(1)Journal of the Korean Chemical Society 2003, Vol

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(1)Journal of the Korean Chemical Society 2003, Vol. 47, No. 5 Printed in the Republic of Korea. Biphenylcarboxylic Acid.

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(3) * (2003. 8. 19 ). Raman Spectroscopy Study on the Adsorption Orientation of Biphenylcarboxlic Acid Derivatives Heay Ran Choi, Kyu Seok Choi, Il Ki Jung, Hong Seok Song, Keunok Han Yu, Ho Seob Choi, Sang Hee Lee, and Soo-Chang Yu* Department of Chemistry, Kunsan National University, Chonbuk 573-701, Korea (Received August 19, 2003). . . Au

(4) Ag 4-biphenylcarboxylic acid(BPCA) 4'-cyano-. BPCA(c-BPCA), 4'-mercapto-BPCA(m-BPCA),. !" 4'-amino-BPCA(a-BPCA)# $%& '() *+, -./0. 1 2345(SER)678) 9*: ;*<=. >? 6@) 1 benzoic acid, biphenyl,. !" BPCA. 6 '( & A/B 0CD 6E & A/B F1GH=. '( & A/B 1 IJ" ! K, C-H LMNOK, carboxylate PQ LMNOK, OY B Z[/\D] ^_ m-BPCA+ thiol. !" RR ST U90 1VW+ KE X. ` ab W" biphenyl. ` 0c$ d e+ fgB. h*" e" ij, 6Ek ab lm& fg n) -.GH=.. : SERS, , BPCA, , Au, Ag ABSTRACT. Surface-enhanced Raman(SER) spectroscopy was utilized to investigate the adorption orientation of the 4-biphenylcarboxylic acid(BPCA) derivatives, such as 4'-cyano-BPCA(c-BPCA), 4'-mercapto-BPCA(m-BPCA), and 4'amino-BPCA(a-BPCA), which were adsorbed on Au and Ag colloid monolayers. For the systematic approach, information regarding the adsorption behavior of benzoic acid, biphenyl, and BPCA was applied to the target molecules. From the spectral behaviors of benzene ring, C-H stretching, carboxylate anion, and the other finger printing vibrational modes, it was concluded that only the m-BPCA was adsorbed tilt with thiol group being adsorbed on Au surface, whereas the other molecules were adsorbed flat on both Au and Ag surfaces. Keywords: SERS, Monolayer, BPCA, Adsorption Orientation, Au, Ag. . . N OPQ! <! HRA 12 89@ STU& V W < X YZRJ KL&=. $[%@ \]. 10

(5) , , ,. - ]^ _ $[& Z` a3; Gb @. , , !, "#$%. a3; cd& ;Ie@ f(g h: ij k/ l. & '()*+ &,- . /0, 12345. ; mngo p X> q9r =s , ;t. 67 89:;! <=. >?@ 34 ABC& D*. uLvJw N%& x y G3 z{&=. &|. 7 EFG! H&; "CG ?IJ KL &M*. ua3 }> z{g $[ 3~J, LvJ, . 1. 439.

(6) 440.

(7) . J, 93J, 3J, ! evJw bgo ]&^. èé7 J#¡ ð- $[7 ¹Õñ. x=. N 34@ ^>$ mng. <=.9-11 Tï ò "ógo5 4-biphenylcarboxylic. oB` &ag & 3t ey JG! <. acid(BPCA); Au. Ag ô7&õbgo Ì- . =. &go5 b 7 34. Ü ¿5 ;t tg A: SERS &. B& t, !C @ b , . : ": ì*+12,13 ê Þ@ ]öJw ÷õ@ ?T*. , 3 'g n! <*+ g A- . 7B` BPCA@ ðø:ù=. óú>g. "%& n8r G! <=.2. @b BPCA û üI1& carboxylate ý&þ*7. b@ ]^ ~bgo@ C@ g @: . GÝ h7o ®Çg G3 z{g û üI1. %@ & G x 3 z{g ~bgo@. Iÿ3 :o 3^*7 À%ÝÀ. Cg A- "; d#& W < =.. I W; <=.13 , «, « Ü ã. ~bgo@ C "¡ , CevJ . wÏ' !C çº$% û üI1 é ¶. ¢%& £G! <=. O£¤ ¥¦§ NZ¨(scanning. ð! <? û üI1& á$7o k: ester. tunneling microscopy), S

