AFM topography and friction studies of hydrogen-bonded bilayers of functionalized alkanethiols

Riet, Joost te; Smit, Tim; Coenen, Michiel J. J.; Gerritsen, Jan W.; Cambi, Alessandra; Elemans, Johannes A. A. W.; Speller, S.; Figdor, Carl G.

doi:10.1039/c0sm00130a

Cited by 8 publications

(9 citation statements)

References 22 publications

(47 reference statements)

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“…Scanning probe based protocols of nanoshaving and nanografting have been applied to measure the local thickness of organic films [19,20,21], for monitoring adsorption kinetics on surfaces [22,23], to identify functional groups of n -alkanethiols [24,25], and to confine spatially the deposition of DNA [26,27], proteins [17,28,29], and metals [18]. Nanofabrication based on scanning-probe methods requires steps of rastering the probe to write each pattern individually.…”

Section: Introductionmentioning

confidence: 99%

Nanoscale Lithography Mediated by Surface Self-Assembly of 16-[3,5-Bis(Mercaptomethyl)phenoxy]hexadecanoic Acid on Au(111) Investigated by Scanning Probe Microscopy

et al. 2014

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Abstract:The solution-phase self-assembly of bidentate 16-[3,5-bis(mercaptomethyl)phenoxy]hexadecanoic acid (BMPHA) on Au(111) was studied using nano-fabrication protocols with scanning probe nanolithography and immersion particle lithography. Molecularly thin films of BMPHA prepared by surface self-assembly have potential application as spatially selective layers in sensor designs. Either monolayer or bilayer films of BMPHA can be formed under ambient conditions, depending on the parameters of concentration and immersion intervals. Experiments with scanning probe-based lithography (nanoshaving and nanografting) were applied to measure the thickness of BMPHA films. The thickness of a monolayer and bilayer film of BMPHA on Au(111) were measured in situ with atomic force microscopy using n-octadecanethiol as an internal reference. Scanning probe-based nanofabrication provides a way to insert nanopatterns of a reference molecule of known dimensions within a matrix film of unknown thickness to enable a direct comparison of heights and surface morphology. Immersion particle lithography was used to prepare a periodic arrangement of nanoholes within films of BMPHA. The nanoholes could be backfilled by immersion in a SAM solution to produce nanodots of n-octadecanethiol surrounded by a film of BMPHA. Test platforms prepared by immersion particle lithography enables control of the dimensions of surface sites to construct supramolecular assemblies.

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Section: Introductionmentioning

confidence: 99%

Nanoscale Lithography Mediated by Surface Self-Assembly of 16-[3,5-Bis(Mercaptomethyl)phenoxy]hexadecanoic Acid on Au(111) Investigated by Scanning Probe Microscopy

et al. 2014

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“…In particular, 2.8- and 5.8-fold higher integrated intensities were observed at the end of the measurements and before the ultrapure water rinse for SAM–NH 2 compared to SAM–CH 3 and SAM–OH, respectively. Here, it must be noted that amino-terminated SAMs tend to form a bilayer due to hydrogen bonding. , The bilayer contribution into the spectrum intensity in the case of SAM–NH 2 can be estimated after the rinse with ultrapure water based on the signal intensity decrease (Figure b). It is also noteworthy that, after the rinse, the ν asym CH 2 band has slightly shifted (≈1 cm –1 ) to the lower wavenumber indicating a small increase in the organization of SAM–NH 2 after breaking the bilayer (Figure b).…”

Section: Resultsmentioning

confidence: 99%

“…However, it was earlier demonstrated by te Riet et al that SAM−OH did not appear to form interlayer hydrogen bonds. 33 As suggested by these authors, this result could be explained by an unfavorable competition with the formation of strong hydrogen bonds between the molecules within the SAM−OH, or an unfavorable competition with the solvent for hydrogen bonding. Based on these findings and from our observations of the low intensities obtained for SAM−OH (Figure 2a), the organization of SAM−OH was represented by a monolayer on ZnSe.…”

Section: Functionalization Of Znse With Alkanethiols Andmentioning

confidence: 88%

Chemical Functionalization of the Zinc Selenide Surface and Its Impact on Lactobacillus rhamnosus GG Biofilms

