Two-dimensional conjugated covalent organic frameworks (2D c-COFs) are emerging semiconductor materials for optoelectronic and photothermal applications. In particular, the highly tailorable, semiconducting thiophene-based 2D c-COFs have attracted considerable interest due to their nontrivial physicochemical properties such as photo-activity, broad optical absorption, tunable electronic structures, and so forth. Herein, we demonstrate a novel, crystalline 2D c-COF based on thienyl-functionalized benzodithiophene (BDT) and biphenyl (BP) via the Schiff-base polycondensation reaction. The resultant BDT-BP-COF exhibits a broad optical absorption up to ca. 600 nm and decent π-conjugation along the 2D polymer skeleton, as revealed by the optical absorption and theoretical calculations. The favorable π-conjugation and the abundant electron-rich thiophene units confer excellent photo-activity to BDT-BP-COF towards the usage of solar energy. As a proof-of-concept application, we explore BDT-BP-COF in photothermal conversion, in which it shows a fast surface-temperature increase upon light irradiation for seconds.

Collagen is one of the most abundant human proteins. It exists as a right-handed superhelix called the triple helix. The triple helix consists of three left-handed polyproline type II (PPII helices) that intertwine around a common axis. Each PPII helix has the repeating peptide sequence (Gly–Xaa–Yaa)n with a high content of (2S)-proline (Pro) in the Xaa position (ca. 28%) and (2S,4R)-hydroxyproline (Hyp) in the Yaa position (ca. 38%). Unique to the prolyl amide is the ease of cis-trans isomerization. Since the triple helix necessitates that all peptide bonds be in the trans conformation, isomerization is the rate-limiting step in collagen folding. However, eliminating isomerization with a trans-locked alkene isostere destabilizes collagen-like peptides. Collagen is stabilized by electronic interactions, namely the n→π* interaction. Halo-alkene isosteres may be used to recapture these electronic interactions and stabilize a collagen-like peptide. An in-depth conformational analysis was conducted at the MP2/6-311+G(2d,p) level of theory to determine the viability of conformationally-locked halo-alkene isosteres. Fluoro-alkenes and chloro-alkenes were modeled at both the Gly–Pro and Pro–Pro (as a Pro–Hyp mimic) amide positions. Compared to the collagen crystal structure PDB ID: 1K6F, we found the fluoro-alkenes were closer geometric matches to both Gly–Pro and Pro–Pro than the corresponding chloro-alkenes. The chloro-alkene was predicted to have stronger n→π* interactions. The trans-locked proteo-alkene was also analyzed to understand why it destabilized the triple helix. We found that these models had other local minima close to the desired PPII geometry, likely leading to enhanced backbone flexibility. This deleterious flexibility was not predicted for either fluoro-alkene or chloro-alkene models. The conformationally-locked halo-alkene isostere Fmoc–Gly–Ψ[(Z)CF=C]-Pro–Hyp(tBu)–OH was designed and synthesized as a (Z)-fluoro-alkene Gly–Pro isostere. We used the chiral catalyst, L-Thr, for asymmetric aldol addition to cyclopentanone, which inadvertently enhanced the yield of the wrong enantiomer, in contrast with aldol addition to cyclohexanone. A Mg2+-promoted Horner-Wadsworth-Emmons reaction afforded the (Z)-fluoro-alkene over the (E)-fluoro-alkene in about a 2:1 ratio. The two diastereomers, Fmoc–Gly–Ψ[(Z)CF=C]-L-Pro–Hyp(tBu)–OH and Fmoc–Gly–Ψ[(Z)CF=C]-D-Pro–Hyp(tBu)–OH were separated by supercritical CO2 chromatography. The collagen-like peptides Ac–(Gly–Pro–Hyp)3–Gly–Ψ[(Z)CF=C]-L-Pro–Hyp–(Gly–Pro–Hyp)4–Gly–Gly–Tyr–NH2, Ac–(Gly–Pro–Hyp)3–Gly–Ψ[(Z)CF=C]-D-Pro–Hyp–(Gly–Pro–Hyp)4–Gly–Gly–Tyr–NH2, and