Department of Analytical Chemistry and Food Chemistry

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Peter A. Lieberzeit

Department of Analytical Chemistry and Food Chemistry

Peter.Lieberzeit@univie.ac.at

Nanostructured Materials with Biomimetic Recognition Abilities for Chemical Sensing

Trends in Nanotechnology Conference, Tenerife, November 22

^nd

, 2011

What is a Sensor?

Transducer Analyte Measuring

electronics

P. A. Lieberzeit, TNTConference, Tenerife, Nov. 22nd, 2011

Receptor Data acquisition

Manufacturing QCM

Basis: Quartz blanks (AT-cut), 168 µm thick 9 Cleaning

9 Screen-printing of the desired electrode pattern 9 Burning of the electrode structures at 400°C

QCM - The Sauerbrey Equation

Motivation

• Natural systems are outstanding in terms of recognition and regeneration.

B t li it d d ti hi h

P. A. Lieberzeit, TNTConference, Tenerife, Nov. 22^nd, 2011

• But: limited ruggedness, sometimes high cost.

• Therefore: Implement biological functionality into artificial materials.

Recognition Strategies

Outer plane – „concave“ Incorporation – „convex“

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Basic Strategy

R SH M _X S

Synthesis, AFM Image and XRD pattern of MoS ₂

B

Mo(CO) ₆ Mo/MoO _x MoS ₂

Slow heating

Sulfur

MoS ₂ Nanoparticles

A

B

100 nm

Sensor response towards 1-Octanethiol

0 5

[H z]

-20 -15 -10 -5

0 10 20 30 40 50

Time [Min.]

Sens or Res p ons e

MoS

2

NPs Reference 30 ppm

20 ppm 10 ppm

5 ppm

Influence of Stoichoimetry

300 400 500 600

ng e ffe ct [H z]

octane thiol

Using slightly substoichiometric amounts of sulphur

0 100 200 300

m a s s s e nsi

1.80 1.85 1.90 1.95 2.00 2.05 2.10 S/Mo ratio in nanoparticles butane thiol

amounts of sulphur increases the sensor

responses.

Cu _2-x S Nanoparticles

CuSO ₄ + Na ₂ S ₂ O ₃ Cu _2-x S

-10 -5 0 5

R e sp o n se [ H z] Reference

3 ppm 6 ppm

9 Cu-Sulfide NPs

Synthesis according to: Y. Ni, F. Wang, Inorg. Chem. Commun. 6 (2003) 1406-1408.

-25 -20 -15

0 10 20 30 40 50 60

Time [min.]

Sen sor

6 pp 9 ppm 12 ppm

15 ppm 18 ppm

Cu

2

S nanoparticles selectivity pattern

20 25 30

p o n se [ H z]

0

5

10 15

S en so r re sp

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Particles Size dependent behavior of sensor

20 30

R es po ns e [ H z ]

0 10

Sens o r R

1- O ct an et h io l 1- B u ta n et hi ol

C u

2

S N P s [< 50nm ]

C u

2

S N P s [50-100nm ]

Comparison Cu ₂ S and CuS NP

-10 -5 0 5

ensor Response [Hz]

25ppm

CuS nanoparticles

-25 -15 -5 5

5 ppm 2 ppm

Sensor Response [Hz]

Cu

₂

S nanoparticles

P. A. Lieberzeit, TNTConference, Tenerife, Nov. 22nd, 2011 -15

0 10 20 30 40

Time [min.]

Se

CuS nanoparticles Reference 30ppm

-35 25

0 10 20 30 40

Cu2S Reference 10 ppm

S

Time [min.]

