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Licensed Unlicensed Requires Authentication Published by Oldenbourg Wissenschaftsverlag March 6, 2018

Surface Enhanced DNP Assisted Solid-State NMR of Functionalized SiO2 Coated Polycarbonate Membranes

Bharti Kumari, Daniel John, Paul Hoffmann, Anne Spende, Maria Eugenia Toimil-Molares, Christina Trautmann, Christian Hess, Philip Ruff, Marcus Schulze, Robert Stark, Gerd Buntkowsky, Annette Andrieu-Brunsen and Torsten Gutmann

Abstract

Surface enhanced solid-state NMR by dynamic nuclear polarization (DNP SENS) enables the characterization of the inner-pore surface functionalization of porous etched ion-track membranes exhibiting low specific surface areas compared to typical SBA- or MCM-type mesoporous silica materials. The membranes were conformally coated with a 5 nm thin SiO2 layer by atomic layer deposition. This layer was subsequently modified by aminopropyl silane linkers that allow further functionalization via the terminal amine group. The results evidence that in principle DNP SENS is a capable tool to analyze more complex porous systems, e.g. bioinspired functional etched ion-track membranes down to the molecular level. These results are relevant also for single nanopore systems, for which a direct analysis of the channel surface functionalization is not feasible by classical characterization methods. The applicability of DNP SENS to complex porous systems requires the optimization of the sample preparation and measurement parameters.

Acknowledgments

This work has been supported by the DFG under contract Bu 911/20-1 (DNP spectrometer) and FOR1583 Grant Nos. Bu 911-18-2, HE 4515/4-2. The authors further thank the project iNAPO by the Hessen State Ministry of Higher Education, Research and the Arts for financial support.

References

1. Z. Ezzeddine, I. Batonneau-Gener, Y. Pouilloux, H. Hamad, Z. Saad, V. Kazpard, Microporous Mesoporous Mater. 212 (2015) 125.10.1016/j.micromeso.2015.03.013Search in Google Scholar

2. Q. Wen, D. Yan, F. Liu, M. Wang, Y. Ling, P. Wang, P. Kluth, D. Schauries, C. Trautmann, P. Apel, W. Guo, G. Xiao, J. Liu, J. Xue, Y. Wang, Adv. Funct. Mater. 26 (2016) 5796.10.1002/adfm.201601689Search in Google Scholar

3. J. Duan, J. Liu, Y. Zhang, C. Trautmann, D. Y. Lei, J. Mater. Chem. C 4 (2016) 3956.10.1039/C5TC03897ASearch in Google Scholar

4. I. Schubert, L. Burr, C. Trautmann, M. E. Toimil-Molares, Beilstein J. Nanotechnol. 6 (2015) 1272.10.3762/bjnano.6.131Search in Google Scholar PubMed

5. G. Pérez-Mitta, C. Trautmann, M. E. Toimil-Molares, O. Azzaroni, Single Ion Track-Etched Nanochannels for Analytical Applications, in “Chemically Modified Nanopores and Nanochannels” (Eds. M. Tagliazucchi, I. Szleifer), William Andrew, Elsevier (2016), P. 61.Search in Google Scholar

6. R. Spohr, Vol. Patent DE 2951376 C2, Germany (1979).Search in Google Scholar

7. A. Mara, Z. Siwy, C. Trautmann, J. Wan, F. Kamme, Nano Lett. 4 (2004) 497.10.1021/nl035141oSearch in Google Scholar

8. I. Vlassiouk, T. R. Kozel, Z. S. Siwy, J. Am. Chem. Soc. 131 (2009) 8211.10.1021/ja901120fSearch in Google Scholar PubMed

9. K. Healy, B. Schiedt, A. P. Morrison, Nanomedicine 2 (2007) 875.10.2217/17435889.2.6.875Search in Google Scholar

10. R. L. Fleischer, P. B. Price, R. M. Walker, Nuclear Tracks in Solids: Principles and Applications, University of California Press, Berkeley (1975).10.1525/9780520320239Search in Google Scholar

