Jinsang Kim Molecular Design for Optical Chemical & Biosensors - PowerPoint PPT Presentation

Jinsang Kim Molecular Design for Optical Chemical & Biosensors Plastic Electronics Circulating Tumor Cell Detection Chemical Sci 2016 Liquid Crystalline CPs Platelet Activation Monitoring Adv. Mater. 2016 Field Effect Transistor miRNA Detection Thermoelectric Polymers Nat. Mater. 2013 Chemical Sci. 2015 Adv. Mater. 2016 Macromolecules 2019 PBTCT PBTCTO PBTPDO PBTFDO 2" 3" O O F S S 1" F S editorials NATURE MATERIALS Organic Light Emitters Designer Functional Organic and Polymer Heat Management in Polymers Nat. Chem. 2011 Nature Materials 2015 Organic Phosphors J. Am. Chem. Soc. 2013 Biomimetic Adhesives and ACS Central Sci. 2015 LED, Sensors, Angew. Chem. 2014 Science Advances 2017 Surface Functionalization Solid-state Lighting, Chem. Mater. 2014 Nat. Commun. 2015 Angew. Chem. 2017 a Chem Mater 2019 HO O O O O O H H n Br Br OH PVA-PVA Hydrogen Bond O O PVA Br6A G1 Suppress the diffusional motion of matrix O OH G1-PVA Hydrogen Bond Reinforce the restriction of vibration of phosphors b H O O H H O O H G1-G1Halogen Bond H O H O O 1. Heavy atom effect O H O H H 2. Restrict vibration motion H O O O O O H G1 in PVA (100%) of phosphors H Ar O O O O Br O O O Ar S Br O Ar O O O T Br H O H O O O O H Vibrational H O H Φ ph ~ up to 24 % Rationally designed strong intermolecular hydrogen and halogen bonds between X O O Dissipation a novel phosphor and a poly(vinyl alcohol) (PVA) matrix led to bright room- O H H temperature phosphorescence with a quantum yield of 24%. J. Kim and co-workers H O show in their Communication (10.1002/anie.201404490) that modulation of the O H Hydrogen bonding strength of halogen and hydrogen bonding in the purely organic phosphor–PVA Phos. system by water enabled reversible switching between phosphorescence (green) O H Halogen bonding and fluorescence (blue). c Water Induced H 2 O writing Phosphorescence to Fluorescence Switching for Drying Water Sensing Applications

Application of Polydiacetylene Sensors Glucose sensor Temperature sensor (boronic acid) (polyNIPAM) DNA sensor + Target Reversible sensor Antigen Antibody-antigen sensor Peptide sensor Peptide receptor Virus Virus sensor Red Color Blue Color Fluorescent Non-fluorescent Developed Sensors target - Nerve Agents - Antibiotics - Melamine - Proteins color change - Hg2+ - Influenza Virus conjugated p-orbital twisted p-orbital - Prostate Specific Antigen - K+ - DNA - Immunofluorescence labeling 0 (Increased response)

Disrupting pi-conjugation of PDA triggers optical signals Repulsion partially twisted p-orbitals conjugated p-orbitals Fluorometric & Colorimetric Dual Signal

Self-signaling and Signal-amplifying Optical Sensors Nerve gas sensor Adv. Func. Mater. 2010 and 2012. K+ Sensor JACS 2008 , 130 , 5010. Antidote ( 2-PAM) 0.01 0.05 0.1 0.25 0.5 1.0 × 10 -3 mol HCl HF H3PO4 DCP DFP Control Melamine sensor Chem Comm 2010, 47, 358. OPTICAL WAVEGUIDING Polychromatic optical waveguiding is achieved for organic nanowires (NWs) hybridized with light-emitting quantum dots (QDs). Remote Mercury Sensor Adv. Mater. 2009, 21, 3674. biosensing using dye-attached biomaterials is presented by J. Kim, J. Kim, J. Joo, and co-workers by adapting the transportation of QD- emitted light through the organic NWs. The cover image shows white- color waveguiding and remote biosensing using blue light-emitting organic NWs hybridized with QDs. Developed Sensors Nerve Agents Bacteria & Influenza Virus A Antibiotics Melamine Prostate Specific Antigen DNA Mercury Potassium + Na + + K + Water

