Unusual Fluorescence of Eu(III)Porphyrin Entrapped In Sol-gel Silica Matrix Unusual Fluorescence of...
-
Upload
oswin-cook -
Category
Documents
-
view
228 -
download
2
Transcript of Unusual Fluorescence of Eu(III)Porphyrin Entrapped In Sol-gel Silica Matrix Unusual Fluorescence of...
Unusual Fluorescence of Unusual Fluorescence of Eu(III)Porphyrin EntrappedEu(III)Porphyrin Entrapped
In Sol-gel Silica MatrixIn Sol-gel Silica Matrix
Stanisław Radzkia, Joanna Dargiewicz-Nowickaa, Magdalena Makarskaa and Janina
Legendziewiczb
aFaculty of Chemistry,
Maria Curie-Skłodowska UniversitybFaculty of ChemistryWrocław University
Porphyrin importance
• Porphyrins and their derivatives are
widely applied in analytical chemistry.
They can be used for analysis of cations,
anions, organic compounds and gases.
Methods are mostly based on porphyrin
spectral and electrochemical properties.
• Energy transfer systems (solar energy,
PDT).
• Possibility of the entrapment of organic
reagents into sol-gel monolithic matrices
and thin coatings. A new unique hybrid
material (mixed organic and inorganic
compounds) can be applied in chemo-
and biosensors.
Analytical applications of
porphyrins
Cu2+ T(1-MPy)PTPPS3
TPPT(3-MPy)PTMAPp-NO2Bz-TPPSCPIT(4-MPy)PTCPP
Cd2+ T(1-MPy)PATPPST(4-MPy)P
Zn2+ TPPS4
TPPS4
TPPTPPS4
Pd2+ TPPS4
Mg2+ T(4-MPy)P
Bi3+ TPPS4
Ag+ TPyP
Ni2+ TPPS4
Li+ OBTPPS
Hg2+ ATPPST(4-MPy)P
Pb2+ T(4-MPy)PTPPS3
Spectrophotometic metal determination
Analytical applications of
porphyrins
Other compounds determinated using porphyrins
pH OEP, OEPK, CP-TEE,CPK-TEE, N-MeEP,PdCP-SBH2TMePyP, H2TPPS4
Sn(IV)TPyP,Sn(IV)TMePyP
I- Zr(IV)TPPN,Co(II)TPPN
Cl- In(III)OEP
SCN- Zr(IV)TPPN,Co(II)TMePyPIn(III)OEP
Salicylan In(III)OEP
Aminy Co(III)TMePyP
Pirydyna Zr(IV)TPPN,Co(II)TPPNZnTPP
DNA TPPS4
Benzen TMePyP, DTMABP
Benzen,heksan, toluen
CuPaz(t-Bu)4
Lotne związkiorganiczne
Co-pNO2TPP,Rh(III)TPP
O2 Co(II)PBiałka hemowePt(II)OEP, Pd(II)OEPPt(II)OEPK,Pd(II)OEPKTPPRu(II)OEPZnTPP, ZnTFPP,ZnEtioP,ZnOEP, ZnTBPCoTPP
NO Białka hemowe
Cl2 Dimer porfiryny cynkut-SAP-Pporfiryna meso-tetra(p-stearamidofenylowa)
HCl TPPTP(OR)P gdzie R =CH3, n-C9H19, n-C8H17,CH2CH(C2H5)C4H9
Aim of this work
• Method of the preparation of
cationic porphyrin doped silica
gels.
• Europium(III) porphyrin complex
synthesis.
• Spectral characterisation of the
cationic porphyrin and its Eu(III)
complex in solutions and
monolithic gel.