11. A. Spende, N. Sobel, M. Lukas, R. Zierold, J. C. Riedl, L. Gura, I. Schubert, J. M. M. Moreno, K. Nielsch, B. Stuehn, C. Hess, C. Trautmann, M. E. Toimil-Molares, Nanotechnology 26 (2015) 335301.10.1088/0957-4484/26/33/335301Search in Google Scholar PubMed

12. N. Sobel, C. Hess, M. Lukas, A. Spende, B. Stühn, M. E. Toimil-Molares, C. Trautmann, Beilstein J. Nanotechnol. 6 (2015) 472.10.3762/bjnano.6.48Search in Google Scholar PubMed

13. J. Blümel, Coord. Chem. Rev. 252 (2008) 2410.10.1016/j.ccr.2008.06.013Search in Google Scholar

14. J. R. Rapp, Y. Huang, M. Natella, Y. Cai, V. S. Y. Lin, M. Pruski, Solid State Nucl. Mag. Res. 35 (2009) 82.10.1016/j.ssnmr.2008.12.004Search in Google Scholar

15. J. W. Wiench, Y. S. Avadhut, N. Maity, S. Bhaduri, G. K. Lahiri, M. Pruski, S. Ganapathy, J. Phys. Chem. B 111 (2007) 3877.10.1021/jp067417xSearch in Google Scholar PubMed

16. T. Gutmann, A. Grünberg, N. Rothermel, M. Werner, M. Srour, S. Abdulhussain, S. Tan, Y. Xu, H. Breitzke, G. Buntkowsky, Solid State Nucl. Mag. Res. 55 (2013) 1.10.1016/j.ssnmr.2013.06.004Search in Google Scholar

17. M. Geppi, S. Borsacchi, G. Mollica, C. A. Veracini, Appl. Spectrosc. Rev. 44 (2009) 1.10.1080/05704920802352564Search in Google Scholar

18. H. Koller, M. Weiss, Solid State NMR of Porous Materials Zeolites and Related Materials, in “Solid State NMR”, (Ed. J. C. C. Chan), Springer-Verlag, Berlin, Heidelberg, Vol. 306 (2012), P. 189–227.10.1007/128_2011_123Search in Google Scholar

19. A. Lesage, M. Lelli, D. Gajan, M. A. Caporini, V. Vitzthum, P. Miéville, J. Alauzun, A. Roussey, C. Thieuleux, A. Medhi, G. Bodenhausen, C. Copéret, L. Emsley, J. Am. Chem. Soc. 132 (2010) 15459.10.1021/ja104771zSearch in Google Scholar PubMed

20. R. G. Griffin, Nature 468 (2010) 381.10.1038/468381aSearch in Google Scholar PubMed

21. M. Werner, A. Heil, N. Rothermel, H. Breitzke, P. B. Groszewicz, A. S. Thankamony, T. Gutmann, G. Buntkowsky, Solid State Nucl. Magn. Reson. 72 (2015) 73.10.1016/j.ssnmr.2015.09.008Search in Google Scholar PubMed

22. A. J. Rossini, A. Zagdoun, M. Lelli, A. Lesage, C. Copéret, L. Emsley, Acc. Chem. Res. 46 (2013) 1942.10.1021/ar300322xSearch in Google Scholar PubMed

23. M. Lelli, D. Gajan, A. Lesage, M. A. Caporini, V. Vitzthum, P. Miéville, F. Héroguel, F. Rascón, A. Roussey, C. Thieuleux, M. Boualleg, L. Veyre, G. Bodenhausen, C. Coperet, L. Emsley, J. Am. Chem. Soc. 133 (2011) 2104.10.1021/ja110791dSearch in Google Scholar PubMed

24. W. R. Gruening, A. J. Rossini, A. Zagdoun, D. Gajan, A. Lesage, L. Emsley, C. Coperet, Phys. Chem. Chem. Phys. 15 (2013) 13270.10.1039/c3cp00026eSearch in Google Scholar PubMed

25. A. Zagdoun, G. Casano, O. Ouari, G. Lapadula, A. J. Rossini, M. Lelli, M. Baffert, D. Gajan, L. Veyre, W. E. Maas, M. Rosay, R. T. Weber, C. Thieuleux, C. Coperet, A. Lesage, P. Tordo, L. Emsley, J. Am. Chem. Soc. 134 (2012) 2284.10.1021/ja210177vSearch in Google Scholar PubMed

26. T. Kobayashi, O. Lafon, A. S. Lilly Thankamony, I. I. Slowing, K. Kandel, D. Carnevale, V. Vitzthum, H. Vezin, J.-P. Amoureux, G. Bodenhausen, M. Pruski, Phys. Chem. Chem. Phys. 15 (2013) 5553.10.1039/c3cp00039gSearch in Google Scholar PubMed

27. E. Pump, J. Viger-Gravel, E. Abou-Hamad, M. K. Samantaray, B. Hamzaoui, A. Gurinov, D. H. Anjum, D. Gajan, A. Lesage, A. Bendjeriou-Sedjerari, L. Emsley, J. M. Basset, Chem. Sci. 8 (2017) 284.10.1039/C6SC02379GSearch in Google Scholar PubMed

28. M. P. Conley, R. M. Drost, M. Baffert, D. Gajan, C. Elsevier, W. T. Franks, H. Oschkinat, L. Veyre, A. Zagdoun, A. Rossini, M. Lelli, A. Lesage, G. Casano, O. Ouari, P. Tordo, L. Emsley, C. Coperet, C. Thieuleux, Chem. Eur. J. 19 (2013) 12234.10.1002/chem.201302484Search in Google Scholar

29. T. Gutmann, J. Liu, N. Rothermel, Y. Xu, E. Jaumann, M. Werner, H. Breitzke, S. T. Sigurdsson, G. Buntkowsky, Chem. Eur. J. 21 (2015) 3798.10.1002/chem.201405043Search in Google Scholar

30. A. Zagdoun, A. J. Rossini, M. P. Conley, W. R. Gruening, M. Schwarzwalder, M. Lelli, W. T. Franks, H. Oschkinat, C. Coperet, L. Emsley, A. Lesage, Angew. Chem. Int. Ed. 52 (2013) 1222.10.1002/anie.201208699Search in Google Scholar

31. A. R. Mouat, T. Kobayashi, M. Pruski, T. J. Marks, P. C. Stair, J. Phys. Chem. C 121 (2017) 6060.10.1021/acs.jpcc.6b11196Search in Google Scholar

32. A. J. Rossini, A. Zagdoun, M. Lelli, D. Gajan, F. Rascon, M. Rosay, W. E. Maas, C. Coperet, A. Lesage, L. Emsley, Chem. Sci. 3 (2012) 108.10.1039/C1SC00550BSearch in Google Scholar

33. O. Lafon, A. S. L. Thankamony, T. Kobayashi, D. Carnevale, V. Vitzthum, I. I. Slowing, K. Kandel, H. Vezin, J.-P. Amoureux, G. Bodenhausen, M. Pruski, J. Phys. Chem. C 117 (2013) 1375.10.1021/jp310109sSearch in Google Scholar

34. D. Lee, G. Monin, N. T. Duong, I. Z. Lopez, M. Bardet, V. Mareau, L. Gonon, G. De Paepe, J. Am. Chem. Soc. 136 (2014) 13781.10.1021/ja506688mSearch in Google Scholar PubMed

35. U. Akbey, B. Altin, A. Linden, S. Ozcelik, M. Gradzielski, H. Oschkinat, Phys. Chem. Chem. Phys. 15 (2013) 20706.10.1039/c3cp53095gSearch in Google Scholar PubMed

