Self-assembly of small molecules at hydrophobic interfaces using group effect

Foster, William; Miyazawa, Keisuke; Fukuma, Takeshi; Kusumaatmaja, Halim; Voïtchovsky, Kislon

doi:10.1039/c9nr09505e

Cited by 30 publications

(22 citation statements)

References 75 publications

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“…A MeOH layer adsorbed on the graphite potentially interferes with this hydrophobic interaction between the peptide and the graphite. In particular, at concentrations more than 30% MeOH, the relatively strong intermolecular interactions between the MeOH molecules and graphite form a thin film of MeOH molecules with a strong network called group effect …”

Section: Resultsmentioning

confidence: 99%

“…These authors have found that the alcohol molecules form a uniform molecular layer having a variety of self-assemblies depending on the alkyl chain length of the alcohol molecules (MeOH, EtOH, 1-prop, and IPA). This effect has been called the “group effect,” which depends on the interactions between the molecules forming the stable network . The layers of the alcohol molecules on the hydrophobic surfaces are stabilized by the group effect and competitively prevent the self-assembly of the peptides.…”

Section: Resultsmentioning

confidence: 99%

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Cosolvents Restrain Self-Assembly of a Fibroin-Like Peptide on Graphite

2021

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Controllable self-assembly of peptides on solid surfaces has been investigated for establishing functional bio/solid interfaces. In this work, we study the influence of organic solvents on the self-assembly of a fibroin-like peptide on a graphite surface. The peptide has been designed by mimicking fibroin proteins to have strong hydrogen bonds among peptides enabling their selfassembly. We have employed cosolvents of water and organic solvents with a wide range of dielectric constants to control peptide self-assembly on the surface. Atomic force microscopy has revealed that the peptides self-assemble into highly ordered monolayer-thick linear structures on graphite after incubation in pure water, where the coverage of peptides on the surface is more than 85%. When methanol is mixed, the peptide coverage becomes zero at a threshold concentration of 30% methanol on graphite and 25% methanol on MoS 2 . The threshold concentration in ethanol, isopropanol, dimethyl sulfoxide, and acetone varies depending on the dielectric constant with restraining self-assembly of the peptides, and particularly low dielectric-constant protic solvents prevent the peptide self-assembly significantly. The observed phenomena are explained by competitive surface adsorption of the organic solvents and peptides and the solvation effect of the peptide assembly.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Cosolvents Restrain Self-Assembly of a Fibroin-Like Peptide on Graphite

2021

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“…SURMOFs are well‐known model systems, based on MOF grown on alkanethiol functionalized gold surfaces [16–18] . Herein, we nanosized the MOF deposits to stimulate defect formation by manipulating the self‐assembly behavior of the thiol molecules promoting/inhibiting MOF growth on the substrates, yielding gapped, and even bifunctional surfaces of HKUST‐1 and ZIF‐8 [19–21] …”

Section: Figurementioning

confidence: 99%

“…[16][17][18] Herein, we nanosized the MOF deposits to stimulate defect formation by manipulating the self-assembly behavior of the thiol molecules promoting/inhibiting MOF growth on the substrates, yielding gapped, and even bifunctional surfaces of HKUST-1 and ZIF-8. [19][20][21] HKUST-1, an archetypical MOF, is highly hydrophilic and has low hydrothermal stability as its paddlewheel SBU hydrolyses in the presence of water vapor. [22,23] On the other hand, Zeolitic-Imidazolate Frameworks (ZIFs), such as ZIF-8, are hydrophobic and show increased hydrothermal and chemical stability.…”

mentioning

confidence: 99%

In situ Nanoscale Infrared Spectroscopy of Water Adsorption on Nanoislands of Surface‐Anchored Metal‐Organic Frameworks

