3.3 Ultrathin PS n -b-PtBA m Polymer Films
65
both polymer systems is less severe than found for related self-assembled monolayers and is in principle controllable via structural modifications on different length
scales (copolymerization or higher order architectures), reactive organic surfaces
with optimized reactivity and loading can be designed based on reactive polymers.
These approaches can also be extended to be compatible with sub- or micrometer
chemical and topographical patterning strategies (see Chaps. 6 and 7). Such reactive
polymers may be used to prepare robust, high-throughout biosensor, and bioarray
platforms in the future.
3.4 Experimental Section
Materials: 11,11
-dithiobis(N-hydroxysuccinimidylundecanoate) (NHS-C10, see
Scheme 1) was synthesized according to the procedure reported previously [18].
Poly(N-hydroxysuccinimidyl-methacrylate) (PNHSMA) was synthesized following
a procedure adapted from Ref. [32] (by AIBN-initiated free radical polymerization
of N-hydroxysuccinimidyl-methacrylate in toluene at 75 °C under argon.
Characterization data of monomer:
1 H-NMR (CDCl 3 , δ in ppm): 6.36 (s, 1 H, C
= CHH), 5.8 (s, 1 H, C = CHH), 2.81 (s, 4 H, CH 2 CH 2cycl ), 1.94 (s, 3 H, CH 3 ) IR
[cm
−1 ]: 2940 (CH), 1794 (C = O), 1759 (C = O), 1735 (C = O), 1632, 1535, 1207,
1682.
Characterization data of polymer: IR [cm
−1 ]: 2947, 2984 (CH), 1809, 1782,
1738, (C = O), 1454, 1362, 1202, 1065,
1 H-NMR (CDCl 3 , δ in ppm): 2.75 (s,
4 H, CH 2 CH 2cycl ), 1.8–2.0 (b, 2 H, CH 2 ), 0.75–1.1 (b, 2 H, CH 3 ); following gel
permeation chromatography (Waters model 410 GPC) using polystyrene standards,
a M n of 3650 g/mol and a polydispersity index M w /M n of 1.30 were determined. The
glass transition temperature of the polymer was 140 °C as measured by differential
scanning calorimetry (Perkin Elmer DSC 7).
Two PS n -b-PtBA m diblock copolymers with different block ratio (the repeat units
were: n 1 = 690, m 1 = 1210; n 2 = 2091, m 2 = 1054, where n i and m i correspond
to the degree of polymerization of the respective blocks of the block copolymers)
were purchased from Polymer Source Company (Dorval, Canada) and were used
as received. The molar masses for two block copolymers were 202.4 kg/mol (PS:
minority) and 352.5 kg/mol (PS: majority) and the polydispersity indices were 1.03
and 1.08, respectively. A PS-b-PtBA diblock copolymer with lower molar mass was
synthesized according to the procedure reported previously by Davis and Matyjaszewski [33]. The
1 H NMR and IR spectroscopic data agreed with the reported
literature data. The synthesized block copolymer PS 88 -b-PtBA 35 had a molar mass
of 13 kg/mol and a polydispersity index of 1.20, as determined by GPC measurements in THF. For the determination of molar mass values PS standards and the
universal calibration approach were used.
65
both polymer systems is less severe than found for related self-assembled monolayers and is in principle controllable via structural modifications on different length
scales (copolymerization or higher order architectures), reactive organic surfaces
with optimized reactivity and loading can be designed based on reactive polymers.
These approaches can also be extended to be compatible with sub- or micrometer
chemical and topographical patterning strategies (see Chaps. 6 and 7). Such reactive
polymers may be used to prepare robust, high-throughout biosensor, and bioarray
platforms in the future.
3.4 Experimental Section
Materials: 11,11
-dithiobis(N-hydroxysuccinimidylundecanoate) (NHS-C10, see
Scheme 1) was synthesized according to the procedure reported previously [18].
Poly(N-hydroxysuccinimidyl-methacrylate) (PNHSMA) was synthesized following
a procedure adapted from Ref. [32] (by AIBN-initiated free radical polymerization
of N-hydroxysuccinimidyl-methacrylate in toluene at 75 °C under argon.
Characterization data of monomer:
1 H-NMR (CDCl 3 , δ in ppm): 6.36 (s, 1 H, C
= CHH), 5.8 (s, 1 H, C = CHH), 2.81 (s, 4 H, CH 2 CH 2cycl ), 1.94 (s, 3 H, CH 3 ) IR
[cm
−1 ]: 2940 (CH), 1794 (C = O), 1759 (C = O), 1735 (C = O), 1632, 1535, 1207,
1682.
Characterization data of polymer: IR [cm
−1 ]: 2947, 2984 (CH), 1809, 1782,
1738, (C = O), 1454, 1362, 1202, 1065,
1 H-NMR (CDCl 3 , δ in ppm): 2.75 (s,
4 H, CH 2 CH 2cycl ), 1.8–2.0 (b, 2 H, CH 2 ), 0.75–1.1 (b, 2 H, CH 3 ); following gel
permeation chromatography (Waters model 410 GPC) using polystyrene standards,
a M n of 3650 g/mol and a polydispersity index M w /M n of 1.30 were determined. The
glass transition temperature of the polymer was 140 °C as measured by differential
scanning calorimetry (Perkin Elmer DSC 7).
Two PS n -b-PtBA m diblock copolymers with different block ratio (the repeat units
were: n 1 = 690, m 1 = 1210; n 2 = 2091, m 2 = 1054, where n i and m i correspond
to the degree of polymerization of the respective blocks of the block copolymers)
were purchased from Polymer Source Company (Dorval, Canada) and were used
as received. The molar masses for two block copolymers were 202.4 kg/mol (PS:
minority) and 352.5 kg/mol (PS: majority) and the polydispersity indices were 1.03
and 1.08, respectively. A PS-b-PtBA diblock copolymer with lower molar mass was
synthesized according to the procedure reported previously by Davis and Matyjaszewski [33]. The
1 H NMR and IR spectroscopic data agreed with the reported
literature data. The synthesized block copolymer PS 88 -b-PtBA 35 had a molar mass
of 13 kg/mol and a polydispersity index of 1.20, as determined by GPC measurements in THF. For the determination of molar mass values PS standards and the
universal calibration approach were used.