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A Novel Approach To Functionalized Nanoparticles: Self-Crosslinking of Macromolecules in Ultradilute Solution
A Novel Approach To Functionalized Nanoparticles: Self-Crosslinking of Macromolecules in Ultradilute Solution
A Novel Approach To Functionalized Nanoparticles: Self-Crosslinking of Macromolecules in Ultradilute Solution
[**] DM thanks the Govierno Vasco for a fellowship. Partial funding from
NIST-ATP Cooperative Agreement 70NANB8H4013 and CPIMA is
gratefully acknowledged.
204
Scheme 1.
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Scheme 2.
Polymer
1a
1b
1c
1d
1e
1f
1g
1h
Poly(e-CL-co-acryloyloxyCL)
Poly(e-CL-co-acryloyloxyCL)
Poly(MMA-co-methacroyloxyEMA)
Poly(MMA-co-methacroyloxyEMA)
Poly(styrene-co- methacroyloxyEMA)
Poly(styrene-co- methacroyloxyEMA)
Poly(styrene-co- methacroyloxyEMA)
Poly(styrene-co- methacroyloxyEMA)
Nanoparticles
Mw/Mn Tg [C]
1.35
1.08
1.32
1.35
1.34
1.29
1.45
1.60
68
62
77
60
98
90
105
95
Conv.
[%] [c]
72
88
90
88
92
85
85
85
Mn [d]
SEC
11600
9000
14500
15600
20000
15000
57000
47000
Mw/Mn
1.35
1.10
1.21
1.25
1.34
1.20
1.50
1.50
Tg [e]
[C]
45
120
124
125
130
Rh [f]
[nm]
4.3
3.8
5.5
6.5
6.2
5.4
13.1
9.2
[a] Molar fraction of (meth)acrylic units in the copolymer. [b] Number average molecular weight measured by SEC using poly(styrene)
calibration standards. [c] Conversion of (meth)acrylic units as measured by 1H NMR. [d] Number average molecular weight measured
by SEC using poly(styrene) calibration standards. [e] Glass transition temperature as measured by DSC. [f] Hydrodynamic radius as
measured by DLS in THF.
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Scheme 3.
Fig. 2. SEC of 4 poly(methyl methacrylate-co-methacryloyloxyethyl methacrylate) (entry 1d) precursor Mn = 32 000 g/mol, Mw/Mn = 1.35; 5 poly(methyl
methacrylate) crosslinked nanoparticle Mn = 15 600 g/mol, Mw/Mn = 1.20; and 6
poly(methyl methacrylate) linear analog Mn = 31 000 g/mol, Mw/Mn = 1.35.
206
Characterization of the nanoparticles by dynamic light scattering (DLS) in tetrahydrofuran (THF) reveals that the sizes
are very small (Rh = 3.813.1 nm, Table 1). To our knowledge,
this range of sizes, which is characteristic of dendrimers and
some micelles, has never been reached before for a nanoparticle. Furthermore, the results indicate that the size of the particle increases with the molecular weight of the functionalized
precursor. This provides some external control over the nano-
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Experimental
Scheme 4.
Materials: Toluene and THF were dried by refluxing over sodium and distilled under nitrogen prior to use. The e-caprolactone (eCL) was dried over
CaH2 and distilled under reduced pressure. The samples were stored under a
dry nitrogen atmosphere until use. All other chemicals were purchased from
Aldrich Chemical Co. and used without further purification.
Synthesis of Crosslinkable Macromolecules: ROP Using Al(OiPr)3: Poly(ecaprolactone-co-4-acryloyloxycaprolactone) random copolymers were prepared
as reported elsewhere [6].
Synthesis of Poly(methyl methacrylate-co-hydroxyethyl methacrylate) Copolymers by Atom Transfer Radical Polymerization (ATRP): In a typical experiment, methyl methacrylate (9 eq.), hydroxyethyl methacrylate (1 eq.), ethyl
2-bromoisobutyrate (0.03 eq.), and NiBr2(PPh)3 (0.03 eq.) were added to a
glass reactor. The flask was then closed with a three-way stopcock and a cycle
of vacuum-nitrogen purges was repeated three times to remove the oxygen.
