Please wait a minute...

Frontiers of Materials Science

Front Mater Sci    2012, Vol. 6 Issue (1) : 60-68     DOI: 10.1007/s11706-012-0161-9
RESEARCH ARTICLE |
Preparation of poly(N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography
Zong-Jian LIU1, Yan-Li LIANG1, Fang-Fang GENG1, Fang LV1, Rong-Ji DAI1(), Yu-Kui ZHANG1,2, Yu-Lin DENG1()
1. School of Life Science, Beijing Institute of Technology, Beijing 100081, China; 2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
Download: PDF(214 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes were densely grafted onto silica surface via surface-initiated atom transfer radical polymerization (SI-ATRP). The grafting reaction started from the surfaces of 2-bromoisobutyrate-functionalized silica particles in 2-propanol aqueous solution at ambient temperature using CuCl/CuCl2/N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) as the catalytic system. Based on thermogravimetric analysis (TGA) results, the grafting amount and grafting density of PNIPAM chains on the surface of silica were calculated to be 1.29 mg/m2 and 0.0215 chains/nm2, respectively. The gel permeation chromatography (GPC) result showed the relatively narrow molecular weight distribution (Mw/Mn=1.21) of the grafted PNIPAAm. The modified silica particles were applied as high-performance liquid chromatography (HPLC) packing materials to successfully separate three aromatic compounds using water as mobile phase by changing column temperature. Temperature-dependent hydrophilic/hydrophobic property alteration of PNIPAAm brushes grafted on silica particles was determined with chromatographic interaction between stationary phase and analytes. Retention time was prolonged and resolution was improved with increasing temperature. Baseline separation with high resolution at relatively low temperatures was observed, demonstrating dense PNIPAAm brushes were grafted on silica surfaces.

Keywords poly(N-isopropylacrylamide) (PNIPAAm)      atom transfer radical polymerization (ATRP)      temperature-responsive chromatography      separation     
Corresponding Authors: DAI Rong-Ji,Email:dairongji@bit.edu.cn (R.J.D.); DENG Yu-Lin,Email:deng@bit.edu.cn (Y.L.D.)   
Issue Date: 05 March 2012
 Cite this article:   
Zong-Jian LIU,Yan-Li LIANG,Fang-Fang GENG, et al. Preparation of poly(N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography[J]. Front Mater Sci, 2012, 6(1): 60-68.
 URL:  
http://journal.hep.com.cn/foms/EN/10.1007/s11706-012-0161-9
http://journal.hep.com.cn/foms/EN/Y2012/V6/I1/60
Service
E-mail this article
E-mail Alert
RSS
Articles by authors
Zong-Jian LIU
Yan-Li LIANG
Fang-Fang GENG
Fang LV
Rong-Ji DAI
Yu-Kui ZHANG
Yu-Lin DENG
Fig.1  Preparation of PNIPAAm grafted silica surface via surface-initiated atom transfer radical polymerization (SI-ATRP).
Fig.2  FT-IR spectra of 3-aminopropyl silica (a), 2-bromoisobutyrate-functionalized silica (b), and PNIPAAm grafted silica (c).
Fig.3  TGA curves of 3-aminopropyl silica (a), 2-bromoisobutyrate-functionalized silica (b), and PNIPAAm grafted silica (c).
Fig.4  GPC of the PNIPAAm grafted on silica surfaces. The PNIPAAm brushes were cleaved from silica particles via etching with hydrofluoric acid.
CodeElemental composition /%a)mp/(mg·m-2)Mnb)MW/Mnb)Grafting density /(chains·nm-2)
NCH
3-aminopropyl silica0.762.520.73
2-bromoisobutyrate-functionalized silica0.673.850.86
PNIPAAm-grafted silica3.6218.543.421.2936,2001.210.0215
Tab.1  Characterization of silica particles
Fig.5  DSC curves of 2-bromoisobutyrate-functionalized silica (a) and PNIPAAm grafted silica (b).
Fig.6  Chromatogram of aromatic compounds on PNIPAAm grafted silica packed column at various temperatures. Mobile phase, water; flow rate, 0.3 mL/min. Detection wavelength: 254 nm. Peaks: 1, toluene; 2, diphenyl ketone; 3, biphenyl.
Fig.7  Temperature dependency of the retention time on PNIPAAm grafted silica packed column: biphenyl (a); diphenyl ketone (b); toluene (c).
Fig.8  The van’t Hoff plots of aromatic compounds on the PNIPAAm grafted silica column with water as the mobile phase: biphenyl (a); diphenyl ketone (b); toluene (c).