the control peptide Ac–(Gly–Pro–Hyp)8–Gly–Gly–Tyr–NH2 were synthesized on solid-phase resin. The CD spectra of all three peptides showed the characteristic collagen triple-helix signature. The folding stability was determined by thermal melting (Tm). The peptide with the fluoro-alkene guest, Gly–Ψ[(Z)CF=C]-L-Pro–Hyp, was found to have a Tm value of 42.2 °C. The Tm of the control peptide was found to be 49.0 °C, a difference in stability of only ΔTm –6.8. Thus, the (Z)-fluoro-alkene as a Gly–Pro isostere forms a relatively stable triple helix. The peptide with the Gly–Ψ[(Z)CF=C]-D-Pro–Hyp guest was shown to have a linear relationship between ellipticity and temperature, indicating that a stable triple helix did not form. The enhanced stability of the (Z)-fluoro-alkene compared to the (E)-alkene Gly–Pro isostere (Tm = 28.3 °C) may be due to a stabilizing n→π* interaction, as determined by NMR deshielding of the 19F nucleus in the collagen-like peptide. In biological systems, isomerization of the prolyl amide is catalyzed by enzymes called PPIases. The PPIase Pin1 specifically catalyzes isomerization of the pSer–Pro sequence from the cis-conformation to the trans-conformation. Pin1 plays a crucial role in the G2→M transition of the cell cycle, implying the importance of cis-trans isomerization. The dipeptides H–Ser–Ψ[(Z)CH=C]-Pro–OH, H–Ser–Ψ[(E)CH=C]-Pro–OH and native H–Ser–Pro–OH were synthesized by literature methods, and activated for aminoacylation of tRNACUA for in vitro transcription-translation. Aminoacylation by chemical methods required the synthesis of a pdCpA dinucleotide. Formation of the dipeptide-dinucleotide complex was not completed because protection of the Ser side chain was problematic. On the other hand, conversion of the dipeptide into the 3,5-dinitrobenzyl ester conjugate allowed for enzymatic aminoacylation using the dFx flexizyme, an RNA enzyme. The native dipeptide was successfully coupled to tRNACUA and is ready for incorporation into a full-length Bora protein by in vitro transcription-translation. Both cis- and trans-locked alkene mimics have been converted to their respective 3,5-dinitrobenzyl ester conjugates. / Doctor of Philosophy / The proline amide (Xaa–Pro) in peptides and proteins is unique in that it allows for cis-trans isomerization. The triple-helix region of human collagen consists mostly of the repeating sequence (Gly–Pro–Hyp)n. Xaa–Pro amide-bond isomerization is rate-limiting for triple-helix formation. We eliminated isomerization at one position in a collagen-like peptide with a locked alkene mimic of Gly–Pro to attempt to stablize the triple-helix. Our computational results predicted that a fluoro-alkene Gly–Pro isostere would be a close geometric match for the native amide. Experimental results showed that a collagen-like peptide with a fluoro-alkene Gly–Pro isostere has an unfolding temperature that is 6.9 °C lower than the native control peptide. 19F NMR data of the collagen-like peptide shows a surprising deshielding of the fluorine nucleus, suggesting its participation in a stabilizing n→π* electronic interaction, similar to the native amide. Isomerization also plays a key role in proper cell division. We followed established methods to synthesize the cis- and trans-locked alkene mimics of Boc–Ser–Pro–OH and converted them into the 3,5-dinitrobenzyl ester conjugates. The 3,5-dinitrobenzyl ester is recognized by the dinitrobenzyl flexizyme (dFx) for enzymatic aminoacylation of tRNA. Once the alkene isosteres are aminoacylated, they will be incorporated into a full-length cell cycle regulatory protein called Bora to determine whether the cis- or trans-Pro state is necessary for healthy human mitosis, and which results in cancerous human mitosis.

