Conclusions and Future Work

In this work a small library of dihydropyranones have been synthesised on a surface through an isothiourea-mediated Michael addition-lactonisation procedure using a range of arylacetic acids. The conversions were in the range of 40-70% and as such this methodology offers an effective route to build a variety of complex surfaces containing this functionality. As this was a proof of concept study only a small range of arylacetic acids were tested but the consistency of this methodology suggests that a wide range of phenylacetic acid derivatives could be applied providing a flexible methodology for surface functionalisation.

It has also been shown in solution that these types of dihydropyranone motifs are prone to ring opening by a range of nucleophiles [174] _{which opens up the possibility for covalent attachment of}

an external nucleophile, such as a protein or amino acid. Such strategies may have applications in biosensor technologies. Several of the resulting dihydropyranones also contain useful functional handles that may allow for further modification, such as transition metal mediated cross-coupling and SNAr reactions.

2.15 References and Notes

[116] K. Bierbaum, M. Kinzler, C. Woell, M. Grunze, G. Haehner, S. Heid, F. Effenberger,

Langmuir 1995, 11, 512-518.

[117] T. Ohtake, N. Mino, K. Ogawa, Langmuir 1992, 8, 2081-2083.

[116] D. K. Aswal, S. Lenfant, D. Guerin, J. V. Yakhmi, D. Vuillaume, Anal. Chim. Acta 2006,

568, 84-108.

[117] W. Kern, J. Electrochem. Soc. 1990, 137, 1887-1892. [118] D. K. Schwartz, Annu. Rev. Phys. Chem. 2001, 52, 107-137.

[119] N. Rozlosnik, M. C. Gerstenberg, N. B. Larsen, Langmuir 2003, 19, 1182-1188.

[120] T. Vallant, H. Brunner, U. Mayer, H. Hoffmann, T. Leitner, R. Resch, G. Friedbacher, J. Phys. Chem. B. 1998, 102, 7190-7197.

[121] Y. Liu, L. K. Wolf, M. C. Messmer, Langmuir 2001, 17, 4329-4335.

[122] J. V. Davidovits, V. Pho, P. Silberzan, M. Goldmann, Surf. Sci. 1996, 352–354, 369-373. [123] L. Sanga, K. M. Knesting, A. Bulusuc, A. K. Sigdel, A. J. Giordanoe, S. R. Marder, J. J.

Berry, S. Graham, D. S. Ginger, J. E. Pemberton, Appl. Surf. Sci., 2016, 389, 190-198. [124] W. Gao , L. Dickinson, C. Grozinger, F. G. Morin, L. Reven, Langmuir, 1996, 12, 6429-

6435.

[125] C. Carraro, O. W. Yauw, M. M. Sung, R. Maboudian, J. Phys. Chem. B. 1998, 102, 4441- 4445.

[126] Y. Cheng, B. Zheng, P. Chuang, S. Hsieh, Langmuir 2010, 26, 8256-8261.

[127] S. G. Moussa, B. J. Finlayson-Pitts, Phys. Chem. Chem. Phys. 2010, 12, 9419-9428. [128] F. Bournel, F. Jolly, F. Rochet, G. Dufour, F. Sirotti, P. Torelli, Phys. Rev. B. 2000, 62,

7645-7653.

[129] A. P. Dementjev, A. de Graaf, M. C. M. van de Sanden, K. I. Maslakov, A. V. Naumkin, A. A. Serov, Diamond Relat. Mater. 2000, 9, 1904-1907.

62 [130] F. R. McFeely, S. P. Kowalczyk, L. Ley, R. G. Cavell, R. A. Pollak, D. A. Shirley, Phys.

Rev. B. 1974, 9, 5268-5278.

[131] D. Janssen, R. De Palma, S. Verlaak, P. Heremans, W. Dehaen, Thin Solid Films 2006,

515, 1433-1438.

[132] A. Razgon, R. G. Bergman, C. N. Sukenik, Langmuir 2008, 24, 2545-2552. [133] R. F. Heck, J. P. Nolley, J. Org. Chem. 1972, 37, 2320-2322.

[134] I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009-3066. [135] R. Franzén, Can. J. Chem. 2000, 78, 957-962.

[136] S. R. Puniredd, O. Assad, T. Stelzner, S. Christiansen, H. Haick, Langmuir 2011, 27, 4764-4771.

[137] K. E. Plass, X. Liu, B. S. Brunschwig, N. S. Lewis, Chem. Mater. 2008, 20, 2228-2233. [138] M. C. Pirrung, Angew. Chem. Int. Ed. 2002, 41, 1276-1289.

[139] Y. Dubowski, J. Vieceli, D. J. Tobias, A. Gomez, A. Lin, S. A. Nizkorodov, T. M. McIntire, B. J. Finlayson-Pitts, J. Phys. Chem. A. 2004, 108, 10473-10485.

[140] L. R. Fiegland, M. McCorn Saint Fleur, J. R. Morris, Langmuir 2005, 21, 2660-2661. [141] A. W. Snow, G. G. Jernigan, M. G. Ancona, Analyst 2011, 136, 4935-4949.

[142] J. W. Lu, L. R. Fiegland, E. D. Davis, W. A. Alexander, A. Wagner, R. D. Gandour, J. R. Morris, J. Phys. Chem. C. 2011, 115, 25343-25350.

[143] J. Vieceli, O. L. Ma, D. J. Tobias, J. Phys. Chem. A. 2004, 108, 5806-5814.

