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Macromolecules 2005, 38, 5743-5747

5743

Thermoresponsive Micellization of Poly(ethylene
glycol)-b-poly(N-isopropylacrylamide) in Water
Wangqing Zhang, Linqi Shi,* Kai Wu, and Yingli An
Key Laboratory of Functional Polymer Materials, Institute of Polymer Chemistry, N&T Joint Academy,
Nankai University, Tianjin 300071, China
Received May 2, 2005

ABSTRACT: Thermoresponsive micellization of poly(ethylene glycol)-b-poly(N-isopropylacrylamide)
(PEG110-b-PNIPAM44) in water is studied by static light scattering and dynamic light scattering. The
critical aggregation temperature of PEG110-b-PNIPAM44 is a little higher than homopolymer PNIPAM,
and it depends on the block copolymer concentration, which increases from 33.7 to 38.4°C when the
copolymer concentration decreases from 2.0 to 0.20 mg/mL. Above the critical aggregation temperature,
thermoresponsive micellization occurs, and the resultant spherical micelles consist of a PNIPAM core
and a PEG shell. The block copolymer concentration exerts a strong influence on the size and structure
of the resultant micelles. Micellization of PEG110-b-PNIPAM44 at higher copolymer concentration favors
formation of narrowly distributed, small, and dense micelles, while large, loose micelles or micellar clusters
form at lower block copolymer concentration.

1. Introduction
Micellization of hydrophobic-hydrophilic block copolymers or amphiphilic block copolymers in blockselective solvents and the resultant micelles are well
documented in scientific literature in the past 20 years.1
Usually, micellization of amphiphilic block copolymers
in block-selective solvent produces core-shell micelles,
where the insoluble block forms the core and the soluble
block forms the shell of the resultant core-shell micelles.1 Besides amphiphilic block copolymers, micellization of hydrophilic-hydrophilic block copolymers,
which are also called double hydrophilic block copolymers, are also widely studied recently.2 Usually, hydrophilic-hydrophilic block copolymers behave as single
chains in aqueous solution like classical polymers or
polyelectrolytes, whereas its micellization similar to that
of amphiphilic block copolymers can occur under the
influence of a given external stimuli, mainly temperature, pH, ionic strength changes, or complexation.2,3
Of all the hydrophilic-hydrophilic block and graft
copolymers, poly(ethylene glycol)-b-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) or poly(ethylene glycol)g-poly(N-isopropylacrylamide) (PEG-g- PNIPAM) is an
interesting one, where the PNIPAM is one of the most
studied responsive polymers that exhibits a lower
critical solution temperature (LCST) in water around
32°C and the PEG is usually used for the stabilization
of dispersions and emulsions.4,5 Below the LCST of the
PNIPAM block, PEG-b-PNIPAM or PEG-g-PNIPAM is
highly soluble in aqueous solution, while above the
LCST, the thermosensitive PNIPAM block precipitates,
and the copolymer self-assembles into polymeric micelles, which consist of a PNIPAM core and a hydrophilic
shell of PEG.6 The thermoresponsive aggregation of
PEG-b-PNIPAM or PEG-g-PNIPAM has been studied
extensively. For example, Tenhu et al. studied the
aggregation of PEG-b-PNIPAM in water by fluorescence
spectroscopy and light scattering;6a Zhu and Napper
studied the gelation of PEG-b-PNIPAM;7 Wu et al.
* To whom correspondence should be addressed. E-mail:
shilinqi@nankai.edu.cn.

