Byrne, Robert

Diamond, Dermot

Fraser, Kevin J.

Gambhir, Sanjeev

Gelmi, Amy

Higgins, Michael

Officer, David

Wagner, Klaudia

Wallace, Gordon

Zanoni, Michele

Name not available

1	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  Michele Zanoni,  PhD student, CLARITY, NCSR, Dublin City University Spiropyran-terthiophene Polymers as Multi-Stimuli-Responsive Platforms for Biochemical Interactions ?Considerate la vostra semenza: fatti non foste per viver come bruti, ma per seguir virtute e canoscenza?.  ?Consider well the seed that gave you birth: you were not made to live your lives as brutes, but to be followers of worth and knowledge?.  Dante Alighieri, Inferno, Canto XXVI, 118-120. UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	   2	  Outline OUTLINE	  !  Introduction   !  p-BSP2 Polymer: Synthesis and Properties  !  Surface Properties  !  AFM Cantilever Functionalisation  !  p-BSP2 - FN interaction: Photochemical Control  •  Conclusion and Remarks 3	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  INTRODUCTION TTh & FN 1876  PHOTOCHROMISM first reported by FRITSCHE 1950  Fischer and Hirshberg studies on SPIRODERIVATIVES 1968 Flannery Jr. TRANSIENT study 1973 Studies on PHOTOCOLOURATION  1978 McDiarmid, Shirakawa and Heeger synthesised the first CONDUCTING POLYMER  1992-1997 Roncali?s reviews on p-TTh SYNTHESIS strategies and electronic properties 2000-2005 Officer et al. studied new substituted p-TTh 2008-2011 study of Conducting Polymers as platforms for tissue regeneration 1974 Surface Proteins role described 1981 FN Wound Healing role described  2000-2010 FN Cell Proliferation studies for anti cancer therapy and Tissue Regeneration   BSP INTRODUCTION	  2005-2010 Functionalisation of BSP on Polymeric Surfaces 2011 2011 first synthesis of a BSP-TTh based DUAL CONTROL molecule (published on JACS!!!!) 1976 FN First evidences for role played in Cancer 2012?? 1997-1999 Goerner studies on  RING OPENING mechanism and ligand activity FN 4	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  SYNTHESIS of BSP-2  SYNTHESIS	  and	  PROPERTIES	  BSP-22 OSSSOC10H21OC10H21OMeOSSSOC10H21OC10H21OHKOHEtOH/H2O 97%N O NO2OSSSOC10H21OC10H21ON O NO2OHDCC/DMAP/0°C[1] Gambhir, S.; Wagner, K.; Officer, D. L. Synth. Met. 2005, 154, 117–120. [2] K. Wagner, R. Byrne, M. Zanoni, S. Gambhir, L. Dennany, R. Breukers, M. Higgins, P. Wagner, D. Diamond, G.G. Wallace, and D.L. Officer, J. Am. Chem. Soc., 2011, 133 (14), pp 5453–5462 BSP-2     MC-2 MeTTh1 AcTTh1 BSP-1 568 nm N O NO2OSSSOC10H21OC10H21OOSSSOC10H21OC10H21ONNO2Oh!1" or h!25	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  Electropolymerisation  Cyclic deposition of p-BSP2 on ITO  Monomer Concentration 8mM solution of monomer in DCM+ACN, 2:3 Electrolyte 0.1M solution of TBAP buffer in DCM+ACN, 2:3 Working electrode ITO, PET-ITO Counter electrode Pt wire Reference electrode Ag/AgCl with AgNO3 10mM non aqueous. Scan range Cyclic deposition From -0.4V to 0.9V Sensitivity 0.05V per sec Sweep segments 8 K. Wagner, R. Byrne, M. Zanoni, S. Gambhir, L. Dennany, R. Breukers, M. Higgins, P. Wagner, D. Diamond, G.G. Wallace, and D.L. Officer, J. Am. Chem. Soc., 2011, 133 (14), pp 5453–5462 N O NO2OSSSOC10H21OC10H21O 0.1M TBAP/DCM/ACNelectropolymerizationN O NO2OSSSOC10H21OC10H21OnSYNTHESIS	  and	  PROPERTIES	  6	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  Photochemical reversibility of p-BSP2 Exposition of p-BSP2 to different cycles of UV-light at 254nm and White light outside the electrolyte.   