Olimpia Mamula Steiner

Prezentarea pe tema: "Olimpia Mamula Steiner"— Transcriere de prezentare:

1 Olimpia Mamula Steiner
• Diaspora, Bucuresti, Olimpia Mamula Steiner A. Sinteza diastereoselectiva de nanostructuri chirale auto-asamblate B. EIA Fribourg

2 Introducere Chiralitate helicoidala in complecsii metalici D L P M
• Introducere Chiralitate helicoidala in complecsii metalici Geometrie T-4 / OC-6: liganzi bidentati - centru metalic chiral (L, D) Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii D L Ag+ ligand tetradentat + P M racemat Olimpia Mamula Steiner

3 Predeterminare chirala
• Predeterminare chirala Stereoizomerii: o problema (amestecuri complicate, greu de analizat) Necesitatea de a controla chiralitatea centrilor metalici Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii Ligand R, S L (D) Metal ion P (M) Helicate Coordination Self-assembly Olimpia Mamula Steiner

4 Predeterminare chirala
• Predeterminare chirala Pinene bipy Ligands Helicat circular Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii + metale d Polimer tip helix Si lanthanidele (metale 4f)? La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Olimpia Mamula Steiner Angew. Chem. Int. Ed., 1998, 289 & 1999, 2945.

5 Predeterminare chirala
• Predeterminare chirala La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Structura electronica LnIII: [Xe]4fn Orbitale 4f ecranate 5s25p6 Legatura dativa LnIII-ligand: electrostatica Pericol de racemizare Preferinte sterice minime (NC variabil, legaturi nedirectionate) Olimpia Mamula Steiner

6 Predeterminare chirala
• Predeterminare chirala Alegerea liganzilor 5 6 4 Enantiopuri (tip 2,2’-pinene-bipyridina) Functionalizati cu un grup carboxyl Centrii chirali in apropierea siteului de coord. Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii Olimpia Mamula Steiner

7 Nanostructuri chirale auto-asamblate
• Nanostructuri chirale auto-asamblate MeOH Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii 6 + 3 Eu(ClO4)3 [Eu3(m3-OH)L6]2+ La Pr Nd Sm Eu Gd Tb Dy Ho Er Compusi isostructurali obtinuti cu Ln(III): Olimpia Mamula Steiner Angew. Chem. Int. Ed., 2005, 44, 2527

8 Structuri raze X M P - Dublu helix: P,M Doua seturi liganzi:
• Structuri raze X M P to C3 axis C3 3.9Å Indeed the X-ray structures obtained show a C3 symmetrical structure containing 3 metals 6 ligands an hydroxo group and 3 water molecules. The metal ions form an equilateral triangle in the center of which slightly out of the plane there is a hydroxo group bridging the 3 metal centers. The C3 axis pass through this hydroxo group. The 6 ligands are divided in 2 sets : the first set contain 3 bidentate ligands coordinating solely via the carboxylic groups while the other set contain 3 symmetry related ligands coordinating via the nitrogen atoms and the carboxylate oxygens. Space filling representation of the structure point out the double helix and the opposite configurations: M (ligands in green)) and P (for the nitrogen uncoordinated ligands). The perpendicular view to the C3 axis display the chiral cavity formed by the bidentate ligands. 3 water molecules of crystallisation are located in this cavity but no randomly. Together with the other 3 coordinated water molecules and free nitrogen atoms from bipyridine they form a network of H-bonds which explain the cis-conformation quite unusual for the free bipyridines. - Dublu helix: P,M Doua seturi liganzi: 3 didentati (OO) - 3 tetradentati (OONN)

9 Nanostructuri chirale auto-asamblate
• Nanostructuri chirale auto-asamblate D set S’’ Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii CH3CN 9 + 4 Eu(ClO4)3 set S’ P M set S Compusi isostructurali obtinuti cu Ln(III): La Pr Nd Sm Eu Tb Olimpia Mamula Steiner Angew. Chem. Int. Ed., 2006, 45, 4940

10 Nanostructuri chirale autoasamblate
• Nanostructuri chirale autoasamblate Comparatie structuri tri- si tetranucleare Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii tris tetra tetra Piramida trigonala: conexiune prin punti carboxyl “Miez” trinuclear similar Olimpia Mamula Steiner Chem. Eur. J., 2007 , 13, 7358.

