nanotechnology for forest products 2006 2… · capacity 0.1-1mg template / g polymer imprint...

NANOTECHNOLOGY FOR FOREST PRODUCTS 2006

Dr. Boris [email protected]

QuickTime™ and aNone decompressor

are needed to see this picture.







QuickTime™ and aTIFF (Uncompressed) decompressor






Biomimetic Paper using Molecularly Imprinted

PolymersBoris Mizaikoff & John Cairney (IPST)

Biomimetic Paper using Molecularly Imprinted

PolymersBoris Mizaikoff & John Cairney (IPST)

Atlanta, April 27, 2006

Nanotechnology Based Sensors

MotivationBiomimetic paper - Toward smart packaging and embedded sensing!


Why biomimetic?

Pathogen recognition

→ Synthetic alternative to natural receptors with similarproperties

→ Robustness (inertness, shelf-life, etc.)→ Works at changing pH, ionicity, T, etc.→ Tailorable to a wide variety of molecules

→ Food/beverage packaging (consumer protection)→ Selective filters (deactivation)→ Diagnostic paper (detection)→ Sensing functionality when coupled to transducer

(monitoring)⇒Capturing molecules with templated materials

MotivationWhy molecularly imprinted polymers?


⇒Biomimetic sensors !

mM rangeBinding strength0.1-1mg template / g polymerCapacity

Repeated use >100 times without reductionImprint Memory

several years without loss of performanceStorage Endurance

Resistant against acids, bases, various organic solvents and metal ions

Chemical Stability

Resistant against mechanical stress, high pressure and elevated temperature

Physical Stability

CharacteristicsFeature

analyte

transducersignalbioreactivelayer

analyte

transducersignalbioreactivelayer

Capturing Molecules with Templated MembranesMolecularly imprinted polymers (MIPs)


J. O’Mahony et. al., Anal. Chim. Acta, 534, 31 (2005)





How to make MIPs… the simple view!

→ Formation of discrete, isolated binding sites via monomer-template self-assembly & polymerization

→ Various MIP formats



A. Molinelli et. al., J. Agric. Food Chem., 50, 1804 (2002)

Successful imprints

→ Herbicides/Pesticides (e.g. 2,4 Dichloro-phenoxy acetic acid)

→ Env. Pollutants (e.g. Nitrophenoles)→ Flavones/Flavonoides (e.g. Quercetin, etc.)→ Estrogens/Endocrine Disruptors (e.g. 17β-

Estradiol, Ethynylestradiol, Estrone,Bisphenol A, etc.)

→ Mycotoxins (e.g. Deoxynivalenol,Zearalenone, etc.)

CURRENT RESEARCH FOCUS …







NO …but it works very well!

?

??

Example

→ Template: quercetin→ Functional monomer: 4-VP→ Filling monomer: ethyleneglycol

dimethacrylate (EGDMA)→ Porogen: acetonitrile/acetone

Do we understand what‘s going on ?





Capturing Molecules with Templated MembranesExample: Nitrophenol MIPs (e.g. pesticides, herbicides, etc. in wine)


M. Janotta et al., IJEAC, 80, 75 (2001)





OH

NO2

4-Nitrophenol

(a) 4-NP imprinted polymer as stationary phase and an organic mobile phase(b) Control polymer as station. phase and organic mobile phase(c) 4-NP imprinted polymer as station. phase and aqueous mobile phase(d) Control polymer as station. phase and aqueous mobile phase

HPLC Results

Capturing Molecules with Templated MembranesExample: Mycotoxin MIPs (e.g. in food, feed, beer, etc.)


R. Weiss et al., Food Addit. and Contamin., 20, 386 (2003) R. Krska et al., Food Addit. and Contamin., 22, 345 (2005) Patents issued (2002-2006)





→ Toxic secondary metabolites ofFusarium fungi

→ Enrichment during beer brewingprocess

(a) DON imprinted polymer as stationary phase and an organic mobile phase(b) Control polymer as station. phase and organic mobile phase

CH3

OOH OH

O

OOH

CH3

Deoxynivalenol (DON)

O

O

CH3OOH

OH

Zearalenone (ZON)

HPLC Results

Capturing Molecules with Templated MembranesExample: Estradiol MIPs (e.g. estrogens in milk, baby food, etc.)