studied the formation of core-shell nanoparticles of
PEG-g-PNIPAM through the coil to globule transition
of the PNIPAM block;6c Feijen et al. studied the thermosensitive micelle formation of PEG-b-PNIPAM.6d
However, the copolymers used in the study mentioned
above usually have relatively high molecular weight of
PNIPAM block of the copolymers. For example, the
molecular weight of the PNIPAM block was as high as
1 × 105-6 g/mol.5-7 Herein, we study the thermoresponsive micellization of PEG-b-PNIPAM with low and
narrowly distributed molecular weight of PNIPAM block
by laser lighting scattering. It is found the critical
aggregation temperature of PEG110-b-PNIPAM44 depends on block copolymer concentration. Besides, the
size of the resultant PEG-b-PNIPAM micelles decreases
when the block copolymer concentration increases,
which is different than the gelation of PEG-b-PNIPAM
or PEG-b-PNIPAM with high molecular weight of
PNIPAM block.
2. Experimental Section
Materials. Polyethylene glycol monomethyl ether (CH3OPEG110-OH) (Mw ) 5000 and the polydispersity index PDI )
1.05) was purchased from Fluka. CuCl was purchased from
Aldrich and purified according to ref 8. Tris[2-(dimethylamino)ethyl]amine (Me6TREN) was synthesized according to ref 8.
The monomer N-isopropylacrylamide (NIPAM, Acros Organics)
was purified by recrystallization in a benzene/n-hexane mixture and dried carefully in a vacuum. All water used in this
study was purified with a Millipore Mill-Q system, and the
resistivity was above 16 MΩ cm. Other reagents were used as
received.
Synthesis of PEG Macroinitiator. The macroinitiator
PEG110-Br was synthesized according to ref 9. The synthetic
procedures and the H NMR spectrum of PEG110-Br can be
found in the Supporting Information.
Synthesis of PEG110-b-PNIPAM44. PEG110-b-PNIPAM44
was synthesized by atom transfer radical polymerization
(ATRP). The typical polymerization procedure was introduced
as follows. 5.0 g of PEG110-Br was added into a reaction flask,
and then a 10 mL solvent mixture of butanone and 2-propanol
(1:1 by volume) was added. The sample was first stirred and
then degassed under nitrogen purge. Subsequently, the CuCl
and Me6TREN catalysts (0.148 g of CuCl and 0.345 g of Me6-

10.1021/ma0509199 CCC: $30.25 © 2005 American Chemical Society
Published on Web 06/02/2005