A l'aide d'un spectre de fluorescence de résonance à bande étroite obtenu avec une nano-cellule d'épaisseur L= [lambda]/2 et des résonances VSOP formées pour une épaisseur L =[lambda] ([lambda] est la longueur d'onde de la radiation résonnante), cette thèse présente pour la première fois une étude expérimentale du comportement en fréquence et en intensité (probabilités de transition) des transitions atomiques de la structure hyperfine entre sous-niveaux Zeeman des raies D1 and D2 pour le 85Rb et le 87Rb en présence de champs magnétiques extérieurs compris entre 5 et 7000 G. Le comportement d'une dizaine de transitions atomiques inétudiées à ce jour a été analysé et nous avons démontré que l'intensité de ces raies peut montrer alternativement de grandes variations : jusqu'à un facteur 10 de taux de croissance ou de décroissance. Pour la première fois, nous avons parfaitement enregistré des résonances VSOP dans le cas où un gaz tampon (néon de pression partielle 6 torr) est introduit dans la nano-cellule d'épaisseur L =[lambda], alors que l'addition d'un gaz tampon (néon) même à une pression partielle de 0,1 torr, dans une cellule d'épaisseur centimétrique conduit à une complète disparition de ces résonances VSOP obtenues par la méthode usuelle d'absorption saturée. Enfin, nous avons montré pour la première fois que la largeur spectrale d'un spectre de fluorescence de résonance d'une nano-cellule de rubidium d'épaisseur L= [lambda]/2, quelques soient les pressions du gaz tampon (néon), est beaucoup plus étroite (6 à 8 fois) que celle obtenue avec une cellule centimétrique de rubidium pour les mêmes valeurs de pressions / Using a narrow-band resonant fluorescence spectra from a nano-cell with a thickness of L= [lambda]/2, and VSOP resonances formed at a thickness L =[lambda] ([lambda] is the wavelength of the resonant radiation), for the first time it was experimentally investigated the behaviour of the frequency and intensity (transition probabilities) of the atomic hyperfine structure transitions between the 85Rb, 87Rb, D1 and D2 lines Zeeman sublevels in external magnetic fields in range 5 - 7000G. The behaviour of tens of previously unstudied atomic transitions was analyzed and it is demonstrated that the intensities of these lines can both greatly increase, and decrease (tenfold). For the first time it is demonstrated that, in the case of partial pressure of neon buffer gas up to 6~torr into the nano-cell of thickness L = [lambda] filled with Rb, VSOP resonances are recorded confidently, while the addition of 0.1~torr neon buffer gas in a cell of a centimeter thickness leads to the complete disappearance of VSOP resonances formed with the help of the widely used technique of saturated absorption. It is demonstrated for the first time that the spectral width of the resonant fluorescence spectra of the rubidium nano-cell with thickness L= [lambda]/2, for all values of the neon buffer gas pressures is much narrower (6-8 times) compared with the resonant fluorescence spectra of an ordinary centimeter cell containing rubidium with the same pressures of neon

Using a narrow-band resonant fluorescence spectra from a nano-cell with a thickness of L= [lambda]/2, and VSOP resonances formed at a thickness L =[lambda] ([lambda] is the wavelength of the resonant radiation), for the first time it was experimentally investigated the behaviour of the frequency and intensity (transition probabilities) of the atomic hyperfine structure transitions between the 85Rb, 87Rb, D1 and D2 lines Zeeman sublevels in external magnetic fields in range 5 - 7000G. The behaviour of tens of previously unstudied atomic transitions was analyzed and it is demonstrated that