Photonic Crystal Photonic Crystal Aqueous Metal Cation Aqueous Metal Cation Sensing MaterialSensing Material

Sanford A. Asher, Anjal C. Sharma, Alexander V. Goponenko, Michelle M. Ward

Analytical Chemistry, 75 (7), 1676-1683. 2003

Metal cation sensing Metal cation sensing materialsmaterials

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

Simple, Inexpensive,

Simple, Inexpensive, VisualVisual

Sense CuSense Cu2+2+, Zn, Zn2+2+, Co, Co2+2+, Ni, Ni2+2+ in water in water

Polymerized crystalline colloidal Polymerized crystalline colloidal array (PCCA)array (PCCA)

Photonic crystalPhotonic crystal

Introduce CCAIntroduce CCAColloidal Crystalline ArrayColloidal Crystalline Array:

3D periodic lattice assembled from monodispersed spherical colloids

R&D review of Toyota CRDL, 39, 33-39

Introduce CCAIntroduce CCA

mmλ=2λ=2 d sin(θ)d sin(θ)

Science Vol 305(2004), 1944-1948

R&D review of Toyota CRDL, 39, 33-39

Introduce CCAIntroduce CCAHow to make CCA?How to make CCA?

Attractive capillary forces caused Attractive capillary forces caused by solvent evaporation by solvent evaporation

Sedimentation in a gravitational Sedimentation in a gravitational field field

Self-organization via entropic Self-organization via entropic forces or electrostatic interactions forces or electrostatic interactions

Introduce CCAIntroduce CCAWerner Luck (1963)Werner Luck (1963) Monodisperse polystyrene and polyacrylate latexes are Monodisperse polystyrene and polyacrylate latexes are

investigatedinvestigated FCC arrangement is formed and particles in array are FCC arrangement is formed and particles in array are

touchingtouching Bragg reflections from 250 to 650 nmBragg reflections from 250 to 650 nm

Jone Vanderhoff (1970)Jone Vanderhoff (1970) Studied the phenomenon quantitativelyStudied the phenomenon quantitatively The interparticle spacing increases when deionized latex The interparticle spacing increases when deionized latex

is dilutedis diluted

P. Anne Hiltner (1968)P. Anne Hiltner (1968) Charged particles may have screening layersCharged particles may have screening layers Dialyzed or treated w/ ion-exchange resin particles are Dialyzed or treated w/ ion-exchange resin particles are

separated by long-range repulsive forceseparated by long-range repulsive force

ChargeCharged d

particlparticleses

UncharUncharged ged

particleparticless

Introduce CCAIntroduce CCA

Applications of CCAApplications of CCA Photonic bandgap Photonic bandgap

(PBG) crystals(PBG) crystals

Inverse opalInverse opal

Chemical Sensor Chemical Sensor

http://www.mtmi.vu.lt/pfk/funkc_dariniai/nanostructures/photonic_crystals.htm

MRS Bulletin Aug,2001, 637-641

AssemblAssembly y

Introduce CCAIntroduce CCANanosecond optical switchNanosecond optical switch CCA diffracts away any light once Bragg CCA diffracts away any light once Bragg

condition is metcondition is met

(when (when nnColloidal particlesColloidal particles ≠≠ nnmediamedia))

nnColloidal particles Colloidal particles decreases whendecreases when sphere is heatedsphere is heated

Colloid Colloid particlparticleses

Dyed Dyed CCACCA

Acylated Oil Blue N PCCPCC

AA

A: 530 nmA: 530 nm

n n = 1.3860= 1.3860

PCCAPCCA

DMSO DMSO nn = = 1.4791.479

++Water Water nn = = 1.331.33

532 nm532 nm

Physical Review Letters, 78 (20), 3860-3863,1997

nnmediamedia= 1.3902= 1.3902

Undyed particleUndyed particle nnmediamedia = 1.3874 = 1.3874

nnmediamedia = 1.3817 = 1.3817

X

Only 2.5 ns delay!!!

Introduce CCAIntroduce CCA

After few ns!!!!

Nanosecond optical switchNanosecond optical switch

First generation PCCAFirst generation PCCA Permanently lock the CCA arrayPermanently lock the CCA array Solid hydrogel is formed Solid hydrogel is formed

around CCAaround CCA PCCA hydrogel contains 30% PCCA hydrogel contains 30%

waterwater Modest alternation of Modest alternation of

diffraction peak happensdiffraction peak happens Stretching the gel causes the Stretching the gel causes the

diffraction peak wavelength to diffraction peak wavelength to changechange

N-vinylpyrrolidoneN,N’-methylene-bis-acrylamideacrylamide

CCACCAUVUV

benzoin methyl ether

Introduce PCCAIntroduce PCCA

CCACCA

PCCPCCAA

J. Am. Chem. SOC.,116 (11),4997-4498.1994

Introduce PCCAIntroduce PCCA

Thermally Thermally switchable PCCAswitchable PCCA

PS spheres + NIPAM PS spheres + NIPAM monomer in aqueous monomer in aqueous solution. solution.

The PS colloid self-The PS colloid self-assembled into a bcc assembled into a bcc CCACCA

Photochemically Photochemically initiated polymerization initiated polymerization of NIPAM with CCA of NIPAM with CCA CCA embedded in a CCA embedded in a PNIPAM hydrogel filmPNIPAM hydrogel film Science 274(5289),959-960,

1996

Diffraction intensity increases!!!

Attch the enzyme glucose oxidase Attch the enzyme glucose oxidase (GOx) to a PCCA of polystyrene (GOx) to a PCCA of polystyrene colloids.colloids.