7 nm. Hydrodynamic diameter distribution f(Dh) of the coils of single chains of PEG110-b-PNIPAM44 in water at 25 °C. and NIPAM conversion was about 70%. and the can be calcuapparent hydrodynamic diameter Dapp h lated from f(Dh) by ∫∞0 f(Dh)Dh dDh. respectively. At last. respectively. All samples were first prepared by filtering about 1 mL of the aqueous solution with a 0. Results and Discussion 3. Since the LCST of PNIPAM in water is about 32 °C and the PEG and PNIPAM blocks are soluble in water at 25 °C.5 g of NIPAM was added into the flask and degassed under nitrogen purge. Clearly. Furthermore. q ) (4πn/λ0) sin(θ/ 2). the solvent refractive index. The results suggest that the critical aggregation temperature of PEG110-b-PNIPAM44 is higher at lower block copolymer concentrations. Compared with the homopolymer of PNIPAM. dn/ dc is the specific refractive index increment. The block copolymer PEG110-b-PNIPAM44 was dissolved in water at room temperature (about 18 °C) to make up a series of aqueous solutions with block copolymer concentration ranging from 0. and then the scattering intensity was measured.C)] ≈ [1/Mw][1 + (Rg2q2)/3] Figure 1. On the basis of SLS theory.7 °C.0 mg/mL. and the wavelength of laser.4 and 33. In this study.20 mg/mL (A) and 2. In the present study. eq 2 can be expressed as [KC/R(θ. the critical aggregation temperature of PEG110-b-PNIPAM44 is a little higher. The Critical Aggregation Temperature of PEG110-b-PNIPAM44.5 to 7. For a pure diffusive relation. Temperature dependence of the normalized intensity I/I0 of PEG110-b-PNIPAM44 at 0. the absolute temperature. The detailed method of DLS and SLS measurements can be seen in our recent works or Wu’s study. T. and η are the Boltzmann constant. for a relatively dilute macromolecule solution at polymer concentration C (g/mL) and at the scattering angle θ.20 to 2.4 to 33. DLS and SLS measurements were performed on a laser light scattering spectrometer (BI-200SM) equipped with a digital correlator (BI-9000AT) at 514 nm.10 3.5744 Zhang et al. where the block copolymer aqueous solution was heated for about 60 min at each temperature. The hydrodynamic diameter Dh of PEG110-b-PNIPAM44 ranges from 7.7 °C when the copolymer concentration increases from 0. and the solvent viscosity.7 The results . it is also found that the critical aggregation temperature ranges from 38.20 mg/mL (O) and 2.0 mg/ mL (b). The composition of the block copolymer PEG110-b-PNIPAM44 was determined by the 1 H NMR spectrum. respectively. Vol.9 nm. and the critical aggregation temperatures of PEG110-b-PNIPAM44 with polymer concentration at 0.0 mg/ mL. the second virial coefficient A2. which is about 7. Figure 2 shows the temperature dependence of the normalized intensity of PEG110-b-PNIPAM44 at two block copolymer concentrations of 0.05 and 1. For a given dilute polymer solution. the angular dependence of the excess absolute average scattered intensity. 2005 TREN) were introduced into the reaction flask. 6. Light Scattering Measurement. 13. The block copolymer PEG110-b-PNIPAM44 was purified by first passing through an Al2O3 column to remove the copper catalyst and then precipitated in cold ether. In DLS measurement.4 the average hydrodynamic diameter of the coils of single chains of PEG110-b-PNIPAM44 is about 7. namic diameter distribution f(Dh) of PEG110-b-PNIPAM44 in water at 25 °C. Figure 1 shows the hydrody- Figure 2. Γ/q2θf0 or D0 of the micelles at given concentration was calculated by extrapolating q2 to 0. where tetrahydrofuran was used as eluent and narrow-polydispersity polystyrene was used for calibration standard. and λ0 being Avogadro’s number.q) in the self-beating mode can result in a line-width distribution G(Γ). Polymerization was performed at 40 °C for 48 h.20 to 2. which is possibly due to the soluble PEG block in water. which is consistent with the results achieved by Zhu and Napper. can be approximated as [KC/R(θ.06. Macromolecules. known as the excess Rayleigh ratio R(θ. No. respectively. (3) On the basis of eq 3.C)] ) [1/Mw][1 + (Rg2q2)/3] + 2A2C (2) where K is the optical constant and K ) 4π2n2(dn/dc)2/(NAλ04) with NA.45 µm Millipore filter into a clean scintillation vial and heating at different temperatures for a given time and then characterized by a combination of static laser scattering (SLS) and dynamic laser scattering (DLS). and the weight-average molar mass of the micelles Mw were calculated from SLS. G(Γ) can be transferred into a translational diffusion coefficient distribution G(D) since Γ/q2θf0.0 mg/mL are 38. 38.20 and 2. the sharp increase of the scattering intensity implies the occurrence of micellization.1. the Laplace inversion of a measured intensity-intensity time correlation function G(2)(t. The PDI of PEG110-Br and PEG110-bPNIPAM44 measured by gel permeation chromatography (GPC) (see the GPC chromatograms in the Supporting Information) was 1. and then the hydrodynamic diameter D0h or the hydrodynamic diameter distribution f(Dh) of the micelles at given polymer concentration was further calculated from eq 1.C) at a set of θ series. as shown in the Supporting Information. n. and q is the magnitude of the scattering wave vector. the apparent radius of gyration Rg and apparent weight-average molar mass Mw of the micelles were calculated after measuring R(θ.Cf0 f D or a hydrodynamic diameter distribution f(Dh) via the Stokes-Einstein equation Dh ) kbT/(3πηD) (1) where kb. respectively.7 nm. The radius of gyration Rg.0 mg/mL (B).C).

