Photonic Crystal Aqueous Metal Cation Sensing Material

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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
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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

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Photonic crystal
Polymerized crystalline colloidal array (PCCA)

• Sense Cu2, Zn2, Co2, Ni2 in water

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Introduce CCA

• Colloidal Crystalline Array
• 3D periodic lattice assembled from monodispersed
  spherical colloids

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Introduce CCA
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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

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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
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Introduce CCA

• Applications of CCA
• Photonic bandgap (PBG) crystals
• Inverse opal
• Chemical Sensor

http//www.mtmi.vu.lt/pfk/funkc_dariniai/nanostruc
tures/photonic_crystals.htm
MRS Bulletin Aug,2001, 637-641
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Introduce CCA

• Nanosecond optical switch
• CCA diffracts away any light once Bragg condition
  is met
• (when nColloidal particles ? nmedia)
• nColloidal particles decreases when sphere 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
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Introduce CCA
Nanosecond optical switch
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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

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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
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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
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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
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Results and Discussion
Cu2 sensor
757 nm
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Results and Discussion
Proposed Mechanism of Sensing Cu2
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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
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Results and Discussion
Diffraction wavelength vs. concentration
S Cu2 mol/ 2 ligandmol
Outmost layer effect
1µM
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Results and Discussion
Cu2 stoichiometry
A? ecl
1.86E04
1.82E04
2.80E03
1.05E03
colloid-free 8-hydroxyquinoline-containing
hydrogel
5-acetamido-8-hydroxyquinoline
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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
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Results and Discussion
Sense gt 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 gt 1µM Cu2
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Results and Discussion
Nonspecific metal cation sensor
Cu2
Ni2
K1109.57 K31018.27
K11010.70 K31021.87
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Results and Discussion
Nonspecific metal cation sensor
Co2
Zn2
N2
air
N2 K1108.11 K3 1015.05
K1108.65 K31016.15
Oxidation Co2 ? Co3
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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.

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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

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Conclusions

• At trace concentration (10-21 M), used as
  dosimeters at low concentration (gt 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

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Epilog who is citing this work?
Purpose Year Journal Cited
1 Photonic band gap 2005 Applied Physics B Lasers and Optics
2 Modeling, sensing material 2005 Materials Today (Oxford, United Kingdom) X
3 Review, sensing material 2005 Materials Today (Oxford, United Kingdom)
4 Sensing material 2005 Analytica Chimica Acta
5 Inverse opal 2004 Journal of Microscopy (Oxford, United Kingdom)
6 Review, sensing material 2004 Diabetes Technology Therapeutics
7 Sensing material 2004 JACS X
8 Review, Photonic crystal 2003 Advanced Materials (Weinheim, Germany)
9 Ligand complex 2003 Journal of Polymer Science, Part A Polymer Chemistry
10 Sensing material 2003 Analytical Chemistry X
X Ashers group Lopzes group from Spain
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Appendix 1-chemical structure



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Appendix 1-chemical structure

(TEMED)
EDC
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Appendix 1-chemical structure
 



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


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Appendix 2-crystal structure
FCC (111)
BCC (110)
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Appendix 2-crystal structure
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Appendix 3-paper published
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Appendix 3- K1 K3
L 8-hydroxyquinoline, M Cu2 LM
Cu(8-hydroxyquinolate) 11 complex L2M
Cu(8-hydroxyquinolate)2 bisliganded complex