Layer Design by Imprinting

Monomers

Template Cross linker Small molecules:

Bulk Imprinting

Large (bio)species:

Surface Imprinting

Stamp

Selectivity by Imprinting

0 -100

-200

meta ortho para

S ens o r re spo n s e [ H z]

-300 -200 -100 0

S en s o r res p onse [Hz ]

300 H 50H 3H

ortho para meta

0 30 60 90 150

-300

120 -236 Hz -221 Hz -197 Hz

Time [min]

S

0 20 40 60 80

Time [min]

S -300 Hz -50Hz -3Hz

Affinity materials

Silicone layer No emphasized selectivity

o-Xylene imprint

Polystyrene/Divinylbenzene High selectivity

E. coli MIP

-1000 -500 0

e kt [H z]

Messelektrode 5 mg/ml B-E.Coli

Selectivity E. coli MIP

-3000 -2500 -2000 -1500

23,3 28,3 33,3 38,3 43,3

Zeit t [min]

Sensoref fe Messelektrode

Referenzelektrode

5 mg/ml W-E.Coli

5 mg/ml W-E.Coli 5 mg/ml W-E.Coli

5 mg/ml W-E.Coli

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-2000 -1500 -1000 -500 0

n so re ff ekt [ H z]

Messelektrode Referenzelektrode 5 mg/ml B-E.Coli

Long Term Stability

-3500 -3000 -2500

10,2 15,2 20,2 25,2

Zeit t [min]

Se n

5 mg/ml W-E.Coli

5 mg/ml W-E.Coli 5 mg/ml W-E.Coli

Bioreactor

• Cultivation of microorganisms under optimal conditions

• important parameters:

the composition of the nutrient, oxygen supply sterility pH

Bioreactor Measurements

oxygen supply, sterility, pH and temperature-controlled

and controllable

• Sensors measure these parameters directly in the exhaust air or in the culture medium

• Process flow assessed

• Sensitive layer: polyurethane imprinted with b- E. coli

• Incorporation of b-E. coli in the cavities of the polyurethane in flow modus and temperature at 37° C

2.05b_flow_1

0 2000

Breeding Experiment

• Start concentration: 80 mg/ml

-18000 -16000 -14000 -12000 -10000 -8000 -6000 -4000 -2000 0

0 5 10 15 20 25 30

Zeit t [min]

Sensoreffekt [Hz]

Messelektrode Referenzelektrode

Comparison MIP/ligand

Lectin

Ligand

MIP ^Compare

Lectins

• Glycoprotein

• Specific binding to oligosaccharide

– Mannose

• ConA, LCH, GNA

– Galactose/N-acetylgalactosamine y g

• RCA, PNA,AIL VVL – N-acetylglucosamine

• WGA, SNA, MAL – Fucose

• UEA, AAL

• Play important role in cells and viruses recognition.

http://www.ebi.ac.uk/pdbe-srv/view/entry/2uvo/quaternary.html

Experimental: Ligand Synthesis

Schematic of artificial synthetic receptor

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QCM Results Ligand

-100 -50 0 50

H z] _{10 µg/ml} ^{5 µg/ml}

-250

-200 -150 100

0 50 100 150 200 250 300 350

Δ f[ H

Time [min]

Receptor (Hz) Cys (Hz)

160 µg/ml 80 µg/ml

40 µg/ml

20 µg/ml µg

Results: STM & Protein Image

26

NANOSMAT-5

QCM results

0 500 1000

Δ f[ H z ]

160 µg/ml 80 µg/ml 40 µg/ml 20 µg/ml 10 µg/ml 5 µg/ml

-1500

-1000 -500

0 20 40 60 80 100 120 140 160 180 200

Δ

Time [min]

MIP Change (Hz) NIP Change (Hz)

Results : Selectivity

Conc160 µg/ml

28 Ag ₂ S-Polymer Nanocomposite

Nanoparticles

Comparison of Sensor Responses

15 20 25 30

R es p o n se [ H z]

100 200

300 400 0

5 10 15

No rmal ized R

Conc. of 1-butanol [ppm]

NIP NIP + Ag

2

S NPs

M IP

Com posite material

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Acknowledgements

S. Bajwa R. Samardzic T. Wangchareansak G. Mustafa

€

€ Austrian Science Fund (FWF) European Commission: EU-FP6 and FP7

Royal Golden Jubilee Grant PhD Program

Thank you for your attention!

Department of Analytical Chemistry and Food Chemistry