O

NH2

acrylamide

1N NaOHTEMED

PCCAPCCA Hydrolyzed Hydrolyzed PCCAPCCA(amide group (amide group carboxy carboxy

group)group)

Introduce PCCAIntroduce PCCApH and Ionic strength sensorpH and Ionic strength sensor

Glucose sensorGlucose sensor

JACS, 122, 9534-9537,2000

Utilizes phenylboronic acid as Utilizes phenylboronic acid as the glucose recognition element the glucose recognition element (bind to sugars)(bind to sugars)

Nature, 389, 829-832,1997Anal.Chem,75, 2316-

2323,2003

Synthesis Cation Sensing Synthesis Cation Sensing MaterialMaterial

0.05g, 0.32mmol

2.00g, PS latexIon exchange

resin, solvent

0.10g, 1.4mmol

Parafilm spacer, 125 um

Quartz disk

1. CCA Self-assemble diffraction film

2. PCCA

365 nm

90 min 3. Hydrolyzed PCCA

0.15g, 0.64mmol

0.20g, 1.04mmol

Results and DiscussionResults and Discussion

CuCu2+ 2+ sensorsensor

757 nm

Results and DiscussionResults and DiscussionProposed Mechanism of Proposed Mechanism of Sensing CuSensing Cu2+2+

Cu2+

Low concentration

- Cu2+

+ Cu2+

Cu(hydroxyquinolatCu(hydroxyquinolate)e)22

Log (KLog (Kff) = 21.87) = 21.87

ShrinkShrink blue shrift blue shrift

bisliganbisligandd

Cu(hydroxyquinolate)Cu(hydroxyquinolate)

Log (KLog (Kff) = 10.70) = 10.70

Breaking crosslonkBreaking crosslonk red shriftred shrift

monoligamonoligandnd

Results and DiscussionResults and DiscussionFormation of the liganded Formation of the liganded complexescomplexes

5-acetamido-8-hydroxyquinoline in acetate-buffered saline

8-hydroxyquinoline-functionalizedCCA-free hydrogel

380380

250-270250-270

Other result: AA shows NO Cu2+ is retained by PCCA w/o 8-hydroxyquinoline

Results and DiscussionResults and DiscussionDiffraction wavelength Diffraction wavelength vs.vs. concentrationconcentration

S = CuS = Cu2+ 2+ molmol/ 2 ligand/ 2 ligandmolmol

Outmost layer Outmost layer effecteffect 11μμ

MM

Results and DiscussionResults and Discussion

5-acetamido-8-hydroxyquinoline

colloid-free 8-hydroxyquinoline-containing hydrogel

CuCu2+ 2+ stoichiometrystoichiometryAAλλ = = εεclcl

1.86E04

1.82E04

2.80E03

1.05E03

Results and DiscussionResults and DiscussionWash effectWash effect

Retention of bisligand Retention of bisligand CuCu2+2+ sites after sites after extensive washing extensive washing with pH 4.2 buffered with pH 4.2 buffered salinesaline

Ligand only hrdrogel

50 mM Cu2+ treated n hydrogel

Washed hydrogel

Partially

Partially reversible !!!

reversible !!!

Dosimeter for ultratrace Dosimeter for ultratrace concentration of Cuconcentration of Cu2+2+

Results and DiscussionResults and DiscussionSense > 1μM CuSense > 1μM Cu2+2+

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 CuReversible sensor for > 1μM Cu2+2+

cross-linked

Results and DiscussionResults and DiscussionNonspecific metal cation sensorNonspecific metal cation sensor

K1=109.57

K3=1018.27

K1=1010.70

K3=1021.87

CuCu2+2+ NiNi2+2+

Results and DiscussionResults and DiscussionNonspecific metal cation sensorNonspecific metal cation sensor

CoCo2+2+ ZnZn2+2+

airair

NN22

N2 : K1=108.11

K3 =1015.05Oxidation Co2+ Co3+ K1=108.65

K3=1016.15

ConclusionsConclusions

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.

ConclusionsConclusions

At low metal concentrations bisligand complexes form crosslink the gelshrink blue shift observedAt higher metal concentrations monoligand complexes form cross-links break red shift observed

ConclusionsConclusions

At trace concentration (～ 10-21 M), used as dosimeters; at low concentration (> 1μM), used as reversible sensorDetects 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

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

Epilog: who is citing this Epilog: who is citing this work?work?

X: Asher’s group * Lopze’s group from Spain

Appendix 1-chemical structure

N

OH

O

HN

5-acetamido-8-hydroxyquinoline

N

OH

8-hydroxyquinoline

O

NH

O

NH

N,N'-methylenebisacrylamide

O

O

O

diethoxyacetophenone

Appendix 1-chemical structure

S

O

Dimethyl Sulfoxide

N

N

N,N,N,N-tetramethylethylenediamine

(TEMED)

N

C

N N

H

Cl

1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride

EDC

Appendix 1-chemical structure

O

NH2

acrylamide

O

NH

O

NH

N,N'-methylenebis(acrylamide)

 

N

O

N-vinylpyrrolidone

O

O

benzoin methyl ether

(photopolymerize initiator)

O

HN

N-isopropylacrylamide

(NIPAM)

Appendix 1-chemical structure

O

HO OH

HO OH

HO

glucose

B

HO

HO

phenylboronic acid

Appendix 2-crystal structure

FCC (111) BCC (110)

Appendix 2-crystal structure

Appendix 3-paper published

0

50

100

150

200

250

300

350

to 1960 1961-1970 1971-1980 1981-1990 1991-2000 2001-now

time

N

O o

f p

aper

CCA

PCCA

Appendix 3- K1 & K3

L = 8-hydroxyquinoline, M =Cu2+

LM= Cu(8-hydroxyquinolate)+ 1:1 complex

L2M = Cu(8-hydroxyquinolate)2 bisliganded complex