After reaction at 85 C for 14 h, the polymer was recovered in 85 % yield by
precipitation in hexanes after dissolution in THF; SEC (Mn = 22 000 g/mol, Mw/
Mn = 1.32); 1H NMR (CDCl3) d 4.06, 3.79, 3.56, 2.260.8(m).
Synthesis of Poly(styrene-co-hydroxyethyl methacrylate): A mixture of the
hydrido alkoxyamine (2,2,5-trimethyl-3-(1-phenylethyoxy)-4-phenyl-3-azahexane) (1 eq.), styrene (90 eq.), and 2-hydroxyethyl methacrylate (10 eq.) was
degassed in three freeze/thaw cycles, sealed under argon and heated at 125 C
for 10 h. The viscous mixture was then dissolved in THF and precipitated in
cold hexanes as a white powder in 7090 % yield; SEC (Mn = 9000 g/mol, Mw/
Mn = 1.15); 1H NMR (CDCl3) d 7.25.6, 33.5, 11.8.
General Procedure for Reaction of Methacrylic Acid with Hydroxyethyl
Methacrylic Pendant Groups: A poly(methyl methacrylate0.9-co-hydroxyethyl
methacrylate0.1) (Mn = 22 000 g/mol, Mw/Mn = 1.30) (3 g, 3 mmol of hydroxyethyl units), methacrylic acid (0.534 g, 6 mmol), and triphenylphosphine (1.5 g,
6 mmol) were dissolved in 30 mL of dry THF. To this mixture (1.21 g, 6 mmol)
of diisopropyl azodicarboxylate (DIAD) were added drop-wise. After 14 h
reaction at room temperature the polymer was quantitatively recovered by precipitation in hexanes; SEC (Mn = 22 000 g/mol, Mw/Mn = 1.30); 1H NMR
(CDCl3) d 6.13, 5.61, 4.30, 4.66, 3.56, 2.260.8(m).
General Procedure for the Preparation of Self-Crosslinked Nanoparticles: In
a typical experiment, a mixture of 0.2 g of poly(methyl methacrylate0.92-comethacryoyloxyethyl methacrylate0.08) (Mn = 22 000 g/mol, Mw/Mn = 1.32)
(0.2 mmol of methacrylic groups) and AIBN (0.02 mmol) were dissolved in
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500 mL of toluene. The mixture was degassed by bubbling N2 for 15 min and
heated for 10 h at 65 C. After reaction, the solvent was evaporated and the
polymer was dissolved in 2 mL of THF and precipitated in an excess of hexanes
(0.18 g, 90 %); SEC (Mn = 14 500 g/mol, Mw/Mn = 1.21); 1H NMR (CDCl3)
d 4.30, 4.66, 3.56, 2.260.8(m).
Characterization: 1H NMR and 13C NMR spectra were recorded with a Bruker AM 250 (250 MHz) spectrometer. SEC was carried out on a Waters chromatograph connected to a Waters 410 differential refractometer, using polystyrene of known molecular weight as the calibration standards. Four 5 lm Waters
columns (300 7.7 mm) connected in series in order of increasing pore size
(100, 1000, 105, and 106 ) were used with THF as elution solvent. Glass transition temperatures were measured in a modulated DSC 2920 TA Instrument
using a 4 C/min heating rate. DLS measurements were performed using a 2 W
Lexel model 95 argon ion laser (k = 514.5 nm) at a power of 500 mW. The scattered light intensity was measured at an angle of 90.0. Samples of 10 mg/mL in
HPLC grade THF were prepared in test tubes which were previously cleaned in
acetone in an ultrasonic bath. The samples were transferred via a syringe filter
(Whatman Anatop 10 0.2 lm) into a second test tube. Data acquisition lasted
3 min and was stored on a Brookhaven Instruments BI-9000 correlator. The
temperature was held constant at 25 C by a Neslab circulating bath.
