Macromolecules
Article
O)CH CH CH −), 23.42 (s, 1C, −C(O)CH CH −). GC−MS
Notes
2
2
2
2
2
(
electron ionization): m/z = 130.1 g/mol; mass = 130.05 g/mol.
Representative Polymerization of ε-tCL with DBU and 1. ε-
The authors declare no competing financial interest.
tCL (100 mg, 0.768 mmol, [1M]) was dissolved in half of the total
ACKNOWLEDGMENTS
CHCl (0.77 mL) used in the reaction and added to a solution of 1-
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3
octadecanethiol (4.4 mg, 0.015 mmol), 1 (14.2 mg, 0.038 mmol), and
This research was supported by NIH under RI-INBRE (8 P20
GM103430-12) and the University of Rhode Island.
DBU (5.9 mg, 0.038 mmol) made with the remaining CHCl . The
3
reaction was left to stir for 180 min, quenched with benzoic acid (3.0
mg), and solvent removed in vacuo to yield a white film. Conversion
was determined by NMR and polymer purified by precipitation from
REFERENCES
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DCM with hexanes. 1H NMR (CDCl ): δ = 3.53−3.49 (t, 2H;
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3
(
CH ) CH S), 2.87−2.82 (t, ∼66H; PB CH S), 2.55−2.50 (t, ∼58H;
2
16
2
2
(
PB C(O)CH ), 1.71−1.52 (m, ∼128H; PB CH ), 1.43−1.33 (m,
2
2
13
∼
=
(
61H; PB CH ), 0.89−0.85 (t, 3H; CH CH ). C NMR (CDCl ): δ
2
3
2
3
(
199.29 (s, 50C, C(O)CH −), 43.86 (s, 50C, -C(O)CH ) 29.29
2
2
s, 50C, −SCH −), 28.53 (s, 50C, −SCH CH −), 28.11 (s, 50C,
2
2
2
(
−
C(O)CH CH CH −), 25.12 (s, 50C, −C(O)CH CH −).
2
2
2
2
2
−1
GPC (UV−vis): M (M /M ) = 8300 g mol (1.8). 80% yield.
n w n
(
Representative Polymerization of ε-tCL with MTBD. ε-tCL
100 mg, 0.768 mmol, [1M]) was dissolved in half of the total CHCl3
0.77 mL) used in the reaction and added to a solution of 1-
Appl.Chem. 2007, 44, 625−649.
(
(
(
(
6) Dove, A. P. ACS Macro Lett. 2012, 1, 1409−1412.
7) Bang, E.-K.; Gasparini, G.; Molinard, G.; Roux, A.; Sakai, N.;
octadecanethiol (4.4 mg, 0.015 mmol) and MTBD (5.9 mg, 0.039)
Matile, S. J. Am. Chem. Soc. 2013, 135, 2088−2091.
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made with the remaining CHCl . Reaction was left to stir for 80 min,
3
(
1
quenched with benzoic acid (3.0 mg), and solvent removed in vacuo to
998, 31, 4746−4752.
yield a white film. Conversion was determined by NMR and purified
1
by precipitation from DCM with hexanes. H NMR (CDCl ): δ =
(9) Overberger, C. G.; Weise, J. K. J. Am. Chem. Soc. 1968, 90, 3533−
3
3
.53−3.49 (t, 2H; (CH ) CH S), 2.87−2.82 (t, ∼66H; PB CH S),
3537.
2
16
2
2
2
.55−2.50 (t, ∼58H; PB C(O)CH ), 1.71−1.52 (m, ∼128H; PB
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3538−3543.
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2
CH ), 1.43−1.33 (m, ∼61H; PB CH ), 0.89−0.85 (t, 3H; CH CH ).
GPC (UV−vis): M (M /M ) = 8400 g mol (1.62). 85% yield.
2
2
3
2
−1
n
w
n
Binding Study Procedure. The titration method and the linear
528.
2
2
forms of the binding equations were used as previously described.
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8583.
Briefly, two stock solutions were made for this experiment: solution A
was 533.3 mM ε-tCL (78.12 mg, 0.6 mmol) dissolved in C D (1.5
6
6
mL, 16.93 mmol). Solution B was 20 mM 1 (7.4 mg, 0.20 mmol)
dissolved in C D (1.0 mL, 11.29 mmol). Several NMR samples were
6
6
made from the above solutions using a calibrated volumetric pipet and
dried NMR tubes. The binding constant was determined by
monitoring the chemical shift of the ortho-aromatic protons of the
thiourea and error was determined by linear regression at the 95%
2
7−29
Determining Thermodynamics of tCL ROP. In a variable
temperature NMR probe, a sample of 100 mg (0.77 mmol) of ε-tCL
was reacted with 0.015 mmol initiator and 0.19 mmol TBD and the
concentration of monomer was determined at multiple temperatures
from 293 to 333 K. The concentrations were recorded twice, once
upon heating and once upon cooling; the values at each temperature
were within error of each other. These concentrations are the
equilibrium monomer concentration ([M]eq = 1/Keq)1 at each
determined by linear regression at the 95% confidence interval.
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Dambacher, T.; Breuer, T.; Ottaway, C.; Fletschinger, M.; Boele, J.;
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7
(
3
(
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ASSOCIATED CONTENT
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S
Supporting Information
(
(
1
Binding data, two views of a calculated equilibrium
geometry, thermodynamic plots, kinetic plots, NMR
(24) Coady, D. J.; Engler, A. C.; Horn, H. W.; Bajjuri, K. M.;
Fukushima, K.; Jones, G. O.; Nelson, A.; Rice, J. E.; Hedrick, J. L. ACS
Macro Lett. 2012, 1, 19−21.
data, and M vs conversion plots (PDF)
n
(
25) Pratt, R. C.; Lohmeijer, B. G. G.; Long, D. A.; Lundberg, P. N.
P.; Dove, A. P.; Li, H.; Wade, C. G.; Waymouth, R. M.; Hedrick, J. L.
Macromolecules 2006, 39, 7863−7871.
AUTHOR INFORMATION
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*
(
26) Shimokawa, K.; Kato, M.; Matsumura, S. Macromol. Chem. Phys.
2
011, 212, 150−158.
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