(8) © NZ¨(atomic force. çº$& m^G3 z{g &X%& J- #go. microscopy), ! (evNZ¨(near field optical. ®Çb& =s 3[g V ;^& <t. microscope) '@ ªN C@ g A- p. ¹/p X& =. o ò óúgo BPCA. «¬:O*+ 7 w t®t ¯;. g 9 Oy, Qy Ü ®Ç>@ ºU'&. =s. M° C a3go $[%@ 93J, 3~J, !. ]ö ;t -CN, -SH, ! -NH2k3% BPCA. evJw ]^ " W <y G=.3,4 , &. @ para g

(9) I *7· BPCA; & / . ,- C±¢%5 ²% "^ C%@ &. Ígo5 ®Çbg V ;^& <t ¹/. "#Jw ]^ ' ³J*7 " ¡ -~. p! M=.. t´! <=. IR& Raman> µ TCe¢. . C k3@ t{KL #£¶*7· C@ . . & "#Jw ]^' hf¸Jw ¢*7 ¹/p 3g Jº- ¢%w¡ &,- ¢% ]r »¼. . ½5 ;t! < ¢& b¾¿À Ce¢, . óúg £Ø IÛ% Aldrich £7B` ". SERS(surface-enhanced Raman spectroscopy)&=. À. M*+, º^- çº$%@ "# 1H NMRg @. Ce¢ Á> $[>@ Âk Ã 1G Á*7. àwM=.. B` CWÄ@ p ÅÆ Ce¢ &+. 4'-Cyanobiphenyl-4-carboxylic acid(c-BPCA): 4-Bromo-. IR> ¶ T Ce¢g Ç-=. À Ce¢@ ;(. benzonitrile ethylene glycol dimethylether(DME)g . È (É I@ Ê¤ Ë& Ì- Ígo5 ÎÏ. :I Ã 4-carboxyphenylboronic acid, Pd(pph3)4, . Ð Å I@ Íg A- CWÄ@ p Å. ! 2M-Na2CO3 ;M=.14 á º$ Û 5. Ñ W <= ¡ <* IÒ@ R3; ¿t Ó. CTï N2 ; go Ûy I Ã 85 oCgo. ÔZ³@ I7B` ÎÏÐ ÅÆ¡ Õ. 12I

(10) Tï ;

(11) I Ã /R*7 . Ö ;t! <=. tÀ, Fleischman 'g @:o. çº$ c-BPCA Å=.. 5. Y7 8×Ø b¾¿ À Ng @: &,- {«. 4'-Mercaptobiphenyl-4-carboxylic acid(m-BPCA):. :V W; <! Ã ÙÇr 89 @ÚÛ. 4'-Hydroxy-biphenyl-4-carboxylic acid gg :. v Ü !C, ' CÝg nG! <*+ Ù. I 1 r ;- Ã ;

(12) I 4-hydroxy-. 3Ý C - Þ@ ß àw 5t áG. biphenyl-4'-carboxylic acid ethyl ester º^! & ç. ! <=.6-8. º$> dimethylthiocarbamoyl chloride #- THF. g â&ãäg k3; åæ çº$@ . g :I Ã sodium hydride ;! M=.. 3#èég A- "; êê ëg @: Gì. á Ã work up ! CH2Cl2/Hexanego . =. & çº$ ír ¨î(rigid):o ïØ 3#. W- çº$ 4-dimethylthiocarbamoyloxyJournal of the Korean Chemical Society.