Monai

Meirer

et al. 2020

Angewandte Chemie

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Despite technological advancements, probing gassolid interfaces at the nanoscale is still a formidable challenge. New nano-spectroscopic methods are needed to understand the guest-host interactions of functional materials during gas sorption, separation, and conversion. Herein, we introduce in situ Photoinduced Force Microscopy (PiFM) to evidence sitespecific interaction between Metal-Organic Frameworks (MOFs) and water. To this end, we developed amphiphilic Surface-anchored MOF (SURMOF) model systems using selfassembly for the side-by-side hetero-growth of nanodomains of hydrophilic HKUST-1 and hydrophobic ZIF-8. PiFM was used to probe local uptake kinetics and to show D 2 O sorption isotherms on (defective) HKUST-1 paddlewheels. By monitoring defect vibrations, we visualized in real-time the saturation of existing defects and the creation of D 2 O-induced defects. This work shows the potential of in situ PiFM to unravel gas sorption mechanisms and map active sites on functional (MOF) materials.

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“…Hydrophobic surfaces can be developed through chemical [ 13 ], electrochemical [ 14 ], and physical surface treatments [ 15 ], thereby increasing surface roughness [ 16 ] or forming a surface coating [ 17 ]. To achieve nanoscale roughness on a hydrophobic surface, different techniques such as polymer solution evaporation [ 18 ], sol–gel coating [ 19 ], electrochemical deposition [ 20 ], photolithography [ 21 ], chemical etching [ 22 ], phase separation [ 23 ], self-assembly [ 24 ], and various spraying techniques are used [ 25 , 26 ]. However, these techniques for preparing hydrophobic surfaces are difficult and expensive.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of hydrophobic PLA filaments for additive manufacturing

2022

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There is an ever-greater need for self-cleaning and water-repelling properties of hydrophobic materials at this time in history, mainly due to the coronavirus disease 2019 (COVID-19) pandemic. However, the fabrication processes used to create hydrophobic materials are typically time-consuming and costly. Thus, this study aims to create hydrophobic materials based on low-cost manufacturing. In this study, polylactic acid (PLA) was mixed with various concentrations of hexadecyltrimethoxysilane (HDTMS) and polytetrafluoroethylene (PTFE) with the aid of solvents, chloroform, and acetone, through the solvent casting and melt extrusion process, which is capable of producing hydrophobic PLA filaments suitable for additive manufacturing (AM). Water contact angle (WCA) measurements were performed to verify the improved hydrophobicity of PLA/HDTMS/PTFE filaments. According to the results, it was discovered that the best filament WCAs were achieved with 2 g (10 wt%) of PLA, 0.2 ml of HDTMS, and 1 ml of PTFE (2 g PLA + 0.2 ml HDTMS + 1 ml PTFE), producing an average WCA of 131.6° and the highest WCA of 132.7°. These results indicate that adding HDTMS and PTFE to PLA significantly enhances filament hydrophobicity. Additionally, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) techniques were utilized to characterize the surface morphology, molecular interactions, and thermal decompositions of the prepared PLA/HDTMS/PTFE filaments. This study revealed that compared to 2 g of pure PLA filament, HDTMS and PTFE altered the microstructure of the filament. Its thermal degradation temperature was impacted, but the melting temperature was not. Therefore, the PLA/HDTMS/PTFE filament is good enough to be printed by the fused filament fabrication (FFF) AM process. Graphical abstract

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Self-assembly of small molecules at hydrophobic interfaces using group effect

Abstract: Group effect allows non-tethered small molecules to form a wide variety of self-assembled structures at solid–liquid interfaces.

Cited by 30 publications

References 75 publications

Cosolvents Restrain Self-Assembly of a Fibroin-Like Peptide on Graphite

Cosolvents Restrain Self-Assembly of a Fibroin-Like Peptide on Graphite

In situ Nanoscale Infrared Spectroscopy of Water Adsorption on Nanoislands of Surface‐Anchored Metal‐Organic Frameworks

Fabrication of hydrophobic PLA filaments for additive manufacturing

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