Hydrogen-Bond-Mediated Biomolecular Trapping: Reversible Catch-and-Release Process of Common Biomolecules on a Glycine-Functionalized Si(111)7×7 Surface

Zhang, L.; Chatterjee, Avisek; Leung, K. T.

doi:10.1021/jz101315m

Cited by 8 publications

(16 citation statements)

References 28 publications

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“…When the P2VP chains are in the bulk (300 nm thick spin-coated film), a main peak is found in the N 1s spectra at 399.1 ± 0.1 eV, which is attributed to a single nitrogen atom of a pyridine ring (the seventh plot shown in Figure c). However, all other P2VP(LB) layers show an additional peak at 401.5 ± 0.1 eV, which is assigned to the hydrogen bonded nitrogen atoms of the N···H–O feature, − which implies that the transferred P2VP chains from the air/water interface can strongly adsorb onto a silicon wafer through H-bonding, as indicated in Figure b.…”

Section: Resultsmentioning

confidence: 99%

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films

Kim

2019

ACS Cent. Sci.

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In polymer thin films, the bottom polymer chains are irreversibly adsorbed onto the substrates creating an ultrathin layer. Although this thin layer (only a few nanometers thick) governs all film properties, an understanding of this adsorbed layer remains elusive, and thus, its effective control has yet to be achieved, particularly in block copolymer (BCP) thin films. Herein, we employ self-assembled copolymer adsorption layers (SCALs), transferred from the air/water interfacial self-assembly of BCPs, as an effective control of the adsorbed layer in BCP thin films. SCALs replace the natural adsorbed layer, irreversibly adsorbing onto the substrates when other BCP is additionally coated on the SCALs. We further show that SCALs guide the thin film nanostructures because they provide topological restrictions and enthalpic/entropic preferences for a BCP self-assembly. The SCAL-induced self-assembly enables unprecedented control of nanostructures, creating novel nanopatterns such as spacing-controlled hole/dot patterns, dotted-line patterns, dash-line patterns, and anisotropic cluster patterns with exceptional controllability.

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Section: Resultsmentioning

confidence: 99%

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films

Kim

2019

ACS Cent. Sci.

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“…Moreover, there is a weak N 1s peak at ∼401.0 eV, which can be assigned to N···H−O feature. 10,11,33 For exposures in the transitional layer regime (i.e., above 45 s), the C 1s spectra have been fitted with four components at 284.5, 285.6, 286.6, and 289.2 eV, which are assigned to −CH 2 −S−Si, −CH 2 −SH, −CH 2 −NH−Si, and −COOH, respectively. 17,20 Further exposure to 2400 s increases the N 1s intensity of the N···H−O feature for transitional layer ∼14 times with respect to that for the 45 s exposure (Figure 2a).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Biofunctionalization of Si(111)7×7 by “Renewable” l-Cysteine Transitional Layer

et al. 2014

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Surface functionalization of an inorganic surface with bio-organic molecules is often aimed at creating a "permanent" bio-organic surface with receptor functional groups. We show here that L-cysteine can be used to transform a highly reactive Si(111)7×7 surface to not just a permanent bio-organic surface but also a semipermanent (or renewable) and a temporary bio-organic surfaces by manipulating the exposure. In the early growth stage, the strong bonding between the first cysteine adlayer and the Si substrate through Si-N or Si-S linkages in unidentate or bidentate arrangement provides permanent biofunctionalization by this interfacial layer. This interfacial layer can be used to build a transitional layer (second adlayer) mediated by interlayer vertical hydrogen bonding between an amino group and a carboxylic acid group. Further exposure of cysteine eventually leads to a zwitterionic multilayer film involving electrostatic interactions between cation (-NH3(+)) and anion moieties (-COO(-)). The interlayer hydrogen bonding therefore provides temporary trapping of bio-organic molecules as the second transitional layer that is stable up to 175 °C. This transitional layer can be easily removed by annealing above this temperature and then regenerated with the same molecular layer or a different one by "renewing" the interlayer hydrogen bonds. We also illustrate coverage-dependent adsorption structures of cysteine, from bidentate to unidentate attachments and to self-assembled multimers, involving formation of intralayer horizontal N···H-O hydrogen bonds, by combining our X-ray photoemission data with the local density-of-state images obtained by scanning tunnelling microscopy.