(13) Biphenylcarboxylic Acid !" #$ %& '(. biphenyl-4'-carboxylic acid ethyl ester C. M=.. 441. £39 3H ¾W7 , > ? /0 Ã £ M=.. & çº$ dichlorobenzeneg :I 180 Cgo Û. À ÎÏÐ CCD(charge Coupled Device: 9. 72I

(14) Tï ;

(15) I Ã Ða7 . º( ) @ª3; (G <! NZ¨*7 I. &

(16) éw 4-dimethylthiocarbamoylsulfanyl-. focus AW< Renishaw£@ Raman microscope. biphenyl 4'-carboxylic acid ethyl ester Å=. & ç. system 2000 £M=. eS*7 AªU 25 mW. º$ !g :Iÿ! Ar ;7 30C & bubble. Æ He/Ne laser7o, 632.8-nm@ %B f( ;t. - Ã 4N-LiOH ;! þgo 2I

(17) Tï . Spectra Physics£@ Model 127-75RP £M=.. o. M=. á º$g 1 W ; 1^*7 À " # g$ /R&Ï7 øª m-BPCA Å=.. . 4'-Aminobiphenyl-4-carboxylic acid(a-BPCA): Biphenyl4-carboxylic acid acetic anhydrideg %w Ã 0 oCg. BPCA ð5é%@ Au Ü Ag ô7&õ bgo@. o - 1> - [1 r ; M=. þ. ¹/p3: Tï ò "ógo ". go 1I

(18) Tï Ã á º$g ! ;. :þ BPCA@ ?T C!7 M=. DE BPCA. acetic anhydride methyl acetate. acetic acid7. Fig. 1@ (a). (b)g xÆ pw XÐ Au. Ag. C: I&=. & '( Å 4'-nitro-biphenyl-. ô7&õ bgo o7 =s ;t X*7 p!. 4-carboxylic acid 1 Ü ¹ô ß go g. G=.12,13 Fig. 1@ (a) Þ@ FG! . carboxylate. ç M=. Ð a7 g @: para g. ý&þ ë& flat(HI) - ¤Í7 Ø X x. nitrationØ g$ g çº$ C - Ã =I ;. Æ! Fig. 1@ (b) carboxylate ý&þ& º 1. WC: û üó1*7 9

(19) M=. Catalytic. ²@ h¬ð9J K: L*7· &M@ FG. hydrogenation(H2, Pd/C)g @: nitro ë amine*. ! ; ¶ %Õo tilt(30) ¤Í7 Ø X. 7 9

(20) I a-BPCA Å=.. xÆ! <=. ;t@ o7 =s SER. . ÎÏÐ xÆ*+ SER ÷õ :±¡ 9. óúg £Ø IÛ% Aldrich £7B` ". 3((EM)> 9&T(CT) &N 9=.17-19. M*+. óúg )& ð 3" *W [HCl-HNO3. ]öJw ÷õ@ ?T OPpb =ý> µ=. DE. (3:1)]g 1I

(21) 5 + Ã 3H ¾W7 R, -. û üI1g :íG ÷õ&=. û üó1 ë@. .go /0 X £M=. SERS 31 À%3 . AQR(Tõ ý&þ, carboxylate7 ß. : 2&õ 3 Jí- a3(9 mm49 mm)7 . z 1440 cm−1 g x¼=. Carboxylate ý&þ&. ! *Wg - I

