Non-covalent Non-covalent modification of modification of luminescent Tb-TCAS- luminescent Tb-TCAS- doped silica doped silica nanoparticles surface by nanoparticles surface by surfactants. surfactants. Bochkova O.D. Bochkova O.D. , Fedorenko S.V. , Fedorenko S.V. Elistratova Yu.G., Mustafina A.R., Elistratova Yu.G., Mustafina A.R., Antipin I.S., Solovieva S.E., Antipin I.S., Solovieva S.E., Konovalov A.I. Konovalov A.I. A.E. Arbuzov Institute of Organic A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan and Physical Chemistry, Kazan Scientific Center of RAS. Scientific Center of RAS.
Transcript
Non-covalent modification of Non-covalent modification of luminescent Tb-TCAS-doped luminescent Tb-TCAS-doped silica nanoparticles surface by silica nanoparticles surface by
surfactantssurfactants
Bochkova ODBochkova OD Fedorenko SV Fedorenko SV Elistratova Elistratova YuG Mustafina AR Antipin IS YuG Mustafina AR Antipin IS
Solovieva SE Konovalov AISolovieva SE Konovalov AI
AE Arbuzov Institute of Organic and AE Arbuzov Institute of Organic and Physical Chemistry KazanPhysical Chemistry Kazan Scientific Center Scientific Center
of RASof RAS
Properties of Tb-TCAS complexesProperties of Tb-TCAS complexes
1 Intensive and narrow emissive bands
2 Long life-time of excited state
1 Toxicity
2 Easy degradation
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
- Na+
Na++ Na+ Na+ Na
Tb-TCASTb-TCAS
Antennae effectAntennae effect
Emission spectrum of Tb-TCAS complexEmission spectrum of Tb-TCAS complex
φ = 0141
++
--
2
The common goal of the investigationThe common goal of the investigation preparing of luminescent silica nanoparticles
their characterization studying of properties
and using
SiO
O Si
OSi SiO(SiO2)n =
3
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
Preparation of Tb-TCAS-doped silica nanoparticlesPreparation of Tb-TCAS-doped silica nanoparticles
n Si(OH)4
NH4OH
-H2On Si(OC2H5)4
+H2O (SiO2)
n
oil
H2OO
SS
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-
H2O
Si(OCSi(OC22HH55))44
4
Advantages of Tb-TCAS-doped silica nanoparticlesAdvantages of Tb-TCAS-doped silica nanoparticles
11 Low toxicityLow toxicity
22 More intensive More intensive luminescenceluminescence
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Properties of Tb-TCAS complexesProperties of Tb-TCAS complexes
1 Intensive and narrow emissive bands
2 Long life-time of excited state
1 Toxicity
2 Easy degradation
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
- Na+
Na++ Na+ Na+ Na
Tb-TCASTb-TCAS
Antennae effectAntennae effect
Emission spectrum of Tb-TCAS complexEmission spectrum of Tb-TCAS complex
φ = 0141
++
--
2
The common goal of the investigationThe common goal of the investigation preparing of luminescent silica nanoparticles
their characterization studying of properties
and using
SiO
O Si
OSi SiO(SiO2)n =
3
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
Preparation of Tb-TCAS-doped silica nanoparticlesPreparation of Tb-TCAS-doped silica nanoparticles
n Si(OH)4
NH4OH
-H2On Si(OC2H5)4
+H2O (SiO2)
n
oil
H2OO
SS
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-
H2O
Si(OCSi(OC22HH55))44
4
Advantages of Tb-TCAS-doped silica nanoparticlesAdvantages of Tb-TCAS-doped silica nanoparticles
11 Low toxicityLow toxicity
