ESF provides the COST Office

through a European Commission contractCOST is supported

by the EU Framework Programme

European Network on New Sensing Technologies for Air Pollution

Control and Environmental Sustainability - EuNetAir

COST Action TD1105

1ST TRAINING SCHOOL

Universitat de Barcelona, Spain, 13 - 15 June 2013

organized by UB, MIND-IN2UB - Dept. of Electronics and CSIC-IDAEA

Action Start date: 01/07/2012 - Action End date: 30/06/2016

Year 1: 2012 - 2013 (Ongoing Action)

Thu-Hoa TRAN-THI

WG2 Member / thu-hoa.tran-thi@cea.fr

CEA-Saclay, Francis Perrin Lab, URA CEA-CNRS 2453

91191 Gif-sur-Yvette/FRANCE

SENSORS which properties?

• Sensitivity ppb level : Pre-concentration

• Selectivity micro-chromatography

doping, T°

molecular recognition

• Rapidity

• Low-cost

2

Chemical sensors based on nanoporous materials

3

Porous Materials Sol-gel

Chemical Reactivity Confined Media

Metrology Gas Mixtures

Sensor Prototypes

Sensors for Environment

& Health

Chemical Sensors

4

Naporous Sponge • Filter • Concentrate

Sol-Gel Simple Cheap

Selectivity

Probe-molecule/Target-analyte

Optical detection: rapidity

Visual detection

Ms Analyte

Mr. Probe

Mr Interfere

5

Sol

S i

O R

O R O R OR

2

3

1

Gel

monolith

EtOH/H2O

1 2

Probe-Mol

4 5

Thin Film

Sol-Gel Process

Hydrolysis & polycondensation

(RO)3-Si-OR + H2O (RO)3-Si-OH + ROH

(RO)3-Si-OH + OH-Si- (RO)3 (RO)3-Si-O-Si-(OR)3 + H2OH2O

6

Doped monolith

Easy-to-do synthesis

6

thermostated bath

Magnetic stirring

3 – water (pH)

1 –organic solvent

2 – Si Alkoxyde + Probe mol.

4 – Molding 5 – drying 6 - Storage

Commercialized alkoxydes

7

Si

OMe

MeO

OMe

CF3

SiEtO

OEt

OEtC

6F

13Si

OMe

MeO

OMe

C8F

19

and others…..

Nanostructured materials (film)

8

Mobil Oil: CMC41

-Br ,+(H3C)3NCH2

H2C

CH2

H3C7

-Br ,+(H3C)3NCH2

H2C

CH2

H3C7

after washing, MET

Surfactants & organic polymers as templates: wash or calcination

Thin film deposition

9

mask

Doping methods

10

Doping

« One Pot » one pot

grafting

Diffusion in

liquid phase

Diffusion in

gas phase

phase

Post-grafting

11

Characterisations Monoliths & films

Porosity

Films thickness

Organisation-nanostructuration

Hydrophilicity or hydrophobicity of materials

Porosimetry micro (<20Å), meso (20-500Å), macro (>500Å)

12

0

100

200

300

400

500

0,00E+00 5,00E-01 1,00E+00Vo

lum

e e

n c

c/g

P/P°

N2 adsorption-desorption isotherms @ -77°K

Série1Série2

0,00E+00

5,00E+00

1,00E+01

1,50E+01

2,00E+01

2,50E+01

3,00E+01

3,50E+01

Pore diameter distribution

Ad

s.

su

rface a

rea

Pore diameter (Å)

Pore volume (cm3.g-1) Specific adsorption surface area (m2.g-1) Pore diameter distribution

Density Functional Theory

Thin film porosity

In-situ Ellipsometry-Porosimetry

13

Polarisability change Film thickness Refraction index Vmolec adsorptive Adsorptive polarisability

Isotherms of adsorption and desorption of toluene V = f(P/P0) → Vp, Rp

Hydrophilicity-hydrophobicity Near-IR Spectroscopy & ATG

TMOS-MeTMOS precursors mixture (film: 580 µm)

14

wavelength / nm

1250 1500 1750 2000 2250 2500

Abso

rban

ce

0.00

0.25

0.50

0.75

1.00

dehydrated

hydrated

Fre

e S

i-O

H (

ham

on

ic 2n)

