fluorogenic task-specific ionic liquid probes for heavy ...€¦ · photoinduced process electron...
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Fluorogenic task-specific ionic liquid probes for heavy metal titration in water FLUOSENSIL
Isabelle Leray, PPSM-ENS-Cachan
ANR-08-CP2D-11-01 FLUOSENSIL
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M.A.C : Maximum Acceptable Concentration
Introduction
2
Cations Provenance Toxicity M.A.C.
(2003)
M.A.C.
(2015)
Pb2+
pumbing, painting, automobile pollution, metallurgy
digestive, neurological, cardiac and mental troubles, highly toxic for children
25 ppb 7.2 ppb
Hg2+
Volcans,coal combustion, gold panning, metallurgy
Kidney, neurological and blood troubles
1 ppb 0.07 ppb
Cd2+
Volcans,metallurgy, fertilizer, battery Kidney, lung, heart
5 ppb 0.2 ppb
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Analytical methods of detection
Sensibility
Selectivity
High spatial and temporal resolution
Low cost
Used Methods :
– Atomic Absorption
– Atomic Emission
– Mass Spectroscopy
– Electrochemistry
– Fluorescence
Fluorescence
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Detection of heavy metal ions in water
Design and synthesis of selective and sensitive fluorescent molecular sensors
Concentration of the heavy metal ion
Realization of a microdevice
cation
Fluorophore
Mineralisation module
Microextractor
Detection module
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A. P. de Silva, Chem. Rev. 97 (1997) 1515; B. Valeur and I. Leray, Coord. Chem. Rev. 205 ( 2000) 3–40.
I. Leray, B. Valeur, Eur. J. Inorg. Chem. 24 (2009) 3525-3535
Fluorescent Sensor for cation : fluoroionophore
Changes of the fluorescence properties of the fluorophore
cation
Fluorophore Fluorophore
Ionophore : Recognition moiety
Fluorophore moiety
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Fluorescent Sensor for cation : fluoroionophore
Perturbation by the bound cation
cation
Fluorophore Fluorophore
Ionophore : Recognition moiety
Fluorophore moiety
Photoinduced Process
Electron transfer (PET)
Charge transfer (PCT)
Energy Transfer (EET)
Excimer Formation
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PSPO (24 nM)
PSPS (9 nM)
Hg2+
P P
S S
ORRO
RO OR
DPPS
O
O
3
P P
X OR
OR
S
2
2
PSPS : X = S
PSPO : X = OR =
I. Leray et. al, Org. Lett. 2007, 9, 1133
I. Leray et al., Org. & Bio. Chem. 2009, 7 ,1665
Y.-B. Jiang et al, Org. Lett. 2005, 7, 19, 4217
Detection limit DPPS (3.8 nM)
N
O
PO
N
O O
ORRO
P
Se
OR
Fluorescent molecular sensors for
Detection limit (0.1 µM)
N
OP
S
OOctyl
N
OO
N+
NTf2-
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Hg2+
5
4
3
2
1
0
I F (
U.A
.)
3.02.52.01.51.00.50.0[Hg
2+] (µmol.L
-1)
1.0
0.8
0.6
0.4
I F (
U.A
.)
16012080400[Hg
2+] (nmol.L
-1)
Detection limit: 0.92 nM
Response time : 10 mn
I. Samb , J. Bell, P. Y. Toullec, V. Michelet and I. Leray, Org. Lett. , 2011, 13 (5), 1182–1185
5
4
3
2
1
0
I F (
U.A
.)
600550500450400350
(nm)
2.5
2.0
1.5
1.0
0.5
0.0
I F (
A.U
.)
8006004002000
Time (s)
PSe3Oc
PSe3Oc + Hg 2+
Fluorescent molecular sensor for
ORRO
P
Se
OR
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hydroxyquinoline derivatives
Hg2+ Fluorescent molecular sensor for
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
I F (
A.U
.)