(22) 5 + Ã 3H ¾W7 R,. ®Ç bg & &:tb g :íG T. ! -.go /0 X £M=. Au ô7&õ . õ @ ¿5g 1370-1400 cm−1 g x. b SilaneçØ 3g Aug A 5 6çU. y G¡12 Fig. 1@ (a) Ð π 9%@ hHç7. ;t(3-aminopropyl)trimethoxysilane(APTMS) . ®Çb> CT& &:tb Tõ 1370 cm−1. ¤^I Ã î¨& Û 13 nmw Au ô7&õ . g x ! Fig. 1@ (b)Ð º1²@ h. bg I=. &,- ¢*7 «#Ø Au. ¬ð9J K: & &:tb 1400 cm−1 . ô7&õ b 7! ?6 b ;=. Au ô. g x¼=. >S FG! g :íG õ%&. 7&õ b SEM> UV-vis Ce¢ £ àw. =. FG! 3vJ*7 carboxylate ý&þë@. M=. Ag ô7&õ «#3 :o Nanoprobes, 15. Inc. 7B` LI-Silver(Light-Intensity Silver Enhancement System) " {8@ ¢g 9=.16 Li-Silver ¾¿« > ÞI« *7 &:ñ <=. â &;(vial)g ¾¿«. ÞI«. 1:17 <! À % Au ô7&õ 31 Û 15C

(23) += I& =.. @ SERS 31 3H ¾Wg += pE! 2003, Vol. 47, No. 5. Fig. 1. Two different orientations of carboxylate group adsorbed on metal surface. (a) flat form, (b) tilt form..

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(25) . 442. Fig. 2. Molecular structure of 4-BPCA derivatives.. g TlØ=. Carboxylate ý&þ ë & HIy Gb &M FG!. LI HI. y & &:[ WUg Ë*+ carboxylate ý&þ ë@ ¿5g çv& $ *=. $ À 6 ¨lg ®Çb> Wî w Tõ ¾¿G b WIw Tõ Û y x ? £ty G '@ ÷õ@ R3 Êç Ý3Iÿ+, çvÀ HIy V ¨lg TW@ &T *ÿy Ø=. VtÀ Jt Wy ÷õR3 Êç. TW&T& TIg EFG35 =. BPCA çº$go FG! ; HIy V ¨. Fig. 3. Raman spectrum of c-BPCA. (a) Ordinary Raman (OR) spectrum, (b) SER spectrum from Au surface, (c) SER spectrum from Ag surface.. lg FG! g Ç Tõ% X C=C Tõ@ ¨lg Û 10 cm−1 5@ (f( &T& E. õ%&=. 1378 cm−1g x¼ ÷õ C; ®Ç. FG! C-H R(õ Ü FG!. breathing õ@. ô7&õ bg çvJ * z û üI1. ¨l % ÷õ R3; NEr ½²G x FG!. go ]u^á(deprotonation)& 9%&. ; HIy Ø X*7 :±G=. Fig. 2. hHç Ø carboxylate ý&þg @:o x¼ ÷õ. BPCAgo EFØ p A7 "-. &=. &X &Z ^Ù- XÐ &5@ TW &. BPCA ð5é%@ C "# x Y&=. Au Ü. T carboxylate ý&þ& HI- *7 G. Ag bgo. =s xÆ!<=.. <ý xÆ! <=. C[N ë Û 7 cm−1 (f( &TØ 2228 cm−1go x_=. C[N ë [²S. c-BPCA

(26) Fig. 3 c-BPCAg A- OR ÎÏÐ(a)> SERS . @ h¬ð 9J& π 9 K & . ÎÏÐ(b, c) x X&=. ÎÏÐgo x¼ ÷. 6 W <=. [²S@ h¬ð9J K: . õ% B ¹ÕZ W < ]öJw ÷õ%7. σ¤@ º &:3 z{g ®Çb*7B`. C-H R(T, carboxylate ý&þ@ A. % y G+ h¬ð9J º^ ;t! <3. Q R(T, ! C[N R(T '*7B` 3w. o FG!. z{g f(&T *=.20 tÀ π¤ º . G X% % W; <=. Fig. 3(a) OR ÎÏÐ*. ¨lg ®Ç*7B` C[N Æ@ π* `57 9a. 7· 3076 cm−1g FG!. C-H R(Tõ. 2235. 5; &TG ºHW; b/c*7o b TW. cm g C[N õ%& x <=. , /î ý&. 7 &TØ=.21 o Au bgo Å ÎÏÐ*7. þ& /´3 z{g 1370-1400 cm−1 g x . B` C[N ë π Id K: HIy G. carboxylate ý&þ ÷õ x t W\=.. =! :± W <=. 3076 cm−1 ÷õ S =t. −1. Fig. 3(b) Au ®Çbgo Å ÎÏÐ&+ O −1. at W\3 z{g ÷õ@ Êç p! FG! @ . P À- ÷õ%7 1006, 1378, 2228, 3077 cm &. B /3; e=. ARg 1006 cm−1g ay. =. & ÷õ% C; ®Ç bg L*7· . ¾¿G x¼ FG! @ breathing mode@ Êç. TW; &TG? ÷õR3@ ¾½*7 x¼ T. pb FG! @ B Ü ¿5 ¹ W; <=. Journal of the Korean Chemical Society.

