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Figure legends
Graphical abstract. Cellulosic bottlebrush regioselectively possessing poly(ethylene glycol)
(PEG) and polystyrene (PS) side chains (PEG-PS-cellulose) was synthesized, and its secondary
structure in dilute solution was investigated with SAXS and SEC-MALS. The relationship
between the cross-sectional mean squared radius of gyration (〈Sc2〉) and molecular weight of PS
chain (MWPS) showed that PEG-PS-cellulose has a core-shell-corona structure in cross section.
The dependency of main-chain stiffness (λ-1) on MWPS was discussed on the basis of the
interactions of the PS and PEG side chains as well as the restricted rotation of the cellulosic main
chain.
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Figure. 1. Chemical structures of heteroBBs (PEG-PS-cellulose 1) and homoBBs (PEG-cellulose
2 and PS-cellulose 3).
Scheme 1. Synthesis of PEG-PS-cellulose 1 and its precursor, PEG-cellulose 2.a
Reagents, conditions and yields: (a) PEG-I, NaOH, DMSO, 50 °C, 4 d, 75%; (b) HCl, H2O, THF,
rt, 5 h, 88%; (c) pentynoic acid, EDC•HCl, DMF, rt, 1 d→50 °C, 2 d, 98%; (d) PS-N3 (DPn = 60
(for 1a), 30 (for 1b), 20 (for 1c)), CuSO4•5H2O, ascorbic acid, DMF, 60 °C, 2 d, 75% (1a), 76%
(1b), 75% (1c).
Figure 2. Cross-sectional Guinier plots for bottlebrushes; 1a, 1b and 1c (red, blue and green
circles); 2 (purple circle); 3a, 3b and 3c (red, blue and green squares). The solid lines represent
the increment of the cross-sectional Guinier approximation. Adapted with permission from Ref.
No.22. Copyright 2011. American Chemical Society.
Figure 3. Schematic illustration and radial density diagram of the cross-sectional structure for the
core-shell model (a) and core-shell-corona model (b) for PEG-PS-cellulose 1. Gray: cellulosic
backbone; orange: PS domain; blue: PEG domain.
Figure 4. The relationship between 〈Sc,SAXS2〉 and MWAGU,PS for PEG-PS-cellulose (1a–c) and
PEG-cellulose (2). The red curve represents the theoretical curve for the core-shell-corona model
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for PEG-PS-cellulose illustrated in Figure 3b (ρcellulose = 1.2 g·cm⁻3, ρsolve,PS = 0.22 g·cm⁻3 and
ρsolve,PEG = 0.30 g·cm⁻3).
Figure 5. Elution-volume dependence of the weight-average molecular weight Mw (blue circles),
mean-square radius of gyration 〈S2〉 (red circles) and polymer mass concentration c (solid line)
(a), and DPM chain dependence of 〈S2〉M in DMF/LiBr for PEG-PS-cellulose (b) for 1a–c. The red
lines in (b) represent the theoretical curves for the unperturbed KP chain.
Figure 6. The dependence of λ⁻1 on the DPn of the side chains (m) for 1 and 3 in DMF/LiBr (red
and blue circles, respectively). The red and blue solid lines represent theoretical curves for 1 and
3, respectively.
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Graphical abstract
Cellulosic Bottlebrush
Regioselectively Possessing PEG and PS Side Chains
PEG
PEG
PS
Stiffness of
Main Chain
Cross-Sectional
Structure
SAXS
〈Sc2〉
N N
SEC-MALS
λ⁻1
MW of PS
MW of PS
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Figure. 1
Ph
16
N N
(m = 60)
1a (m = 30)
1b (m = 20)
1c
Me
Me
16
16
MeO
Me
16
N N
OMe
Me
Ph
(m = 60)
3a (m = 30)
3b (m = 20)
3c
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Scheme 1
OMe
HO
OMe
OH
16
Me
16
16
Me
16
Me
Me
16
16
Me
16
OH
Ph
N N
Me
Me
16
Me
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ln[q I(q) / nm ]
Figure 2
q2 / nm⁻2
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Figure 3
(b)
density
density
(a)
Radius
Radius
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〈Sc,SAXS2〉 / nm2
Figure 4
MWAGU,PSt / 103 g·mol⁻1
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log
Figure 5
1c
Mw
1c
〈S2〉
Elution volume / mL
log[DPM]
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λ⁻1 / nm
Figure 6
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Table 1. Characteristics of cellulosic bottlebrushes 1, 2 and 3.