the intensities of these lines can both greatly increase, and decrease (tenfold). For the first time it is demonstrated that, in the case of partial pressure of neon buffer gas up to 6~torr into the nano-cell of thickness L = [lambda] filled with Rb, VSOP resonances are recorded confidently, while the addition of 0.1~torr neon buffer gas in a cell of a centimeter thickness leads to the complete disappearance of VSOP resonances formed with the help of the widely used technique of saturated absorption. It is demonstrated for the first time that the spectral width of the resonant fluorescence spectra of the rubidium nano-cell with thickness L= [lambda]/2, for all values of the neon buffer gas pressures is much narrower (6-8 times) compared with the resonant fluorescence spectra of an ordinary centimeter cell containing rubidium with the same pressures of neon

Ο σχεδιασμός και η εφαρμογή Περιφερειακών Δορυφόρων Λογαριασμών Τουρισμού (Π-ΔΛΤ) στον ελλαδικό χώρο αποτελεί ένα από τα κύρια ζητούμενα από πλευράς τουριστικής και γενικότερα οικονομικής πολιτικής σε επίπεδο περιφέρειας. Η παρούσα διατριβή προσεγγίζει το πλαίσιο των Δορυφόρων Λογαριασμών Τουρισμού (ΔΛΤ) και την μεθοδολογία προσαρμογής τους σε περιφερειακό επίπεδο. Παρεμβαίνει με τις απαραίτητες μεθοδολογικές αναδιατάξεις σε ένα συστηματοποιημένο πλαίσιο που προτείνει ο Παγκόσμιος Οργανισμός Τουρισμού (ΠΟΤ) για την αξιολογική προσέγγιση των στατιστικών πηγών και δεδομένων με αναλυτική αξία για την κατάρτιση ΔΛΤ. Οι αναδιατάξεις στο πλαίσιο συντελούνται σε δύο επίπεδα. Το πρώτο αφορά στην επέκταση των αναλυτικών του δυνατοτήτων σε περιφερειακό επίπεδο ανάλυσης. Σε δεύτερο επίπεδο οι τροποποιήσεις στο πλαίσιο ακολουθούν τις θεωρητικές και μεθοδολογικές αναθεωρήσεις που έχουν συντελεστεί στα προσφάτως αναθεωρημένα διεθνή πρότυπα για την τουριστική στατιστική, τους Δορυφόρους Λογαριασμούς Τουρισμού και τα μακροοικονομικά πλαίσια με τα οποία συνδέονται. Ως παράδειγμα εφαρμογής του αναβαθμισμένου πλέον πλαισίου έχει επιλεγεί η περίπτωση της Ελλάδος. Η μεθοδολογική και αξιολογική προσέγγιση της διατριβής επιφέρει βελτιώσεις στο πλαίσιο καταγραφής και αξιολόγησης του ΠΟΤ και χαρτογραφεί το στατιστικό σύστημα της χώρας κατά τρόπο συστηματοποιημένο ως προς τις αναλυτικές ανάγκες των Π-ΔΛΤ, συνιστώντας ένα από τα πρώτα θεμελιώδη βήματα προς την μακρά και απαιτητική πορεία για την κατάρτισή τους στην χώρα μας. / Designing and implementing Regional Tourism Satellite Accounts (R-TSA) in Greece is one of the key objectives in terms of tourism and general economic policy at regional level. This thesis approaches the Tourism Satellite Account (TSA) framework and its methodological adaptation to regional level. It proposes the necessary methodological adjustments in a systematic framework recommended by the World Tourism Organization (UNWTO) for documenting tourism statistics for TSA compilation. Framework adjustments take place at a twofold level: a) expanding the analytical capability at regional level and b) adapting the structure according to the theoretical and methodological revisions that have taken place in recently revised international standards for tourism statistics, Tourism Satellite Accounts and the macroeconomic frameworks with which they are linked. Greece has been chosen as a case study for applying the adjusted framework at regional level. The followed methodological and evaluative approach has improved the UNWTO framework for documenting tourism statistics and has led to a systemised mapping of the Greek statistical system in relation to the analytical needs projected for the compilation of R-TSAs, constituting one of the first fundamental steps towards a long and demanding process.