11 Stabilitate in solutie
Proprietati Stabilitate in solutie ES-MS [Eu4L9(OH)]2+ [Eu3L6(OH)(ClO4)]+ [Eu3L6(OH)]2+ 1H-NMR

12 Proprietati Activitate optica Spectroscopie de Dichroism Circular
• Proprietati Activitate optica Spectroscopie de Dichroism Circular - prop. chiroptice in stare fundamentala Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii tetra-Eu{(-)-L} tris-Eu{(+)-L} Am zis ca am obtinut compusi enantiopuri? Cum o dovedim in solutie? Prin determinarea activitatii optice. Exista doua metode de a determina activitatea optica pt acesti complecsi: prin spectroscopie de dicroism circular si – dar aceasta metoda e numai pt compussi care emit lumina: CPL circularly p On peut considerer que la lumière plane polarisée est la somme vectorielle de la lumière circulaire polarisée gauche et droite d’amplitude égales. olarized light Si les amplitudes ne sont pas égales Alors une lumière circulaire polarisée est produite Relatie imagine-imagine in oglinda intre complecsii cu liganzi (+)-L si cei cu liganzi (-)-L Benzi mai intense pt tetranuclear (contributia unitatii ML3) Olimpia Mamula Steiner

13 * 07/16/96 * Luminescenta… Tb3+ Eu3+ tris-Tb{(+)-L} tris-Eu{(+)-L} 400
500 600 400 500 600 N l /nm l /nm COOH (+)-HL tris-Tb{(+)-L} tris-Eu{(+)-L} *

14 Proprietati Activitate optica
• Proprietati Activitate optica Spectroscopie de Luminescenta Circular Polarizata (CPL) - prop. chiroptice in stare excitata Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii tris-Eu{(+)-L} tris-Eu{(-)-L} Relatie imagine-imagine in oglinda Am zis ca am obtinut compusi enantiopuri? Cum o dovedim in solutie? Prin determinarea activitatii optice. Exista doua metode de a determina activitatea optica pt acesti complecsi: prin spectroscopie de dicroism circular si – dar aceasta metoda e numai pt compussi care emit lumina: CPL circularly p On peut considerer que la lumière plane polarisée est la somme vectorielle de la lumière circulaire polarisée gauche et droite d’amplitude égales. olarized light Si les amplitudes ne sont pas égales Alors une lumière circulaire polarisée est produite Spectrul total de luminescence (EuIII transitions) Olimpia Mamula Steiner

15 Proprietati Switching supramolecular tris
• Proprietati tris 6 (+)-L- + 3 Ln(ClO4)3 ∙ x H2O MeOH Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii + H2O - H2O a [Ln3L6(OH)(H2O)3](ClO4) b [Ln4L9(OH)](ClO4)2 + {c Ln3+ + d L- + e OH- + f ClO4- + 3a H2O} tris tetra minor species Switching supramolecular Solvent: CH3CN tetra 9 (+)-L- + 4 Ln(ClO4)3 ∙ x H2O CH3CN Olimpia Mamula Steiner Inorg. Chem., 2008, 47 (18), 8000

16 Proprietati Recunoastere Chirala RACEMAT + Ln3+ NO LIGAND MIXING
• Proprietati Recunoastere Chirala RACEMAT Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii + Ln3+ NO LIGAND MIXING 100% in cazul speciilor tris numai partiala in cazul speciilor tetra Olimpia Mamula Steiner

17 • Concluzii Utilizarea liganzilor de tip pinen-bipiridina functionalizati cu un grup carboxyl permite obtinerea de complecsi enantiopuri de lanthanide O noua clasa de nanostructuri enantiopure tri- si tetranucleare auto-asamblate a fost obtinuta prin sinteza diastereoselectiva Interconversia intre speciile tri- si tetranucleare a fost studiata In cazul in care auto-asamblarea se face plecand de la racematul ligandului, recunoasterea chirala poate sa fie totala (racemat final) Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii Olimpia Mamula Steiner