650600550500450400
(nm)
(CH3CN, exc = 350 nm)
Emission spectra with Hg2+
Hg2+
8HQ-4St-PS
N
OH
O
N
OPSPh2
O
N
O
On-C8H17
PS
Ph Ph
NaH, THF, 0°C
ClPSPh2
76 %
OnC8H17Ph3P
Br
NaH, 18-crown-6,THF
40°C then I2 / CH2Cl2 53 %
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8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
I F (
A.U
.)
109876543210
[Hg2+
] (nmol.L-1
)
Fluorescent molecular sensor for
|DΦF| = 0,049 |DΦF| = 0,001
CH3CN/H2O pH 3
0.5 nM
Detection Limit : 0.075 nM= 15ppt
1.0
0.8
0.6
0.4
0.2
0.0
I F (
A.U
.)
750700650600550500450
(nm)
2.52.01.51.00.50.0
[Hg2+
] (10-5
.mol.L-1
)
IF @ 565 nm
Hg2+
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Fluorescent molecular sensor for Pb2+
0
0.5
1
1.5
2
400 500 600 700 800
I F (
u.a
.)
(nm)
log K = 10,0
L
M2L3
ML
log K = 33,5 O N ON
SO2O2S
NMe2 NMe2
O OOO
ONH
O2S
Me2N
ON
SO2
NMe2
Pb2+
-
O NH OHNSO2O2S
NMe2 NMe2
O OOO
ONH
O2S
Me2N
OHN
SO2
NMe2
• Pb2+ complexation
– deprotonation of the sulfonamide groups
– Time-resolved fluorescence measurements. Determination of the number of fluorophore implied in the complexation
0.5
1
1.5
0 1 2 3
I F 5
15nm
/ I
F 5
65nm
[Pb2+] (M)
- Detection limit = 20 nM= 4 ppb (CMA = 7.2 ppb en 2013)
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Fluorescent molecular sensor for Cd2+
DPP G. Cockrell et al. J. Am. Chem. Soc. 2008, 130, 1420-1430
DPPMSt
Styryl fluorophore
logb (ML2)
[(DPP)2-Cd]2+ 12,2 l
og b
Ca2+
Mn2+
Ni+
Zn2+
Cd2+
Pb2+
2,9
12,2
N N
N NCd2+
N N
NOOctyl
N
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Fluorescent molecular sensor for
0.10
0.08
0.06
0.04
0.02
0.00
Ab
so
rba
nce
500450400350300250
(nm)
3210
[Cd2+
] (µmol.L-1
)
Abs @ 337 nm
Abs @ 401 nm
5
4
3
2
1
0
I F (
U.A
.)
750700650600550500450
(nm)
43210
[Cd2+
] (µmol.L-1
)
IF @ 570 nm 4.9
4.8
4.7
4.6
4.5
4.4
4.3
I F (
U.A
.)
1.00.80.60.40.20.0
[Cd2+
] (nmol.L-1
)
(CH3CN/H2O 50/50; v/v, pH = 2,95, CL = 3,7 µM, exc = 400 nm)
logb (ML2) logb (ML) logb (M2L) ΦF
DPPMSt - - - 0,008
[DPPMSt-H]+ - 3,08 - 0,071
[DPPMSt-H2]2+ - - 5,06 0,013
[DPPMSt-Cd]2+ 14,7 7,3 - 0,001
0.5 nM
Cd2+
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Fluorescent molecular sensors
Cation
Fluorescent molecular sensor
8HQ-4St-PS Calix-DANS4 DPPMSt
Detection limit
0.015 ppb 4 ppb 0.05 ppb
European Standard 2015
0.070 ppb
0.35 nM
7.2 ppb
20 nM
0.2 ppb
1.8 nM
Hg2+ Pb2+ Cd2+
N N
NOOctyl
N
O NH OHNSO2O2S
NMe2 NMe2
O OOO
ONH
O2S
Me2N
OHN
SO2
NMe2
N
OP
S
OOctyl
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Concentrating extraction using ionic liquid
