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Formation Ad Reaction Ofinterchain Garboxylic Anhydride Groups On Formationand Reaction of Interchain GarboxylicAnhydride Groups on Self-AssembledMonolayers 0nGold LinYan, Ghristian Marzolin, Andreas Terfort, andGeorge M. Whitesides Departmentof Chemistry, Harvard University, 12Oxford Street, Cambridge,Massachusetts 02138 Reprintedfrom Volume13, Number 25, Pages 6704-6712 6704 Langmuir 1997, 13, 6704-6712 Fomation and Reaction of Interchain Carboxylic Anhydride Groups on Self-Assembled Monolayers on Gold Lin Yan, Christian Marzolin, Andreas Terfort, and George M. Whitesides* Department of Chemistry, Haruard Uniuersity, 12 Oxford Street, Cambridge, Massachusetts 02 138 Receiued July 9, 1997. In Final Form: September 29, 1997@ This paper demonstrates a new method for the synthesis of mixed self-assembled monolayers (mixed SAMs) by reaction of a reactive intermediate-an interchain carboxyiic anhydride-with alkylamines. The interchain anhydride was prepared in high yield from a SAM of l6-mercaptohexadecanoic acid (HS- (CHzhsCOOH) on gold by treatment with trifluoroacetic anhydride. Alkylamines reacted cleanly with the interchain anhydride to generate a mixed SAM, which comprised a mixture of acids and amides in approximately 1:l ratio on the surface. The SAMs of the interchain anhydride and the mixed SAM were characterized using polarized infrared external reflectance spectroscopy,X-ray photoelectron spectroscopy, contact angle, and ellipsometry. Control of the wettability of the SAMs was demonstrated by allowing the interchain anhydride to react with alkylamines having different alkyl groups;this model system gave wetting data consistent with earlier studies of mixed monolayers and verified the ability of this method to manipulate interfacial physical properties. In certain circumstances, this method is experimentaily simpler as a method to produce mixed SAMs than are conventional methods involving coadsorption of two thiols from a mixture in solution. It also assures two other characteristics of the mixed SAM: that the composition of the SAM is roughly 1:1in carboxylic acid and amide groups, and that these two groups are well mixed on the surface. Introduction for generation of patterned SAMs,10'11fbnnation of three- dimensional multilayers, 12-14 synthesis of two-dimensional This paper describes a new method of synthesizing arrays for combinatorial libraries,15 immobilization of DNA (mixed for rapid sequencing,ls'16preparation of certain types of mixed, functionalized self-assembled monol ayers 1 biosensors and enzymatic microreactors, 7and attachment SAMs) of carboxylic acids and amides by reaction of a 21 reactive intermediate-an interchain carboxylic anhy- of functional molecules and polymers to surfaces.ls functional groups on SAMs have dride-with amines. The interchain anhydride is easily Efforts to manipulate focused on alkylsiloxanes on SilSiO2, because this class of prepared by dehydration of a SAM of 16-mercaptohexa- SAMs is believed to be (and probably often is) more stable decanoicacid (HS(CH2)IsCOOH)on gold (Scheme1). There than SAMs on gold.2z 28 Development of new methods to are three general strategies to synthesize mixed SAMs: modify SAMs on gold is, however, important because: ( 1) ( 1) to synthesize the differently functionalized alkanethiols many analytical systems and sensors are being developed and prepare mixed SAMs by coadsorption from a solution 1 containing two different thiol s; (2) to prep are a symmetric W.;Frisbie.C. D.:Wnghtpn, M. S.l'angmuir 1993, q dialkyl disulfidesl'2 and asymmetric dialkyl sulfidesswith F. J.; Testoff. M. A.: Nielsen,T. B.; Stenger, D. A.; requisite functional groups and then self-assemblethem Rudolph, A. S Proc. Natl. Acod. Sci. u.s.A.1994.9.t. on gold; (3) to introduce the desired functionality into a SAM after its assembly. While the fi.rst two strategies R. H.: Mallouk. have been widely used to synthesize a variety of func- 1989.5.101- tionalized SAMs for a broad range of applications, such Soc as biocompatibility,a wetting,s adhesion,Gcorrosion pre- G. K.: Marks. T. J. J. Am. Chem. venting,T and micro- and nanofabrication,s'e the last Lu.A. T.; method has beenless used. It would be especiallyvaluable tel, (617)495- gwhitesides@ J. Langmuir inAduance ACS Abstracfs. November 15. R. M. J. Am. Chem. Soc. 1996. /18, 3988- L988,110,6560- E.:Crooks. R. 11.:Wells, H. A.; Whitesides, G. M. Langmuir lgg4, 19,1825- 1995. 11. 3913- M. L.; Engelhard, M. H.; Kim, E.;Whitesides, G.M. J. Am. Chem. Wiacek, R. J.; Lee, L.; Kim, E.; Whitesides, G. Adu. Mater. 