Reversible Nanopatterning on Self-Assembled Monolayers on Gold

The reversible fabrication of positive and negative nanopatterns on 1-hexadecanethiol (HDT) self-assembled monolayers (SAMs) on Au(111) was realized by bias-assisted atomic force microscopy (AFM) nanolithography using an ethanol-ink tip. The formation of positive and negative nanopatterns via the bias-assisted nanolithography depends solely on the polarity of the applied bias, and their writing speeds can reach 800,um/s and go beyond 1000 mu m/s, respectively. The composition of the positive nanopatterns is gold oxide and the nanometer-scale gold oxide can be reduced by ethanol to gold, as proved by X-ray photoelectron spectroscopy (XPS) analysis, forming the negative nanopatterns which can be refilled with HDT to recover the SAMs.

Surface-enhanced Raman scattering of 4-aminothiophenol self-assembled monolayers in sandwich structure with nanoparticle shape dependence: Off-surface plasmon resonance condition

A universal metal-molecule-metal sandwich architecture by the self-assembly of Ag nanoparticles (NPs) and Au NPs of various shapes interconnected with 4-aminothiophenol (4-ATP) molecules was presented. These Ag NPs/4-ATP/Au NPs sandwich structures were characterized by surface enhanced Raman scattering (SERS) using an off-surface plasmon resonance condition. Enhancement factors (EF) on the order of 10(8) for 9b(b(2)) vibration mode were observed for the 4-ATP self-assembled monolayers (SAMs) in such sandwich structures. The factors are 2 orders of magnitude larger than that on the monolayer of Au NPs of various shapes under similar condition. More importantly, remarkable increase in the intensity of b(2) vibrational modes, which is characteristic of the charge transfer (CT) behavior between metal NPs and 4-ATP molecules, was observed in these sandwich structures under 1064 nm excitation. The obtained EF on these sandwich structure for 9b(b(2)) is larger than that for 7a vibration mode by a factor of similar to 10(2), demonstrating the importance of the contribution of the CT mechanism and the CT behavior of metal contacts, which play a significant role in metal-molecule-metal nanosystems.

Effects of bridge ions, DNA species, and developing temperature on flat-lying DNA monolayers

Recently, we have successfully constructed flat-lying DNA monolayers on a mica surface (J. Phys. Chem. B 2006, 110, 10792-10798). In this work, the effects of various factors including bridge ions, DNA species, and developing temperature on the configuration of DNA monolayers have been investigated by atomic force microscopy (AFM) in detail. AFM results show that the species of bridge ions and developing temperature play a crucial role during the formation process. For example, the divalent cation Zn2+ resulted in many DNA chains stuck side by side in the monolayers due to the strong interactions between it and DNA's bases or the mica surface. Most DNA chain's conglutinations disappeared when the developing temperature was higher than 40 degrees C. Cd2+ and Ca2+ produced more compact DNA monolayers with some obvious aggregations, especially for the DNA monolayers constructed by using Ca2+ as the bridge ion. Co2+ produced well-ordered, flat-lying DNA monolayers similar to that of Mg2+. Furthermore, it was found that the flat-lying DNA monolayers could still form on a mica surface when plasmid DNA pBR 322 and linear DNA pBR 322/Pst I were used as the DNA source. Whereas, it was hard to form DNA monolayers on a (3-aminopropyl)triethoxysilane-mica surface because the strong interactions between DNA and substrate prevented the lateral movement of DNA molecules.

Interfacial supramolecular self-assembled monolayers of C-60 by thiolated beta-cyclodextrin on gold surfaces via monoanionic C-60

The supramolecular self-assembled monolayers (SAMs) of C-60 by thiolated beta-cyclodextrin (CD) on gold surfaces were constructed for the first time using C-60 monoanion. The results indicate that monoanionic C-60 plays a crucial role in the formation of the C-60-containing self-assembled monolayers. The generation of C-60 monoanion and the formation process of C-60 SAMs were monitored in-situ by UV-visible and near-IR spectroscopy. The resulting C-60 SAMs were fully characterized by spectroscopic ellipsometry (SE), cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. After the immobilization of C-60 by the SAMs of thiolated beta-CD, the film thickness increased by approximately 1 nm from 0.8 to 1.8 nm as determined by SE, demonstrating the formation of the supramolecular self-assembled monolayers of thiolated beta-CD/C-60. The new C-60 SAMs exhibited one quasi-reversible redox couple at half wave potential of -0.57 V vs SCE in aqueous solution containing 0.1 M KCl. The surface coverage of C-60 on the gold surfaces was estimated to be 1.1 x 10(-10) mol cm(-2). The XPS showed the assembly of C-60 over the thiolated beta-CD SAMs.

