Fluorogenic task-specific ionic liquid probes for heavy ...€¦ · Photoinduced Process Electron...

ANR Sustainable Chemistry Conference « FLUOSENSIL »

Fluorogenic task-specific ionic liquid probes for heavy metal titration in water FLUOSENSIL

Isabelle Leray, PPSM-ENS-Cachan

[email protected]

ANR-08-CP2D-11-01 FLUOSENSIL


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


Analytical methods of detection

Sensibility

Selectivity

High spatial and temporal resolution

Low cost

Used Methods :

– Atomic Absorption

– Atomic Emission

– Mass Spectroscopy

– Electrochemistry

– Fluorescence

Fluorescence


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


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


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


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-


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


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 %


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

)


|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+


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)


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



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+


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


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


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


Complete analyser Flow Pattern

Mineralization module

Microconcentrator

Detection module


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 »


Micro-concentrator


Optical module

• Experimental bench

0,5 mm

Silicium

Pyrex

Excitation

Emission


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


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


Complete analyser Flow Pattern

DEL

concentrator BDD

Anode

Ionic liquid

sewer sewer

photomultiplier

pH modification

cell

filtrated sample


Electronic Card OPML (Optic Heavy Metal)


Man-Machine Interface

=> Fluosensil software in construction


Industrial Testing Model

Electronical box

Optical box

Black SAO

Hydraulic system

Mineralization

module

Chemical supply

MMI


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 :


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)


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

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