Novel Emissive Materials by Design Fundamentals: Color Tuning & Understanding the Conducting Property • Materials Chemistry Intermolecular Phenomena • Electron Density of the Core Unit • Halogen Bonding • Molecular Photophysics • Extended Conjugation in the Core Unit • Crystallography and Photophysics • Device Physics • Conducting Property • Emission Intensity vs. Crystal Applications: • Solid-state Lighting • Light Emitting Diodes • Photovoltaics • Polarized Emission Devices Argon Air “On” Nanoparticles Hot water Cold water Rationally designed strong intermolecular hydrogen and halogen bonds between a novel phosphor and a poly(vinyl alcohol) (PVA) matrix led to bright room- temperature phosphorescence with a quantum yield of 24%. J. Kim and co-workers show in their Communication (10.1002/anie.201404490) that modulation of the strength of halogen and hydrogen bonding in the purely organic phosphor–PVA Phosphorescence*Intensity* system by water enabled reversible switching between phosphorescence (green) and fluorescence (blue). Nature Chemistry 2011, 3, 205 . J. of Am. Chem. Soc. 2013 , 135 , 6325. Angew. Chem. Inter. Ed. 2014, 53, 11177. Chem. Mater. 2014 , 26 , 6644. Nature Communications 2015 , 6 , 8947. Angew. Chem. Inter. Ed. 2017, 56, 16207.

Lyotropic Liquid Crystalline CP Design for Directed Conjugated Polymer Alignment CP1 2" 1. Concentra,on-induced Chain Planariza,on 3" O O 2. Non-interdigita,ng Large Side Chain F 3. Out-of-plane Tetrahedral Carbon Linker S S 1" S F Shear field Solvent evaporation causes chain planarization and CP assembly Shear field aligns CP substrate 1 Concentration induced Suppressed Enabled chain planarization •Strong π−π aggregation LC-like mobility 2 Bulky side chain attached on •Side chain interdigitation & directed alignment 3 a Tetrahedral carbon Bong-Gi Kim, Eun Jeong Jeong, Jong Won Chung, Sungbaek Seo, Bonwon Koo, Jinsang Kim Nature Materials 2013, 12, 659.

2" 3" 90 o$ O O 45 o$ F S S 1" S F 0 o# 125 mg/ml 250 mg/ml Hole mobility by TFT o to polarizer 0 0 10 o 45 o 90 PL intensity (a. u.) -1 10 o 2 /Vs) 135 -2 mobility (cm 10 -3 10 -4 10 -5 10 600 650 700 750 800 0 o 90 o spin casting 45 o Aligned direction to S-D electrode Wavelength (nm)

High Thermal Conductivity in Amorphous Polymers Polymer Blend System Polyelectrolyte System - - - - - - - - - - - - - - - - - - - - - - - - - - - Coiled and entangled Extended or swollen polyelectrolyte chains polyelectrolyte chains Low k High k High pH Low pH m m O - O OH O Na + PAA n O PVP Gun-Ho Kim + , Dongwook Lee + , Apoorv Shanker + et al Apoorv Shanker + , Chen Li + et al Nature Materials 2015 , 14 , 295. Science Advances 2017, 3, 1700342.

1. Through Interpolymer Bonding Gun-Ho Kim + , Dongwook Lee + , Apoorv Shanker + , Lei Shao, Min Sang Kwon, David Gidley, Jinsang Kim* and Kevin Pipe* “High thermal conductivity in amorphous polymer blends by engineered interchain interactions” Nature Materials 2015 , 14 , 295.

2. Electrostatically Induced Random Chain Extension Apporv Shanker + , Chen Li + , Gun-Ho Kim, David Gidley, Kevin Pipe*, Jinsang Kim* “Electrostatically induced random chain extension for high thermal conductivity in amorphous polymers” Science Advances 2017 , 3 , 1700342.