Analysis of Oligopeptide Self-Assembled Monolayer Using XPS and AFM

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1 HWAHAK KONGHAK Vol. 41, No. 1, February, 2003, pp XPS AFM * Chikashi Nakamura**Jun Miyake** * **!"#, $%&'!( Higashi, Tsukuba , Japan (2002) 7* 30+,-, 2002) 11* 2+./) Analysis of Oligopeptide Self-Assembled Monolayer Using XPS and AFM Seong-Hun Song, Jin-Young Park, Woo-Sik Kim*, Chikashi Nakamura**, Jun Miyake** and Sang-Mok Chang Department of Chemical Engineering Dong-A University, 840 Hadan 2-dong, Saha-gu, Busan , Korea *Department of Chemical Engineering Kyunghee University, 1 Seochun-ri, Kiheung-eup, Yongin , Korea **Tissue Engineering Research Center, The National Institute of Advanced Industrial Science and Technology, Higashi, Tsukuba , Japan Received 30 July 2002; accepted 2 November 2002) Au!" #$% & '() *+.,-./ "5 6)789 PSP1: PSP24 ; MOPS <= >?@ AB (self-assembled monolayer; SAM) CD X-ray photoelectron spectroscopy(xps) atomic force microscopy(afm) ; BEF+. G : PSP2 HI" PSP1 HIJ+ Au?@ SAM KL K M () *N O P *Q) MOPS <=> RS T U VW0 O P *Q+. :!A XYZ [\]X ^_ SAM steric energy ` a b [: cdf+. Abstract Recently, the self-assembled monolayer(sam) of thiols on noble metals has been studied intensively. Oligopeptides such as PSP1(Tyr-Ala-Gly-Tyr-Cys) and PSP2(His-Ala-Ser-Tyr-Ser-Cys) with thiol group, which interact strongly with a typical cationic porphyrin derivative, are synthesized. Peptides adsorption from the liquid phase on Au has been studied using X-ray photoelectron spectroscopy(xps) and AFM image. XPS provides further evidence that the primary adsorbate species is bonded to Au through the sulfur atom. By the analysis of XPS spectra and AFM image, it is found that PSP2 is self-assembled better than PSP1 and the sulfur ion in MOPS buffer solution has an effect on the self-assembling performance. This result is coincident with the calculation result of steric energies of Au-Peptide bonded SAM structure. Key words: Self-Assembly, Self-Assembled Monolayer(SAM), XPS, AFM Nuzzo Allrar[1]Au,! " # $% &' ()[2, 3] *+,-./ : " ;<= monolayer; SAM)! A BC DE+,- F G 4 H! A BC " To whom correspondence should be addressed. smjang@mail.donga.ac.kr ;< I () 5J/0 12K L3 4,M, N,-C * += () 12F 5. " ;< O () Langmuir-Blodgett(LB)PQ 1R SPQ! TP UV- G2WXI, LBPQ 1RSPQ! YZ [G \]# ^_- 5. `aa bc Q d eq f gh ij,- = k 89 SAM!, TP! f@/xi lm 89 /0 :5. qr+= s tu j /, SAMC, ws+= qr )x# Ayz5[5]. )x sf { } 8~ 5. >%? TP! bc# /3 4 j,! ` 15

bcq Au $% g~# / k X-ray photoelectron spectroscopy (XPS)[13-18] C 45. ` C 5J TP Œj /3 4,A, %9 y k 89: SAM œª /3, 89: SAM [9 / / XPS 8g / atomic force microscopy(afm)# j/ xœ «/ 5.