(27) Biphenylcarboxylic Acid !" #$ %& '(. 443. & ÷õ S 1000 cm−1 go - X*7 F G! ; HIy Gb Tõ@ & b > Wî&f7 T õ ¾¿I ÷õ@ A Jw R3; ¾;-=.20 Fig. 3(b) ÎÏÐgo5 &, - N& 8×G=. &,- ¾?7 p/ FG! % 5 HIy G g & C@ " BC& Au ®Ç bg HI- ;t! Gý ¹ W ; <=. Fig. 3(c) Ag bgo Å ÎÏÐ&=. 3(b). h: pb ÷õ%@ g Û

(28) @ H& p&! < =. carboxylate ý&þg :íG ÷õ 1390 cm−1g x_¡ &X Fig. 1@ (b)go hi- â. µ& 1²@ h¬ð 9J K: carboxylate ý&þ ë & Û

(29) 30 ¤Í7 G=! :± W; < =. C[N Û 4 cm−1 5 b TW7 &T- 2231 cm−1go x_!, ¾½@ Êç; at WtÀ C-H Tõ; £ X*7 p/ C[N ë& æ< FG! ; Ag bg HIy Ø X*7 : ±Ø=. , C[N ÷õ@ &T Û 4 cm−17 Au go p= j ky &TM*+, FG! @ breathing. Fig. 4. Raman spectrum of m-BPCA. (a) OR spectrum, (b) SER spectrum from Au surface, (c) SER spectrum from Ag surface.. õ LI ky x¼ X*7 Z: p/ Ag bg Þ@ FG! ; TIg HI. /p| Âk& Ëý xÆ! <=. &,- &ð. y G=! p3; e=. Carboxylate ý&þ. o Augo. å. û üI1 p= thiol ë& Aug j ¿- dÂ5. & ý&þ 1²@ h¬ð9J K: G<3. p&! ®Çbg oo & G3 z{&=.. z{g /5 Þ@ FG! âkX FG! . Laibinis '22 thiol> µ soft base û üI1>. hJ HIy G* carboxylate ý&þ l. µ hard base p= Au. µ soft metal> j q . @ =s Û