1 Heskins M, Guillet J E. Solution properties of poly(N-isopropylacrylamide). Journal of Macromolecular Science: Part A- Chemistry , 1968, 2(8): 1441-1455
2 Takei Y G, Aoki T, Sanui K, . Dynamic contact angle measurement of temperature-responsive surface properties for poly(N-isopropylacrylamide) grafted surfaces. Macromolecules , 1994, 27(21): 6163-6166
3 Sun T L, Wang G J, Feng L, . Reversible switching between superhydrophilicity and superhydrophobicity. Angewandte Chemie International Edition , 2004, 43(3): 357-360
4 Idota N, Nagase K, Tanaka K, . Stereoregulation of thermoresponsive polymer brushes by surface-initiated living radical polymerization and the effect of tacticity on surface wettability. Langmuir , 2010, 26(23): 17781-17784
5 Rao G V R, Krug M E, Balamurugan S, . Synthesis and characterization of silica-poly(N-isopropylacrylamide) hybrid membranes: Switchable molecular filters. Chemistry of Materials , 2002, 14(12): 5075-5080
6 Fu Q, Rao G V R, Ista L K, . Control of molecular transport through stimuli-responsive ordered mesoporous materials. Advanced Materials , 2003, 15(15): 1262-1266
7 Guan Y Q, Li Z B, Wang X, . Synthesis of a kind of temperature-responsive cell culture surface for corneal sheet. Journal of Materials Science and Technology , 2010, 26(12): 1119-1126
8 Yan C, Elaissari A, Pichot C. Loading and release studies of proteins using poly(N-isopropylacrylamide) based nanogels. Journal of Biomedical Nanotechnology , 2006, 2(3-4): 208-216
9 Shamim N, Hong L, Hidajat K, . Thermosensitive-polymer-coated magnetic nanoparticles: adsorption and desorption of bovine serum albumin. Journal of Colloid and Interface Science , 2006, 304(1): 1-8
10 Nagase K, Kobayashi J, Kikuchi A, . Thermally-modulated on/off-adsorption materials for pharmaceutical protein purification. Biomaterials , 2011, 32(2): 619-627
11 Huber D L, Manginell R P, Samara M A, . Programmed adsorption and release of proteins in a microfluidic device. Science , 2003, 301(5631): 352-354
12 Hosoya K, Kimata K, Araki T, . Temperature-controlled high-performance liquid chromatography using a uniformly sized temperature-responsive polymer-based packing material. Analytical Chemistry , 1995, 67(11): 1907-1911
13 Go H, Sudo Y, Hosoya K, . Effects of mobile-phase composition and temperature on the selectivity of poly(N-isopropylacrylamide)-bonded silica gel in reversed-phase liquid chromatography. Analytical Chemistry , 1998, 70(19): 4086-4093
14 Lynen F, Heijl J M D, Du Prez F E, . Evaluation of the temperature responsive stationary phase poly(N-isopropylacrylamide) in aqueous LC for the analysis of small molecules. Chromatographia , 2007, 66(3-4): 143-150
15 Song Y-X, Wang J-Q, Su Z-X, . High-performance liquid chromatography on silica modified with temperature-responsive polymers. Chromatographia , 2001, 54(3-4): 208-212
16 Kanazawa H, Yamamoto K, Matsushima Y, . Temperature-responsive chromatography using poly(N-isopropylacrylamide)-modified silica. Analytical Chemistry , 1996, 68(1): 100-105
17 Kanazawa H, Kashiwase Y, Yamamoto K, . Temperature-responsive liquid chromatography. 2. Effects of hydrophobic groups in N-isopropylacrylamide copolymer-modified silica. Analytical Chemistry , 1997, 69(5): 823-830
18 Kanazawa H, Matsushima Y, Okano T. Temperature-responsive chromatography. Trends in Analytical Chemistry , 1998, 17(7): 435-440
19 Yakushiji T, Sakai K, Kikuchi A, . Effects of cross-linked structure on temperature-responsive hydrophobic interaction of poly(N-isopropylacrylamide) hydrogel-modified surfaces with steroids. Analytical Chemistry , 1999, 71(6): 1125-1130
20 Idota N, Kikuchi A, Kobayashi J, . Thermal modulated interaction of aqueous steroids using polymer-grafted capillaries. Langmuir , 2006, 22(1): 425-430
21 Ayano E, Okada Y, Sakamoto C, . Study of temperature-responsibility on the surfaces of a thermo-responsive polymer modified stationary phase. Journal of Chromatography A , 2006, 1119(1-2): 51-57
22 Ayano E, Nambu K, Sakamoto C, . Aqueous chromatography system using pH- and temperature-responsive stationary phase with ion-exchange groups. Journal of Chromatography A , 2006, 1119(1-2): 58-65
23 Roohi F, Antonietti M, Titirici M M. Thermo-responsive monolithic materials. Journal of Chromatography A , 2008, 1203(2): 160-167