2 16 Chikashi NakamuraJun Miyake 2I,-C bc qr+,- tu SAM 89/0 :5. bc s C 3 1 C- s 3 s ˆ Š= -Œ /, ` $Q Ž bc U@{ s U@{ 3t :5 5[6, 7]. a 9 j/ L, T,! 5J j ()[8, 9]C 2kX3 45.? 4K š9 5 œ m- () 3 43, / k *Q! 5J * žg ()[10] V Ÿ - C! () R ˆ A 1R SAM 89 Qo O () 123 4,A, SAM 89& ;< [9A )x# / / scanning tunneling microscopy(stm)[11, 12] 3C 45. bcq Au $% g~# / k X-ray photoelectron spectroscopy (XPS)[13-18] C 45. ` C 5J TP Œj /3 4,A, %9 y k 89: SAM œª /3, 89: SAM [9 / / XPS 8g / atomic force microscopy(afm)# j/ xœ «/ 5. %9 y ± ²³ 89: SAM XPS AFM,- «/3, ` $Q steric energy ] «/3 /M, U +,- µ0 K1 - / %9 y ˆ_ ¹ º/3 4»¼½Q! œš# C¾/ 3DE+ y - š9 À/ ` Á Œj %9 y PSP1Q PSP2 )x# Fig. 1 A yâw5. >%? ÃKÄ G 4CÅ bc 4 Cys# ÆÆ X3 4 PSP1(Tyr-Ala-Gly-Tyr-Cys)Q PSP2(His-Ala-Ser-Tyr-Ser- Cys) Fmoc 3g %9 TP[19] j y %9\](PepPlus 9050 synthesizer)- %9/ 3, oç/x È! y ¹g HPLC &ÉÊQ LibraKit RPC18 Ë7(Shimadzu) Œj/ oç Ì Œj / 5. l»íé# m¾&î R# Ç{ g~ 1RC Ï Pa mica Au# 2,000Å,- É Ð Ì Au Au(111) )x- Ñtu/ / É Ð \] Â 45 o C- 12&f annealing/ Œj/ 5. >%? TrifluorethanolQ 10 mm MOPS bufferj 0.5 mm Fig. 2. High-resolution Al K-α induced XPS spectra of the wide range of binding energy from a PSP1(a) and PSP2(b). Fig. 1. Structures of PSP1 and PSP Fig. 3. High-resolution Al K-α induced XPS spectra of the oxygen(1s) core levels from a PSP1(a) and PSP2(b) (A: from C-O binding).

3 XPS AFM! 17 Fig. 4. High-resolution Al K-α induced XPS spectra of the carbon(1s) core levels from a PSP1(a) and PSP2(b) (B: from benzene group, C: from CH 2 -S). y# jk&ò j 12&fÓn =ÔÕ Â &/ 3, Au SAM $Q XPS AFM# Ö/ =/ bc ÙK 4 j ` 2 k ÃKA3, bc Ú s s d /0 / 89 " ;<Û- ÆÆ %9 y PSP1Q PSP2 Au Q $% oc# Üo/ / Al K-α ¾ŒÝ j/ &Ò Ý XPS ÉÞß7 xœ/! $Q# Æ Æ Fig. 2(a) (b) AyÂW5. ` 3 XPS Üo,- K1 ÆÆ s kº/ ¼}# Gaussian/Lorentzial fitting TP j/ /3 à, á, Ú Æ s O/ âã ä5. à s O XPS ÉÞß7 k $Q Fig. 3(a) (b) Ay ÂW3, á s O k! Fig. 4(a) (b) AyÂW5. ` 3 >%? 4K \ ˆ 3 4 Ú s O k $ Q# Fig. 5(a) (b) AyÂW5. å æç- à (1s) èk éê 4K PSP1(Fig. 3(a)) YZ $%ëx ev= ì ¼} Ayí «/ PSP2(Fig. 3(b)) YZ ev î 5ï /A ¼}# ð m3 45. á (1s) èk éê PSP1(Fig. 4(a))Q PSP2(Fig. 4(b)) { "Œ ¼}# m3 45. >%? m_ ¹ º/3 4 Ú(2p) èk éê O $Q# âã PSP1(Fig. 5(a)) 5 ¼}# PSP2 (Fig. 5(b)) 6 ¼} AyA3 45. ÆÆ ¼} $%ëx ev MOPS ñòj SO 3 Ú s# AyÂM ev Fig. 5. High-resolution Al K-α induced XPS spectra of the sulfur(2p) core levels from a PSP1(a) and PSP2(b) (A, B: from SO 3 of MOPS, C: from SH of unbinding PSP2, D, E, F: from SH of binding PSP2). PSP1, PSP2 bc S# Ayz5. Ú XPS 2p ¼} óg 2p 1/2 Q 2p 3/2 ô ¼} œª $%ëx ev õ A ¼} 2p 1/2 kº/m, ev õ B¼} 2p 3/2 kº:5. ô ¼} + %k «/ 5. bc ˆ 165 ev õ!? + $% lö + AyÂM, ev õ? + $% bc# Ayz5. Ù ¼} + *à/ «/ MOPS ñòj ˆ Ú Q c 3 y ø! $% go+= J «G 45. Ù ¼}# $Q PSP1 Au +,- W ù, Ï ô t kº/ ô PSP1 Au? +,- $%K 4ú û G 4 3 î 12 SO 3 Au ÂX $% /3 4ú û G 4 5. ` 3 PSP2 Au +,- /3 4 ù ` ü t = ü PSP2 Au? + $% /3 4ú û G 43, î 12 SO 3 Au ÂX $% /3 4ú û G 45. ý PSP2 YZ, bc Au SAM 89 ù MOPS ñòj ˆ SO 3 ij 6 Au $% /3 PSP1 Y Z bc Au SAM 89 ù MOPS ñòj ˆ SO 3 ij 4 Au $% /3 4ú û G 45. ý MOPS ñòj PSP2 PSP toC ð $%/3 4ú û G 45. `aa bc SAM< 89&, ñòj ˆ Ú þÿ Æ/0 3k 5. Fig. 6(a) (b) Ú s $%/ Au(4f) èk éê ¼}# / Au : SAM< ô# *à G 45. SAM 89 ÌC Au œª3 4 Au¼}= 85 ev electron mean free path 5-10 ÅM escaping depth 2-3 nm= 3/ Ã/0 ñ Ø PSP1Q PSP2- ;< 53 o/ PSP1Q PSP2 Ì ô 2nm 5 i,- Æ:5. HWAHAK KONGHAK Vol. 41, No. 1, February, 2003

