Aqueous Self-Assembly of Fp Derivatives: Multifunctional Metal-Carbonyl Nanovesicles (MCsomes) 38 th IPR Symposium-May 4 th 2016 Nimer Murshid and Xiaosong Wang Aqueous Self-Assembly of Fp Derivatives: Multifunctional Metal-Carbonyl Nanovesicles (MCsomes) 38 th IPR Symposium-May 4 th 2016 Nimer Murshid and Xiaosong Wang Nimer Murshid Department of Chemistry Waterloo Institute for Nanotechnology University of Waterloo, Ontario, Canada 1

Overview – challenges – objectives Targeted molecules Aqueous solution behaviour Aggregation induced properties Conclusions OUTLINE 2

Application of Metal-Carbonyl Complexes (MCCs) MCCs are potentially useful for a range of biomedical applications including: CO-delivery Antitumor Bioassay Cell imaging Strong CO stretching vibrations in the region (1800–2200 cm -1 ) Relatively free of interference from absorbance of water and biomolecules J. Am. Chem. Soc. 2010, 132, 18273−18280; Inorg. Chem. 2015, 54, 215−220; Angew. Chem. Int. Ed. 2011, 50, 860 –864 Probes for vibrational based sensing 3

Low stability and solubility in aqueous solution Signals is difficult to detect in diluted solution Structure characterization and rational synthesis Challenges for MCCs Applications!!! 4

Research Objectives Rational design of MC complexes that can self assemble in water and have: High stability Strong detectable signals in solution Fluorescence Vibrational Can be optically trapped and manipulate 5

Target Molecules Synthesized through migration insertion reaction FpC6 FpC3-Bt 6 Lanigan et al. ACS Macro Lett. 2014, 3, 1281–1285Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A Murshid et al. Chem. Eur. J. 2015, 21, –19230

Hydrophobic Hydrophilic Conventional surfactant Aqueous Solution Behaviour of Amphiphes 7 CO-releasing J. AM. CHEM. SOC. 2010, 132, 18273– Can self-assemble in water above their critical micelle concentration (CMC) Colloidally unstable upon dilution below CMC

Hydrophilic part= ???? D h = 170 nm PDI = 0.02 ζ = mV BUT can self-assemble in water Target molecule Aqueous Solution Behaviour of Fp derivatives H 2 O dilution 8 4  M 154  M Murshid et al. Chem. Eur. J. 2015, 21, –19230 Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A Cao et al. Macromolecules, 2015, 48, 7968–7977

Hydrophobic Non-surface active No detectable CMC Highly integrated structure (stable upon dilution) High colloidal stability for several months 9 Aqueous Solution Behaviour of Fp derivatives Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A

10 ζ = mV Nanostructure of the MCsome SLS/DLS TEM AFM Cryo-TEM SAXS CV Bilayer nanovesicle (MCsomes) Water carbonyl interactions (WCI) direct and stabilize the aqueous self-assembly of FpC3-Bt The structure is confirmed as bilayer vesicle with the bithiophene moieties interdigitated and associated within the inner wall and the iron-carbonyl units exposed to water. Murshid et al. Chem. Eur. J. 2015, 21, –19230 Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A

Aggregation Induced Emission (AIE) In THF In water Restriction of Intramolecular Rotation RIR 11 The RIR of the aggregated bithiophene units within the the interdigitated membrane and the spatially separation from the iron centres resulting in AIE. Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A

Aggregation Induced Emission (AIE) (different conditions) 12 AIE DMSO CH 3 CN 90% water 90% water AIE Different solvent Different pH Different concentrationDifferent temperature Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A

Vibrational Based Sensing 13  Enhancement occurs when the molecules adsorb at the surface of a substrate Conventional surface enhanced IR absorption (SEIRA) Tsang et al. Phys. Rev. Lett. 1980, 45, 201 Conventional Surface enhanced Raman scattering (SERS) Olivo et al. Angew. Chem. Int. Ed. 2012, 51, 9796 –9799 The metal islands are polarized by the incident photon field The induced dipole in an island generates a local EM field stronger than that for the incident photon Osawa, M., Top. Appl. Phys. 2001, 81, 163−187 with AuNPs without AuNPs Applied Spectroscopy 2004, 58, 324A-338A

Aggregation Enhanced IR Absorption (AEIRA) External substrates: Au, Ag, Ru, Al 2 O 3, SiC, ……. Plasmon resonance or/and phonon resonance Traditional surface IR Enhancement: SEIRA Developed self IR Enhancement: AEIRA Self-enhancement …. No External substrates Zeta potential = mV Local electric field 14 Aggregation Enhanced IR Absorption (AEIRA) IR absorption intensity of the CO groups enhanced with more than 100-fold Murshid et al. Chem. Eur. J. 2015, 21, –19230 Traditional surface IR Enhancement: SEIRA Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A

Laser Trapping Trapping force is directly depends on Refractive index contrast between the particle and the surrounding Particle size RI in RI out Laser trapping of nanosize lipid vesicles is challenging Similar interior and exterior environment Thin wall, negligible contribution RI of water : 1.33 RI of Lipids: 1.45 RI in RI out Can be trapped Different RI between the particle and the surrounding 15 Masuhara et al. Acc Chem Res, 2012, 45, 1946–1954 Oddershede et al. Nano Lett., 2011, 11, 5431–5437 Harris et al. Anal. Chem., 2003, 75, 6621–6628 Choi et al. Soft Matter, 2014, 10, 8406–8412

Laser Trapping of the MCsome 1 s FpC3-Bt vesicles have been successfully optically trapped and manipulated WITHOUT ANY MODIFICATION OR ADDITIVES 3 s 6 s 16 Murshid et al. J. Mater. Chem. C, 2016, DOI: /C6TC01222A

The metal carbonyl complex FpC3-Bt is hydrophobic and non-surface active FpC3-Bt molecules can self assemble in water into nanovesicles (MCsomes) with high integrated structure CONCLUSION 17

Acknowledgments NSERC and WIN for Funding IPR members My supervisor Prof. Xiaosong Wang Wang’s group members Our collaborators (National Chiao Tung University)  Prof. Chien‐Lung Wang  Prof. Hiroshi Masuhara  Dr. Ken-ichi Yuyama NSERC and WIN for Funding IPR members My supervisor Prof. Xiaosong Wang Wang’s group members Our collaborators (National Chiao Tung University)  Prof. Chien‐Lung Wang  Prof. Hiroshi Masuhara  Dr. Ken-ichi Yuyama 18

38 th IPR Symposium-Waterloo-May 4 th 2016 Nimer Murshid

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21 Here E denotes the electric field, and represents a gradient with respect to the spatial coordinates. he parameter of represents the permittivity of the surrounding medium. The polarizability of the nanoparticle, , under the dipole approximation, is given by