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Photonic Crystal Aqueous Metal Cation Sensing Material

Photonic Crystal Aqueous Metal Cation Sensing Material. Sanford A. Asher, Anjal C. Sharma, Alexander V. Goponenko, Michelle M. Ward. Analytical Chemistry, 75 (7), 1676-1683. 2003. Simple, Inexpensive, Visual. Metal cation sensing materials.

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Photonic Crystal Aqueous Metal Cation Sensing Material

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  1. Photonic Crystal Aqueous Metal Cation Sensing Material Sanford A. Asher, Anjal C. Sharma, Alexander V. Goponenko, Michelle M. Ward Analytical Chemistry, 75 (7), 1676-1683. 2003

  2. Simple, Inexpensive, Visual Metal cation sensing materials • 2000-current, more than 160 papers regarding this topic were published • Most of them need plasma, atomic absorption, or emission spectroscopy. • Recently, ISE gains popularity • Can test Pb2+, Ca2+, Cd2+, K+ in water • Small, Portable

  3. Photonic crystal Polymerized crystalline colloidal array (PCCA) Sense Cu2+, Zn2+, Co2+, Ni2+ in water

  4. R&D review of Toyota CRDL, 39, 33-39 Introduce CCA Colloidal Crystalline Array: 3D periodic lattice assembled from monodispersed spherical colloids

  5. mλ=2d sin(θ) Introduce CCA

  6. Science Vol 305(2004), 1944-1948 R&D review of Toyota CRDL, 39, 33-39 Introduce CCA How to make CCA? • Sedimentation in a gravitational field • Attractive capillary forces caused by solvent evaporation • Self-organization via entropic forces or electrostatic interactions

  7. Introduce CCA Charged particles Werner Luck (1963) • Monodisperse polystyrene and polyacrylate latexes are investigated • FCC arrangement is formed and particles in array are touching • Bragg reflections from 250 to 650 nm Jone Vanderhoff (1970) • Studied the phenomenon quantitatively • The interparticle spacing increases when deionized latex is diluted P. Anne Hiltner (1968) • Charged particles may have screening layers • Dialyzed or treated w/ ion-exchange resin particles are separated by long-range repulsive force Uncharged particles

  8. Introduce CCA Applications of CCA • Photonic bandgap (PBG) crystals • Inverse opal • Chemical Sensor http://www.mtmi.vu.lt/pfk/funkc_dariniai/nanostructures/photonic_crystals.htm MRS Bulletin Aug,2001, 637-641

  9. X A: 530 nm nmedia= 1.3902 532 nm Undyed particle nmedia = 1.3874 nmedia = 1.3817 Introduce CCA Nanosecond optical switch • CCA diffracts away any light once Bragg condition is met (when nColloidal particles≠nmedia) • nColloidal particles decreases whensphere is heated Colloid particles Dyed CCA Acylated Oil Blue N PCCA Assembly n = 1.3860 DMSO n = 1.479 + Water n = 1.33 Only 2.5 ns delay!!! PCCA Physical Review Letters, 78 (20), 3860-3863,1997

  10. After few ns!!!! Introduce CCA Nanosecond optical switch

  11. N-vinylpyrrolidone N,N’-methylene-bis-acrylamide acrylamide CCA benzoin methyl ether CCA UV PCCA J. Am. Chem. SOC.,116 (11),4997-4498.1994 Introduce PCCA First generation PCCA • Permanently lock the CCA array • Solid hydrogel is formed around CCA • PCCA hydrogel contains 30% water • Modest alternation of diffraction peak happens • Stretching the gel causes the diffraction peak wavelength to change

  12. Diffraction intensity increases!!! Introduce PCCA Thermally switchable PCCA • PS spheres + NIPAM monomer in aqueous solution. • The PS colloid self-assembled into a bcc CCA • Photochemically initiated polymerization of NIPAM with CCA  CCA embedded in a PNIPAM hydrogel film Science 274(5289),959-960, 1996

  13. 1N NaOH Hydrolyzed PCCA PCCA TEMED (amide group carboxy group) Introduce PCCA pH and Ionic strength sensor Glucose sensor • Attch the enzyme glucose oxidase (GOx) to a PCCA of polystyrene colloids. • Utilizes phenylboronic acid as the glucose recognition element (bind to sugars) JACS, 122, 9534-9537,2000 Nature, 389, 829-832,1997 Anal.Chem,75, 2316-2323,2003