(30) %Õ<=! :± W; <=.. º-=! p!M=. o- Ulman '23 cB£ r. m-BPCA

(31) . Jcd "go Aug Ø biphenyl thiol ë. Fig. 4 t-BPCAg A- OR ÎÏÐ> SERS Î. ®Çbg A- ¢d*7B` I £- . ÏÐ xÆ! <=. J*7 thiol ë Au . g As 14-17o 5 30ñ Ø=! p!-. bg /O ¿y G X*7 ¹Õñ <=. m-BPCA. â <=. o thiol ë> û üI1& - Cg. @ SERS ÎÏÐgo OP À- a@ 2564. µ& ß z thiol ë& DE Aug åæ! ¢d. cm−1w S-H R(Tõ&=. Fig. 4(a) OR ÎÏÐ. *7B` 14-17o 5 30 Í7 G3 z{. −1. go x¼ 2564 cm @ ÷õ; Au. Ag SERS Î. g carboxylate ý&þ õ FG! @ C-H R(. ÏÐgo £ X m W <=. &ð thiol&. Tõg Êç; x t W X*7 t=.. ®Çg & Gb proton& nñ thiolate(S−); ¤. b Fig. 4(c)g x¼ â. µ& Ag bgo Å. ^G ®Ç> & G3 z{&=. & ÎÏÐgo. Ø C@ ÎÏÐ Au bgo Å X. o =s ]ö Au. Aggo x¼ ÷õ; c-BPCA. > #® = y x_=. ]& £u SH T. @ ¨> = = X&=. Fig. 4(b)go carboxylate. õ; £t! carboxylate ý&þ ÷õ; 1371 cm−1g. ý&þ@ ÷õ; x t W\! X C-H R(. x¼ É&=. & thiol> carboxyl acid; TIg Ag. Tõ LI R3@ Êç; Ë=. &X û üI1. b> Âk ! <ý p O X&=. &. ë& g C t W\! FG!. Ag; Au p= j hard 3 z{g thiol ë> carboxylate. 2003, Vol. 47, No. 5. LI ®Ç>.

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(33) . 444. ý&þ ë@ dÂ5; hv: TIg Ø X*7. ¹/p îJw ¢*7 pK 300 cm−1 &. t=. -H Zharnikov' thiol ë@ S. go x N-®Ç ÷õ àw X&=. ¯. ; Au(111)go SP3 ^ ¤^! Ag(111)go. {y5 ò ÎÏÐgo 400 cm−1 &À x_3. 24. 25. SP ^`5 ¤^:o o7 =s ;. z{g î àw W; Ë=. , /y ë& . =! p!- â <=. $N ò óúg £- Au. Gý ¹ W < o =s ¢ /yë& . Ag ô7&õ b Au(111) Ag(111)> ír =. V z x y V NH2 rocking mode(|} õ)@. 3 z{g wµ& J W Ë=. tÀ &,-. TW &T àw X&=. Kim '28 /y& Ag. £ó7B` 1:pb S ®Ç@ ¤Í. ~g & &:[ z NH2@ |} õ; aÎ. (morphology) g =s ^`5 ¤^ . ÏÐ*7B` Û 70 cm−1 5 &TG 980 cm−1 . 3[g Jºy ;^ ;t! <=. o. g x¼= X p!- â <=. ó«7 Fig. 5@. ò óúgo5 Þ@ ë& TIg G3 :. (c)go p& Ag ô7&õ bgo Å ÎÏÐ. thiolate ý&þ@ S; 3vJ*7 Jº- ^. go5 980 cm−1g ÷õ EF W; <=. &,-. x: & ¼ X*7 m W <=.. óúJw >7B` /y& ®Çô7&õg G. a-BPCA

(34) . =! / W <=.. Fig. 5 a-BPCAg A- ÎÏÐ xÆ! <=.. &« Ø /y

(35) é; AHg ß û . /y [² Sg < h ¬ð 9J K: Au. üI1@ g K Z t OPp\=. Fig.. Ü Ag ®Çô7&; /O q G X*7 ¹Õñ. 5(a). (b) pb Ø carboxylate ý&þg :íG. Natan ' &,- /y@ ]^ &. ÷õ; 1383 cm−1> 1373 cm−1g x <=. . ð g APTMS C z§I =ý /y@. Gt W z 1440 cm−1 g x¼ ÷õ; L. h¬ð9Jg Au Ü Ag ô7&õ I SER. *7· 1373 cm−17 &T- X ír carboxylate ý. [ À%=.15,16 /yë& ®Çg Gt. &þ@ hHçØ π 9; g E ¶*7· H. <=.. 26,27. I- ¤Í7 Ø X x=. tÀ 1383 cm−1 57 &T- X 1390 cm−1. 1373 cm−1@