Free Si-OH

(stretching +bending)

Films thickness: Profilometry & Absorbance

15

Durée de polymérisation (min)

160 180 200 220 240 260

Absorb

ance à

298 n

m

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Epaisseur du film (nm)

0 50 100 150 200 250

Ab

so

rba

nce

à 2

98 n

m

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Thin film

Substrate

Longueur d'onde (nm)

240 260 280 300 320 340

Abs

orba

nce

à 29

8 nm

0

1

2

3

tem

ps

Sol (TMOS) + Fluoral-P

Ab

sorb

ance

@ 3

00 n

m

Wavelength (nm)

Ab

sorb

ance

@ 3

00 n

m

Condensation duration (min)

Film thickness (nm)

Ab

sorb

ance

@ 3

00 n

m

Hydrophobic Films : Contact Angle

16

Sol-Gel Films :

References:

Quartz: SiO2 Teflon: CF3

20-30° 95-110°

TMOS MeTMOS 8:2 FluoProTMOS 8:2

80° 20-30° 35-40°

Thermogravimetric analysis (TGA)

17

Mass loss measurement with T°

0 1500 3000 Time (sec)

Tem

pera

ture

(°C

)

Mas

s lo

ss

(mg

) H2O

Silicate+ Fluoral-P

Fluoral-P

METROLOGY

18

Generation of calibrated gas mixtures

Solid compounds (paraformaldehyde,

naphthalene….)

Liquid compounds

Compounds formed in situ (chloramines)

Generation of calibrated gas mixtures

N 2

F M

F M

F M

F M

FM Liq

90°C 4 bars

N2

To flow cell

H2O injection

Permeation oven

Dilution stages

Paraformaldehyde permeation tube

[CH2O] = 400 ppt to 2 ppm, Flux: 50 – 2000 mL.min-1

Sensors for Environment

20

Indoor Air Quality

(Formaldehyde, BTXs, nitrogen trichloride)

Are we safe indoors?

21

BTX,NO2,CO NCl3, CHCl3,

CH2O,B

B, CH2O

CO,Acrolein,CH2O

NO2, cooking

CH2O

CH2O,B,T,

hexanal

Trichloro-

ethylene,

naphthalene

…. Incense burning,

mosquito repellent,

detergent, deodorizer

Insulating foam cigarette

22 22

benzene toluene xylenes mesitylene naphthalene

formaldehyde acetaldehyde hexanal acrolein

alkanes alcohols acids estersesters

CnHn+2

Most common indoor air pollutants

styrene

Outdoor and indoor VOC French national campaign in 2005 (600 dwelling-houses)

0

5

10

15

20

25

Intérieur Extérieur

2-butoxy-éthylacétate

1-méthoxy-2propylacétate

styrène

trichloroéthylène

Acroléine

tétrachloroéthylène

2-butoxyéthanol

1 méthoxy2propanol

Benzène

Éthylbenzène

o-xylène

1,2,4-triméthylbenzène

1,4-dichlorobenzène

n-décane

m/p xylène

n-undécane

Acétaldéhyde

toluène

Hexaldéhyde

Formadéhyde

Co

nce

ntr

ation

µg

/m3

formaldehyde

acetaldehyde

hexaldehyde

acrolein

benzene

toluene

m/p xylene

1,2,4-trimethylbenzene

23

80 - 85 % of time indoor

Indoor Outdoor

24

2006 : List of 50 indoor air pollutants (INDEX list & ANSES)

2007-2009 : Guide Values for Indoor Air (ANSES)

Formaldehyde, Benzene, NO, Naphtalene

Nov. 2009 : Values for Risk Management (HCSP)

Formaldehyde : 10 µg/m3, 30 µg/m3, 50 µg/m3

Jan. 2012 : Labelling of materials (Law)

Juil. 2012 : IAQ monitoring in public buildings (Law)

