Comparison of Chromatographic Performance for L-Phenylalanine-Derived Organic Phases on Silica by “Grafting from” and “Grafting to” Strategies
Mohammed Mizanur Rahman, Makoto Takafuji, Hirotaka Ihara
DOI: 10.4236/ajac.2011.27091   PDF    HTML     4,496 Downloads   7,926 Views  


L-phenylalanine-derived polymerizable organogel, N’-octadecyl-Nα-(4-vinyl)-benzoyl-L-phenylalanineami- de (4) has been prepared according to the procedure described elsewhere. Compound 4 was successfully polymerized by surface initiated atom transfer radical polymerization (ATRP) from the initiator grafted silica particles (sil-poly4). It was also telomerized with 3-mercaptopropyltrimethoxysilane (MPS) and the telomer (T4) was grafted on to silica (sil-T4). TGA and elemental analysis measurement revealed that higher amount of polymer can graft by ATRP process than that of “grafting to” strategy. The results of 13C CP/MAS NMR measurement showed that the N-alkyl chain of the grafted polymers for both sil-poly4 and sil-T4 remained as less ordered gauche conformational form on silica surface and no inversion to trans form was occurred until temperature is increased up to 50?C. The retention of alkylbenzene samples showed that sil-poly4 prepared by “grafting from” method yielded extremely higher retention than conventional C18 phase however, sil-T4 prepared by conventional “grafting to” method showed lower retention than C18 phase. Aspects of molecular recognition were evaluated by the retention studies of a series of polycyclic aromatic hydrocarbons (PAHs) and aromatic positional isomers. We have observed sil-T4 yielded slightly higher selectivity for PAHs than sil-poly4 regardless the fact that it has low surface coverage and lower hydrophobic interactions. The enhanced selectivity observed for sil-T4 than C18 phases and sil-poly4 can be explained by the π - π interactions between the guest PAHs and carbonyl groups present in the polymer chain. In addition the aromatic moieties of compound 4 that aggregates through π - π interactions also contribute to the separation of PAHs for both sil-poly4 and sil-T4. The minimal π - π interactions between the carbonyl groups and guest molecules for sil-poly4 probably due to the presence of long chain initiator which restrict the polymer to form order thin layer over silica surface.

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M. Rahman, M. Takafuji and H. Ihara, "Comparison of Chromatographic Performance for L-Phenylalanine-Derived Organic Phases on Silica by “Grafting from” and “Grafting to” Strategies," American Journal of Analytical Chemistry, Vol. 2 No. 7, 2011, pp. 795-808. doi: 10.4236/ajac.2011.27091.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] S. B. Roscoe, A. K. Kakkar, T. J. Marks, A. Malik, M. K. Durbin, W. Lin, G. K. Wong and P. Dutta, “Self-Assembled Chromophoric NLO-Active Monolayers. X-Ray Reflectivity and Second-Harmonic Generation as Complementary Probes of Building Block-Film Micro-structure Relationships,” Langmuir, Vol. 12, No. 17, 1996, pp. 4218-4223. doi:10.1021/la950142k
[2] Y. N. Xia, M. Mrksich, E. Kim and G. M. Whitesides, “Microcontact Printing of Octadecylsiloxane on the Sur-face of Silicon Dioxide and Its Application in Microfa-brication,” Journal of the American Chemical Society, Vol. 117, No. 37, 1995, pp. 9576-9577. doi:10.1021/ja00142a031
[3] X. Y. Huang and M. J. Wirth, “Surface-Initiated Radical Polymerization on Porous Silica,” Analytical Chemistry, Vol. 69, No. 22, 1997, pp. 4577-4580. doi:10.1021/ac9704523
