Amphiphilic cationic star block copolymers. - Tenhu - New... · IR-sintering of ink-jet printed...
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www.helsinki.fi/yliopisto New functional polymers and hybrid materials Heikki Tenhu Department of Chemistry University of Helsinki 1 2 Cryo-EM Amphiphilic cationic star block copolymers. Thermo and pH sensitive.
Transcript of Amphiphilic cationic star block copolymers. - Tenhu - New... · IR-sintering of ink-jet printed...
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New functional polymers and hybrid materials
Heikki TenhuDepartment of Chemistry
University of Helsinki
1
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Cryo-EM
Amphiphilic cationic star block copolymers.Thermo and pH sensitive.
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Synthesis of star polymers
Tg ~ 100 °C Tg ~ - 60 °C
ATRP
ATRP
23.5.2012
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Phase transition(PBuA-PDMAEMA)6& PDMAEMA-PBuA-PDMAEMA
23.5.2012
-5
5
15
25
35
0 20 40 60 80 100 120
Cp
(kca
l/mol
e/°C
)
T (°C)
linear, area=553 cal/mol
star, area=1054.0 cal/mol Tm=85.3°C
Tm=87.8°C
-50
-40
-30
-20
-10
0
10
0 20 40 60 80 100 120
Cp
(kca
l/mol
e/°C
)
T (°C)
linear, area=-805.7 cal/mol
star, area=-1316.8 cal/mol
Tm=84.7°C
Tm=93.4°C
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Polymerized ionic liquids
Cl
O+ Br
OH O
O
Br
N NO
ON N
+
Br-
O
ON N
+
BF4-
RT, CH2Cl2,Et3N
NaBF4(aq)
40 °C
S
S
O
N
N
O
N
O
OH
+
ACPA,CPA
MeCN, 75 °C
NHOO
N
N
O
S
N
O
OH
S
+
BF4-
ACPA,NIPA
MeCN,Dioxane, 60 °C
n
n m
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CryoTem image of a PIL micelle
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Thermal behavior of the micelle
www.helsinki.fi/yliopisto 23.5.2012 8Szymon Wiktorowicz
New photo switchablepoly(azocalix[4]arenes)
LiAlH4, THFor
Red-Al, toluene
Calix[4]arene polymerPhotoswitchabilityPreserved conformation
S.Wiktorowicz, V.Aseyev and H.Tenhu , Polym. Chem., 2012, DOI: 10.1039/C2PY20020A
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Conducting water dispersable polymers
○● n-type intrinsically conducting polymer○● derivatised with poly(ethylene oxide), water dispersable
N
O
N
N
N*
*
O*
* n
○● Poly(benzimidazobenzophenanthroline) (BBL)
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Hybrid nanomaterials
Carriers for active agents
○● Montmorillonite grafted with polymers○● Silica particles grafted with PVCL
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Grafting clay particles with hydrophilic polymer
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Polymer grafting to clay
Polymerization initiator attached to clay
Clays grafted withPDMAEMA PAA, PNIPAM, BuA-MMA‒ Clays dispersable either in
water or organic solvents
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§ Fluorescence§ 1-anilinonaphthalene-8-sulfonate ammonium (1,8-ANS)§ emission intensity depends on polarity§ polarization anisotropy
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The effect of pH
Emission intensity
Anisotropy
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Mesoporous silica particles grafted with PVCL
16.3.2011 14Matemaattis-luonnontieteellinen tiedekunta / Mikko Karesoja
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§Size 300nm
§Pore diameter 3-4 nm
§Surface area 700 m2/g
§Pores are protected by surfactant
16.3.2011 15Matemaattis-luonnontieteellinen tiedekunta / Mikko Karesoja
Mesoporous Silica Particles
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§Polymerisation of N-vinylcaprolactam
§Azide functionality
16.3.2011 16Matemaattis-luonnontieteellinen tiedekunta / Mikko Karesoja
Syntheses
www.helsinki.fi/yliopisto 16.3.2011 17Matemaattis-luonnontieteellinen tiedekunta / Mikko Karesoja
Thermoresponsive Properties
Dynamic light scattering of SiO2-PVCL-b-PEO Diffusion of PVCL and PEO blocks by 1H-NMR
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Similar chemistry can be used to graft surfaces
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01.01.2006Osaston tai henkilön nimi, esityksen nimi 19
Nanosilver coating (non-toxic)n The particles on the surface were 19 ± 4 nmnCovering 15 ± 4 % of the surface
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Gold nanoparticles
”grafting from”
”grafting to”
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Compression isotherms of particle monolayers
(a) Au-PNIPAM265 (solid line: 20 C, dashed line: 33 C) and (b) Au-PNIPAM270-co-NPAM113 (solid line: 20 C, dashed line: 30 C).
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Inkjet-Printed Gold Electrodes on Paper: Characterization and Functionalization
ACS Appl. Mater. Interfaces 2012, 4, 955−964
Anni Määttänen, Petri Ihalainen, Petri Pulkkinen, Shaoxia Wang, Heikki Tenhu,and Jouko Peltonen
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IR-sintering of ink-jet printed metal-nanoparticles on paperDaniel Tobjörk, Harri Aarnio, Petri Pulkkinen, Roger Bollström, Anni Määttänen, Petri Ihalainen, Tapio Mäkelä, Jouko Peltonen, Martti Toivakka,Heikki Tenhu, Ronald Österbacka
Thin Solid Films 520 (2012) 2949–2955
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Complexation of Calix[4]arene Protected Gold Nanoparticles with Pyridinium and Bipyridinium Compounds
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Conclusions
New functional polymers○● amphiphilic, sel-assembling, responsive to temperature and pH○● photoactive polymers with complexing ability○● water dispersable conducting polymers
Hybrid nanomaterials○● silver, gold○● clay, silica
