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National Technical University of Athens School of Applied Mathematical and Physical sciences Foundation for Research and Technology - Hellas (FORTH) Institute of Electronic structure and Laser (IESL) National Technical University of Athens School of Applied Mathematical and Physical sciences Terahertz detection of harmful residues in honey Dr. M. Massaouti PHOTOTECH: BIOSENSORS & BIOCHIPS 21 st -25 th October 2013 , Athens , Greece

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National Technical University of Athens

School of Applied Mathematical and Physical sciences

Foundation for Research and Technology-Hellas (FORTH)

Institute of Electronic structure and Laser (IESL)

National Technical University of Athens

School of Applied Mathematical and Physical sciences

Terahertz detection

of harmful residues in honey

Dr. M. Massaouti

PHOTOTECH: BIOSENSORS & BIOCHIPS21st-25th October 2013 , Athens , Greece

[email protected]

National Technical University of Athens

THz radiation and Food industry

2

Motivation

New methods for food analysis and inspection:

rapid portable (increase of testing capacity) non-destructive with no need of food pre-treatment real-time testing on the production line

Current analytical methods (few of them…)

High-performance liquid chromatography (HPLC)

Gas chromatography (GC)

mass spectrometry (MS)

nuclear magnetic resonance (NMR)

infrared spectroscopy (IR)

Fluorescence spectroscopy

Electrochemical (including also biosensors here), and so forth.

Contaminantsin food products

[email protected]

National Technical University of Athens

Terahertz radiation

3

Molecular rotations ImagingLattice phononsSuperconductivity gap

Photonic “THz gap” Electronic

λ 10μm - 3mm

hν 120 - 0.413 meV

Hydrogen Bonds, Torsions, collective vibrational modes

[email protected]

National Technical University of Athens

Terahertz radiation

4

Non–ionizing/invasive radiation

Transparent to non-conductingmaterials (paper, wood, plastic, etc.)

High sensitivity to water

Fingerprint spectrum:low-frequency torsional and vibrationalmotion of molecules

ImagingSecurity Drugs and explosives

Medical- Cancer

THz pump/probe

Plant stress

Ubiquitin: 76-residue, β-sheet protein

Protein folding DNA damage or repair

Discrimination of molecular structures

[email protected]

National Technical University of Athens

THz radiation and Food industry

5

Detection of foreign bodies in food Non–ionizing/invasive radiation

Transparent to non-conductingmaterials (paper, wood, plastic, etc.)

High sensitivity to water

Fingerprint spectrum:low-frequency torsional and vibrationalmotion of molecules

Opt. Eng., 47 (3), 037003 (2007)

Moisture detectionJ Infrar. Milli. Terahz. Waves.33,97 (2012)

Grain wheat

Detection of Antibiotics/ pesticides (in milk, egg powders, rice, dried tomato)

Analyst, 136, 1733 (2012)IEEE Trans., 58, 7, 2064 (2010)

Appl. Spectr. Rev.,48, 439 (2013)

THz and Food industry

More to be done!!!

[email protected]

National Technical University of Athens

Food industry: Honey

6

Honey: Natural and healthy product…….…..Polluted via different sources of contamination

(mainly to improper use of beekeeping practices)

Need: novel detection technologies rapid, non-destructive able todetermine the presence of multi-residues in honey.

Real-time detection

[email protected]

National Technical University of Athens

Terahertz source

7

Broadband (0.1-35 THz), intense THz pulses (200 kV/cm)generated through 2-color femtosecond laser filaments in air.

THz source:

Coherent detection in time domain of the THz electric field.

[email protected]

National Technical University of Athens

Terahertz source

8

Broadband (0.1-35 THz), intense THz pulses (200 kV/cm)generated through 2-color femtosecond laser filaments in air.