The present Doctoral Thesis focuses on the investigation, characterization and influence of polyacrylic materials in different scientific and technological disciplines via a detailed computer simulation using the Molecular Dynamics (MD) technique, in conjunction with the very accurate, all-atom Dreiding force-field. The main research concepts and objectives are discussed and analyzed in three separate parts. In the first part, atomistic configurations of two model pressure-sensitive acrylic adhesives (PSAs), the atactic homopolymer poly(n-BA) [poly(n-butyl acrylate)] and the atactic copolymer poly(n-BA-co-AA) [poly(n-butyl acrylate-co-acrylic acid)] in the bulk phase or confined between two selected substrates, glassy silica (SiO2) and metallic α-ferrite (α-Fe), were built and simulated by MD in the NPT statistical ensemble. First, an equilibration cycle consisting of temperature annealings and coolings was followed, in order to generate well-equilibrated configurations of the PSA systems. Detailed results from the atomistic simulations are presented concerning their volumetric behavior, glass transition temperature, conformational, structural, viscoelastic and dynamic properties. Particular emphasis was given to the analysis and characterization of the hydrogen bonds that form in the poly(n-BA-co-AA) system. By analyzing the MD trajectories, poly(n-BA-co-AA) was found to exhibit a higher density than poly(n-BA) by about 7% at all temperatures, to be characterized by smaller-size chains for a given molecular weight (MW), to exhibit significantly slower terminal and segmental dynamics properties, and to be characterized by a glass transition temperature that was approximately 40% higher than that of poly(n-BA). We also examined the type and degree of adsorption of the two acrylic systems on the selected substrates by analyzing the MD results for the local mass density as a function of distance from the solid plane and the distribution of adsorbed chain segments in train, loop, and tail conformations, and by computing the work of adhesion at the two substrates. The results revealed a stronger adsorption for both acrylics on the SiO2 surface due to highly attractive interactions between polymer molecules and substrate atoms, and as a consequence a higher value for the work of adhesion compared to that on the α-Fe surface. Furthermore, we have developed a generalized non-equilibrium molecular dynamics (NEMD) algorithm to simulate the mechanical response of the two adhesives under a uniaxial stretching deformation. In the second part of the Thesis, results have been obtained from a hierarchical simulation methodology that led to the prediction of the thermodynamic, conformational, structural, dynamic and mechanical properties of two polymer nanocomposites based on syndiotactic poly(methyl methacrylate) or sPMMA. The first was reinforced with uniformly dispersed graphene sheets and the second with fullerene particles. How graphene functionalization affects the elastic constants of the resulting nanocomposite has also been examined. The phase behavior of the nanocomposite (in particular as we varied the relative size between the sPMMA chains and the diameter of fullerene molecules) has also been studied as a function of fullerene volume fraction. The simulation strategy entailed three steps: 1) Generation of an initial structure, which was then subjected to potential energy minimization and detailed molecular dynamics (MD) simulations at T = 500K and P = 1atm to obtain well relaxed melt configurations of the nanocomposite. 2) Gradual cooling of selected configurations down to room temperature to obtain a good number of structures representative of the glassy phase of the polymer nanocomposite. 3) Molecular mechanics (MM) calculations of its mechanical properties following the method originally proposed by Theodorou and Suter. By analyzing the results under constant temperature and pressure, all nanocomposite systems were found to exhibit slower terminal and segmental relaxation dynamics than the pure polymer matrices. The addition of a small fraction of graphene sheets led in all cases to the enhancement of the elastic constants; this was significantly more pronounced in the case of functionalized graphene sheets. We further mention that, for all polymer/fullerene nanocomposites addressed here, no phase separation or variation of polymer chain dimensions was observed as a function of fullerene size and/or fullerene volume fraction. In the third part of the Thesis, and motivated by the use of acrylic polymers for the design of membranes with aligned carbon nanotubes (CNTs) for several separation technologies (such as water