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Sulfamide Chemistry Applied to the Functionalization of Self-Assembled Monolayers on Gold Surfaces

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Sulfamide Chemistry Applied to the Functionalization of Self-Assembled Monolayers on Gold Surfaces Sulfamide chemistry applied to the functionalization of self-assembled monolayers on gold surfaces Loïc Pantaine1, Vincent Humblot2, Vincent Coeffard*3 and Anne Vallée*1 Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2017, 13, 648–658. 1Institut Lavoisier de Versailles, UMR 8180, Université Paris-Saclay, doi:10.3762/bjoc.13.64 Université de Versailles Saint-Quentin, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France, 2Sorbonne Universités, UPMC Univ. Received: 23 January 2017 Paris 06, Laboratoire de Réactivité de Surface, UMR CNRS 7197, 4 Accepted: 13 March 2017 place Jussieu, 75005 Paris, France and 3Université de Nantes, Published: 04 April 2017 CNRS, CEISAM, UMR 6230, Faculté des Sciences et des Techniques, rue de la Houssinière, BP 92208, 44322 Nantes Cedex Associate Editor: P. J. Skabara 3, France © 2017 Pantaine et al.; licensee Beilstein-Institut. Email: License and terms: see end of document. Vincent Coeffard* - [email protected]; Anne Vallée* - [email protected] * Corresponding author Keywords: gold surfaces; hydrolysis; IRRAS; reversibility; SAM; sulfamide; XPS Abstract Aniline-terminated self-assembled monolayers (SAMs) on gold surfaces have successfully reacted with ArSO2NHOSO2Ar (Ar = 4-MeC6H4 or 4-FC6H4) resulting in monolayers with sulfamide moieties and different end groups. Moreover, the sulfamide groups on the SAMs can be hydrolyzed showing the partial regeneration of the aniline surface. SAMs were characterized by water contact angle (WCA) measurements, Fourier-transform infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelec- tron spectroscopy (XPS). Introduction Self-assembled monolayers (SAMs) have raised considerable of reactive end groups in the monolayers enabling the chemical interest in the past decades because of their potential applica- functionalization of solid surfaces [3,5-7]. Within this context, tions in various areas such as biomaterials, tissue engineering, noncovalent and covalent strategies have been investigated for biosensors and electronics [1-3]. The seminal work of Nuzzo the immobilization of a target molecule through a reaction with and Allara on the adsorption of disulfides on gold surface has the terminal groups of the SAMs. The most common methods triggered numerous research activities in the preparation and ap- to covalently functionalize these materials involve the Huisgen plications of sulfur-based SAMs on Au surfaces [4]. Important cycloaddition between an azide and an alkyne [8,9], Thiol- contributions have been notably driven by the implementation Michael addition [10,11], amide formation [12-14], Diels–Alder 648 Beilstein J. Org. Chem. 2017, 13, 648–658. reaction [15,16] or the imine/oxime condensation [17,18]. The sulfamide functionality with R2NSO2NR’2 structure can be These reactions tend to produce strong covalent interactions be- found in several biorelevant compounds [21]. Besides applica- tween the surface and the molecules in solution which ensure a tions in medicinal chemistry, sulfamide groups have been incor- stable immobilization. One limitation of the covalent strategy porated in self-assembling molecules [22-27], peptides [28], lies in the irreversible permanent functionalization of the SAMs polymers [29], ligands [30], chiral auxiliaries [31-33] and in which precludes reusable properties. A reversible strategy could organocatalysts [34-37]. In light of the importance of the find applications in a wide range of fields such as the con- sulfamide functionality, our group has recently reported a trolled engineering of SAMs, the formation of patterns with straightforward preparation of unsymmetrical sulfamides from capture-and-release properties, the reusability of the surface for commercially available amines and N-hydroxyarenesulfon- further functionalization or the ability to tune the properties of amide O-derivatives under simple conditions [38,39]. The SAMs by controlled spatial functionalization. A scant number method works at room temperature without needing inert atmo- of examples have reported reversible covalent reactions on sphere or dry solvent. The ease of formation of sulfamides and SAMs on gold surfaces; for instance, Ravoo and Reinhoudt their propensity to be cleaved under mild conditions [40] have described the formation of imine SAMs prepared by reac- prompted us to consider the sulfamide functional group for the tion of an amino-terminated SAM with an aldehyde in solution linkage and the potential regeneration of amine-terminated or the condensation of an aldehyde-terminated SAM with an SAMs on gold surface. amine in solution [19]. These surfaces were stable in water but readily erased by acid-catalyzed hydrolysis at pH 3. The Here, we present a new strategy to modify in situ amino termi- propensity of imines to be hydrolyzed under acidic conditions nated SAMs on gold based on the sulfamide chemistry and to has also been harnessed for the formation of aromatic mixed partially