12 Besides. 2005 Figure 3. 0. Plots of Γ/q2 vs q2 of the PEG110-b-PNIPAM44 micelles formed at block copolymer concentration of 0.20 to 2. Figure 4. 38. 0. It is well-known that the Rg/Rh value. indicates the particle shape in solution.6.80.Macromolecules.20 (D).20 to 2. It is also found that the Γ/q2 values of the PEG110-b-PNIPAM44 micelles formed at different block copolymer concentrations are almost independent of q2.20. and 2. Besides.0 mg/ mL. Figure 6 shows the apparentradius of gyration Rg of the PEG110-b-PNIPAM44 micelles formed at different block copolymer concentrations at 47 °C. 1. 0. and 10. 0.0 mg/mL at 47 °C.0 mg/mL.2.40.13-16 The Rg/Rh value of the PEG110-b-PNIPAM44 micelles as shown in Figure 7 . The PEG110-b-PNIPAM44 Micelles. which is much higher than the critical aggregation temperature of PEG110-b-PNIPAM44. In fact. 13. and 2. Clearly.40 (B). based on eq 1. Vol. 4. and the values are shown in Figure 4. No. respectively.42 × 10-8 cm2/s.20.20 (A). where Rh is the hydrodynamic radius. Hydrodynamic diameter distribution f(Dh) of the PEG110-b-PNIPAM44 micelles formed at block copolymer concentration of 0.0 mg/mL is narrowly distributed with a relative width µ2/Γ2 lower than 0. 5. the Rg of the resultant micelles decreases from 153 to 44 nm as the block copolymer concentration increases from 0. 0.80 (C). the PEG110-b-PNIPAM44 micelles formed at block copolymer concentration of 2. Block copolymer concentration dependence of the radius of gyration Rg of the PEG110-b-PNIPAM44 micelles formed at 47 °C.05.91 × 10-8.0 mg/mL (E) at 47 °C.67 × 10-8. Figure 5 shows the hydrodynamic diameter distribution f(Dh) of the PEG110-b-PNIPAM44 micelles formed at block copolymer concentration ranging from 0. the hydrodynamic diameter distribution f(Dh) of the PEG110b-PNIPAM44 micelles becomes progressively narrower with increasing block copolymer concentration. 0.0 mg/ mL (E) at 47 °C. 3. Clearly. the hydrodynamic diameter of the PEG110-b-PNIPAM44 micelles decreases with increasing block copolymer concentration. and 2.20 (A). the values of the hydrodynamic diameter Dh of the PEG110-b-PNIPAM44 micelles formed at different copolymer concentrations can be calculated. narrowly distributed core-shell micelles. 1.7 We think the reason that large-sized micelles formed at lower copolymer concentration is possibly due to the relatively slow micellization of PEG110-b-PNIPAM44. have found that micellization of PEG-b-PNIPAM at high temperature favors formation of narrowly distributed micelles. Hennink et al. where the diameter of the resultant micelles or nanoparticles usually increases at higher block copolymer concentration. which are 3. the sample of about 1 mL of aqueous solution of PEG110-b-PNIPAM44 was bathed at 47 °C.44 × 10-8. From the fit lines in Figure 3. 1. Thus. which suggests that the micelles are spherical. Block copolymer concentration dependence of the hydrodynamic diameter Dh of the PEG110-b-PNIPAM44 micelles formed at 47 °C.0 mg/mL can be calculated by extrapolating q2 to 0. and then the resultant micelles are studied. Figure 6. the values of the translational diffusion coefficient D0 of the resultant micelles formed at block copolymer concentration of 0. This means that micellization of PEG110-b-PNIPAM44 at high polymer concentration favors formation of small.20 to 2. Figure 3 shows the plots of Γ/q2 vs q2 of the PEG110-b-PNIPAM44 micelles formed at different block copolymer concentrations at 47 °C.11 Thus. 6. It can be clearly seen in Figure 4 that the hydrodynamic diameter Dh of the resultant PEG110-b-PNIPAM44 micelles decreases from 227 to 78 nm when the block copolymer concentration increases from 0. in the following study.20 (D). PNIPAM or PEG-g-PNIPAM with a high molecular weight PNIPAM block.80 (C).40 (B). also mean that micellization of PEG110-b-PNIPAM44 occurs easily at higher copolymer concentration.58 × 10-8. the micellization of PEG110-b-PNIPAM44 is very different than the aggregation of the PEG-b- Micellization of PEG110-b-PNIPAM44 5745 Figure 5.