[4] C. A. Chang, H. Abdel-Aziz, N. Melchor, Q. H. Wu, K. H. Pannell and D. W. Armstrong, “Liquid Chromato-graphic Retention Behavior of Organometallic Compounds and Ligands with Amine-, Octadecylsilica- and Beta-Cyclodextrin-Bonded Phase Columns,” Journal of Chromatography A, Vol. 347, 1985, pp. 51-60. doi:10.1016/S0021-9673(01)95468-8
[5] A. Zlatkis, R. P. J. Ranatunga and B. S. Middleditch, “Concentration of Organics from Aqueous Solutions Us-ing Uncoated Capillary Columns,” Analytical Chemistry, Vol. 62, No. 22, 1990, pp. 2471-2478. doi:10.1021/ac00221a012
[6] D. Schmalzing, C. A. Piggee, F. Foret, E. Carrilho and B. L. Karger, “Characterization and Performance of a Neutral Hydrophilic Coating for the Capillary Electrophoretic Separation of Biopolymers,” Journal of Chromatography A, Vol. 652, No. 1, 1993, pp. 149-159. doi:10.1016/0021-9673(93)80655-R
[7] M. Chiari, N. Dell’Orto and A. GelainChiari, “Synthesis and Characterization of Capillary Columns Coated with Glycoside-Bearing Polymer,” Analytical Chemistry, Vol. 68, No. 17, 1996, pp. 2731-2736. doi:10.1021/ac960158v
[8] Unger and K. K. P. Silica, “Its Properties and Use as Sup-port in Column Liquid Chromatography,” Elsevier, Amsterdam, 1979.
[9] B. Zhao and W. J. Brittain, “Synthesis of Polystyrene Brushes on Silicate Substrates via Carbocationic Polyme-rization from Self-Assembled Monolayers,” Macromole-cules, Vol. 33, No. 2, 2000, pp. 342-348. doi:10.1021/ma9910181
[10] M. Hessemann, D. Mecerreyes, C. J. Hawker, J. L. He-drich, R. Shah and N. L. Abbott, “Polymerization for Amplification of Self-Assembled Monolayers Patterned by Microcontact Printing,” General & Introductory Che-mistry, Vol. 38, No. 5, 1999, pp. 647-649. doi:10.1002/(SICI)1521-3773(19990301)38:5<647::AID-ANIE647>3.0.CO;2-0
[11] J. M. Song, F. M. Winnik and J. L. Brash, “Synthesis and Solution Properties of Fluorescently Labeled Amphiphilic (N-alkylacrylamide) Oligomers,” Macromolecules, Vol. 31, No. 1, 1998, pp. 109-115. doi:10.1021/ma971111u
[12] G. J. Kluth, M. M. Sung and R. Maboudian, “Interaction of H(D) Atoms with Octadecylsiloxane Self-Assembled Monolayers on the Si(100) Surface,” Langmuir, Vol. 13, No. 24, 1997, pp. 6491-6496. doi:10.1021/la970641g
[13] R. Zajac and A. Chakrabarti, “Irreversible Polymer Ad-sorption from Semidilute and Moderately Dense Solu-tions,” Physical Review E, Vol. 52, No. 6, 1995, pp. 6536-6549. doi:10.1103/PhysRevE.52.6536
[14] K. Matyjaszewski, “Controlled-Living Radical Polyme-rization: Progress in ATRP, NMP and RAFT,” American Chemical Society, Washington, D. C., 2000.
[15] J.-S. Wang and K. Matyjaszewski, “Controlled/“Living” Radical Polymerization. Atom Transfer Radical Polyme-rization in the Presence of Transition-Metal Complexes,” Journal of the American Chemical Society, Vol. 117, No. 20, 1995, pp. 5614-5615. doi:10.1021/ja00125a035
[16] M. Kato, M. Kamigaito, M. Sawamoto and T. Higashi-mura, “Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris-(triphenylphosphine) ruthenium(II)/Methylaluminum Bis (2,6-di-tert-butylphe- noxide) Initiating System: Possibility of Living Radical Polymerization,” Maromolecules, Vol. 28, No. 5, 1995, pp. 1721-1723. doi:10.1021/ma00109a056
[17] A. M. Balachandra, G. L. Baker and M. L. Bruening, “Preparation of Composite Membranes by Atom Transfer Radical Polymerization Initiated from a Porous Support,” Journal of Membrane Science, Vol. 227, No. 1-2, 2003, pp. 1-14. doi:10.1016/j.memsci.2003.07.009
[18] K. Yamada, H. Ihara, T. Ide, T. Fukumoto and C. Hirayama, “Formation of Helical Super Structure from Single-Walled Bilayers by Amphiphiles with Oligo-L-Glutamic Acid-Head Group,” Chemistry Letters, 1984, pp. 4821-4822.