regenerate the amino SAM. The surface modification self-assembled monolayers containing both imine functionali- process is studied by water contact angle measurements ties and protonated anilines on the surface [20]. In order to (WCA), Fourier transform infrared reflection absorption spec- bring a new class of reusable surfaces, we describe herein the troscopy (PM-IRRAS) and X-ray photoelectron spectroscopy use of sulfamide chemistry for the generation of reversible (XPS). patterns of sulfur-based SAMs on a gold surface (Scheme 1). To the best of our knowledge, the formation of sulfamide for Results and Discussion the chemical modification of monolayers on gold surfaces has In order to monitor the successful formation of the sulfamide never been reported. functional group on a gold surface, a reference molecule Scheme 1: General strategy for surface functionalization based on sulfamide chemistry. 649 Beilstein J. Org. Chem. 2017, 13, 648–658. sulfamide 1 was first synthesized to prepare a model sulfamide SAM (SAM 1). The XPS and infrared signatures of the sulfamide moiety obtained from sulfamide 1 SAM were system- atically used as reference when analyzing the modified gold surfaces after the reaction process. Synthesis of sulfamide 1 The disulfide 1 was synthesized following our previous proce- dure from commercially available 4-aminophenyl disulfide and the readily prepared 4-methyl-N-(tosyloxy)benzenesulfonamide in the presence of triethylamine (Scheme 2) [38]. The desired product sulfamide 1 was obtained in 60% yield after purifica- Figure 1: Contact angles of the gold surface, the 4-ATP SAM, the tion on silica gel and was fully characterized before the prepara- 4-ATP SAM after reaction with ArSO2NHOSO2Ar tion of sulfamide-terminated SAMs (Supporting Information (Ar = 4-MeC6H4 or 4-FC6H4), respectively SAM a and SAM b and the sulfamide 1 SAM. File 1). Sulfamide formation on gold substrates of the SAMs after the reaction, which is coherent with the intro- The elaboration of the aniline terminated surface (SAM 4-ATP) duction of methyl or fluorine-terminated groups. The contact is the first step in creating SAMs bearing a sulfamide group, see angles are lower than that for pure aromatic CF3 or CH3 termi- Figure 1. For this purpose, 4-amino-thiophenol (4-ATP) was nated film ( ≈81° and ≈80°, respectively) [42]. This behaviour first adsorbed on gold surfaces. The aniline-terminated can be explained by two reasons. (1) The conversion of the cou- surface obtained can then react with ArSO2NHOSO2Ar pling reaction is not complete, some amino groups still remain (Ar = 4-MeC6H4 and 4-FC6H4), respectively SAM a and at the top of the layer and it contributes to the lower contact SAM b, to form sulfamide cross linkage. The reaction on the angles values observed. (2) The sulfamide moieties in the aro- surface was investigated through contact angle measurements, matic skeletons which are more hydrophilic than pure aromatic PM-IRRAS and XPS analysis of the surfaces. skeletons contribute to the decrease of the contact angle values compared to the pure aromatic layers. Moreover, as it was Water contact angle measurements were performed to investi- already observed in many works the F-containing SAM and the gate the hydrophilic character of grafted surfaces after the dif- CH3 containing one, display similar contact angle values while ferent reaction steps. The values presented in Figure 1 display F moiety is known to be more hydrophobic than the CH3 group water contact angles for bare Au around 67 ± 2° as expected for [41-43]. As mentioned above, the SAMs a and b are probably a clean gold surface [41]. Upon 4-ATP adsorption the water heterogeneous, thus the hydrophobic end groups resulting of the contact angle decreases compared to the clean gold sample with coupling reaction are in the outer part of the monolayer and are a value of 54 ± 2° indicating the increase of the hydrophilicity free to become disordered [43]. Moreover, the F end group is of the surface, which is in agreement with the formation of an smaller than the CH3 one and thus may be more flexible, induc- amino-terminated monolayer [19]. ing a more disordered layer and lowered hydrophobic proper- ties than the one expected. SAM a (4-MeC6H4SO2NHOSO2-4-MeC6H4) and SAM b (4-FC6H4SO2NHOSO2-4-FC6H4) exhibit both a similar con- The reference SAM 1 which is not heterogeneous also exhibits tact angle around 65 ± 2° showing a more hydrophobic nature a similar value, lower than the expected one. In this case, the Scheme 2: Synthesis of the reference molecule sulfamide 1. 650 Beilstein J. Org. Chem. 2017, 13, 648–658. lower value can be explained by the sulfamide moieties in the aromatic skeletons which are more hydrophilic than pure aro- matic skeletons but also by a more disordered layer as it is common for SAM prepared with big molecules. Although the water contact angle measurements suggest the for- mation of the sulfamide moieties, in this work the contact angle values are very similar for the SAMs a, b, 1 and the gold bare. This technique is therefore not sufficient alone to ascertain the good formation of the conversion; the different samples have also been characterized by PM-IRRAS and XPS.
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