(36) 5&f7 & ÷õ @ ?TÀ EF 13 ; t; W=. FG! @ breathing õ X C-H R(Tõ@ ?T µ& C± N Æ ÕÝ ày ¹ W; <=. Carboxylate ý&þ ë & HIy Gb 3vJ*7 &M@ FG! 5 HIy GÝ -=. Fig. 5(b)go 1007 cm−1 g ay x¼ breathing õ ,- £ó q Q:O! <=.20 o 1383 cm−1g :íG ÷õ ¿5 ÛtÀ 1373 cm−1g :íG ÷õ Ð ®Çbg HIy G< X*7 t=. , breathing õg :íG ÷õ@ R3 h :m z 5(b)go ay x_tÀ 5(c)go ky x E^& Ë pw=. U& ¿- 5(c)g o j ay x Ý V X*7 m G > A 7 x_=. &Vy x¼ &ð @ /5 ÷õ@ R3; Ug K Q\=3 p= C Fig. 5. Raman spectrum of a-BPCA. (a) OR spectrum, (b) SER spectrum from Au surface, (c) SER spectrum from Ag surface.. @ a5g @: j È K Q X*7 m Ø =. =I /:, C@ U 5(c); 5(b)p= Rt À a5 b/o ÷õ@ R3; Ûy x Journal of the Korean Chemical Society.

(37) Biphenylcarboxylic Acid !" #$ %& '(. 445. Fig. 6. Adsorption orientations of c-BPCA (a), m-BPCA (b), and a-BPCA (c) on Au and Ag colloid monolayers.. X*7 :±Ø=.. I- *7 G <*+ Ag bgo Û

(38) −1. t*7 3076 cm g x¼ C-H R(Tõ. 30 ¤Í7 x_=. SH ë*7

(39) I m-. @ ?T Êç=. & Tõ a3; l ktÀ Au. BPCA Au. Aggo. = y x_=. Aug. . Ag ®Çbgo q9r £ý & ¹ W. o SH ë@ Aug A- 5 6çU*7 thiolate. ; <=. & Tõ@ ² FG! ; HIy. ý&þ K: ®Çbg A- ¢d*7B` Û

(40) . V z f7 biphenyl& o7 HI- "#. ty G!, Aggo thiolate ý&þ>. 7 ®Çbg Gý ¹ W; <=. &,- . carboxylate ý&þ& u go TIg Ø ¤. >%7 Z: p/, a-BPCA Au Ü Ag ®Çbg. Í ;t X*7 x_=. /y&

(41) é7 k. HIy G <ý ¹ W <=.. - a-BPCA /y> ®Çô7&õ

(42) @ ÂkU & ¿ Au. Ag ®Ç ô7&õ bg ¬r . . . & &: X*7 :±G*+ carboxylate ý& þ ë LI ¿5H& <tÀ u ®Çbg HI. BPCA@

(43) éw CN, SH, ! NH2 k3%&. y G X*7 x_=.

(44) é@ 9Oy. ^w û üI1@ g Ì- K Z t. Qy@ EÉgo pb CN ë 9Qy ëg :. ¹/p\=. & : ®Çb*7o Au Ü Ag ô. íG! NH2 SH 9Oy ë*7 C W <. 7&õ £M*+ C±¢*7o b. =. , carboxylate ý&þ ë@ Ü . ¾¿À Ce¢ &M=. DE O ÷õ% t. R3 OPpb ëg @- H&É 8×. - Ã, OR ÎÏÐ> SERS ÎÏÐ h C±. W; Ë=. NJ*7 R ;t =s

(45) é

(46). M=. óú >g @b û üI1 ^w Í. é@ 9 Oy Qy ]^p= -rÕ

(47) é@ ®. 7 I& z 5 Ü k3 Ü ®Ç. Çb>@ ºUg @- û üI1@ ð5 &. @ g = y x_=. CN&

(48) Ø C. &: X*7

(49) OØ=.. go @ ¿5H& <tÀ Au. Ag bg & &:ñ<ý y àw W; < =. Augo CN ë> carboxylate ý&þ& H 2003, Vol. 47, No. 5. ò " -g>v PJ3Y"(R05-2002-00001125-0)tS*7 WGý..