[18a] = 10-4M [Hg(ClO4)2] = 2,5 10-6M
M. Blanchard-Desce et al. Angew. Chem. Int. Ed. 2010, 49, 424-427.
Detection limit : 60 ppb
5000 ppb
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Extraction properties
LITS-DPPO-N+
LITS-8HQ-4St-PS-N+
N+ N+
N+ N+
N+
E = 85 %
E > 60 % Extraction of Hg2+ (1 nM )
LITS-Calix-DANS4
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Complete analyser Flow Pattern
Mineralization module
Microconcentrator
Detection module
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Mineralization Module in collaboration with the LGC (Laboratoire de Génie Chimique)
Degradation : 98 % of organic matter
(25 mg/L)
t = 10 minutes
I = 350 mA
Electrolyte : HNO3 0,5 M
Patent pending for
« Electrolysis Cell inserted in an on-
line heavy metal analysis system »
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Micro-concentrator
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Optical module
• Experimental bench
0,5 mm
Silicium
Pyrex
Excitation
Emission
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detector
Diode
CEA-LETI Chip
dichroic mirror
Optical module
Hg2+ Detection limit < 1nM 0.2 ppb
26
24
22
20
18
S (
mV
)
150100500
time (s)
pH = 3 10-9
10-8
10-6
10-5
10-7
8HQ-PS-N+
Test on homogeneous conditions
(CH3CN/H2O pH 2.3)
Hg2+
Hg2+
Hg2+
Hg2+
Hg2+
DEL 365 nm
2mW, 10°
P.B. 365nm
P.H. 416nm
Silica lenses
M.D. 380 nm
PM
Hamamatsu R928
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Optical module & extraction measurements
LITS-8HQ-4St-PS-N+
pH variation in the water phase Mercury extraction
50
40
30
20
10
0
Sig
na
l (m
V)
140120100806040200
Time (s)
pH 5 pH 5
pH 3
100
90
80
70
60
50
40
S (
mV
)
300250200150100500
time (s)
pH = 3
pH = 5
500 ppb
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Complete analyser Flow Pattern
DEL
concentrator BDD
Anode
Ionic liquid
sewer sewer
photomultiplier
pH modification
cell
filtrated sample
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Electronic Card OPML (Optic Heavy Metal)
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Man-Machine Interface
=> Fluosensil software in construction
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Industrial Testing Model
Electronical box
Optical box
Black SAO
Hydraulic system
Mineralization
module
Chemical supply
MMI
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Conclusion
Design, synthesis and photophysical properties of efficient fluorescent molecular sensor
Possible extraction using ionic liquid
Efficient mineralisation and optical module
Perspectives … for the remaining time of this project, and later for further projects: Accomplish the complete set-up : automatisation, electronic .. Measurements in real sample For further developments Increase the efficiency of the preconcentration set-up : change the configuration of the microextractor Detection of other cations :
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Publications, presentations, … Publications
patents
Oral presentation
• M. H. Ha-Thi, M. Penhoat, V. Michelet, I. Leray, Org. Biomol. Chem. 2009, 7, 1665-1673.
• F. Loe-Mie, G. Marchand, J. Berthier, N. Sarrut, M. Pucheault, M. Blanchard-Desce, F. Vinet, M. Vaultier, Angew. Chem. Int. Ed. 2010, 49, 424-427.
• V. Alain-Rizzo, D. Drouin-Kucma, C. Rouxel, I. Samb, J. Bell, P. Y. Toullec, V. Michelet, I. Leray, M. Blanchard-Desce, Chem. Asian J. 2011, 6, 1080-1091.
• I. Samb, J. Bell, P. Y. Toullec, V. Michelet, I. Leray, Org. Lett. 2011, 13, 1182-1185. • J. Bell, I. Samb, P. Y. Toullec,O. Mongin, M. Blanchard-Desce, V. Michelet, I. Leray,
2012, submitted
1 patent (CEA LETI) , 1 pending + 1 in preparation
4 oral presentations in international or domestic meetings (including 2 plenary or invited presentations)
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Acknowledgements
J. Bell V. Alain J.P. Lefevre I. Leray
V. Michelet P. Toullec I. Samb
M. Blanchard-Desce Y. Chandrasekaran O. Mongin M. Pucheault M. Vaultier
F. Ricoul A. Jacquart C. Vauchier
O. Mauvais A. Ruffien Ciszak M. Freyssinier