Electroactive oligoaniline-containing self-assembled monolayers for tissue engineering applications

A novel electroactive silsesquioxane precursor, N-(4-aminophenyl)-M-(4'-(3-triethoxysilyl-propyl-ureido) phenyl-1,4-quinonenediimine) (ATQD), was successfully synthesized from the emeraldine form of amino-capped aniline trimers via a one-step coupling reaction and subsequent purification by column chromatography. The physicochemical properties of ATQD were characterized using mass spectrometry as well as by nuclear magnetic resonance and UV-vis spectroscopy. Analysis by cyclic voltammetry confirmed that the intrinsic electroactivity of ATQD was maintained upon protonic acid doping, exhibiting two distinct reversible oxidative states, similar to polyaniline. The aromatic amine terminals of self-assembled monolayers (SAMs) of ATQD on glass substrates were covalently modified with an adhesive oligopeptide, cyclic Arg-Gly-Asp (RGD) (ATQD-RGD). The mean height of the monolayer coating on the surfaces was similar to 3 nm, as measured by atomic force microscopy. The biocompatibility of the novel electroactive substrates was evaluated using PC12 pheochromocytoma cells, an established cell line of neural origin. The bioactive, derivatized electroactive scaffold material, ATQD-RGD, supported PC12 cell adhesion and proliferation, similar to control tissue-culture-treated polystyrene surfaces.

Immobilization of the nanoparticle monolayer onto self-assembled monolayers by combined sterically enhanced hydrophobic and electrophoretic forces

The immobilization of surface-derivatized gold nanoparticles onto methyl-terminated self-assembled monolayers (SAMs) on gold surface was achieved by the cooperation of hydrophobic and electrophoretic forces. Electrochemical and scanning probe microscopy techniques were utilized to explore the influence of the SAM's structure and properties of the nanoparticle/SAM/gold system. SAMs prepared from 1-decanethiol (DT) and 2-mercapto-3-n-octylthiophene (MOT) were used as hydrophobic substrates. The DT SAM is a closely packed and organized monolayer, which can effectively block the underlying gold and inhibit a variety of solution species including organic and inorganic molecules from penetrating, whereas the MOT monolayer is poorly packed or disorganized (because of a large difference in dimension between the thiophene head and the alkylchain tail) and permeable to many organic probes in aqueous solution but not to inorganic probes. Thus, the MOT monolayer provides a more energetically favorable hydrophobic surface for the penetration and adsorption of organic species than the DT monolayer.

Structure and identity of 4,4 '-thiobisbenzenethiol self-assembled monolayers

Self-assembled monolayers (SAMs) of 4,4'-thiobisbenzenethiol (TBBT) can be formed on Au surface spontaneously. The structural characteristics and adsorption behavior of TBBT SAMs on Au have been investigated by surface enhanced Raman scattering (SERS), electrochemical cyclic voltammetry (CV), ac impedance spectroscopy (EIS), and atomic force microscopy (AFM). It is demonstrated that TBBT adsorbed on Au by losing a H atom, forming one Au-S bond, and the other mercapto group is free at the surface of the monolayer owing to the presence of the nu(S-H) at 2513 cm(-1) and the delta(C-S-H) at 910 cm(-1) in SERS. The enhancement of the vibration of C-S (1064 cm(-1)), the aromatic C-H vibration (3044 cm(-1)), and the absence of the vibration of S-S illustrate TBBT adsorbed on Au forming a monolayer with one benzene ring tilted with respect to the Au surface. The interpretation of the observed frequencies is aided by ab initio molecular orbital (MO) calculations at the HF/6-31G* level of theory. Electrochemical CV and EIS indicate TBBT monolayers can passivate the Au effectively for its low ratio of pinhole defects (theta = 99.6%). AFM studies give details about the surface morphology. The applications of TBBT SAMs have been extensively investigated by exposure of Cu2+ ion to TBBT SAMs on Au and covalent adsorption of metal nanoparticles.

