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3 protocols using 4 aminobenzenethiol

1

Fabrication of SERS-Active Nanostructures

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In our experiments, we used the following reagents: extra clean acetone and isopropyl alcohol (AO Reachem, Moscow, Russia); phosphate-buffered saline (PBS) tablets (Ecoservice, Saint Petersburg, Russia); fetal calf serum (FCS); the fetal bovine serum (HyClone, Logan, UT, USA); L-glutamine and penicillin/streptomycin (PanEco, Moscow, Russia); glutaric aldehyde (CAS Number: 111-30-8, AppliChem GmbH, Darmstadt, Germany).
We also used four metals for evaporation, Cr, Ag, Au (GIRMET Ltd., Moscow, Russia), and Al (RD Mathis Company, Signal Hill, CA, USA). In lithography processes, we utilized AZ5214E photoresist (MicroChemicals, Ulm, Germany) and AZ 726 MIF Developer (Merck, Darmstadt, Germany). To optimize the nanoperiodic structure, we analyzed the intensity of the SERS signal from the 4-ABT (4-Aminobenzenethiol, CAS Number: 1193-02-8, Sigma-Aldrich, St. Louis, MO, USA) test molecules.
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2

Synthesis of Aromatic Thioethers

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With exception of DMSO and THF all solvents were from Fisher Scientific; DMSO, THF, Et3N, CuI, NH4OAc, propanedinitrile, 4-aminobenzenethiol, and 4-methylbenzenethiol were from Sigma Aldrich. 1-Iodo-2-trifluoromethylbenzene was from Alfa Aesar, K2CO3 was from EM Scientific, CDCl3 was from Cambridge isotope laboratories Inc, and DMSO-d6 and CD3OD were from Acros Organics. The deionized water used was obtained from a Millipore Milli-Q Plus Ultra-Pure Water System.
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3

Novel Schiff Base Molecular Switch Synthesis

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Au (111) films on mica were purchased from Phasis, Switzerland. The STM tip was prepared from Pt/Ir wire cut under ambient conditions. All chemicals were used as received: chloroform (>99%, Merck), ethanol (>99%, Sigma-Aldrich), phenylacetylene (>98%, Sigma), ethynyltrimethylsilane (>98%, Sigma), 4-bromobenzaldehyde (>99%, Sigma), 4-aminobenzenethiol (>98%, Sigma), bis(triphenylphosphine)palladium(II) dichloride (>98%, Sigma-Aldrich), copper(I) iodide (>98%, Sigma), hexane (>98%, Sigma-Aldrich), and diethyl ether (99%, Sigma-Aldrich). Dichloromethane (CH 2 Cl 2 ) was dried over calcium hydride. THF was freshly prepared over Na metal in the presence of benzophenone as an indicator. Column chromatography was conducted with a silica gel 200-425 mesh. The structure of the prepared compounds was confirmed using 1 H NMR (500 MHz) and 13 C NMR (125 MHz).
The detailed procedures and characterization data for the prepared compounds are given in supporting information. Briefly, during the construction of novel Schiff base molecular switch EPBB, palladium/copper-catalyzed Sonogashira coupling between alkynylaryl and aryl halide which has an aldehyde moiety was conducted. Afterwards dehydration reaction between aldehyde and aminothiol yielded the product EPBB. The synthesis of the EPBB molecule depicted in figure 1 is described in the supporting information.
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