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“…Molecular interactions of biomaterials with semiconductor surfaces have attracted much recent attention because of their applications in biosensors, biocompatible materials, and biomolecule-based electronic devices. − Among the most fundamental biomolecules, amino acids and nucleotides are the basic building blocks of larger biological materials such as proteins, peptides, and DNAs. One of the most challenging questions when studying the adsorption behavior of amino acids on a metal or semiconductor surface is “What are the driving forces and film growth mechanisms for their adsorption on these surfaces?” Despite the large number of studies of adsorbed amino acids on various surfaces of single-crystal metals, − only a few investigations of their adsorption on semiconductor surfaces − have been reported. A major impetus behind the research in biological surface chemistry of semiconductors is their potential to convert biological information directly into electrical signals.…”

Section: Introductionmentioning

confidence: 99%

Surface-Mediated Hydrogen Bonding of Proteinogenic α-Amino Acids on Silicon

2016

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Understanding the adsorption, film growth mechanisms, and hydrogen bonding interactions of biological molecules on semiconductor surfaces has attracted much recent attention because of their applications in biosensors, biocompatible materials, and biomolecule-based electronic devices. One of the most challenging questions when studying the behavior of biomolecules on a metal or semiconductor surface is "What are the driving forces and film growth mechanisms for biomolecular adsorption on these surfaces?" Despite a large volume of work on self-assembly of amino acids on single-crystal metal surfaces, semiconductor surfaces offer more direct surface-mediated interactions and processes with biomolecules. This is due to their directional surface dangling bonds that could significantly perturb hydrogen bonding arrangements. For all the proteinogenic biomolecules studied to date, our group has observed that they generally follow a "universal" three-stage growth process on Si(111)7×7 surface. This is supported by corroborating data obtained from a three-pronged approach of combining chemical-state information provided by X-ray photoelectron spectroscopy (XPS) and the site-specific local density-of-state images obtained by scanning tunneling microscopy (STM) with large-scale quantum mechanical modeling based on the density functional theory with van der Waals corrections (DFT-D2). Indeed, this three-stage growth process on the 7×7 surface has been observed for small benchmark biomolecules, including glycine (the simplest nonchiral amino acid), alanine (the simplest chiral amino acid), cysteine (the smallest amino acid with a thiol group), and glycylglycine (the smallest (di)peptide of glycine). Its universality is further validated here for the other sulfur-containing proteinogenic amino acid, methionine. We use methionine as an example of prototypical proteinogenic amino acids to illustrate this surface-mediated process. This type of growth begins with the formation of a covalent-bond driven interfacial layer (first adlayer), followed by that of a transitional layer driven by interlayer and intralayer hydrogen bonding (second adlayer), and then finally the zwitterionic multilayers (with intralayer hydrogen bonding). The important role of surface-mediated hydrogen bonding as the key for this universal three-stage growth process is demonstrated. This finding provides new insight into biomolecule-semiconductor surface interactions often found in biosensors and biomolecular electronic devices. We also establish the trends in the H-bond length among different types of the hydrogen bonding for dimolecular structures in the gas phase and on the Si(111)7×7 surface, the latter of which could be validated by their STM images. Finally, five simple rules of thumb are developed to summarize the adsorption properties of these proteinogenic biomolecules as mediated by hydrogen bonding, and they are expected to provide a helpful guide to future studies of larger biomolecules and their potential applications.

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Hydrogen-Bond-Mediated Biomolecular Trapping: Reversible Catch-and-Release Process of Common Biomolecules on a Glycine-Functionalized Si(111)7×7 Surface

Cited by 8 publications

References 28 publications

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films

Biofunctionalization of Si(111)7×7 by “Renewable” l-Cysteine Transitional Layer

Surface-Mediated Hydrogen Bonding of Proteinogenic α-Amino Acids on Silicon

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