PEG-
heteroB
PS-
cellulos
Sampl
DSPE
DSP
Mn,PS/g·mol
M0a/g·mol
wbackbone
wPEG
wPS
dn/dcc/g·mol
Mwd/g·mol
⁻1
⁻1
⁻1
⁻1
1a
1.6
1.0
6.4×103
8.1×103
0.03
0.14
0.139
9.7×105
1b
1.6
1.0
3.3×103
4.7×103
0.05
0.24
0.126
6.1×105
1c
1.6
1.1
2.2×103
3.8×103
0.06
0.31
0.117
4.8×105
1.6
1.4×103
6.2×104e
3ag
1.1
6.4×103
7.4×103
0.04
0.154
8.1×105
3bg
1.1
3.3×103
3.8×103
0.07
0.150
4.6×105
3cg
1.2
2.2×103
2.9×103
0.10
0.148
3.2×105
0.8
0.7
0.6
PEGcellulos
DPMd
1.2×10
1.3×10
1.3×10
Đd
〈Sc,SAXS2〉f/n
m2
2.3
12
2.4
5.4
2.4
3.6
4.4×10
1.5
1.8
homoB
PScellulos
ee
0.9
0.9
0.9
1.1×10
1.2×10
1.1×10
1.6
13
1.7
6.4
1.7
4.3
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Average molecular weight per AGU. Weight fraction of the main chain and PEG and PS side chains. Refractive index increment calculated from
equation 1. Determined by SEC-MALS in DMF/LiBr. Determined by SEC with PMMA standard with the cross-sectional Guinier approximation.
Mean-square radius of gyration determined from the SAXS profile. Adapted with permission from Ref. No.22. Copyright 2011. American Chemical
Society.
Table 2. Model parameters for cellulosic bottlebrushes 1, 2 and 3.
Homogeneous
Core-shell model
model
Core-shell-corona model
ρcellulose ρsolve,PS ρsolve,PEG Rcore
Rshell ρcellulose ρsolve,PS ρsolve,PEG Rcore
Rshell
Rcorona
/nm
/ g∙cm / g∙cm
/nm / g∙cm / g∙cm / g∙cm
/ nm
/nm
1a
4.9
0.28c
0.048c
2.0f
5.6f
PEG-PS-cellulose 1b
3.3
0.30c
0.10c
2.0f
4.0f
1c
2.7
0.32c
0.16c
2.0f
3.4f
1.9
0.29c
2.0
2.0f
3a
5.1a
5.3e
3b
3.6
3.8
2.9
3.2
PEG-cellulose
PS-cellulose
3c
–3
1.2b
1.2
–3
0.26
/ g∙cm
–3
/ nm
–3
–3
–3
/ nm
5.0
0.46d
0.50
3.4
2.7
1.2b
0.22
0.30
0.46d
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Data in ref. 22. b Constant parameter. c Depending on Rshell. d Depending on ρcellulose. e Depending on ρcellulose and ρsolve,PS. f Depending on ρcellulose, solve,PS
and ρsolve,PEG
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Table 3. Stiffness parameters for PEO-PS-cellulose 1 and PS-cellulose 3.
DPn of PS-side chain (m)
λ–1/nm
1a
60
22
1b
30
18
1c
20
17
3a
60
16
3b
30
12
3c
20
12
Sample
PEG-PS-cellulose
PS-cellulosea
From reanalysis of the data in ref. 22 using the core-shell model.
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