THz source:

Fourier transform the time signal

[email protected]

National Technical University of Athens

THz time-domain spectroscopy (THz-TDS)

9

Refractive index

( )2ln

( )

S

R

Aa T

d A

Absorption coefficient:

( ) ( )1

s R cn

d

2( ( ) 1)

4 ( )

nT

n

( )( ) Ri

RA e

( )( ) si

SA e

[email protected]

National Technical University of Athens

THz spectra: Antibiotics & Acaricides

10

Concentration 20% w/w

Thickness ~1 mm

Diameter 7 mm

Weight 40 mg

SAMPLE HOLDER(pellets)

PELLETS: mixture of HDPE powder + chemical compound

Antibiotics

Sulfapyridine

Sulfathiazole

Tetracycline

Acaricides Coumaphos

Amitraz

[email protected]

National Technical University of Athens

THz spectra : Antibiotics

11

Sulfapyridine

Sulfapyridine

Sulfathiazole

Tetracycline

Tetracycline

THz region (0.5-2.6 THz)

1.064 THz

Sulfathiazole

1.88 THz2.04

Distinct resonance peaks in the THz regime

Massaouti et al. J. Appl. Spectr. (2013)

[email protected]

National Technical University of Athens

THz spectra : Acaricides

12

Coumaphos

Amitraz

THz region (0.5-2.6 THz)

1.88 THz

Amitraz

Coumaphos

Distinct resonance peaks(0.5-2.6 THz)

↓Discrimination of:

Sulfapyridine

Sulfathiazole

Coumaphos

Massaouti et al. J. Appl. Spectr. (2013)

[email protected]

National Technical University of Athens

THz spectra : Antibiotics

13

Sulfapyridine

Sulfathiazole

Tetracycline

THz region (0.5-6.0 THz)

Amitraz

Coumaphos

Detection in a wider THz region0.5-6.0 THz

↓Additional resonance peaks

↓Discrimination of:

Sulfapyridine

Sulfathiazole

Coumaphos

Amitraz

[email protected]

National Technical University of Athens

THz spectrum of honey

14

SAMPLE HOLDER(liquids)

HDPE

Spacer 620 μm

Highly absorptive: α = 50 cm-1 (1 THz)

Refractive index: n = 1.8

Massaouti et al. J. Appl. Spectr. (2013)

[email protected]

National Technical University of Athens

Sulfapyridine in honey

15

SAMPLE HOLDER(liquids)

HDPE

Spacer 620 μm

+

Mixture:

Sulfapyridine Honey

different concentrations(w/w)

1.064 THz

.

mixture honey sylfapyridine

mixture

THz ref

A

A

Massaouti et al. J. Appl. Spectr. (2013)

[email protected]

National Technical University of Athens

Sulfapyridine in honey

16

SAMPLE HOLDER(liquids)

HDPE

Spacer 620 μm

+

Mixture:

Sulfapyridine Honey

different concentrations(w/w)

1.064 THz

Detection of Sulfapyridine in honey at relatively low concentrations (1% w/w)

[email protected]

National Technical University of Athens

Sulfapyridine & Sulfathiazole in honey

17

+

Mixture:

Sulfapyridine (9%)

Honey

andSulfathiazole (11%)

binary mixture honey honey/ /

,

i ii

B

i sulfapyridine sulfathiazole

Multiple residues in honey

Potential of THz-TDS to be used in the near future as a fast, real-time technique for detecting and discriminating multi-residues strictly related

to food safety issues.

Massaouti et al. J. Appl. Spectr. (2013)

[email protected]

National Technical University of Athens

Ultrashort Nonlinear Interactions and Sources Lab

Acknowledgments

UNIS - THz group

Prof. S. Tzortzakis (Head of the UNIS group)

Dr. M. Massaouti

Dr. A. Gorodetsky

M. Loulakis

T. Koulouklidis

C. Daskalaki

http://www.iesl.forth.gr/

LASERLAB-EUROPE

UNIS group

http://unis.iesl.forth.gr/