[19] H. Hachisako, H. Ihara, C. Hirayama and K. Ya-mada, “Chirally Arranged Monomeric Dyes on Helical Bilayer Membranes,” Liquid Crystals, Vol. 13, No. 2, 1993, pp. 307-311. doi:10.1080/02678299308026304
[20] H. Hachisako, T. Yamazaki, H. Ihara, C. Hirayama and K. Yamada, “Formation of Specific Hydrophobic Sites for Incorporation of Methylene Blue by Laterally Arranged L-Glutamate Residues in Anionic, Crystalline Bilayer Aggregates,” Journal of the Chemical Society, Perkin Transactions 2, No. 7, 1994, pp. 1671-1680. doi:10.1039/p29940001671
[21] H. Ihara, M. Takafuji, C. Hirayama and D. F. O’Brien, “Effect of Photopolymerization on the Morphology of Helical Supramolecular Assemblies,” Langmuir, Vol. 8, No. 6, 1992, pp. 1548-1553. doi:10.1021/la00042a010
[22] H. Ihara, M. Takafuji and T. Sakurai, “Encyclopedia of Nanoscience and Nanotechnology,” American Scientific Publishers, Stevenson Ranch, 2004, p. 473.
[23] M. Takafuji, M. M. Rahman, M. Derakshan, H. R. Ansa-rian and H. Ihara, “Dioctadecyl L-Glutamide-Derived Li-pid- Grafted Silica as a Novel Organic Stationary Phase for RP-HPLC,” Journal of Chromatography A, Vol. 1074, No. 1-2, 2005, pp. 223-228. doi:10.1016/j.chroma.2005.03.090
[24] M. M. Rahman, M. Takafuji, H. R. Ansarian and H. Ihara, “Molecular Shape Selectivity through Multiple Carbonyl-π Interactions with Noncrystalline Solid Phase for RP-HPLC,” Analytical Chemistry, Vol. 77, No. 20, 2005, pp. 6671-6681. doi:10.1021/ac050851v
[25] H. Ihara, T. Sagawa, Y. Goto and S. Nagaoka, “Crystal-line Polymer on Silica. Geometrical Selectivity for Azo-benzenes through Highly-Oriented Structure,” Polymer, Vol. 40, No. 10, 1999, pp. 2555-5562. doi:10.1016/S0032-3861(98)00485-6
[26] M. M. Rahman, M. Czaun, M. Takafuji and H. Ihara, “Synthesis, Self-Assembling Properties, and Atom Transfer Radical Polymerization of an Alkylated L-Phenylalanine-Derived Monomeric Organogel from Si-lica: A New Approach To Prepare Packing Materials for High- Performance Liquid Chromatography,” Chemi-stry―A European Journal, Vol. 14, No. 4, 2008, pp. 1312-1321. doi:10.1002/chem.200701302
[27] H. Ihara, M. Takafuji, C. Hirayama and D. F. O’Brien, “Effect of Photopolymerization on the Morphology of Helical Supramolecular Assemblies,” Langmuir, Vol. 8, No. 6, 1992, pp. 1548-1553. doi:10.1021/la00042a010
[28] H. R. Ansarian, M. Derakshan, M. M. Rahman, T. Sa- kurai, M. Takafuji, I. Taniguchi and H. Ihara, “Evalu- ation of Micro-Structural Features of a New Polymeric Organic Stationary Phase Grafted on Silica Surface: A Paradigm of Characterization of HPLC-Stationary Phases by a Combination of Suspension State 1H-NMR and Solid-State 13C-CP/MAS-NMR,” Analytica Chimica Act a, Vol. 547, 2005, pp 179-187.