Bulk polymers: irregular shape, 10-25 mμ Microspheres: 2-3 mμ Nanospheres: 400 nm

HPLC, SPE HPLC, SPE Binding assays

S. Wei et al., Biosens. Bioel., 21, 1943 (2006)

Capturing Molecules with Templated MembranesExample: Estradiol MIPs (e.g. estrogens in milk, baby food, etc.)






Characterization of MIP

0 0.5 1 1.5 2

MIP

CTL

C18

Capacity Factor

estronealpha-estradiolbeta-estradiol

Liquid chromatography (HPLC):→ Separation of 17α-ethynylestradiol (1), estrone (2), 17a-ethynylestradiol (3), estriol (4) and 17β-estradiol (5) demonstrated→ Superior capacity factor of MIP vs. control and commercial C18 stat. phase

Solid phase extraction (SPE):→ LOD in river water of 1-10 ng/L, and in waste water of 10-50 ng/L with recoveries of 85-98% achieved

Radioligand binding assay:→ Separation of 17β-estradiol from17α-estradiol (opt. isomer) achieved

S. Wei et al., Biosens. Bioel., 21, 1943 (2006)

Capturing Molecules with Templated MembranesAnalytical characterization of MIP synthesis: Example - Quercetin MIP


J. O’Mahony et al., Biosens. Bioel., 21, 1383 (2006) J. O’Mahony et al., Anal. Chem., submitted (2006)





The truthabout MIPs …

Collaboration: DCU (Nolan, Smyth, Regan), ARCS (Jakusch), TUM (Niessner)

Capturing Molecules with Templated MembranesNext step …


M. Jakusch et al., Anal. Chem., 71, 1185 (1999) S. Wei et al., Biosens. Bioel., 21, 1943 (2006)

If we can analyze the pre-polymerization solution …… can we model the governing interactions?

Cl

Cl

O C O O H

2,4-Dichlorophenoxy-acetic acid (2,4-D)

Two examples

(Because we thought we understand the system …… and we did not!)

(Because we need to understand the system!)





Capturing Molecules with Templated MembranesMolecular dynamics simulations - 2 molecules in explicit solvent


J. O’Mahony et al., Biosens. Bioel., 20, 1884 (2005) A. Molinelli et al., Anal. Chem., 77, 5196 (2005)

Water

Chloroform

2,4-D / 4-VP MIP:

• IR Job’s Plot Analysis• NMR Job’s Plot Analysis• NMR T1 Relaxation Time Analysis

… after extensive analysis !

QuickTime™ and aCinepak decompressor








Water

Chloroform

MIPs in Food/Beverage IndustriesTremendous potential for smart packaging !


Membrane ResearchApplied Sensors Laboratory






SiO

O

OPTMOS

SiO

O

OMTMOS

Polymer libraries

Sol-gels

Molecularly imprinted polymers

AcknowledgementsApplied Sensors Laboratory & Funding Agencies


ASL Team (current):Boris Mizaikoff

Research Scientists:Christine Kranz (SRS)Martin Brucherseifer(RS, FIB2 Center)

Postdocs:Jean-Francois MassonHeungjoo ShinCarla Riccardi

Ph.D.s:Nick MenegazzoChristy CharltonGary DobbsShuting WeiRuth WangJustyna WiedemairDan MenashaChristina YoungRongwei ZhangJong-Seok Moon

Visiting Scientists:Federico Polo (Italy)Keith Farrington (Ireland)

… and all former students andpostdocs !!!

Funding

- National ScienceFoundation (4)

- U.S. Geological Survey

- U.S. Dept. of Energy

- National Inst. ofHealth (3)

- European Union

- Max Kade Foundation

- Army ResearchOffice (3)

- ExxonMobil Res. Corp.

- SNF Corp.

nanotechnology for forest products 2006 2… · capacity 0.1-1mg template / g polymer imprint...

Documents