24 Kobayashi J, Kikuchi A, Sakai K, . Aqueous chromatography utilizing pH-/temperature-responsive polymer stationary phases to separate ionic bioactive compounds. Analytical Chemistry , 2001, 73(9): 2027-2033
25 Kobayashi J, Kikuchi A, Sakai K, . Aqueous chromatography utilizing hydrophobicity-modified anionic temperature-responsive hydrogel for stationary phases. Journal of Chromatography A , 2002, 958(1-2): 109-119
26 Kanazawa H, Sunamoto T, Ayano E, . Temperature-responsive chromatography using poly(N-isopropylacrylamide) hydrogel-modified silica. Analytical Sciences , 2002, 18(1): 45-48
27 Sakamoto C, Okada Y, Kanazawa H, . Temperature- and pH-responsive aminopropyl-silica ion-exchange columns grafted with copolymers of N-isopropylacrylamide. Journal of Chromatography A , 2004, 1030(1-2): 247-253
28 Kanazawa H, Ayano E, Sakamoto C, . Temperature-responsive stationary phase utilizing a polymer of proline derivative for hydrophobic interaction chromatography using an aqueous mobile phase. Journal of Chromatography A , 2006, 1106(1-2): 152-158
29 Liu Z J, Dai R J, Liang X, . Preparation of temperature-responsive chromatographic materials containing acidic groups for separation of amino acids. Transactions of Beijing Institute of Technology , 2011, 31(9): 1104-1108 (in Chinese)
30 Kanazawa H, Yamamoto K, Kashiwase Y, . Analysis of peptides and proteins by temperature-responsive chromatographic system using N-isopropylacrylamide polymer-modified columns. Journal of Pharmaceutical and Biomedical Analysis , 1997, 15(9-10): 1545-1550
31 Kanazawa H, Nishikawa M, Mizutani A, . Aqueous chromatographic system for separation of biomolecules using thermoresponsive polymer modified stationary phase. Journal of Chromatography A , 2008, 1191(1-2): 157-161
32 Mizutani A, Nagase K, Kikuchi A, . Preparation of thermo-responsive polymer brushes on hydrophilic polymeric beads by surface-initiated atom transfer radical polymerization for a highly resolutive separation of peptides. Journal of Chromatography A , 2010, 1217(38): 5978-5985
33 Dai R J, Chen L, Liu Z J, . Preparation and characterization of temperature-responsive chromatographic column containing poly(N-isopropylacrylamide) and poly([2-(methacryloyloxy)-ethyl]trimetylammonium chloride). Journal of Applied Polymer Science , 2011, 121(4): 2233-2238
34 Dai R J, Zhang X J, Hu N, . Preparation and characterization of temperature-responsive capillary electrochromatographic column using poly(N-isopropylacrylamide). Electrophoresis , 2009, 30(4): 616-617
35 Nagase K, Kobayashi J, Kikuchi A, . Interfacial property modulation of thermoresponsive polymer brush surfaces and their interaction with biomolecules. Langmuir , 2007, 23(18): 9409-9415
36 Nagase K, Kobayashi J, Kikuchi A, . Effects of graft densities and chain lengths on separation of bioactive compounds by nanolayered thermoresponsive polymer brush surfaces. Langmuir , 2008, 24(2): 511-517
37 Kim D J, Kang S M, Kong B, . Formation of thermoresponsive gold nanoparticle/PNIPAAm hybrids by surface-initiated, atom transfer radical polymerization in aqueous media. Macromolecular Chemistry and Physics , 2005, 206(19): 1941-1946
38 Fulghum T M, Estillore N C, Vo C-D, . Stimuli-responsive polymer ultrathin films with a binary architecture: Combined layer-by-layer polyelectrolyte and surface-initiated polymerization approach. Macromolecules , 2008, 41(2): 429-435
39 Seino M, Yokomachi K, Hayakawa T, . Preparation of poly(N-isopropylacrylamide) grafted silica bead using hyperbranched polysiloxysilane as polymer brush and application to temperature-responsive HPLC. Polymer , 2006, 47(6): 1946-1952
40 Nagase K, Kobayashi J, Kikuchi A, . Preparation of thermoresponsive cationic copolymer brush surfaces and application of the surface to separation of biomolecules. Biomacromolecules , 2008, 9(4): 1340-1347
41 Nagase K, Kobayashi J, Kikuchi A, . Preparation of thermoresponsive anionic copolymer brush surfaces for separating basic biomolecules. Biomacromolecules , 2010, 11(1): 215-223
42 Ye J, Narain R. Water-assisted atom transfer radical polymerization of N-isopropylacrylamide: nature of solvent and temperature. The Journal of Physical Chemistry B , 2009, 113(3): 676-681
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed