title: Enantiomeric interactions between liquid crystals and organized monolayers of tyrosine-containing dipeptides.
abstract: We have examined the orientational ordering of nematic liquid crystals (LCs) supported on organized monolayers of dipeptides with the goal of understanding how peptide-based interfaces encode intermolecular interactions that are amplified into supramolecular ordering. By characterizing the orientations of nematic LCs (4-cyano-4'-pentylbiphenyl and TL205 (a mixture of mesogens containing cyclohexane-fluorinated biphenyls and fluorinated terphenyls)) on monolayers of l-cysteine-l-tyrosine, l-cysteine-l-phenylalanine, or l-cysteine-l-phosphotyrosine formed on crystallographically textured films of gold, we conclude that patterns of hydrogen bonds generated by the organized monolayers of dipeptides are transduced via macroscopic orientational ordering of the LCs. This conclusion is supported by the observation that the ordering exhibited by the achiral LCs is specific to the enantiomers used to form the dipeptide-based monolayers. The dominant role of the -OH group of tyrosine in dictating the patterns of hydrogen bonds that orient the LCs was also evidenced by the effects of phosphorylation of the tyrosine on the ordering of the LCs. Overall, these results reveal that crystallographic texturing of gold films can direct the formation of monolayers of dipeptides with long-range order, thus unmasking the influence of hydrogen bonding, chirality, and phosphorylation on the macroscopic orientational ordering of LCs supported on these surfaces. These results suggest new approaches based on supramolecular assembly for reporting the chemical functionality and stereochemistry of synthetic and biological peptide-based molecules displayed at surfaces.
authors.affiliation: Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, USA.
authors.forename: Yiqun
authors.initials: Y
authors.lastname: Bai
authors.forename: Nicholas L
authors.initials: NL
authors.lastname: Abbott
mesh_terms: D004151:Dipeptides / Q000737:chemistry*; D050866:Liquid Crystals / Q000737:chemistry*; D010748:Phosphopeptides / Q000737:chemistry; D011485:Protein Binding; D013237:Stereoisomerism; D013499:Surface Properties; D014443:Tyrosine
chemical_list: D004151:Dipeptides; D010748:Phosphopeptides; D014443:Tyrosine
references.citation: Science. 2009 Jul 24;325(5939):452-6
references.pmid: 19628863
references.citation: Langmuir. 2005 Jul 5;21(14):6451-61
references.pmid: 15982053
references.citation: Proc Natl Acad Sci U S A. 1996 Oct 1;93(20):10566-71
references.pmid: 8855218
references.citation: J Phys Chem B. 2008 Apr 3;112(13):4022-35
references.pmid: 18331017
references.citation: ACS Appl Mater Interfaces. 2010 Mar;2(3):722-31
references.pmid: 20356273
references.citation: J Am Chem Soc. 2007 Sep 12;129(36):11223-31
references.pmid: 17705384
references.citation: J Am Chem Soc. 2011 Feb 9;133(5):1438-50
references.pmid: 21208003
references.citation: Nat Biotechnol. 2002 Mar;20(3):270-4
references.pmid: 11875428
references.citation: J Am Chem Soc. 2004 Feb 11;126(5):1563-8
references.pmid: 14759216
references.citation: Nat Mater. 2003 May;2(5):324-8
references.pmid: 12692537
references.citation: Angew Chem Int Ed Engl. 2005 Mar 18;44(13):1948-51
references.pmid: 15724264
references.citation: J Phys Chem B. 2007 Dec 13;111(49):13833-44
references.pmid: 18020441
references.citation: Biophys J. 2003 Feb;84(2 Pt 1):750-6
references.pmid: 12547759
references.citation: J Phys Chem B. 2006 Dec 28;110(51):26081-8
references.pmid: 17181261
references.citation: J Chem Phys. 2004 Jun 8;120(22):10792-8
references.pmid: 15268106
references.citation: Langmuir. 2011 May 17;27(10):5719-38
references.pmid: 21090596
references.citation: J Med Chem. 2006 Dec 28;49(26):7902-6
references.pmid: 17181174
references.citation: Methods Enzymol. 1989;177:263-82
references.pmid: 2607982
references.citation: Science. 1993 Jul 30;261(5121):585-8
references.pmid: 8342021
references.citation: Langmuir. 2010 Nov 2;26(21):16305-11
references.pmid: 20593799
references.citation: Anal Chem. 2009 Jul 1;81(13):5503-9
references.pmid: 19492802
references.citation: J Am Chem Soc. 2005 Aug 10;127(31):11047-52
references.pmid: 16076212
references.citation: Appl Spectrosc. 2009 Jul;63(7):767-74
references.pmid: 19589214
references.citation: Chem Rev. 1996 Jun 20;96(4):1533-1554
references.pmid: 11848802
references.citation: J Am Chem Soc. 2003 Aug 6;125(31):9359-66
references.pmid: 12889964
references.citation: ACS Nano. 2010 Feb 23;4(2):1218-26
references.pmid: 20092357
references.citation: Phys Rev E Stat Nonlin Soft Matter Phys. 2009 Dec;80(6 Pt 1):060701
references.pmid: 20365110
references.citation: Nature. 2002 Feb 21;415(6874):891-3
references.pmid: 11859364
references.citation: J Am Chem Soc. 2008 Jul 2;130(26):8188-94
references.pmid: 18528984
references.citation: J Am Chem Soc. 2011 Apr 27;133(16):6243-53
references.pmid: 21452815
references.citation: Proc Natl Acad Sci U S A. 2010 Oct 12;107(41):17497-502
references.pmid: 20876125
references.citation: Nat Biotechnol. 2001 Apr;19(4):317-8
references.pmid: 11283582
references.citation: Nano Lett. 2006 May;6(5):1053-8
references.pmid: 16683850
references.citation: Biochim Biophys Acta. 2007 Jun;1770(6):912-8
references.pmid: 17360121
references.citation: Langmuir. 2008 Sep 16;24(18):10390-4
references.pmid: 18489190
references.citation: J Phys Chem B. 2010 Nov 25;114(46):15319-30
references.pmid: 21043521
references.citation: J Mol Biol. 2001 Sep 14;312(2):393-404
references.pmid: 11554795
references.citation: J Am Chem Soc. 2004 Jul 28;126(29):9024-32
references.pmid: 15264835
references.citation: Langmuir. 2006 May 9;22(10):4654-9
references.pmid: 16649778
references.citation: Langmuir. 2010 Feb 2;26(3):1427-30
references.pmid: 19961190
references.citation: Langmuir. 2009 Jan 20;25(2):919-23
references.pmid: 19105790
references.citation: Langmuir. 2006 Aug 29;22(18):7776-82
references.pmid: 16922563
references.citation: Int J Biochem. 1992;24(1):19-28
references.pmid: 1582530
references.citation: Phys Rev Lett. 2010 Jun 25;104(25):257801
references.pmid: 20867414
references.citation: Biochemistry. 1987 Oct 20;26(21):6696-707
references.pmid: 3427038
references.citation: Phys Rev Lett. 1993 Apr 19;70(16):2447-2450
references.pmid: 10053564
references.citation: Langmuir. 2008 Oct 7;24(19):11282-6
references.pmid: 18781785
references.citation: Anal Chem. 2008 Apr 15;80(8):2637-45
references.pmid: 18355089