Yunda

Alem

Francius

et al. 2020

ACS Appl. Mater. Interfaces

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Bacteria grow on surfaces and form communities called biofilms. Bacterial adhesion and properties of the derived biofilms depend on, among others, the nature of the supporting substrate. Here, we report how the surface properties of the substrate affect the biofilm growth of probiotic Lactobacillus rhamnosus GG (LGG). Hydrophilic (OH), hydrophobic (CH3) and positively charged (NH3 + ) surfaces were obtained by the functionalization of a ZnSe crystal with alkanethiol self-assembled monolayers (SAM). The self-assembly of alkanethiols onto ZnSe was studied in situ using infrared spectroscopy in Attenuated Total Reflection mode (ATR-FTIR). The organization of grafted SAMs was analyzed based on the results of ATR-FTIR, high-energy elastic backscattering spectrometry, and contact angle measurements. The kinetics and adhesion strength of LGG initial attachment as well as its physiological state on surfaces terminated by the different functional groups were assessed by the combination of ATR-FTIR, force measurements based on atomic force microscopy, and fluorescent staining of bacteria. The strength of interactions betweenLGG and the surface was strongly affected by the terminal group of the alkanethiol chain.The -NH3 + groups displayed the highest affinity with LGG at the first stage of interaction. The surface properties also played an important role when LGG biofilms were further grown in a nutritive medium for 24 hours under flow conditions. Notably, the analysis of the infrared spectra recorded during the biofilm cultivation revealed differences in the kinetics of growth and in the polysaccharide features of the biofilm depending on the substrate functionality. LGG biofilm was stable only on the positively charged surface upon rinsing. Findings of this work clearly show that the adhesion features and the growth of LGG biofilms are substrate-dependent.

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“…Moreover, COOH-terminated surfaces are of interest for a wide range of applications. [25][26][27][28][29][30][31][32] There is conicting evidence in the literature regarding the structural properties of such lms showing in some cases a high degree of disorder. 29,31 Since the terminated Soft Matter PAPER carboxylic acid groups are signicantly ionized to carboxylate anions (COO À ) in supporting electrolyte solutions, 33 we have taken the route of exploring layers of the negatively charged carboxylate-functionalized alkanethiols on gold.…”

Section: Introductionmentioning

confidence: 99%

“…[25][26][27][28][29][30][31][32] There is conicting evidence in the literature regarding the structural properties of such lms showing in some cases a high degree of disorder. 29,31 Since the terminated Soft Matter PAPER carboxylic acid groups are signicantly ionized to carboxylate anions (COO À ) in supporting electrolyte solutions, 33 we have taken the route of exploring layers of the negatively charged carboxylate-functionalized alkanethiols on gold. Ultimately, the properties of these monolayers will also be compared with those obtained for both hydroxyl and amino-terminated SAMs in order to study the effect of variations in the polarity of the local microenvironment in the electrochemical process.…”

Section: Introductionmentioning

confidence: 99%

Atomistic and energetic descriptions of self-assembled monolayers of differently endgroup-functionalized alkanethiols adsorbed on the gold substrate by using molecular simulations

2013

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In this paper, we employ molecular dynamics (MD) simulations to obtain microscopic structures and the energy picture of FcC 11 S-/X-C 11 S-Au as a function of the terminal groups (e.g., X ¼ CH 3 , COOH, COO À , CH 2 NH 2 , CH 2 OH). A perturbation formalism has been performed to calculate the macroscopic redox properties of FcC 11 S-/X-C 11 S-Au as a function of the terminal groups. Since the shift as a function of the endgroups is fairly modest, it appears that the magnitude of the change in the simulated redox properties seems to vary with the polarity of the terminal groups of the alkanethiol coadsorbate. To deeply investigate the molecular scale architecture and its effect on the redox properties, the tilt angle, the film thickness and also the distribution of dihedral angles in the trans and gauche configurations have been determined as a function of the terminal groups. From this microscopic description, we have underlined the tendency of the carboxylate-functionalized alkanethiols to deviate from well-arranged structures. The results reported herein underscore the role of H-bonding in the structural properties. A link between the number of intra-layer hydrogen bonds and the disorder of monolayers is clearly established. This work is also completed with an energetic characterization of the SAMs.

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AFM topography and friction studies of hydrogen-bonded bilayers of functionalized alkanethiols

Cited by 8 publications

References 22 publications

Nanoscale Lithography Mediated by Surface Self-Assembly of 16-[3,5-Bis(Mercaptomethyl)phenoxy]hexadecanoic Acid on Au(111) Investigated by Scanning Probe Microscopy

Nanoscale Lithography Mediated by Surface Self-Assembly of 16-[3,5-Bis(Mercaptomethyl)phenoxy]hexadecanoic Acid on Au(111) Investigated by Scanning Probe Microscopy

Chemical Functionalization of the Zinc Selenide Surface and Its Impact on Lactobacillus rhamnosus GG Biofilms

Atomistic and energetic descriptions of self-assembled monolayers of differently endgroup-functionalized alkanethiols adsorbed on the gold substrate by using molecular simulations

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