[29] M. Chamberg, R. Parnas and Y. Cohen, “Graft Polyme-rization of Polyvinylpyrrolidone onto Silica,” Journal of Applied Polymer Science, Vol. 37, No. 10, 1989, pp. 2921-2931. doi:10.1002/app.1989.070371011
[30] T. I. Korányi and J. B. Nagy, “Distribution of Aluminum in Different Periodical Building Units of MOR and BEA Zeolites,” Journal of Physical Chemistry B, Vol. 109, No. 33, 2005, pp. 15791-15797. doi:10.1021/jp051793k
[31] D. M. Grant and B. V. Cheney, “Carbon-13 Magnetic Resonance. VII. Steric Perturbation of the Carbon-13 Chemical Shift,” Journal of the American Chemical So-ciety, Vol. 89, No. 21, 1967, pp. 5315-5316. doi:10.1021/ja00997a001
[32] A. E. Tonelli, F. C. Schiling and F. A. Bovey, “Confor-mational Origin of the Nonequivalent Carbon-13 NMR Chemical Shifts Observed for the Isopropyl Methyl Car-bons in Branched Alkanes,” Journal of the American Chemical Society, Vol. 106, No. 4, 1984, pp. 1157-1158. doi:10.1021/ja00316a079
[33] H. Englhardt and M. Jungheim, “Determination of Inor-ganic Anions, Carboxylic Acids and Amino Acids in Plant Matrices by Capillary Zone Electrophoresis,” Chromatographia, Vol. 45, No. 1, 1997, pp. 59-62. doi:10.1007/BF02505538
[34] K. Kimata, K. Iwaguchi, K. Jinno, R. Eksteen, K. Hosoya, M. Araki and N. Tanaka, The Journal of Chromato-graphic Science, Vol. 27, 1989, p. 721.
[35] A. Shundo, T. Sakurai, M. Takafuji, S. Nagaoka and H. Ihara, “Molecular-Length and Chiral Discriminations by Beta-Structural Poly(L-Alanine) on Silica,” Journal of Chromatography A, Vol. 1073, No. 1-2, 2005, pp. 169- 174. doi:10.1016/j.chroma.2004.08.062
[36] H. Ihara, W. Dong, T. Mimaki, M. Nishihara, T. Sakurai, M. Takafuji and S. Nagaoka, “Poly(4-Vinylpyridine) as Novel Organic Phase for RP-HPLC. Unique Selectivity for Polycyclic Aromatic Hydrocarbons,” Journal of Liquid Chromatography & Related Technologies, Vol. 26, No. 15, 2003, pp. 2473-2485. doi:10.1081/JLC-120023796
[37] H. A. Claessens, M. A. Van Straten, C. A. Cramers, M. Jezierska and B. Buszewski, Journal of Chromatography A, Vol. 826, 1998, p. 135.
[38] P. C. Sadek and P. W. Carr, The Journal of Chromato-graphic Science, Vol. 21, 1983, p. 314.
[39] K. Jinno, K. Yamamoto, H. Nagashima, T. Ueda and K. Itoh, “Silicas Chemically Bonded with Multidentate Phenyl Groups as Stationary Phases in Reversed-Phase Liquid Chromatography Used for Non-Planarity Recog-nition of Polycyclic Aromatic Hydrocarbons,” Journal of Chromatography A, Vol. 517, 1990, pp. 193-207. doi:10.1016/S0021-9673(01)95721-8
[40] K. Jinno, T. Ibuki, N. Tanaka, M. Okamoto, J. C. Fretzer, W. R. Biggs, P. R. Griffiths and M. J. Olinger, The Jour-nal of Chromatographic Science, Vol. 461, 1989, p. 209.
