hand, this doping induced the decrease of cis segments in P2EPtBu. Raman spectroscopy supported these conclusions too. This difference was interpretated as due to the side group volume, which could favour one or another isomerization. Electronic conductivity increased by doping for all these three polymers, however the conductivity is considerably lower than the presented by polyacetylene (from 10-5 to 10-7 S cm-1 for these substituted polyacetylenes against typically 10-2 S cm-1 for polyacetylene).

Ο αρχικός στόχος της εργασίας μας ήταν η παρασκευή ετερομεταλλικών συμπλόκων Cd(II)/Ln(III) [Ln=λανθανίδιο] για να μελετηθούν οι φωτοφυσικές τους ιδιότητες. Διάφορα συστήματα αντιδράσεων Cd(II)/Ln(III)/οργανικός υποκαταστάτης έδωσαν μόνο ομομεταλλικές ενώσεις Cd(II) ή Pr(III).Χρησιμοποιώντας διάφορα αντιδρώντα Cd(II) και Pr(NO3)3∙6H2O, παρασκευάστηκαν τα ακόλουθα σύμπλοκα: [CdCl2(PhpaoH)]n (1), [Cd(O2CMe)2(NH2paoH)2] (2), [Cd(ΝΟ3)2(tzpy)2] (3), [CdI2(tzpy)2] (4), [Pr(ΝΟ3)3(tzpy)2]∙tzpy (5∙tzpy), [Cd4(NO3)4{(py)2C(H)(O)}4] (6) [(py)2C(H)(O)- είναι το ανιόν της δι-2-πυρίδυλο μεθανόλης που σχηματίζεται in-situ από τη μεταλλο-υποβοηθούμενη αναγωγή της (py)2CO με MeOH κάτω από σολβοθερμικές συνθήκες], [Cd(ΝΟ3)2(aphz)2] (7), [CdI2(aphz)2]n (8), [Pr(ΝΟ3)3(aphz)2] (9), [CdI2(bphz)2] (10), [Cd(NO3)2(bzdhz)2] (11). Η αντίδραση του Pr(NO3)3∙6H2O με δύο ισοδύναμα bzdhz σε H2O/Me2CO οδήγησε στην απομόνωση της Ν,Ν’-δι-ισοπροπυλιδενε-βενζίλιο διυδραζόνη (L’). Οι δομές των ενώσεων 1-11 προσδιορίσθηκαν με κρυσταλλογραφία ακτίνων Χ μονοκρυστάλλου. Όλα τα σύμπλοκα χαρακτηρίσθηκαν με φασματοσκοπία IR, και επιλεγμένες ενώσεις με τεχνικές RAMAN και 1H NMR. Τα φασματοσκοπικά δεδομένα εξετάζονται σε σχέση με τις γνωστές δομές των ενώσεων και των τρόπων ένταξης των υποκαταστατών.Πιστεύουμε ότι τα αποτελέσματα που παρουσιάζονται στη Διπλωματική Εργασία συνιστούν συνεισφορά στη χημεία του καδμίου(ΙΙ) και του πρασεοδυμίου(ΙΙΙ), καθώς επίσης και στη χημεία ένταξης των οργανικών υποκαταστατών. / The original goal of this work was to prepare heterometallic Cd(II)/Ln(III) complexes (Ln=lanthanide) in order to study their photophysical properties. A variety of CdII/PrIII/organic ligand reaction schemes led to only homometallic Cd(II) or Pr(III) complexes.Employing various Cd(II) sources and Pr(NO3)3∙6H2O, as starting materials, the following complexes have been prepared: [CdCl2(PhpaoH)]n (1), [Cd(O2CMe)2(NH2paoH)2] (2), [Cd(ΝΟ3)2(tzpy)2] (3), [CdI2(tzpy)2] (4), [Pr(ΝΟ3)3(tzpy)2]∙tzpy (5∙tzpy), [Cd4(NO3)4{(py)2C(H)(O)}4] (6) [(py)2C(H)(O)- is the anion of di-2-pyridyl methanol formed in-situ by the metal ion-assisted reduction of (py)2CO in MeOH under solvothermal conditions], [Cd(ΝΟ3)2(aphz)2] (7), [CdI2(aphz)2]n (8), [Pr(ΝΟ3)3(aphz)2] (9), [CdI2(bphz)2] (10), [Cd(NO3)2(bzdhz)2] (11). The reaction of Pr(NO3)3∙6H2O and 2 equivalents of bzdhz in H2O/Me2CO led to the isolation of N,N’-di-isopropylidene-benzil dihydrazone (L’). The structures of 1-11 and L’ have been determined by single-crystal X-ray crystallography. All the complexes have been characterized by IR spectroscopy, and selected compounds by RAMAN and 1H NMR techniques. The spectroscopic data are discussed in terms of the known structures and the coordination modes of the ligands.We believe that our results contribute into the chemistry of cadmium(II) and the praseodymium(III), and into the coordination chemistry.