A novel nanometer-scale "gold electrode-molecular wires-silver" junction: An efficient test bed for electrochemical investigation of electron transportation through molecular wires in self-assembled monolayers

A novel "gold electrode-molecular wires-silver" junction was facilely fabricated for electrochemical study on the electron transportation through molecular wires. Rapid electron transportation through this sandwich-like structure was indeed observed by cyclic voltammograms and ac impedance measurements. Since rather reproducible and reliable results are easily available by electrochemical techniques, it would be an efficient and reliable test bed for electrochemical investigation of charge transportation through molecular wires in self-assembled monolayers on electrodes.

Surface enhanced Raman scattering of p-aminothiophenol self-assembled monolayers in sandwich structure fabricated on glass

A sandwich structure consisting of Ag nanoparticles (NPs), p-aminothiophenol (p-ATP) self-assembled monolayers (SAMs), and Ag NPs was fabricated on glass and characterized by surface enhanced Raman scattering (SERS). The SERS spectrum of a p-ATP SAM in such sandwich structure shows that the electromagnetic enhancement is greater than that on Ag NPs assembled on glass. The obtained enhancement factors (EF) on solely one sandwich structure were as large as 6.0 +/- 0.62x10(4) and 1.2 +/- 0.62x10(7) for the 7a and 3b(b(2)) vibration modes, respectively. The large enhancement effect of p-ATP SAMs is likely a result of plasmon coupling between the two layers of Ag NP (localized surface plasmon) resonance, creating a large localized electromagnetic field at their interface, where p-ATP resides. Moreover, the fact that large EF values (similar to 1.9 +/- 0.7x10(4) and 9.4 +/- 0.7x10(6) for the 7a- and b(2)-type vibration modes, respectively) were also obtained on a single sandwich structure of Au NPs/p-ATP SAMs/Ag NPs in the visible demonstrates that the electromagnetic coupling does not exist only between Ag NPs but also between Au and Ag NPs.

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

Diluting thiol-derivatized oligonucleotide monolayers on Au(111) by mercaptohexanol replacement reaction

Surface replacement reaction of thiol-derivatized, single-stranded oligonucleotide (HS-ssDNA) by mercaptohexanol (MCH) is investigated in order to reduce surface density of the HS-ssDNA adsorbed to Au(111) surface. Cyclic voltammograms (CVs) and scanning tunneling microscopy (STM) are employed to assess the composition and state of these mixed monolayers. It is found that each CV of mixed self-assembled monolayers (SAMs) only shows a single reductive desorption peak, which suggests that the resulted, mixed SAMs do not form discernable phase-separated domains. The peak potential gradually shifts to negative direction and the peak area increases step by step over the whole replacement process. By analyzing these peak areas, it is concluded that two MCH molecules will replace one HS-ssDNA molecule and relative coverage can also be estimated as a function of exposing time. The possible mechanism of the replacement reaction is also proposed. The DNA surface density exponentially reduces with the exposing time increasing, in other words, the replacement reaction is very fast in the first several hours and then gradually slows down. Moreover, the morphological change in the process is also followed by STM.

Self-assembling process of alkanethiol monolayers on gold surface via underpotential deposition

It was demonstrated feasible that underpotential deposition(UPD) of copper on a monolayer-modified gold substrate can be used to determine the gold electrode area. The deposition and stripping of a Cu adlayer can take Place reversibly and stably at a bared or a self-assembled monolayer modified gold electrode. The growth kinetics of decanethiol/Au was also investigated via Cu UPD. The difference between the assembling kinetics determined by UPD and that by quartz crystal microbalance measurements reveals the configuration transmutation of the assembled molecules from a disordered arrangement to an ordered arrangement during the self-assembling processes.