18 Concluzii Multumiri Marco Lama: PhD student
• Concluzii Multumiri Marco Lama: PhD student Prof. Reiko Kuroda & Prof. Asao Nakamura (Japan): CPL Prof. Luisa de Cola (Germany): Photophysics Prof. H. Stoeckli-Evans (Switzerland) Dr. R. Scopelitti (Switzerland) Dr. S. Shova (Moldavia) Swiss National Science Foundation EPFL Introducere Predeterminare chirala Nanostructuri Chirale Proprietati Concluzii X-ray Olimpia Mamula Steiner

19 Chimie @ EIA (Universitatea de Stiinte Aplicate din vestul Elvetiei)
Institut of Chemistry and Life sciences • Olimpia Mamula Steiner EIA (Universitatea de Stiinte Aplicate din vestul Elvetiei)

20 Institut of Chemistry and Life sciences
JNA 20

21 Ingineri Chimisti: Bachelor / Master
Institut of Chemistry and Life sciences Ingineri Chimisti: Bachelor / Master -- capabili sa identifice si sa rezolve probleme stiintifice / tehnice in domeniul chimiei aplicate si industriale Sinteza Scale – up Productie Caracterizare Oameni capabili sa dezvolte un produs incepand cu molecula dorita, trecand prin faza analitica, apoi scale-up si productie. Olimpia Mamula Steiner

22 Lucrari practice avansate
Institut of Chemistry and Life sciences Curriculum Bachelor An I An II An III Mate & Fizica 2 Chimie aplicata 2 Mate & Fizica 1 11 12 Chimie industriala 3 24 Chimie aplicata 1 12 Lucrari practice avansate 21 Chimie 18 Chimie Industriala 1 & 2 21 Proiect semestru Limbi & Comunicare 6 9 22 Proiect Bachelor Cursuri la alegere Cursuri la alegere 12 6 6 Teorie Laborator Olimpia Mamula Steiner

23 Curriculum Master of Science HES-SO
Institut of Chemistry and Life sciences Curriculum Master of Science HES-SO Orientare: Chemical Development and Production” Master Thesis 40 Credits Chemical development & production 20 Credits Basic theory 12 Credits Advanced theory 18 Credits Olimpia Mamula Steiner

24 Activitati R&D: chimie aplicata
Institut of Chemistry and Life sciences Activitati R&D: chimie aplicata Sinteza organica: Cataliza chirala Reactii de oxidare Modificari de sinteze in sens ecologic Solventi ecologici Lichide ionice Reactii in sistem continu - Microreactoare Chimie fizica: Termocinetica - Calorimetrie - Spectroscopie optica (IR, Raman) - Chimioluminescenta Modificare de suprafete - Electrochimie Formulari de produsi finali - Rheologie Chimie analitica: On-line monitoring - IR, UV-Vis, HPLC, GC, MS Dezvoltare de sisteme de masura “low-cost” - Electroforeza capilara depistarea rapida a medicamentelor contrafacute Olimpia Mamula Steiner

25 Activitati R&D: chimie industriala
Institut of Chemistry and Life sciences Activitati R&D: chimie industriala Optimizarea procedeelor: Screening technologies with microreactors including on line analytics (IR, MS) Automatizare: on-line monitoring with GC on industrial distillation columns nanoparticule cu suprafata modificata Productie: microparticule nanoparticule cu suprafata modificata Tehnici de separare: reciclarea solventilor tratament de deseuri in situ Olimpia Mamula Steiner

26 Département • date Auteur

27 « Nu exista drum spre fericire, fericirea e drumul… »
Institut of Chemistry and Life sciences « Nu exista drum spre fericire, fericirea e drumul… » EIA Fibourg : Prof. Swatch Group R&D (Basel, Neuchatel) Conducator Doctorat UNIL + EPFL: Prof. Asist. Univ. Basel: Postdoctorat Edwin C. Constable Alex von Zelewsky Univ. Fribourg: Doctorat EPFL: Master in ingineria si managementul mediului Bursa a Confederatiei obtinuta prin concurs (Ambasada Elvetiei) Univ. Bucuresti – Chimie anorganica Maria Brezeanu … Scoala generala dintr-un sat fagarasan de 1000 de locuitori

28 Département • date Auteur