18 Chikashi NakamuraJun Miyake Fig. 6. High-resolution Al K-α induced XPS spectra of the gold(4f) core levels from a PSP1(a) (Thickness of PSP1 2 nm) and PSP2(b) (Thickness of PSP2 2-3 nm). `aa Fig.

$` 3 AFM 3ws X < ô # $QC XPS ;< ô Ã]/ 5. žñx 3[20, 21]: / ÃB+,- \ no g~ SAM )x Au ü s Ú s $%/ ù5. Au ü s Ú s $%53 o5, 89: ;< ô w %9 y# )9/3 4 )9@ w C gœ 453 Æ:5.$

4 18 Chikashi NakamuraJun Miyake Fig. 6. High-resolution Al K-α induced XPS spectra of the gold(4f) core levels from a PSP1(a) (Thickness of PSP1 2 nm) and PSP2(b) (Thickness of PSP2 2-3 nm). `aa Fig. 5 $Q PSP1, PSP2 Ÿô? +, - bc $% C 43 + C 4K Ã/0 < 89K 4,- ÆM, œª: < ôc PSP1 2nm# X Èä,A, PSP2 YZ 2-3 nmoc ô# AyÂW5. XPS $Q# =/ / PSP1Q PSP2 AFM 8g X# œª/ Fig. 7 AyÂW5. %9 y= PSP1Q PSP2 Au $%: y 4,Û- 0,- Ayí5. Fig. 7 C û G 4 PSP1(Fig. 7(a)) Y Z B 99/0 K 4,A, PSP2(Fig. 7 (b)) Y Z lm x /0 89K 4ú û G 45. $Q XPS $Q(Fig. 5(a), (b)) Ã]5. ` 3 AFM 3ws X < ô # $QC XPS ;< ô Ã]/ 5. žñx 3[20, 21]: / ÃB+,- \ no g~ SAM )x Au ü s Ú s $%/ ù5. Au ü s Ú s $%53 o5, 89: ;< ô w %9 y# )9/3 4 )9@ w C gœ 453 Æ:5. a o ÀO- Cambridge Soft Œ Chem Office(Version 5.0, Cambridge soft Corporation, USA) ßK# Œj/ Au bc $% PSP1Q PSP2 Ÿ & é,- *à += ;< PSP1! nm, PSP nmw5. $QC go+,- XPS$Q AFM 3 ws X "Œ/ 5. XPS AFM k K1 $Q MOPS ñòj PSP2 YZ PSP1 YZ 5 >%? ú û G 45. PSP1Q PSP2 >%? oc a w # 3 4 "- ZD \ 3 G 4! %9 y# )9/3 4 )9@ w5. a œ bc Au s 3 $%53 o/3 Au s 3 SAM Fig. 7. AFM Topography of Self-Assembled PSP1(a) and PSP2(b) onto gold surface of Mica(Dim. 250 nm 250 nm). 89 PSP1Q PSP2 steric energy )x# CHEM Office- )/, PSP1 YZ steric energy kcal/mol3, PSP2 Y Z steric energy kcal/mol- PSP1 PSP2 5 Ï t steric energy# AyÂW5. PSP1 SAM PSP2 SAM 5 u¹ +,- no g~# 5. ²³ ]I «/ð³ C PSP2 YZ PSP1 YZ 5 >%? ð 89 û G 43, $Q XPS AFM $Q Ã]/ bc# X %9 y PSP1Q PSP2 < 89 XPS AFM Ö/ âã ä3, ` $Q PSP2 YZ PSP1 YZ 5 Au >%? ð :5 Œ XPS AFM Ö/ S G 4W3, +,- *à: y # )9/ )9@ : SAM< steric energy w C Ü š/ 5. () 1Ñ@(KRF E00057) ()«- G 2W Œ 5.