[144] C. Rogero, B. T. Chaffey, E. Mateo-Martí, J. M. Sobrado, B. R. Horrocks, A. Houlton, J. H. Lakey, C. Briones, J. A. Martín-Gago, J. Phys. Chem. C. 2008, 112, 9308-9314. [145] A. Hozumi, H. Taoda, T. Saito, N. Shirahata, Surf. Interface Anal. 2008, 40, 408-411. [146] L. Horner, H. Hoffmann, H. G. Wippel, G. Klahre, Chem. Ber. 1959, 92, 2499-2505. [147] L. Horner, H. Hoffmann, H. G. Wippel, Chem. Ber. 1958, 91, 61-63.

[148] K. Tamura, H. Mizukami, K. Maeda, H. Watanabe, K. Uneyama, J. Org. Chem. 1993,

58, 32-35.

[149] J. K. Lee, Y. S. Chi, I. S. Choi, Langmuir 2004, 20, 3844-3847. [150] F. Shamsi, H. Coster, K. A. Jolliffe, Surf. Sci. 2011, 605, 1763-1770. [151] S. Zheng, Q. Yang, B. Mi, Appl. Surf. Sci. 2016, 363, 619-626.

[152] S. Pookpanratana, I. Savchenko, S. N. Natoli, S. P. Cummings, L. J. Richter, J. W. F. Robertson, C. A. Richter, T. Ren, C. A. Hacker, chem, 30, 10280-10289.

[153] N. Balachander, C. N. Sukenik, Langmuir 1990, 6, 1621-1627.

[154] J. Böhmler, A. Ponche, K. Anselme, L. Ploux, ACS Appl. Mater. Inter. 2013, 5, 10478- 10488.

[155] Y. S. Cohen, A. Vilan, I. Ron, D. Cahen, J. Phys. Chem. C. 2009, 113, 6174-6181. [156] S. Zhang, J. T. Koberstein, Langmuir 2012, 28, 486-493.

[157] W. R. Ashurst, C. Carraro, R. Maboudian, IEEE T. Device. Mat. Re. 2003, 3, 173-178. [158] Y. X. Zhuang, O. Hansen, T. Knieling, C. Wang, P. Rombach, W. Lang, W. Benecke, M.

Kehlenbeck, J. Koblitz, J. Microelectromech. Syst. 2007, 16, 1451-1460.

[159] T. Koga, M. Morita, H. Ishida, H. Yakabe, S. Sasaki, O. Sakata, H. Otsuka, A. Takahara,

Langmuir 2005, 21, 905-910.

[160] E. Darlatt, A. Nefedov, C. H. H. Traulsen, J. Poppenberg, S. Richter, P. M. Dietrich, A. Lippitz, R. Illgen, J. Kühn, C. A. Schalley, C. Wöll, W. E. S. Unger, J. Electron. Spectrosc. Relat. Phenom. 2012, 185, 621-624.

[161] T. Heinrich, C. H. H. Traulsen, E. Darlatt, S. Richter, J. Poppenberg, N. L. Traulsen, I. Linder, A. Lippitz, P. M. Dietrich, B. Dib, W. E. S. Unger, C. A. Schalley, RSC Adv.

2014, 4, 17694-17702.

[162] C. H. Haensch, S.; Schubert, U. S., Nanotechnology 2008, 19, 035703.

[163] X. Song, Y. Ma, C. Wang, P. M. Dietrich, W. E. S. Unger, Y. Luo, J. Phys. Chem. C.

2012, 116, 12649-12654.

[164] D. S. B. Daniels, S. R. Smith, T. Lebl, P. Shapland, A. D. Smith, Synthesis 2015, 47, 34- 41.

63 [165] M. James, S. Ciampi, T. A. Darwish, T. L. Hanley, S. O. Sylvester, J. J. Gooding,

Langmuir 2011, 27, 10753-10762.

[166] J. Wang, F. Wu, M. Watkinson, J. Zhu, S. Krause, Langmuir 2015, 31, 9646-9654. [167] T. Palacin, H. L. Khanh, B. Jousselme, P. Jegou, A. Filoramo, C. Ehli, D. M. Guldi, S.

Campidelli, J. Am. Chem. Soc. 2009, 131, 15394-15402.

[168] P.-J. Wei, G.-Q. Yu, Y. Naruta, J.-G. Liu, Angew. Chem. Int. Ed. 2014, 53, 6659-6663. [169] M. Giesbers, A. T. M. Marcelis, H. Zuilhof, Langmuir 2013, 29, 4782-4788.

[170] S. Diegoli, P. M. Mendes, E. R. Baguley, S. J. Leigh, P. Iqbal, Y. R. Garcia Diaz, S. Begum, K. Critchley, G. D. Hammond, S. D. Evans, D. Attwood, I. P. Jones, J. A. Preece,

J. Exp. Nanosci. 2006, 1, 333-353.

[171] F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen, R. Taylor, J. Chem. Soc. Perkin Trans. 2 1987, S1-S19.

[172] S. P. Pujari, E. Spruijt, M. A. Cohen Stuart, C. J. M. van Rijn, J. M. J. Paulusse, H. Zuilhof, Langmuir 2012, 28, 17690-17700.

[173] S. R. Wasserman, Y. T. Tao, G. M. Whitesides, Langmuir, 1989, 5, 1074–1087.

[174] N. Attaba, J. E. Taylor, A. M. Z. Slawin, A. D. Smith, J. Org. Chem. 2015, 80, 9728- 9739.

64