22 More intensive More intensive luminescenceluminescence
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
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Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
The common goal of the investigationThe common goal of the investigation preparing of luminescent silica nanoparticles
their characterization studying of properties
and using
SiO
O Si
OSi SiO(SiO2)n =
3
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
Preparation of Tb-TCAS-doped silica nanoparticlesPreparation of Tb-TCAS-doped silica nanoparticles
n Si(OH)4
NH4OH
-H2On Si(OC2H5)4
+H2O (SiO2)
n
oil
H2OO
SS
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-
H2O
Si(OCSi(OC22HH55))44
4
Advantages of Tb-TCAS-doped silica nanoparticlesAdvantages of Tb-TCAS-doped silica nanoparticles
11 Low toxicityLow toxicity
22 More intensive More intensive luminescenceluminescence
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Preparation of Tb-TCAS-doped silica nanoparticlesPreparation of Tb-TCAS-doped silica nanoparticles
n Si(OH)4
NH4OH
-H2On Si(OC2H5)4
+H2O (SiO2)
n
oil
H2OO
SS
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-
H2O
Si(OCSi(OC22HH55))44
4
Advantages of Tb-TCAS-doped silica nanoparticlesAdvantages of Tb-TCAS-doped silica nanoparticles
11 Low toxicityLow toxicity
22 More intensive More intensive luminescenceluminescence
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Advantages of Tb-TCAS-doped silica nanoparticlesAdvantages of Tb-TCAS-doped silica nanoparticles
11 Low toxicityLow toxicity
22 More intensive More intensive luminescenceluminescence
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
The covalent modification of silica nanoparticles surfaceThe covalent modification of silica nanoparticles surface
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Images of the recognition of black death antigens
SiOSiO22 Tb-TCAS as biomarker for the Black Death antigens Tb-TCAS as biomarker for the Black Death antigens 7
SiO2 - COOH
nanoparticles containing Tb- TCAS via
luminophores
N(CH2CH2OH)3 pH=82
antibody ofblack death
modified antigen ofblack death
HOOCO
ONH+CH3
NH
NCH3CH3
CH3N
CH3
N N CH3
NH2
HOOC
HOOC
COOH
COOH
COOH
R
R
RR
R
antigens ofblack death
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
The next step of our workThe next step of our work is the investigation of Tb-TCAS-doped silica nanoparticles behavior in different media
Methods of investigationMethods of investigation
1 Luminescent spectroscopy
2 UV-Vis spectroscopy
3 Dynamic light scattering (DLS)
4 Electrophoresis
5 Transmission electron microscopy (TEM)
6 Atomic force microscopy (AFM)
8
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Si
OH
O
O
SiO
O
SiOH-
Si
OH
O
O
SiO
O
SiOH-
aggregationaggregation
TEM image of Tb-TCAS doped silica nanoparticles
Size of Tb-TCAS-doped silica nanoparticlesSize of Tb-TCAS-doped silica nanoparticles
d = 40d = 40plusmn5 nmplusmn5 nm
0
5
10
15
01 1 10 100 1000 10000
Inte
nsity
(
)
Size (dnm)
Size Distribution by Intensity
Record 1 SiO2 Tb-TCAS 0028 gl 1 Record 2 SiO2 Tb-TCAS 0028 gl 2Record 3 SiO2 Tb-TCAS 0028 gl 3 Record 4 SiO2 Tb-TCAS 0028 gl 4Record 5 SiO2 Tb-TCAS 0028 gl 5 Record 6 SiO2 Tb-TCAS 0028 gl 6
d = 180plusmn5 nm рН = 6-7