36. D. Gajan, M. Schwarzwälder, M. P. Conley, W. R. Gruning, A. J. Rossini, A. Zagdoun, M. Lelli, M. Yulikov, G. Jeschke, C. Sauvee, O. Ouari, P. Tordo, L. Veyre, A. Lesage, C. Thieuleux, L. Emsley, C. Coperet, J. Am. Chem. Soc. 135 (2013) 15459.10.1021/ja405822hSearch in Google Scholar PubMed

37. A. S. L. Thankamony, O. Lafon, X. Y. Lu, F. Aussenac, M. Rosay, J. Trebosc, H. Vezin, J. P. Amoureux, Appl. Magn. Reson. 43 (2013) 237.10.1007/s00723-012-0364-3Search in Google Scholar

38. G. S. Foo, J. J. Lee, C. H. Chen, S. E. Hayes, C. Sievers, C. W. Jones, ChemSusChem 10 (2017) 266.10.1002/cssc.201600809Search in Google Scholar PubMed

39. E. Ravera, V. K. Michaelis, T. C. Ong, E. G. Keeler, T. Martelli, M. Fragai, R. G. Griffin, C. Luchinat, Chemphyschem 16 (2015) 2751.10.1002/cphc.201500549Search in Google Scholar PubMed

40. T. Kobayashi, D. Singappuli-Arachchige, Z. R. Wang, Slowing, II, M. Pruski, Phys. Chem. Chem. Phys. 19 (2017) 1781.10.1039/C6CP07642DSearch in Google Scholar PubMed

41. J. Q. Liu, P. B. Groszewicz, Q. B. Wen, A. S. L. Thankamony, B. Zhang, U. Kunz, G. Sauer, Y. P. Xu, T. Gutmann, G. Buntkowsky, J. Phys. Chem. C 121 (2017) 17409.10.1021/acs.jpcc.7b06807Search in Google Scholar

42. T. Gutmann, B. Kumari, L. Zhao, H. Breitzke, S. Schöttner, C. Rüttiger, M. Gallei, J. Phys. Chem. C 121 (2017) 3896.10.1021/acs.jpcc.6b11751Search in Google Scholar

43. G. Mollica, D. Le, F. Ziarelli, G. Casano, O. Ouari, T. N. T. Phan, F. Aussenac, P. Thureau, D. Gigmes, P. Tordo, S. Viel, ACS Macro Lett. 3 (2014) 922.10.1021/mz500459pSearch in Google Scholar

44. P. V. Der Voort, E. F. Vansant, J. Liq. Chromatogr. Relat. Technol. 19 (1996) 2723.10.1080/10826079608015107Search in Google Scholar

45. A. Spende, PhD Thesis, TU Darmstadt (2016).Search in Google Scholar

46. M. F. P. Wagner, F. Völklein, H. Reith, C. Trautmann, M. E. Toimil-Molares, Phys. Status Solidi B 213 (2016) 610.10.1002/pssa.201532616Search in Google Scholar

47. I. Scholz, P. Hodgkinson, B. H. Meier, M. Ernst, J. Chem. Phys. 130 (2009) 114510.10.1063/1.3086936Search in Google Scholar PubMed

48. A. E. Bennett, C. M. Rienstra, M. Auger, K. V. Lakshmi, R. G. Griffin, J. Chem. Phys. 103 (1995) 6951.10.1063/1.470372Search in Google Scholar

49. A. Grünberg, X. Yeping, H. Breitzke, G. Buntkowsky, Chem. Eur. J. 16 (2010) 6993.10.1002/chem.200903322Search in Google Scholar

50. K. Albert, R. Brindle, J. Schmid, B. Buszewski, E. Bayer, Chromatographia 38 (1994) 283.10.1007/BF02269769Search in Google Scholar

Supplementary Material:

The online version of this article offers supplementary material (https://doi.org/10.1515/zpch-2017-1032).

Received: 2017-09-08
Accepted: 2018-02-14
Published Online: 2018-03-06
Published in Print: 2018-07-26

©2018 Walter de Gruyter GmbH, Berlin/Boston