  14. Synthesis Cation Sensing Material 2. PCCA 3. Hydrolyzed PCCA 90 min 0.15g, 0.64mmol 365 nm Quartz disk 0.20g, 1.04mmol Parafilm spacer, 125 um 0.05g, 0.32mmol 0.10g, 1.4mmol 2.00g, PS latex 1. CCA Self-assemble diffraction film Ion exchange resin, solvent

  15. Results and Discussion Cu2+ sensor 757 nm

  16. + Cu2+ Cu2+ Low concentration - Cu2+ bisligand monoligand Cu(hydroxyquinolate) Log (Kf) = 10.70 Breaking crosslonk red shrift Cu(hydroxyquinolate)2 Log (Kf) = 21.87 Shrink blue shrift Results and Discussion Proposed Mechanism of Sensing Cu2+

  17. 250-270 380 Results and Discussion Formation of the liganded complexes 5-acetamido-8-hydroxyquinoline in acetate-buffered saline 8-hydroxyquinoline-functionalized CCA-free hydrogel Other result: AA shows NO Cu2+ is retained by PCCA w/o 8-hydroxyquinoline

  18. Results and Discussion Diffraction wavelength vs. concentration S = Cu2+ mol/ 2 ligandmol Outmost layer effect 1μM

  19. Results and Discussion Cu2+ stoichiometry Aλ = εcl 1.86E04 1.82E04 2.80E03 1.05E03 colloid-free 8-hydroxyquinoline-containing hydrogel 5-acetamido-8-hydroxyquinoline

  20. Ligand only hrdrogel 50 mM Cu2+ treated n hydrogel Washed hydrogel Results and Discussion Wash effect Retention of bisligand Cu2+ sites after extensive washing with pH 4.2 buffered saline Partially reversible !!! Dosimeter for ultratrace concentration of Cu2+

  21. Results and Discussion Sense > 1μM Cu2+ cross-linked Response of washed Cu2+cross-linked 8-hydroxyquinoline PCCACS Two runs showing reproducible and reversible nature of the sensor response to Cu2+ Reversible sensor for > 1μM Cu2+

  22. Results and Discussion Nonspecific metal cation sensor Cu2+ Ni2+ K1=109.57 K3=1018.27 K1=1010.70 K3=1021.87

  23. Results and Discussion Nonspecific metal cation sensor Co2+ Zn2+ N2 air N2 : K1=108.11 K3 =1015.05 K1=108.65 K3=1016.15 Oxidation Co2+  Co3+

  24. Conclusions • Novel sensing material is formed to evaluate metal concentrations in drinking water. • Metal cation concentrations can be determined visually from the color of the diffracted light or detected by reflectance measurements using a spectrophotometer.

  25. Conclusions At low metal concentrations bisligand complexes form crosslink the gelshrink blue shift observed At higher metal concentrations monoligand complexes form cross-links break red shift observed

  26. Conclusions • At trace concentration (～10-21 M), used as dosimeters; at low concentration (> 1μM), used as reversible sensor • Detects metal cations such as Cu2+, Ni2+,Co2+, Co3+, Ca2+, Zn2+AND other cation such as Th4+,Sm3+, Fe3+, Gd3+, and Er3+ which has similar 8-hydroxyquinoline association constants

  27. Epilog: who is citing this work? X: Asher’s group * Lopze’s group from Spain

  28. Appendix 1-chemical structure

  29. Appendix 1-chemical structure (TEMED) EDC

  30. Appendix 1-chemical structure (NIPAM) (photopolymerize initiator)

  31. Appendix 1-chemical structure

  32. Appendix 2-crystal structure FCC (111) BCC (110)

  33. Appendix 2-crystal structure

  34. Appendix 3-paper published

  35. Appendix 3- K1 & K3 L = 8-hydroxyquinoline, M =Cu2+ LM= Cu(8-hydroxyquinolate)+ 1:1 complex L2M = Cu(8-hydroxyquinolate)2 bisliganded complex

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