5 1. Nuzzo, R. G. and Allara, D. L., Adsorption of Bifunctional Organic Disulfides on Gold Surfaces, J. Am. Chem. Soc., 105, 4481(1983). 2. Ulman, A., Formation and Structure of Self-Assembled Monolayers, Chem. Rev., 96(4), (1996). 3. Takiguchi, H. and Sato, K., Delicate Surface Reaction of Dialkyl Sulfide Self-Assembled Monolayers on Au(111), Langmuir, 16(4), (2000). 4. Ogawa, H., Takamura, T. and Shimoyama, Y., Self-Assembly Process of Alkanethiol Monolayers, Jpn. J. Appl. Phys., 38, (1999). 5. Strong, L. and Whitesides, G. M., Structures of Self-Assembled Monolayer Films of Organosulfur Compounds Adsorbed on Gold Single Crystals: Electron Diffraction Studies, Langmuir, 4(3), (1988). 6. Samant, M. G., Brown, C. A. and Gordon, J. G., Structure of an Ordered Self-Assembled Monolayer of Docosyl Mercaptan on Gold(111) by Surface X-ray Diffraction, Langmuir, 7(3), (1991). 7. Whitesides, G. M. and Laibinis, P. E., Wet Chemical Approaches to the Characterization of Organic Surfaces: Self-Assembled Monolayers, Wetting, and the Physical-Organic Chemistry of the Solid-Liquid Interface, Langmuir, 6(1), 87-96(1990). 8. Lawrence, D., Jiang, S. T. and Levett, M., Self-Assembling Supramolecular Complexes, Chem. Rev., 95, 2229(1995). 9. Yamada, R. and Uosaki, K., STM Investigation of the Self-Assembly Process of Decanethiol on Au (111), Denki Kagaku, 65(6), 440 (1997). 10. Whelan, C. M., Smyth, M. R. and Barnes, C. J., HREELS, XPS, and Electrochemical Study of Benzenethiol Adsorption on Au(111), Langmuir, 15(1), 116(1999). XPS AFM! Chiang, S., High-Resolution Imaging of the Self-Assembly of Organic Monolayers, Science, 272, 1123(1996). 12. Poirier, G. E. and Pylant, E. D., The Self-Assembly Mechanism of Alkanethiols on Au(111), Science, 272, (1996). 13. Takamura, T., Matsushita, K. and Shimoyama, Y., X-Ray Diffraction Study of Langmuir-Blodgett Films of Mn-Arachidate, Jpn. J. Appl. Phys., 35, (1996). 14. Castner, D. G., Hinds, K. and Granger, D. W., X-Ray Photoelectron Spectroscopy Sulfur 2p Study of Organic Thiol and Disulfide Binding Interactions with Gold Surfaces, Langmuir, 12(21), (1996). 15. Laibinis, P. E., Bain, C. D. and Whitesides, G. M., Attenuation of Photoelectrons in Monolayers of n-alkanethiols Adsorbed on Copper, Silver, and Gold, J. Phys. Chem., 95, (1991). 16. Walezak, M. M., Alves, C. A., Lamp, B. D., Porter, F. and Electroanal, J., Electroanal. Chem., 396, 103(1995). 17. Jager, B., Schurmann, H., Muller, H. U., Himmel, H. J., Neumann, M., Grunze, M. and Woll, Ch. Z., Phys. Chem., 202, 263(1997). 18. Biebuyck, H. A., Bain, C. D. and Whitesides, G. M., Comparison of Organic Monolayers on Polycrystalline Gold Spontaneously Assembled from Solutions Containing Dialkyl Disulfides or Alkanethiols, Langmuir, 10(6), (1994). 19. Atherton, E., Gait, M. J., Sheppard, R. C. and Willams, B. J., Bioorg. Chem., 351(1979). 20. Noh, J. and Hara, M., Nanoscopic Evidence for Dissociative Adsorption of Asymmetric Disulfide Self-Assembled Monolayers on Au(111), Langmuir, 16(5), (2000). 21. Carron, K. T. and Turley, G., Axial and Azimuthal Angle Determination with Surface-Enhanced Raman Spectroscopy: Thiophenol on Copper, Silver, and Gold Metal Surfaces, J. Phys. Chem., 95(24), (1999). HWAHAK KONGHAK Vol. 41, No. 1, February, 2003

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