K. Wagner, R. Byrne, M. Zanoni, S. Gambhir, L. Dennany, R. Breukers, M. Higgins, P. Wagner, D. Diamond, G.G. Wallace, and D.L. Officer, J. Am. Chem. Soc., 2011, 133 (14), pp 5453–5462  UV light at 254 nm p-BSP2 533 = p-MC2 474 430 SYNTHESIS	  and	  PROPERTIES	  p-MC2 7	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  p-BSP2 reduced at -0.4V Reversibility of pBSP2       pMC2:  analysis with CONTACT ANGLE p-BSP2 oxidized at 0.8V p-BSP2 reduced at -0.4V. Contact Angle=107.85deg ELECTROCHEMICAL p-MC2 oxidized at 0.8V: contact angle=86.47deg SYNTHESIS	  and	  PROPERTIES	  8	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  Reversibility of pBSP2       pMC2:  analysis with CONTACT ANGLE p-BSP2 reduced at -0.4V Exposure to 254nm UV light for 10minutes Exposure to white light for 10minutes PHOTOCHEMICAL SYNTHESIS	  and	  PROPERTIES	  9	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  AFM and SEM measurements AFM SEM reduced oxidised reduced oxidised SURFACE	  PROPERTIES	  	  pBSP2 at oxidised state pBSP2 at reduced state 10	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  AFM Morphology Study 1.8 µm 13.49 nm pBSP2 at oxidised state pBSP2 at reduced state SURFACE	  PROPERTIES	  	  11	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  AFM Cantilever Functionalisation with FN AFM	  CanClever	  FUNCTIONALISATION	  • Gold reflective Nanoworld tips  • Cleaned in plasma cleaner for 5 minutes  • 2 hours in 1% 3-EDSPA solution (in Toluene), then rinsed with toluene and PBS  • 1 hour in GAH solution in PBS and rinsed with PBS  • 1 hour in 10 mg/ml of FN in PBS and rinsed with PBS.  • Stored in PBS in fridge till immediately prior the usage  • Fluorescence spectrum to prove presence of FN  • Calibration 12	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  p-BSP2 and FN Interaction: PHOTOCHEMICAL CONTROL  Exposure to 254nm UV light for 10minutes prior the AFM detection 1 nN!!! p-MC2 induced PHOTOCHEMICAL	  CONTROL	  13	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  p-BSP2 and FN Interaction: PHOTOCHEMICAL CONTROL  Exposure to white light for 10minutes prior the AFM measurement 3 nN!!! p-BSP2 induced PHOTOCHEMICAL	  CONTROL	  14	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  PHOTOCHEMICAL	  CONTROL	  FN Interaction with poly-Pyrrole M. Higgins et al., Chem. Mater. 2012, 24, 828-839!15	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  p-BSP2 and FN Interaction: PHOTOCHEMICAL CONTROL  PHOTOCHEMICAL	  CONTROL	  15	  16	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  CONCLUSIONS !  A new Class of Dual-Control Stimuli Responsive Materials has been Synthesised and Characterised  !  Photo - Electrochromic Properties Have Been Studied   !  p-BSP2 Presents Photo-Actuation and Photo-Reversibility  • p-BSP2 is Able to Generate Lipophilic Interactions with a Fundamental Protein: FN  • The Process is Reversible and Repeatable Over Time CONCLUSION	  17	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	     • Prof. Dermot Diamond and Dr. Robert Byrne (DCU).  • Prof. Gordon G.Wallace and Prof. David L. Officer (IPRI)  • Dr. Klaudia Wagner, Dr. Michael Higgins and Mrs. Amy Gelmi(IPRI).  • Dr. Kevin J. Fraser, Dr. Fernando Benito-Lopez (DCU).  	  	Special	  Thanks	  to:	  18	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  AND	  YOU	  ALL	  FOR	  YOUR	  ATTENTION	  19	  UNIVERSITY	  COLLEGE	  DUBLIN	  	  	  	  	  	  DUBLIN	  CITY	  UNIVERSITY	  	  	  	  	  	  TYNDALL	  NATIONAL	  INSTITUTE	  	  Questions???  

Spiropryan-terthiophene polymers as multi-stimuli-responsive platforms for biomechanical interactions

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Spiropryan-terthiophene polymers as multi-stimuli-responsive platforms for biomechanical interactions

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