Received: June 19, 2000
Final version: September 25
[1] Y. Xia, B. Gates, Y. Yin, Y. Lu, Adv. Mater. 2000, 12, 693.
[2] K. Landferter, W. Bechthold, S. Forster, M. Antonietti, J. Macromol. Rapid
Commun. 1999, 20, 81.
[3] Q. Zhang, E. E. Remsem, K. L. Wooley, J. Am. Chem. Soc. 2000, published on the web. K. B. Thurmond, T. Kowalewski, K. L. Wooley, J. Am.
Chem. Soc. 1997, 119, 6656. A. Guo, G. Liu, J. Tao, Macromolecules 1996,
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[4] J. M. Frechet, Science 1994, 263, 1710. G. R. Newkome, Advances in Dendritic Macromolecules, JAI Press, Greenwich, CT 19941995, Vols. 12.
[5] a) M. Antonietti, Angew. Chem. Int. Ed. 1998, 27, 1743. b) V. A. Davankov,
M. M. Ilyin, M. P. Tsyurupa, G. I. Timofeeva, L. V. Dubrovina, Macromolecules 1996, 29, 8398.
[6] D. Mecerreyes, R. D. Miller, J. L. Hedrick, P. Lecomte, C. Detrembleur,
R. Jerome, J. Macromol. Rapid Commun., in press.
[7] D. Benoit, V. Chaplinski, R. Braslau, C. J. Hawker, J. Am. Chem. Soc.
1999, 121, 3904. K. Matyjaszewski, in Controlled Radical Polymerization,
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[8] K. Roovers, D. Toporowski, Macromolecules 1983, 16, 483.
[9] R. D. Miller, Science 1999, 286, 421. C. Nguyen, K. Carter, C. J. Hawker,
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Solvatochromism of a Copper(II)
(Tetramethylethylenediamine)(acetylacetonate)+
Complex Encapsulated in EMT Zeolite Cages**
By Julia L. Meinershagen and Thomas Bein*
The inclusion of the copper chelate CuII(N,N,N,N-tetramethylethylenediamine)(acetylacetonate)+ in the nanopores
of hexagonal faujasite type zeolites has been studied for optical sensing applications. Optical vapor sensing of analytes has
[**] The authors acknowledge Dr. D. E. De Vos for measuring the solution
phase EPR spectra and for many helpful discussions.
208
vent independent representation of the donor ability of a molecule.[7,11] The Cu(tmen)(acac)+ complex shows impressive
color changes in going from weakly donating to strongly
donating solvents. For example, a pink color is observed for a
solution of Cu(tmen)(acac)BPh4 in the non-donating solvent
dichloroethane (DN = 0), whereas in the strongly donating
solvent piperidine (DN = 52.3) the solution is green. Noting
the strong solvent effects in the solution phase, it was anticipated that by ion exchanging the chelate into zeolites, an optical sensor related to solvent basicity was feasible. The goals of
this work were to relate geometrical changes of the copper
complex to optical responses. Electron paramagnetic spectroscopy proved to be an invaluable tool for better understanding
of the axial coordination and resulting changes in the d orbital
energy levels. Finally, demonstration of optical responses and
sensing properties were shown.
The zeolite used was the large pore hexagonal faujasite type
zeolite EMT. EMT is comprised of hexagonally packed sodalite cages connected by double six rings giving rise to 6.9
7.2 windows leading into 13 14 hyper-cages,[12] with an
average crystal size of 10 lm. These small windows leading to
large cages are ideal for encapsulating a wide range of functional molecules.
Cu(tmen)(acac)ClO4 was prepared according to a published
procedure.[6] The compound was recrystallized and the perchlorate anion was exchanged for tetraphenylborate (BPh4)
in order to assure ion exchange, excluding the large BPh4
anion which can not penetrate into the zeolite pores.[8,13] The
purity was determined by infrared (IR) and chemical ioniza-
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