24

Decisions resulting from the campaigns

ANSES = Agence nationale de sécurité sanitaire de l’alimentation, de l’environnement

et du travail

HCSP = Haut Conseil de la Santé Publique

Classification of compounds to be monitored European working group INDEX & ANSES

25

Indoor Air quality

Detection of the ubiquiteous formaldehyde

26

Sensors for Environment

Formaldehyde detection

27

Concentration

Measu

rem

en

t ti

me

10 µg/m3 100 µg/m3

Sec

Min

H

ou

r D

ay

50 µg/m3

Draëger

PPM Technology

Draëger, Gastec…

RKI Instruments

Radiello

3M

Delayed analyses in laboratory

Aerolaser GmbH

Greywolf

Indoor air quality in homes

ETHERA

Chemical Sensor

Principle of detection of CH2O

28

NH2O

+

O

N

H

O

2 HCHO-H

2O

- NH3

Fluoral P 3,5-diacetyl-1,4-dihydrolutidine (DDL) 2D Graph 1

Wavelength (nm)

200 300 400 500

Abso

rban

ce

0.0

0.1

0.2

0.3

0.4

Wavelength (nm)200 300 400 500 600

Abso

rban

ce

0.2

0.4

0.6

0.8

1.0

Flu

oresc

enc

e int

ens

ity

(cps

)

0.0

5.0e+6

1.0e+7

1.5e+7

H. Paolacci et al, Sensors & Transducers,

82, 1423-1431, 2007

Sol-Gel thin film doped with Fluoral-P TMOS/CH3OH+Fluoral-P 0,5M/H2O: 1/4/4

29

Durée de polymérisation (min)

160 180 200 220 240 260

Absorb

ance à

298 n

m

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Epaisseur du film (nm)

0 50 100 150 200 250

Ab

so

rba

nce

à 2

98 n

m

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Thin film

Substrate

Longueur d'onde (nm)

240 260 280 300 320 340

Abs

orba

nce

à 29

8 nm

0

1

2

3

tem

ps

Sol (TMOS) + Fluoral-P

Ab

sorb

ance

@ 3

00 n

m

Wavelength (nm)

Ab

sorb

ance

@ 3

00 n

m

Condensation duration (min)

Film thickness (nm)

Ab

sorb

ance

@ 3

00 n

m

Thin film of sol-gel doped with Fluoral-P

30

Sol formulation: TMOS/MeOH+FP 0,5M/H2O: 1/4/4 Dip-coating: 50 mm.min-1, film thickness : 200 nm

He

igh

t (0

-15

mm

)

Length (0-8 mm) Length (0-8 mm)

He

igh

t (0

-15

mm

)

31

Detection of DDL abs & fluo

Flow-cell holder Micro-pump

Ocean Optics

Spectrophotometer

UV-visible Lamp

LED 420 nm

Detection units

32

Gas in

Gas out

Light from lamp

Light to spectrometer

Light from LED

Gas in

Gas out

Dual detection of CH2O via abs and fluo

33

Films doped with Fluoral-P and exposed to a gas mixture

containing 10 ppb CH2O

Longueur d'onde (nm)

200 250 300 350 400 450 500

Ab

sorb

an

ce

0.0

0.2

0.4

0.6

0.8

1.00 min

1

11

21

31

41

55

65

75

95

105

DDL

Incident

light Fluorescence

En

erg

y

Ground state

Excited state

Wavelength (nm) Longueur d'onde (nm)

450 500 550 600

Inte

nsité d

e F

luo

(cp

s)

0

500

1000

1500109 min907560 453015810

Wavelength (nm)

Fluo

resce

nce

inte

nsity (cp

s)

110

100

80

70

60

46

36

26

16

6

Kinetics of formation of DDL

34

FP + CH2O I

FP + I DDL

k1

k2

[DDL]t= 𝐹𝑃 0 (1 − 𝑒−𝑘1[𝐶𝐻2𝑂]𝑡)

Durée d'exposition (min)

0 100 200 300 400

Inte

nsité

de

flu

o

0

500

1000

1500

2000

I(Fluo) = f(t)

I = a (1 - e-bt

)

Exposure duration (min)

Flu

ore

sce

nce

are

a

Slope = k1 * [FP]0 * [CH2O]

Intermittent exposure to CH2O 1 film ~ 20 measurements

35

0

5

10

15

20

25

0 50 100 150 200 250

Measurement Concentration

(ppb) C

on

cen

trati

on

of

CH

2O

(p

pb

)

Time (min)