desalination and wastewater treatment), we report results from a detailed computer simulation study for the nano-sorption and mobility of four different small molecules (water, tyrosol, vanillic acid, and p-coumaric acid) inside smooth single-wall CNTs (SWCNTs). Most of the results have been obtained with the molecular dynamics (MD) method, but especially for the most narrow of the CNTs considered, the results for water molecule were further confirmed through an additional Grand Canonical (μVT) Monte Carlo (GCMC) simulation using a value for the water chemical potential μ pre-computed with the particle deletion method. Issues addressed in the Thesis include molecular packing and ordering inside the nanotube for the four molecules, average number of sorbed molecules per unit length of the tube, and mean residence time and effective axial diffusivities, all as a function of tube diameter and tube length. In all cases, a strong dependence of the results on carbon nanotube diameter was observed, especially in the way the different molecules are packed and organized inside the CNT. For water for which predictions of properties such as local structure and packing were computed with both methods (MD and GCMC), the two sets of results were found to be fully self-consistent for all types of SWCNTs considered. Water diffusivity inside the CNT (although, strongly dependent on the CNT diameter) was computed with two different methods, both of which gave identical results. For large enough CNT diameters (larger than about 13 Å), this was found to be higher than the corresponding experimental value in the bulk by about 55%. Surprisingly enough, for the rest of the (phenolic) molecules simulated in this Thesis, the simulations revealed no signs of mobility inside nanotubes with a diameter smaller than the (20, 20) tube. This has been attributed to strong phenyl-phenyl attractive interactions, also to favorable interactions of these molecules with the CNT walls, which cause them to form highly ordered, very stable structures inside the nanotube, especially under strong confinement. The interaction, in particular, of the methyl group (present in tyrosol, vanillic acid, and p-coumaric acid) with the CNT walls seems to play a key role in all these compounds causing them to remain practically immobile inside nanotubes characterized by diameters smaller than about 26 Å. It was only for larger-diameter CNTs that tyrosol, vanillic acid, and p-coumaric acid were observed to demonstrate appreciable mobility. / Η παρούσα Διδακτορική Διατριβή εστιάζει στη μελέτη της σχέσης μεταξύ δομής και μακροσκοπικών φυσικών ιδιοτήτων υλικών από πολυακρυλικά μέσω μίας λεπτομερούς προσομοίωσης στον υπολογιστή με τη μέθοδο της Μοριακής Δυναμικής (ΜΔ), σε συνδυασμό με ένα πολύ επακριβές πεδίο δυνάμεων (το Dreiding) σε ατομιστική λεπτομέρεια. Οι κύριες ερευνητικές έννοιες καθώς και οι στόχοι συζητιούνται και αναλύονται σε τρία ξεχωριστά μέρη. Στο πρώτο μέρος, ατομιστικές απεικονίσεις δύο προτύπων πίεσο-ευαίσθητων συγκολλητικών υλικών (acrylic pressure sensitive adhesives ή PSAs), του ατακτικού πολυ-βουτυλικού-ακρυλικού εστέρα (poly(n-BA)) και του συμπολυμερούς του με ακρυλικό οξύ (poly(n-BA-co-AA)), τόσο μακριά όσο και κοντά σε υποστρώματα σίλικας (SiO2) και α-φερρίτη (α-Fe), μελετήθηκαν στη βάση ενός φάσματος ιδιοτήτων (θερμοδυναμικές, δομικές, ιξωδοελαστικές, δυναμικές, και συγκολλητικές), όπως και η μηχανική τους απόκριση υπό συνθήκες μονοαξονικής εκτατικής παραμόρφωσης. Στο δεύτερο μέρος παρουσιάζονται τα αποτελέσματα που εξήχθησαν από μία ιεραρχική μεθοδολογία προσομοίωσης που οδήγησε στην πρόβλεψη της φασικής συμπεριφοράς και των μηχανικών ιδιοτήτων νανοσύνθετων πολυμερικών υλικών (polymer nanocomposites ή PNCs) βασισμένων στο συνδιοτατκτικό πολυ-μεθακρυλικό μεθυλεστέρα (syndiotactic poly(methyl methacrylate) ή sPMMA), ενισχυμένο με ομοιόμορφα διεσπαρμένα φύλλα γραφενίου (graphene sheets) ή σωματίδια φουλερενίου (fullerene particles). Στο τρίτο μέρος, υποκινούμενοι από τη χρήση των ακρυλικών πολυμερών στο σχεδιασμό μεμβρανών με ενσωματωμένους ευθυγραμμισμένους νανοσωλήνες άνθρακα (ΝΑ, carbon nanotubes ή CNTs) σε διάφορες τεχνολογίες διαχωρισμού μορίων (με έμφαση στον καθαρισμό του νερού), παρουσιάζουμε αποτελέσματα από προσομοιώσεις, για τη νανο-ρόφηση και την κινητικότητα τεσσάρων διαφορετικών μικρών μορίων (water, tyrosol, vanilic acid, και p-coumaric acid) στο εσωτερικό λείων μονο-στρωματικών ΝΑ (single-wall CNTs ή SWCNTs). Τα θέματα που εξετάζονται περιλαμβάνουν τη μοριακή διευθέτηση και τη διάταξη στο εσωτερικό Ν.Α. των τεσσάρων μορίων, το μέσο χρόνο παραμονής τους, καθώς και τους αξονικούς συντελεστές διάχυσής του, συναρτήσει της διαμέτρου και του μήκους των ΝΑ.