Macromolecules.50). and the chain density F of the PEG110-b-PNIPAM44 micelles formed at different copolymer concentrations. the dn/dc value of PEG110-b-PNIPAM44 in water can be calculated. decreases from 1. In comparison with random coils of homopolymers (Rg/Rh ∼1. respectively.7 to 38.13 the Rg/Rh value of the PEG110-b-PNIPAM44 micelles is much smaller.6c is shown in Figure 9. 4. which confirms the formation of the micelles. loose micelles or micellar clusters form at low block copolymer concentration. The results suggest that the apparent Mw of the PEG110-b-PNIPAM44 micelles linearly decreases from 2. while large.16 while the smaller aggregates formed at high polymer concentration of 2.0 mg/mL are well-defined micelles. and 23028407).53 × 10-3 to 3.4°C when the copolymer concentration decreases from 2. 2005 Figure 7. The block copolymer concentration exerts a strong influence on the size and structure of the PEG110-b-PNIPAM44 micelles. while large.6c this justifies the use of eq 4.20 to 2. Figure 9. the temperature dependence on dn/dc of the block copolymer has also been observed to be minimal.76 × 106 g/mol as the block copolymer concentration increases from 0. Besides.5746 Zhang et al.775)12. Block copolymer concentration dependence of the apparent weight-average molar mass Mw of the PEG110-bPNIPAM44 micelles formed at 47 °C.0 to 0. radius of gyration Rg. The polymer chain density F of the PEG110-bPNIPAM44 micelles. We think the larger aggregates formed at low concentration of PEG110-b-PNIPAM44 are possibly loose compound micelles or micellar clusters.13 or the aggregates of homopolymer PNIPAM (∼0.20 to 2. the dn/dc value is calculated to be 0. On the basis of all the results such as the hydrodynamic diameter Dh.20 to 2.0 mg/mL. 38.0 mg/mL. The critical aggregation temperature of PEG110-b-PNIPAM44 is a little higher than that of the PNIPAM homopolymer. Acknowledgment. which is possibly due to the relatively long coronal PEG block.62) formed above its LCST. The results show the chain density F of the PEG110-b-PNIPAM44 micelles linearly increases from 6.20 mg/mL. Conclusions The thermoresponsive micellization of PEG110-bPNIPAM44 in water above the critical aggregation temperature of the PNIPAM block forms spherical coreshell micelles with the PNIPAM block as core and the PEG block as shell. However. The micellization of PEG110-b-PNIPAM44 at high copolymer concentration favors formation of narrowly distributed. compared with typical amphiphilic block copolymer crew-cut micelles (∼0. No. the Rg/Rh value.83 × 10-2 g/cm3 when the block copolymer concentration increases from 0. The financial support by the Outstanding Scholar Program of Nankai University. small. In the present study. and the temperature depends on the block copolymer concentration. compact micelles.41 × 107 to 5. which is calculated as F ) Mw/(NAπ/ 6Dh3). and Chinese Education Ministry Foundation for Nankai University and Tianjin University Joint Academy is gratefully acknowledged. dense micelles. The critical aggregation temperature increases from 33.15. the apparent weight-average molar mass Mw of the PEG110b-PNIPAM44 micelles can be calculated by a Zimm plot. Block copolymer concentration dependence of the chain density F of the PEG110-b-PNIPAM44 micelles formed at 47 °C. Assuming that the specific refractive index increment (dn/dc) of the micelles can be approximately expressed as6a dn/dc ) wA(dn/dc)A + wB(dn/dc)B (4) in which wA and wB are the mass fractions of the PNIPA and PEG block and (dn/dc)A and (dn/dc)B are their refractive index increments.17 the Rg/Rh value of the PEG110b-PNIPAM44 micelles is much bigger. Rg/Rh value of the PEG110-b-PNIPAM44 micelles formed at different block copolymer concentrations.0 mg/mL. loose micelles or micellar clusters form at low block copolymer concentration. 20474032. it can be concluded that micellization of PEG110-b-PNIPAM44 at high block copolymer concentration favors formation of small nar- Figure 8. rowly distributed.38 to 1. Thus. the apparent Mw. Vol. .13 when the block copolymer concentration increases from 0. which is shown in Figure 8.161. National Natural Science Foundation of China (No. 13. 50273015.

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