Preparation of poly(<italic>N</italic>-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography

doi:10.1007/s11706-012-0161-9

Frontiers of Materials Science

2012, Vol. 6

Issue (1): 60-68 https://doi.org/10.1007/s11706-012-0161-9

RESEARCH ARTICLE

本期目录

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 ZHANG^1,2, 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

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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 (M_w/M_n=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.

Key words： poly(N-isopropylacrylamide) (PNIPAAm) atom transfer radical polymerization (ATRP) temperature-responsive chromatography separation

收稿日期: 2012-01-09 出版日期: 2012-03-05

Corresponding Author(s): DAI Rong-Ji,Email:dairongji@bit.edu.cn (R.J.D.); DENG Yu-Lin,Email:deng@bit.edu.cn (Y.L.D.)

引用本文:

. Preparation of poly(N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography[J]. Frontiers of Materials Science, 2012, 6(1): 60-68.
Zong-Jian LIU, Yan-Li LIANG, Fang-Fang GENG, Fang LV, Rong-Ji DAI, Yu-Kui ZHANG, Yu-Lin DENG. Preparation of poly(N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography. Front Mater Sci, 2012, 6(1): 60-68.

链接本文:

https://academic.hep.com.cn/foms/CN/10.1007/s11706-012-0161-9
https://academic.hep.com.cn/foms/CN/Y2012/V6/I1/60

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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

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