PA

US

E

L. Chiappini et al. Air. Qual. Atmos. Health, (2011), 4, 211-220

T.-H. Tran-Thi et al., Chem. Soc. Rev., (2011), 40, 621-639

Increasing the exposure duration with monolith doped with Fluoral-P

36

Ocean Optics

S. Mariano et al, Procedia Engineering, 5 (2010) 1184-1187

PROFIL’AIR of ETHERA

37

DD

L f

orm

ati

on

ra

te (

min

-1)

CH2O concentration (ppb)

Sampling time: 15 min at 200 mL.min-1

1 ppb -1 ppm, RH = 50 % 5 ppb: 20 min 1 ppb: 90 min

T.-H. Tran-Thi et al., l’actualité chimique, Valorisation de la recherche, N°366, Sept. 2012.

Detection of CH2O: comparison

38

AEROLASER GmbH : 42 k€, 20kg (45*15*56cm) Reactant solution at 4°C: 5 days max Fluorimetry: 0.1 ppb to 3 ppm 90 s (10%-90%) every 5 min

Hantzsch reaction

NTT technology, GrayWolfSensing FM801 (1.515 £) Vycor glass doped with acetylacetone 5 cartridges: 530 £ Absorbance @ 420 nm, 20 ppb-1 ppm, 30 min

LFP technology, ETHERA Profil’Air (1.260 €) Sol-Gel material doped with Fluoral-P 5 cartridges: 225 € Absorbance @ 420 nm, 5 ppb-2 ppm, 20 min

Sensors for Environment

39

Indoor Air Quality

Monocyclic Aromatic Hydrocarbons

BTX: Benzene, Toluene, Xylenes (o-, m-, -p)

JAPAN USA(EPA) EU(WHO) max. Cont.

indoor air (WHO)

Benzene 3 µg/m-3

1 ppb

1.3-4.5 µg/m-3

1.7 µg/m-3

10 µg/m-3

Toluene 260 µg/m-3

70 ppb

400 µg/m-3

260 µg/m-3

200 µg/m-3

Xylenes 870 µg/m-3

200 ppb

400 µg/m-3

_ 100 µg/m-3

Styrene 2200 µg/m-3

50 ppb

1000 µg/m-3

260 µg/m-3

20 µg/m-3

Ethylbenzene 2800µg/m-3

880 ppb

1000 µg/m-3

_ 100 µg/m-3

40

Regulations for monocyclic aromatic hydrocarbons

41

Tsutomu Horiuchi et al., NTT Technical Review, Vol. 4 No. 1, 30-37, Jan. 2006

BTX detection: what are the needs?

Europe

Mesoporous powder for BTX trapping

42 Tsutomu Horiuchi et al., NTT Technical Review, Vol. 4 No. 1, 30-37, Jan. 2006

TEOS/Pluronic/HCl/H2O Triblock copolymer Pluronic F127; Mw = 12,600) as template agents Dongyuan Zhao et al.,

JACS,120,6024, (1998)

Pre-concentration unit T = 50 min Flow rate: 4 – 6 mL.min-1

Optical detection unit

43

Tsutomu Horiuchi et al., NTT Technical Review, Vol. 4 No. 1, 30-37, Jan. 2006

33 cm

17

cm

Absorption & spectral deconvolution

44

Measurement in a garage Tprecon = 50 min Desorption via heating TM = 10 s

Differential absorption spectrum (…….)

After deconvolution:

B = 23 ppb and T = 250 ppb

Limit of detection: 10 ppb of B

0.04

0.03

0.02

0.01

0

0.01

Ab

so

rban

ce

220 240 250 260 270 280 290 300

Wavelength (nm)

Sensors for Environment

45

Air quality in swimming pools

Detection of nitrogen trichloride (NCl3)

46

Water

Cl2 (g) + H2O ClO- + 2H+ + Cl-

Air

NH2Cl NHCl2 NCl3

CHCl3

+ N

What air do we breathe in swimming pools?

Toxicity of NCl3

47

– Classified as « irritant »

– Troubles reported for kids and pool attendants

–Acute exposure: eyes irritation & breathing trouble

– Long time exposure : asthma

– French regulation for exposed workers (INRS, 2001)

– 0,3 to 0,5 mg/m3 in air = 60 to 100 ppb

– Typical levels measured in swimming-pools

– 10 to hundreds of ppb (number of swimmers & ventilation system)

Generation of NCl3 Reproducing swimming pool atmosphere

Chloramines: NH2Cl, NHCl2 & NCl3

48

(NH4)2SO4 + 2 HClO →2 NH2Cl + H2SO4 + 2 H2O

NH2Cl + HClO → NHCl2 + H2O

NHCl2 + HClO → NCl3 + H2O

T.-H. Nguyen et al, Sensors & Actuators, submitted

NCl3 detection methods

49

Acidic silica

NH2Cl,

NHCl2

HClO

Quartz Filters containing

diarsenic trioxide & sodium

carbonate

Air flow

NCl3

2 hours of pumping + HPLC or 45 min of pumping + liquid phase colorimetry (TRIKLORAM)

Needs : Easy-to-use method

Direct & fast measurements

Principle of NCl3 detection

50

6 I- + NCl3 + 3 H+ → 3 I2 + NH3 + 3 Cl- (1)

I2 + I- → I3- (2)

I3- + Amylose → complex Amylose/I3

- (3)

-0,001

0,009

0,019

0,029

0,039

270 470 670

Ab

sorb

ance

Wave length / nm

TMOS/H2O/Amylose/I- Sads = 700±100 m2.g-1

Dpore = 30 Å

T.-H. Nguyen et al, Sensors & Actuators, submitted

Kinetics of formation of I3-/amylose

51

y = 0,0008x R² = 0,9951

0

0,01

0,02

0,03

0,04

0,05

0 20 40 60

Ab

sorb

ance

at

54

0 n

m

Time / min

200 mL.min-1

NCl3 : 50 ppb

Slope proportional to NCl3 concentration

Calibration curve for NCl3 detection

52

Flux = 200 ml.L-1, %RH 60%

* : Batch of January 24, 2011

Δ : Batch of March 25, 2011 : Batch of Sept. 19, 2011

T.-H. Nguyen et al, Sensors & Actuators, submitted

Technology transfer to ETHERA

53

Commercialized by CIFEC since December 2012

Sensors for Health

54

CO2 detection

Specific VOC markers detection

CO2: Environment & Health CO2 = end product in organisms in cellular respiration (breaking down sugars, fats and amino acids with O2)

Plants → Photosynthesis

Animals → blood to lung &

in exhaled breath

Fungi

Some Bacteria

55

CO2 in fresh air: 0. 036 to 0.039% 360 to 390 ppm

Detection of CO2 : principle

56

1.5%

3.0%

6%

12%

25%

50%

Abs(Sudan III) Fluo(Ru complex)

Abs(Sudan III(H+))

C. von Bültzingslöwen et al. / Analytica Chimica

Acta 480 (2003) 275–283

Food Packaging

Hybrid Ormosil-cellulose film for the detection of CO2

57

CO2 + H2O HCO3- + H+

Detection: Fluorescence lifetime of Ru complex via phase fluorimetry

Si alkoxyde Cellulose Ru(II)complex Sudan III Ammonium

C. von Bültzingslöwen et al.

Analytica Chimica Acta 480 (2003) 275–283

CO2 detection via fluorescence phase modulation

58

𝝉𝒎𝒂𝒙 𝝉𝟎−𝟏 − 𝝉𝒎𝒂𝒙

𝝉−𝟏 𝝉𝒎𝒂𝒙

𝝉−𝟏 = R = kpCO2 =

cot 𝜃0−cot 𝜃

cot 𝜃−cot 𝜃𝑚𝑎𝑥

tan 𝜽 = 𝝎𝝉

angular modulation frequency

Ph

ase

an

gle

/deg

ree

R

CO2 (%)

Response time: 30s Limit of detection: 0.06% RH: 90%

VOC markers detection

59

Fluorescence Absorbance

probe product

Escherichia coli

Microbiology analysis for the detection of pathogens

Breath analysis for non-invasive diagnosis

VOC emitted by bacteria

60

M. Lechner et al., Current Microbiology, 2005, 51, 267.

Escherichia

Coli

Klebsiella

pneumoniae

Citrobacter Helicobacter

pylori Staphylococcus

areus Pseudomonas

aeruginosa

Co

ncen

trati

on

(p

pb

V)

209 masses: 21-229 amu VOC= alkanes, alkenes, alcohols, ketones, aldehydes, organic acids indole….