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(51) . !"# 1. , 2000, 141, 64. 2. Bubert, H.; Jenett, H. Surface and thin film analysis, Wiley-VCH.: Weinheim 2002. 3. Bumm, L. A. et al. Science 1996, 271, 1705. 4. Chen, J.; Reed, M. A.; Rawlett, A. M.; Tour, J. M. Science 1999, 286, 1550. 5. Fleischman, M.; Hendra, P. J.; Mcquillan, A. Chem. Phys. Lett. 1974, 26, 163. 6. Nie, S.; Emory, S. R. Science 1997, 275, 110. 7. Kneipp, K.; Wang, Y.; Kneipp, H.; Perelman, L. T.; Itzkan, I.; Dasari, R. R.; Feld, M. S. Phys. Rev. Lett. 1997, 78, 1667. 8. Michaels, A. M.; Nirmal, M.; Brus, L. E. J. Am. Chem. Soc. 1999, 121, 9932. 9. Adlkofer, K.; Eck, W.; Grunze, M.; Tanaka, M. J. Phys. Chem. B. 2003, 107, 7. 10. Ulman, A. Acc. Chem. Res. 2001, 34, 855. 11. Joo, S. W.; Chung, T. D.; Jang, W.; Gong, M.-S.; Geum, N.; Kim, K. Langmuir 2002, 18, 8813. 12. Yu, K. H.; Rhee, J. J.; Ko, S.; Yu, S. C. Langmuir 2001, 17, 8184. 13. Yu, K. H.; Rhee, J. M.; Lee, Y.; Lee, K.; Yu, S.-C. Langmuir 2001, 17, 52. 14. Zhuravel, M. A.; Nguyen, S. T. Tetrahedron Lett. 2001, 42, 7925. 15. Grabar, K. C.; Freeman, R. G.; Hommer, M. B.; Natan,. M. J. Anal. Chem. 1995, 67, 735. 16. Right, R. M.; Walter, D. G.; Musik, M.D.; Jackson, M. A.; Allison, J.; Natan. M. J. Langmuir 1996, 12, 810. 17. Lu, Y.; Xue, G. Polymer 1993, 34, 3750. 18. Boerio, F. J.; Hong, P. P.; Tsai, H. W.; Young, J. T. Surface and interface analysis. 1991, 17, 448. 19. Moskovits, M. J. Chem. Phys. 1992, 77, 4408. Moskovits, M.; Suh, J. S. J. Phys. Chem. 1984, 88, 5526. 20. Gao, P.; Weaver, M. J. J. Phys. Chem. 1985, 89, 5040. 21. Nakamoto, K. “Infrared and Raman Spectra of Inorganic and Coordination Compounds”, Wiley; NewYork, 1978, pp. 267-387. 22. Laibinis, P. E.; Hickman, J. J.; Qrighton, M. S.; Whitesides, G. M. Science 1989, 245, 845. 23. Kang J. F.: Ulman, A.; Liao, S.; Jordan R. Langmuir, 1999, 15, 2095. 24. Huheey, J. E.; Inorganic Chemistry: Principles of Structure and Reactivity. Harper & Row: New York, 1978; pp. 276-288. 25. Heister, K.; Rong, H.-T.; Buck, M.; Zharnikov, M; Grunze, M.; Johansson, L. S. O. J. Phys. Chem. B. 2001, 105, 6888. 26. Williams, J.; Haq, S.; Raval, R. Surf. Sci. 1996, 368, 303. 27. Barrow, S. M.; Kitching, K. J.; Haq, S.; Richardson, N. V. Surf. Sci. 1998, 401, 322. 28. Park, H.; Lee, S. B.; Kim, K.; Kim, M. S. J. Phys. Chem. 1990, 94, 7576.. Journal of the Korean Chemical Society.

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