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Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme” 27 Septembrie 2012

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Page 1: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Cristina Rusu - Senior scientist

MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS

Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme” 27 Septembrie 2012

Page 2: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Cristina Rusu / Diaspora 27 Sept2012

Imego

department

Page 3: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Advanced Technology for Demanding Measurements

Cristina Rusu / Diaspora 27 Sept2012

Page 4: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

IMUs for

unmanned

vehicles (UAV,

ROV)

High dynamics,

high bandwidth

(e.g. crash tests)

Inertial

Navigation

(e.g. personal

navigation)

World-leading

MEMS gyro

systems

Data processing,

motion

classification,

wireless interfaces

MEMS

accelerometers

for navigation

and seismic

applications

World leading MEMS inertial sensor and system R&D center

Cristina Rusu / Diaspora 27 Sept2012

Inertial sensors and systems

Page 5: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Magnetic

sensor system

- Field scanning - Traffic detection - The DynoMag system

- High frequency dynamic

AC susceptometry

- Finite Element analysis

Magnetic

analysis

Magnetic

sensor system

AC

susceptometry Magnetic

simulation

- Static and dynamic

characterization

- Magnetic shielded

room

- Magnetic consultants

and lectures

Cristina Rusu / Diaspora 27 Sept2012

Electromagnetics sensors

Page 6: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Cristina Rusu / Diaspora 27 Sept2012

Bio-chemical sensors

Page 7: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Cristina Rusu / Diaspora 27 Sept2012

Wireless sensors networks

Page 8: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

• Homogeneous assays

• Non-labelled sensing

• Nanoparticles & colloidal solutions

• Biomolecule – surface & receptor – ligand interactions

Bio-chemical applications

Molecularly Imprinted Polymers

Cristina Rusu / Diaspora 27 Sept2012

Page 9: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Why Molecularly Imprinted Polymers?

Problems Associated with Natural Compounds / Antibodies

Low stability of the biomolecules

High price of enzymes and receptors

Poor performance in non-aqueous media

Poor compatibility with micro fabrication technology,

resulting in difficulties with design of sensors

Cristina Rusu / Diaspora 27 Sept2012

Page 10: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

The art of molecular imprinting

Zimmerman et al.

Nature (2002) 418, p. 399

Cross-linked polymer formed around a molecule that acts as a template,

template subsequently removed.

Imprints containing functional groups complementary to those of

template are left behind

Cristina Rusu / Diaspora 27 Sept2012

Page 11: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Advantages of MIPs

Cristina Rusu / Diaspora 27 Sept2012

Page 12: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Disadvantages of MIPs

Cristina Rusu / Diaspora 27 Sept2012

Page 13: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Target molecules

Toxins, eg., marine toxins

Narcotics

Chemical warfare agents

Explosives

Peptides

Pharmaceutical waste

Tannins, caffeine

Sugars, (sorbitol, glucose)

• Pharmaceutical Industry

• Food Industry

• Veterinary Industries

• Doping Laboratories

• Monitoring Agencies

• etc.

Application areas of MIPs

Cristina Rusu / Diaspora 27 Sept2012

Page 14: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

MIP Application: Selective Phase extraction

Selective extraction of low levels of target compounds in the

presence of a mixture of potentially interfering matrix components.

Cristina Rusu / Diaspora 27 Sept2012

Page 15: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

MIP Application: Sensors

Cristina Rusu / Diaspora 27 Sept2012

Page 16: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Our motivation of using MIPs

One of the very few techniques that allows one

to detect specific contaminations in water / fluid

outside the laboratory environment

Cristina Rusu / Diaspora 27 Sept2012

Page 17: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

MIP-based sensors: Transductions

Volume changes upon imprint adsorption (swelling /

shrinkage)

Changes of charge state surface assay (QCMD,

interdigital electrodes

Changes of charge states upon analyte binding Reaction

induced aggregation homogeneous assay (PCS, Z-

potential light scattering)

Electrochemical Impedance Spectroscopy surface assay,

interdigital electrodes

Cristina Rusu / Diaspora 27 Sept2012

Page 18: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Microelectrodes = allows to vary penetration depth of the electric field inside the fluid

Impedance: Apply constant AC-voltage of different frequencies;

Measure AC - current amplitude and phase at each frequency.

Plot imaginary part of impedance (ImZ) vs. its real part (ReZ)

C = Q(w)/V(w) = f(t,w,s,V,ε) x (ε0εrA)/d

I(w) = ∫Qdt

measure Z(w) = Re Z(w) + Im Z(w)

MIP MIP MIP

Passive polymer matrix

MIP

+

Si wafer/glas

+ -

Buffer

teff

MIP MIP MIP

Passive polymer matrix

MIP

Si wafer/glas

-

E(w,x) = dV(w,x)/dx

+

w s

Cristina Rusu / Diaspora 27 Sept2012

MIP- based sensor: detection by

impedance spectroscopy (IS)

Page 19: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

MIP-based sensor – IS setup

Planar coil

electrode

Cristina Rusu / Diaspora 27 Sept2012

Interdigital

electrodes

MIP particles

sizes 170 nm –

few µm

(Lund University)

Page 20: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Cristina Rusu / Diaspora 27 Sept2012

MIP-based sensor – IS setup

Page 21: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

MIP imprinted against propranolol - IS

Cristina Rusu / Diaspora 27 Sept2012

0

100

200

ImZ

DL-propranolol

Atenolol

0

100

200

300

400

0 200 400 600

Re

Z

Concentration (µM)

0

100

200

ImZ

DL-propranolol

Atenolol

0

100

200

ImZ

DL-propranolol

Atenolol

0

100

200

300

400

0 200 400 600

Re

Z

Concentration (µM)

0

100

200

300

400

0 200 400 600

Re

Z

Concentration (µM)

Interdigitated finger electrode

lowest concentration detected ≈ 10µM

Atenolol is chemically very similar to propranolol

Page 22: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Communication

Battery

Pumps - fluidics

Switches

- fluidics

Inlet fluidics

Detection

area

Electronics &

microcontroller

Top-view MIP system including detection system, fluidics, power supply,

communication

MIP – field instrument

Cristina Rusu / Diaspora 27 Sept2012

Page 23: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Cristina Rusu / Diaspora 27 Sept2012

MIP imprinted against propranolol –

optical detection

Size changes and agglomeration of MIP - propranolol upon target

adsorption measured using dynamic light scattering.

Particle translational motion

Translational relaxation time, t

Particle size distribution r

TqkB

2

6t

– solvent viscosity

T – temperature

q – scattering wave vector

r – particle radius

Page 24: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

CONCLUSIONS – Present & Future

MIP-based sensing = quantitative detection

Sample deposition method of MIP manufacturing

MIP / NIP signal analysis MIP / NIP theory & modelling

Optical detection seems ‘easier’

NIP utilization reduced false positive / negative

Field measurement system

Portable, low power

Pre-concentration of sample

Reliable

Cristina Rusu / Diaspora 27 Sept2012

Page 25: MOLECULARLY IMPRINTED POLYMERS for …Cristina Rusu - Senior scientist MOLECULARLY IMPRINTED POLYMERS for CHEMICAL SENSORS Diaspora workshop “Micro-Nanoelectronica, Micro-Nanosisteme”

Acknowledgement

Andrea Astalan, Kristina Fogel, Anatol Krozer, Christer Johansson Fredrik Ahrentorp, Torbjörn Pettersson, John Roswell EU-FP7 Emergency Support System www.ess-project.eu

EU-FP7 Total Airport Security System www.tass-project.eu

[email protected]

Multumesc pentru atentie