GC-MS

Discriminating indole(+) and indole(-) bacteria

61

NH

NH2

H

O

NH

Tryptophanase

TryptophaneIndole

Indole emitted by pathogens (Salmonella, E. coli, …)

Objective Detect indole in the gas phase above a bacteria culture

Detection of Indole with DMACA

(p-dimethylaminocinnamaldehyde)

62 Wavelength (nm)

abso

rban

ce

lmax = 624 nm

e(624nm) = 97000 M-1.cm-1

N

H

CH

NCH3H3C

N

H

HC

N+CH3

CH3

+

H+

CH

O

+

Cl-

Indole

DMACAAzafulvenium chloride

S. Crunaire et al., Procedia Chemistry, (2012), 6, 125-131

Nanoporous sensor doped with DMACA

63

Sol-gel synthesis with TMOS and APTS

TMOS (0.97)/APTS (0.03)/MeOH (5) /HCl (0.06)/H20 (4) /DMACA (0.004)

SBET = 610 m2.g-1

Smicropore = 130 m2.g-1 Vpore = 0.525 cm3.g-1

Pore diameter: 30 Å

Transparent pastille D = 3 mm, thickness = 1,5 mm

S. Crunaire et al., Procedia Chemistry, (2012), 6, 125-131

Detection of indole in the gas phase

above a bacteria culture

64

2

1

3

1 Petri dish

2 agar nutrient medium + Tryptophan

3 desiccant powder

nanoporous sensor doped with DMACA

Tests with E. Coli, H. Alvei and non-inoculated culture (37 °C, 24H)

S. Crunaire et al., Procedia Chemistry, (2012), 6, 125-131

Discrimination of Indole (+) Bacteria

65

E. Coli non-inoculated H. alvei

Color change visible with naked eye after 7 hours of incubation Bacteria: 105 cfu (colony forming unit)

24 H

S. Crunaire et al., Procedia Chemistry, (2012), 6, 125-131

Discriminating bacteria

66

colorimetric nose

alcohols aldehydes alkanes alkenes organic acids amines

CO2

H2S, CH3SH, (CH3)2SH CS2, OCS NH3

67

Petri dish with tryptic soy broth inocculated with 7 107 to 4 108 cfu

36 colorimetric sensors

Colorimetric nose

Colors change with time collected

J. R. Carey et al., JACS, 133, 7571-7576, (2011)

with a scanner

68

Bacteria discrimination

E.coli 25922 Specific kinetics pattern with color stabilisation

after 8H

7 107 to 4 108 cfu

J. R. Carey et al., JACS, 133, 7571-7576, (2011)

2nd strategy: exogen VOC detection

69

Substrate VOC free

VOC

Enzyme

Advantages: Specific enzyme of the targeted pathogen bacteria choice of VOC not emitted by bacteria detection of the gas phase

A. P. Snyder et al., J. Microbiol. Methods 1991, 14, 21-32 (Ion mobility spectroscopy).

Proof of concept: E. Coli detection

70

Enzyme β-D-glucuronidase

p-nitrophenol

Nanoporous sensor (12*5*2 mm)

Plastic cuvette for spectroscopy

Eppendorf tip filled with E. Coli culture (1.5mL, 1.5 105 cfu)

Absorbance measurement as function of time

L.-H. Guillemot et al., Phys. Chem. Chem. Phys, submitted

Detection of released p-nitrophenol

71

Enzyme β-D-glucuronidase

p-nitrophenol

L.-H. Guillemot et al., Phys. Chem. Chem. Phys, submitted

72

CONCLUSIONS

• Sol-Gel nanoporous materials well-suited for:

– Selective and sensitive sensors (nanoreactors with specific probes)

– Analyte preconcentration (sponge, high Sad)

– Analyte filter (tailored pores)

• Many domains of application

– Environment : chemical sensors for air quality

specific filters for depollution

– Health : Microbiology, food industry (discrimination of bacteria)

Non-invasive diagnosis of diseases

• Other potential uses

– Filtering membranes for other sensors (pore size monitoring)

– Up-stream specific filters trapping of undesired pollutants)