[41] H. A. Claessens, E. A. Vermeer and C. A. Cramers, LC-GC International, Vol. 6, 1993, p. 692.
[42] J. Layne, “Characterization and Comparison of the Chromatographic Performance of Conventional, Polar- Embedded, and Polar-Endcapped Reversed-Phase Liquid Chromatography Stationary Phases,” Journal of Chro-matography A, Vol. 957, No. 2, 2002, pp. 149-164. doi:10.1016/S0021-9673(02)00193-0
[43] J. E. O’Gara, B. A. Alden, T. H. Walter, J. S. Petersen, C. L. Niederlaender and U. D. Neue, “Simple Preparation of a C8 HPLC Stationary Phase with an Internal Polar Func-tional Group,” Analytical Chemistry, Vol. 67, No. 20, 1995, pp. 3809-3813. doi:10.1021/ac00116a032
[44] T. Czajkowska, I. Hrabovsky, B. Buszewski, R. K. Gilpin and M. Jaroniec, “Comparison of the Retention of Organic Acids on Alkyl and Alkylamide Chemically Bond- ed Phases,” Journal of Chromatography A, Vol. 691, No. 1-2, 1995, pp. 217-224. doi:10.1016/0021-9673(94)01034-C
[45] W. Wielandt, A. Ellwanger, K. Albert and E. Lindner, “n-Alkyl Fluorenyl Phases in Chromatography: I. Syn-thesis and Characterization,” Journal of Chromatography A, Vol. 805, No. 1-2, 1998, pp. 71-83. doi:10.1016/S0021-9673(98)00014-4
[46] A. Ellwanger, R. Brindle, M. Kaiser, W. Wielandt, E. Lindner and K. Albert, “n-Alkyl Fluorenyl Phases in Chromatography: II. Dynamic Behavior and High-Per- formance Liquid Chromatography Applications,” Journal of Chromatography A, Vol. 858, No. 2, 1999, pp. 133- 153. doi:10.1016/S0021-9673(99)00828-6
[47] R. Brindle and K. Albert, “Stationary Phases with Chem-ically Bonded Fluorene Ligands: A New Approach for Environmental Analysis of π-Electron Containing So-lutes,” Journal of Chromatography A, Vol. 757, No. 1-2, 1997, pp. 3-20. doi:10.1016/S0021-9673(96)00682-6
[48] K. Jinno and K. Kawasaki, “Correlation of the Retention Data of Polyaromatic Hydrocarbons Obtained on Various Stationary Phases Used in Normal- and Reversed-Phase Liquid Chromatography,” Chromatographia, Vol. 18, No. 1, 1984, pp. 44-46. doi:10.1007/BF02279465
[49] S. Sakaki, K. Kato, T. Miyazaki, K. Ohkubo, H. Ihara and C. Hirayama, The Journal of Chromatographic Science, Faraday Transaction 2, Vol. 9, 1993, p. 659.
[50] C. S. Sychov, M. M. Ilyin, V. A. Davankov and K. O. Sochilina, “Elucidation of Retention Mechanisms on Hypercrosslinked Polystyrene Used as Column Packing Material for High-Performance Liquid Chromatography,” Journal of Chromatography A, Vol. 1030, No. 1-2, 2004, pp. 17-24. doi:10.1016/j.chroma.2003.10.098
[51] E. S. P. Bouvier and S. A. Oehrle, LC-GC International, Vol. 8, 1995, p. 338.
[52] R. Brindle and K. Albert, “Stationary Phases with Chem-ically Bonded Fluorene Ligands: A New Approach for Environmental Analysis of π-Electron Containing So-lutes,” Journal of Chromatography A, Vol. 757, 1997, pp 3-20. doi:10.1016/S0021-9673(96)00682-6

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