Supplementary Material for Chemical Communications
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Supporting Information
A typical protocol for the homopolymerization of 2-gluconamidoethyl
methacrylate (GAMA) via methanolic ATRP at 20 oC
2-Gluconamidoethyl methacrylate (GAMA; 2.0 g, 6.5 mmol) was heated to 40 oC to
aid its dissolution in methanol (4.0 ml). The PEG23-Br initiator (0.13 g, 0.013 mmol,
target degree of polymerization = 50) was then added and this solution was purged
with nitrogen for 10 minutes. Copper(I) bromide (0.018 g, 0.013 mmol) and two
equivalents of 2,2’-bipyridine (0.040 g, 0.026 mmol) were added and the resulting
dark brown solution was stirred under a nitrogen atmosphere. The extent of
polymerization was monitored by 1H NMR. High conversion (> 97 %) was only
achieved after 15 h at 20 oC. GPC data for the GAMA polymer indicated an Mn of
11,400 and an Mw/Mn of 1.23. The spent ATRP catalyst was removed by passing the
reaction solution through a column packed with basic alumina. The methanol was
removed under vacuum and the white polymer was re-dissolved in water and freezedried overnight. The isolated yield of GAMA homopolymer was 78 %. The same
protocol was used for ATRP syntheses in water or water/methanol mixtures except
that the GAMA did not require heating for dissolution under these conditions. The
reaction times required for high conversions were significantly reduced in the
presence of water.
GPC protocols used in this work:
1. Aqueous GPC at neutral pH (GAMA homopolymer)
GPC chromatograms for the homopolymers were recorded using a Viscotek
instrument equipped with a Viscotek TSK alpha-3000 column, 0.10 M sodium
nitrate/0.01 M sodium dihydrogen phosphate as eluent at a flow rate of 1.0 ml min -1at
35 C using a refractive index detector. Calibration was achieved using poly(ethylene
oxide) standards.
2. Aqueous GPC at low pH (GAMA-DEA diblock copolymer)
GPC chromatograms for the diblock copolymers were obtained using a Viscotek TSK
G5000PWXL column at 30 C in conjunction with an ERC-7515A refractive index
detector. The eluent used was 0.50 M acetic acid/0.30 M sodium sulfate
(approximately pH 2) at a flow rate of 1.0 ml min-1. Calibration was achieved using
poly(2-vinylpyridine) standards.
3. DMF GPC (selected homopolymers and copolymers)
GPC chromatograms were obtained from RAPRA, UK using a Waters 150 CV
instrument equipped with two 30 cm (10 micron) Mixed Bed-B Plgel columns
operating at 80 C with a refractive index detector. DMF containing 0.01 M lithium
Supplementary Material for Chemical Communications
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bromide was used as the eluent at a flow rate of 1.0 ml min-1. Calibration was
achieved using poly(methyl methacrylate) standards.
Supplementary Material for Chemical Communications
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(a)
3
2
O
6
4 O
1
5
O
5,8
N
H
7
OH
12
9 10 11 CH OH
2
8
OH
9
OH
OH
1
6,10,11,12
3
3’
 (ppm)
1
(b)
3
8,9,10,11,12,
5
6
7 4
2
 (ppm)
Fig. 3 (a) 1H and (b) 13C NMR spectra of 2-gluconamidoethyl methacrylate (GAMA)
monomer
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3
2
O
6
4 O
1
5
O
N
H
7
OH
8
OH
OH
12
9 10 11 CH OH
2
OH
(m/z
307)
[M+1
]+
Fig. 4. Mass spectrum of 2-gluconamidoethyl methacrylate (GAMA)
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(a
)
4
Water
3.5
Methanol/water
(9:1)
Ln([M]0/[M])
3
2.5
2
1.5
Methanol
1
0.5
0
0
5
10
15
16000
1.8
14000
1.7
12000
1.6
10000
1.5
8000
1.4
6000
1.3
4000
1.2
2000
1.1
0
(b
)
M w/M n
Mn
Time (h)
1
0
20
40
60
80
100
Conversion (%)
Fig. 5 (a) Kinetic plots for the homopolymerization of GAMA (target degree of
polymerization = 50) at 20 oC using PEG23-Br as initiator and CuBr/2bpy as catalyst
in methanol, water and a 9:1 methanol/water mixture, respectively; (b) evolution of
Mn with conversion for the homopolymerization of GAMA at 20 oC in methanol. In
both (a) and (b) the reaction conditions were 2.0 g GAMA in 4.0 ml methanol and the
relative molar ratios of GAMA: PEG23-Br: Cu(I)Br: bpy were 50:1:1:2.
Supplementary Material for Chemical Communications
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2
2
14,15
1
O
O
O
x
m
O
O
7
14,15
3
4
8
N
3,7,8,9,10,11,12,13
O
10
HO
5
N
5
9
HO
pH 2.5
n
O
1
O
OH
6
6
11
12
HOCH2
OH
13
4
1
pH 10
GAMA
Homopolymer
 (ppm)
Fig. 6 1H NMR spectra (D2O) of GAMA homopolymer and the PEG23-(GAMA)50(DEA)100 block copolymer at pH 10 and 2.5, respectively. The solution pH was
adjusted using NaOD and DCl, respectively
2
Supplementary Material for Chemical Communications
This journal is © The Royal Society of Chemistry 2002