Beilstein J. Org. Chem. 2012, 8, 1929–1935.
scattering data, by using the Zimm model. As concentration ArH) 7.20 (br, NH), 3.84 (s, CH), 2.62 (br, CH2), 2.46 (br,
source, the refractive index was used. Calibration of the system CH2), 1.3–2.2 (backbone), 1.04 ppm (s, 6H, CH3); SEC
was performed with bovin serum albumin. Turbidity experi- measurements: Mn 3.4 kDa, PD 1.3; 1H NMR: 3.3 kDa.
ments were performed on a Tepper cloud-point photometer
TP1. The relative transmission of a laser beam with a wave-
Supporting Information
length of 670 nm was recorded for each experiment. The
measurements were performed in a temperature range between
The Supporting Information contains experimental
5
and 60 °C and at a heating rate of 1 °C min−1 by using Hellma
procedures for the preparation of 5, HPG,
propargyl-modified HPG, CD-monoazide, HPG bearing
β-CD (7), and spectroscopic data of 6 and the complex of 6
and RAMEB-CD.
Suprasil precision cells 110 Q-S. Critical solution temperatures
derived from these experiments were determined at 50% rela-
tive transmission. Dynamic light scattering (DLS) experiments
were carried out with a Malvern Zetasizer Nano; ZS ZEN 3600
at a temperature of 20 °C. The particle size distribution is
derived from a deconvolution of the measured intensity autocor-
relation function of the sample by a general purpose method,
i.e., the non-negative least squares algorithm, included in the
DTS software.
Supporting Information File 1
Synthesis of 3. N-Isopropylacrylamide (1, 2 g, 0.02 mol) was References
dissolved in 10 mL of ethanol and flushed with argon for
1
1
0
5 min. To this solution, 3-mercaptopropionic acid (2, 0.1 mL,
mmol) and 4,4’-azobis(4-cyanovaleric acid) (24.7 mg,
.09 mmol) were added under an argon atmosphere. After being
2.
3.
stirred at 70 °C overnight, the corresponding polymer was sep-
arated by precipitation with cold diisopropyl ether. The precipi-
tate was washed three times with diethyl ether and dried under
reduced pressure. FTIR (diamond) ν (cm−1): 3287 (NH), 2970
4
5.
(
(
CH), 2930 (CH),1712 (CO), 1640 (CO), 1539 (NH), 1456
CH), 1365 (CH), 1230 (CH2), 1171 (CC); 1H NMR (300 MHz,
6.
D2O) δ 7.19 (br, 1H, NH), 3.85 (br, 1H, CH), 2,67 (br, 2H, 7. Beija, M.; Charreyre, M.-T.; Martinho, J. M. G. Prog. Polym. Sci. 2011,
CH2), 2,4 (br, 2H, CH2), 1.3–2.2 (backbone), 1.02 ppm (s, 6H,
CH3).
8
9
1
1
1
.
.
Synthesis of 6. The carboxy-terminated PNIPAM (3, 2 g) was
dissolved in 5 mL of dry DMF. To this solution, thionyl chlo-
ride (0.15 mL, 2 mmol) and triethylamine (0.28 mL, 2 mmol)
were added and stirred for 3 h. The precipitated triethylammo-
nium chloride was filtered and the excess of thionyl chloride
was removed in vacuum from the DMF-solution. To the
obtained solution, triethylamine (0.28 mL, 2mmol) and N,N-
2.Yamaguchi, H.; Kobayashi, Y.; Kobayashi, R.; Takashima, Y.;
dimethyl-[4-(4’-aminophenylazo)phenyl]amine (5, 360 mg, 13.Bléger, D.; Liebig, T.; Thiermann, R.; Maskos, M.; Rabe, J. P.;
1
.5 mmol) were added and stirred overnight at room tempera-
ture. The triethylammonium chloride was filtered off, and the
terminated polymer was isolated by precipitation with cold
diisopropyl ether. The precipitate was washed three times with
diethyl ether and dried under reduced pressure. FTIR (diamond)
ν (cm−1): 3287 (NH), 2970 (CH), 2930 (CH), 1712 (CO), 1640
1
1
5.Böhm, I.; Kreth, S. K.; Ritter, H.; Branscheid, R.; Kolb, U.
1
6.Duan, Q.; Miura, Y.; Narumi, A.; Shen, X.; Sato, S.-I.; Satoh, T.;
(
(
CO), 1539 (NH), 1456 (CH), 1365 (CH), 1230 (CH2), 1171
CC), 881 (CN), 838 (aromatic C-H, 2 neighboring H atoms);
1
H NMR (300 MHz, DMSO-d6) δ 7.97 (d, 8.88 Hz, ArH), 7.98
(
d, 7.15 Hz, ArH), 7.58 (d, 7.17 Hz, ArH), 7.36 (d, 8.88 Hz,
1934