DLS image of Tb-TCAS doped silica nanoparticles
In a solid stateIn a solid state In an aqueous solutionIn an aqueous solution
9
ζζ = -30 = -30 mVmV
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
SiO
Si OH
Si O
Tb-TCAS
+
+ +
+Tb-TCAS
SiO
SiOH
SiO
aggregation
Tb-TCAS
--
-
+
++
repulsion Tb-TCAS
-
-
-
++
+
b) С CTAB = 510-4 - 110-2 moll
Nanoparticles average size and zeta-potential dependence on CTAB concentration
ζ = +744 mV
а) С CTAB = 510-5 moll
N+
Br
Interaction of Tb-TCAS-doped silica nanoparticles with cationic Interaction of Tb-TCAS-doped silica nanoparticles with cationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
10
+ CTAB
(CMC = 85middot10-3 moll)
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
(CH3)2 N+
C16H33
(CH2)6 (CH3)2N+
C16H33
Gemini 16-6-16
Interaction of Tb-TCAS-doped silica nanoparticles with dicationic Interaction of Tb-TCAS-doped silica nanoparticles with dicationic surfactant cetyltrimethylammonium bromide (CTAB)surfactant cetyltrimethylammonium bromide (CTAB)
(CMC = 2middot10-5 moll)
СGemini M d nm PDI ζplusmn10 mV
1middot10-5 237 plusmn 2 0197 +36
5middot10-5 228 plusmn 4 0182 +41
1middot10-4 238 plusmn 14 0280 +38
1middot10-3 224 plusmn 2 0159 +43
1middot10-2 237 plusmn 6 0224 +53
Average diameter (d) polydispercity indexe (PDI) and zeta-potential values (ζ) of SiO2 Tb-TCAS at various concentrations of Gemini
11
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
UV-Vis spectra of Phenol Red (PhR aqueous solutionPhR aqueous solution) in presence of SiOSiO22 Tb-TCAS Tb-TCAS
GeminiGemini and SiOSiO22 Tb-TCAS covered by Gemini Tb-TCAS covered by Gemini
OH O
SO3
O O
SO3
H+
--Na
+-Na
+
pKpKаа = 80 = 80
Molecular form
pHpH = 82 = 82
Interaction of Tb-TCAS-doped silica nanoparticles with acid-base Interaction of Tb-TCAS-doped silica nanoparticles with acid-base indicator Phenol Redindicator Phenol Red
Anionic form
12
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
Possible locations of Phenol RedPossible locations of Phenol Red
-
-
-
H2O
13
Stern layer
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
-
(SiO2)n-
-
++
+
+
+
+
II00I = 1 + kI = 1 + kqqCCPhRPhR
Emission spectra Stern-Folmer dependence
UV-Vis spectra
SiOSiO22 Tb-TCAS covered by Gemini in presence of Phenol Red Tb-TCAS covered by Gemini in presence of Phenol Red
kkq q ~ r~ r-6-6
14
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
-
-+ - =
- HPO42-=
15
DS--
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
HPO42-=-
+ -
(SiO2)n++
+
+
++
++
-
-
-
-
-
-
(SiO2)n++
+
+
++
++
-
-
-
СGemini
M5middot10-5
CHPhR
M5middot10-6
CNa2HPO4
M1middot10-4 1middot10-3 1middot10-2
d nm 278 plusmn 2 314 plusmn 4 aggregation
PDI 0311 0249 0878
ζplusmn10mV
27 16 19
16Interaction of HPOInteraction of HPO442- 2- with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
SiO2 +
+ +
+
++
++
++
++
+
-
-
=
17Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
DS-
Emission spectra
Zeta-potential (ζ) dependence on SDS concentration
-
-
-
-
-
-
SiO2 +
++
+
-
++
++
++
++-
-
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
(SiO2)n
I a
u
450 500 550 600 6500
50000
100000
150000
200000
250000
300000
nm
-
-
-
18Interaction of DSInteraction of DS- - with SiOwith SiO22 Tb-TCAS covered by micellar layer containing Tb-TCAS covered by micellar layer containing