50743-7463(97)00762-2 CCC: $14.00 O 1997 American Chemical Society Interchain Carboxylic Anhydride Groups on SAMs Langmuir, VoL 13, No. 25, 1997 6705 Scheme 1. Schematie Representation of Formation of olateson gold are substantially better defrned structurally the Interchain Anhydride and Reaction of the than other classesof SAMs.es-sz Interchain Anhydride with an Alkylamine' Why are there so few methods available for the modification of SAMs on gold after their assembly? There are, at present, only few synthetic methods that are used, and are more or less restricted in their generality. Terminal aryl azide groupslO have been activated pho- tochemically to produce nitrenes and perhaps other reactive intermediates; the chemistry and yield of this type of coupling are not easy to predict. Terminal amino groups react with isocyanates in solution.33 Amines on the surface of SAMs react at significant rates with atmospheric COz and other environmental components, and this chemistry is difficult to control. Three methods are known for modification of the SAMs of carboxylic acid I groups: formation of acyl chlorides;38generation ofmixed (CF3CO)2O,Et3N, DMF, rt anhydrides;lein situ activation with carbodiimide reagents | for amide coupling3e and ester formation.aO In more Y general terms, many organic reactions do not transpose easily from solution to the surface for a number of reasons: the surface is a very sterically hindered envi- ronment and backside reactions (e.g., the Sp2 reaction) and reactions with large transition states (e.g., esterifi- cation or saponification) often proceedslowly. In addition, the technical problems of establishing the identities of products,and their yields, for organic reactions proceeding on the surface remain substantial. Here we report a new method for preparation of mixed SAMs that has three steps: (1) preparation of a well- orderedhomogeneous SAM of l6-mercaptohexadecanoic Au acid on gold;(2) conversionofthe terminal carboxylicacid groups into interchain anhydrides by reaction with trifluoroacetic anhydride; (3) reaction of the interchain RNH2,NMP, rt anhydride with an alkylamine to give a mixed SAM presentingcarboxylic acids and amides on its surface.The SAMs of the interchain anhydride and mixtures of R carboxylic acids and alkylamides were studied and characterized by X-ray photoelectron spectroscopy(XPS), polarized infrared external reflectance spectroscopy (PIERS), contact angle, and ellipsometry. All three of these steps take place rapidly and in high yield; the last step will, we believe, have broad generality. This reaction thus seems a very good sequence to use in introducing organic functionality into SAMs. The organic amines required are readily available and compatible with most other organic structures. The one characteristic of this reaction that will restrict it from some applications is that Au it produces a 1:1 mixture of functional groups on the (-CO2H -CONHR -CONRR'), " The alkyl chains of the original SAM of the carboxylic acid surfaceofthe SAM and or in these three SAMs are in trans conformation;the methylene ratherthan a single species. In somecircumstances, when groups near the functional groups may adapt gauche confor- a mixed SAM containing COzH groups is required, this mation and are less ordered. Carboxylic acids in the SAMs of characteristic may be an advantage. the carboxylic acid and in the mixed SAMs of amides and carboxylic acids involve in hydrogen bonding. The interchain anhydrides orient largely perpendicular to the surface Results and Discussion Preparation of the Interchain Anhydride. SAMs that are based on eombinations of SAMs on gold and of l6-mercaptohexadecanoic acid were prepared by im- -33 surface plasmon resonance,zs,30 mass mersing precleaned gold slides in a 2 mM ethanolic measurement using the quartz "l"r1tochemistry,31crystal microbalance,ss'34 solution of the thiol as described previously.al Terminal or surface acoustic wave devices:le (2) SAMs of alkanethi- (35) Ulman, A. An Introduction to Ultrathin Organic Films from (29) Mrksich, M. ; Sigal, G. B.; Whitesides, G. M. Langmuir l9fi.il, 11, Langmuir-Blodgett to Self-Assernbly; Academic Press, Inc.: San Diego, 4383-4385. cA, 1991. (30) Sigal, G. B.; Bamdad, C.; Barberis, A.; Strominger, J.; Whitesides, (36) Whitesides, G. M.; Gorman, C. B. ln Handbook of Surfa.ce G. M. AnaL Chern. 1996, 68, 490-497. Imaging and.Visualization; Hubbard, A.T., Ed.; CRC Press: Boca Raton, (31) Rubinstein,I.; Steinberg, S.; Tor, Y.; Shanzer, A.; Sagjv,J.Nature FL, 1995;pp 713-733. 1988, 332, 426-429. (37) IIlman, A. Chem. Rev. 1998,96, 1533-1554. (12)Yelzen, E.U.T. v.; Engbersen, J. F. J.; Reinhoudt, D. N. J. Anr. (38) Duevel, R. V.; Corn, R. M. Anal. Chem. 1992,64,337-342. Chem. Soc. 1994, .116,3597-3598. (39) l,eggett, G. J.; Roberts, C. J.; Wilhams, P. M.; Davies, M. C.; (33) Marx-Tibbon, S.; Ben-Dov,I.; WiIIner, I.J.Arn. Chem. Soc. 1996, Jackson, D. E.; Tendler, S. J. B. Langmuir 1993, 9, 2356-2362. 118,4717-4718. (40) Hutt, D. A.; Leggett, G. J. Langmuir L997, 13,2740-2748. (34) Schierbaum,
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