Sol-gel processing
basics
Alcohol metal
solution
HydrolysisPolicondenstion
Sol
coating
coat
ing
Gelation
percipitation
spinning
Ceramic fibers
Solvent removing
Evaporation
Xerogell
Glass,dense
ceramics
Aerogel
Heating
Dense filmHeating
Xerogel film
Wet gel
Unisized Gelled spheres
Oven
1. HYDROLYSISS i(OR)4 + nH2O (OR)4-n-Si-(OH)n + nROH
2. CONDENSATION
(RO)3Si-OR + HO-Si(OR)3 (RO)3Si-O-Si(OR)3 + ROH
(RO)3Si-OH + HO-Si(OR)3 (RO)3Si-O-Si(OR)3 + H2O
Sol-gel methodCatalysator pH of
starting solution
Gelation timr (h)
HF 1.90 12 HCl 0.05 92
HNO3 0.05 100 H2SO4 0.05 106 HOAc 3.70 72 NH3 9.95 107 brak 5.00 1000
Element M(OR)n Si Si(OCH3)4
SiO(OC2H5)4 Al Al(O-izo C3H7)4
Al(O-sec C4H9)3 Ti Ti(O-C2H5)4
Ti(O-izo C3H7)4
Ti(O-C4H9)4
Ti(O-C5H7)4 B B(OCH3)3
Ge Ge(O-C2H5)4 Zr Zr(O-izo C3H7)4
Zr(O-C4H9)4 Y Y(O-C2H5)3 Ca Ca(O-C2H5)2
Sol-gel method advantages
• Material homogenization
• High purity
• Mixing in the atomic scale of the
various compounds (possibility of
organic material addition)
• Good control over surface or
powder size
TEOS(tetraethyl
orthosilicate)
Si(OC2H5)4 + nH2O (OC2H5)4-n-Si-(OH)n + nC2H5OH
(C2H5O)3Si-OC2H5 + HO-Si(OC2H5)3 (C2H5O)3Si-O-Si(OC2H5)3 + C2H5OH
(C2H5O)3Si-OH + HO-Si(OC2H5)3 (C2H5O)3Si-O-Si(OC2H5)3 + H2O
EuTMePyP(acac) synthesis
Eu(acac)3 + H2TMePyP EuTMePyP(acac) + 2Hacac
[nm]
500 525 550 575 600 625 650 675 700 725 750 775 800 825 850 875 900
A
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
0,16
0,18
0,20
0,22
0,24
0,26
0,28
0,30
0,32
Zmiany widma absorpcji podczas syntezy EuTMePyP(acac)
[nm]
300 325 350 375 400 425 450 475 500
A
0,0
0,5
1,0
1,5
2,0
2,5
3,0
po ogrzaniu do wrzeniat = 1 ht = 2 ht = 3 ht = 4 h(w 24 h po zakoñczeniu reakcji)
EuTMePyP(acac)
NN
NN
N NN
N
CH3
CH3
CH3
CH3
+
+
+
+
OO
Eu
CH3CH3
Europium(III)(meso-tetrakis(1-methyl-4-pirydyl)porphyrin) acetylacetonate)
EuTMePyP(acac)
EuP(acac) + 4H+ H4P2+ + Eu3+ + acac-
EuP(acac) + 3H2O Eu(OH)3 + Hacac + H2P
[nm]
300 350 400 450 500 550 600 650 700
A
0,00
0,25
0,50
0,75
1,00
1,25
1,50
1,75pH 8.0 pH 6.0 pH 4.0 pH 3.0 pH 1.8 pH 0.8
[nm]
475 500 525 550 575 600 625 650 675 700
A
0,000
0,025
0,050
0,075
0,100
420nm420nm421nm431nm428nm440nm
pH 8.0 pH 6.0 pH 4.0 pH 3.0 pH 1.8 pH 0.8
554nm553nm554nm559nm
520nm558nm
589nm 636nm
EuTMePyP(acac)Pasmo Soreta
Pasmo Q
H2TMePyP
[nm]
300 350 400 450 500 550 600 650 700
A
0,00
0,25
0,50
0,75
1,00
1,25
1,50
1,75
Pasmo Q 10 x
Pasmo Soreta
H2O 423.1
MeOH 424.7EtOH 425.8DMSO 425.5 DMF 425.4
518.9516.4517.6517.1516.7
555.5552.9554.3552.2552.6
586.2591.9593.3589.2588.9
642.0651.0649.0643.8644.9
Eu(III)TMePyP(acac)
[nm]
300 350 400 450 500 550 600 650 700
A
0,00
0,25
0,50
0,75
1,00
1,25
1,50
1,75
2,00
Pasmo Q 10 x
Pasmo Soreta
H2O 420.3
MeOH 424.2EtOH 424.8DMSO 431.8 DMF 430.6
553.2557.1556.2563.1563.1
H2TMePyP and EuTMePyP(acac) uv-vis absorption spectra in various
solvents
H2TMePyP and EuTMePyP(acac) uv-vis spectra in
hydrogel
[nm]
300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700
A
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1 Pasmo Q~ 15 x
Pasmo Soreta 428 nm
520 nm
553 nm
546 nm
590 nm
EuTMePyP(acac)
H2TMePyP
EuTMePyP(acac)(czêœciowo roz³o¿ony)
417 nm542 nm
426 nm550 nm
Conclusion
• Synthesis of the EuTMePyP(acac)
complex not earlier described in
the literature
• No fluorescence in solutions
• Strong fluorescence emission in
hydrogel, probably due to the
„axial ligand exchange” or silica-
Eu(III)P reaction
Porphyrin monolayer
formation on the silica gel
surface
N
N
N
N
N N
NN
H
H
OH
O
O
O
Si CH2Cl +
N
N
N
N
N N
NN
H
H
OH
O
O
O
Si CH2
+*Cl -
D. Delmarre, R. Meallet, C. Bied-Charreton, R.B. Pansu: “Heavy metal ions detection in solution, in sol-gel and with grafted porphyrin monolayers”, J. Photochem. and Photobiol. A, 1999, 124, 23.