Phenol RedPhenol Red
on
off
on
-
-
-
-
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
Slide 1
Slide 2
Slide 3
Slide 4
Slide 5
Slide 6
Slide 7
Slide 8
Slide 9
Slide 10
Slide 11
Slide 12
Slide 13
Slide 14
Slide 15
Slide 16
Slide 17
Slide 18
Slide 19
Slide 20
Slide 21
Slide 22
Slide 23
Slide 24
Slide 25
Slide 26
Slide 27
Slide 28
Slide 29
Slide 30
Slide 31
Slide 32
ConclusionConclusion 19
onon offoff onon
OS
S
SS
O3S
O3S SO3
SO3
OOH
O
Tb3+
-
- -
-+ Na
+ Na Na +
Na +
SiO2 +
+ +
+
++
++
++
++
SiO2 +
++
+
++
+ TEOS + Gemini + Gemini
+ PhR + SDS
SiO2 +
+ +
+
++
++
++
++
-
-
-SiO2 +
++
+
-
++
++
++
++-
-
20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
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20AcknowledgementsAcknowledgements
Mustafina AR
Fedorenko SV
Elistratova YuG
Konovalov AI
Initial substances Antipin IS
Solovieva SE
AFM method Kahirov RK
RFBR project N 09-03-12260 Ofi_M for financial supportingRFBR project N 09-03-12260 Ofi_M for financial supporting
IOPC named after AE ArbuzovIOPC named after AE Arbuzov
Kazan Federal UniversityKazan Federal University
Method of Mostovaya OA
luminescence spectroscopy Stoikov II
InstituteInstitute of Macromolecular Compoundsof Macromolecular Compounds St PetersburgSt Petersburg
TEM method Menshikova AYu
MM Shemyakin and YuA Ovchinnikov MM Shemyakin and YuA Ovchinnikov InstituteInstitute of Bioorganic Chemistry Moscowof Bioorganic Chemistry Moscow
Bioorganic investigations Zubov VP
=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
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=Tb(III)-TCAS
S O
O
Si
Si
OSi
O
Si
OSi
O
HOOH
O SiO
Si
O
Si
Si
O
O
Si
Si
Si
O
O
O
O
O
O
O
HO
OH
OH
OH
O
OH
Na+
Na+
Na+
Na+
Na+
Na+
SO3-
SS SS
-O3S
-O3S
SO3-
O OOOH
Tb3+Tb3+
O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
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O
Si
O
SiOH
CH2CH2CH2NH2Tb-TCAS
O
Si
O
SiOH
CH2CH2CH2NHC(O)CH2CH2COOHTb-TCAS
(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
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(OCH2CH2)xOH
CH3
CH3
H2CCH3
CH3
CH3
x=10
Nonionic surfactant Triton X-100
СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
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СGemini M CHPhR M d nm PDI ζplusmn10 mV
5middot10-5
0 228 plusmn 4 0182 41
2middot10-5 226 plusmn 4 0150 42
4middot10-5 223 plusmn 4 0208 36
6middot10-5 238 plusmn 13 0067 29
8middot10-5 250 plusmn 50 0242 29
СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
5middot10-5 5middot10-6
1middot10-6 246 plusmn 4 0183 35
5middot10-6 236 plusmn 3 0179 42
1middot10-5 216 plusmn 3 0166 35
2middot10-5 216 plusmn 2 0151 43
3middot10-5 227 plusmn 4 0175 46
4middot10-5 271 plusmn 4 0237 46
5middot10-5 325 plusmn 4 0225 47
6middot10-5 369 plusmn 5 0251 47
7middot10-5 420 plusmn 4 0243 46
8middot10-5 494 plusmn 6 0287 43
9middot10-5 aggregation 1000 18
1middot10-4 aggregation 1000 0
5middot10-4 - 0462 -33 296 plusmn 30 47 plusmn 4
1middot10-3 - 0429 -34 256 plusmn 17 45 plusmn 5
capillary
hν hνluminescence Noluminescence
12
SiO2
H2O
60-80 nm
SiO2
40plusmn5 nm
SiO2
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СGemini M CHPhR M CSDS M d nm PDI ζplusmn10 mV Peak means nm
