Limits to the Effect of Substrate Roughness or Smoothness on the Odd–Even Effect in Wetting Properties of n-Alkanethiolate Monolayers

This study investigates the effect of roughness on interfacial properties of an n-alkanethiolate self-assembled monolayer (SAM) and uses hydrophobicity to demonstrate the existence of upper and lower limits. This article also sheds light on the origin of the previously unexplained gradual increase in contact angles with increases in the size of the molecule making the SAM. We prepared Au surfaces with a root-mean-square (RMS) roughness of ∼0.2–0.5 nm and compared the wetting properties of n-alkanethiolate (C10–C16) SAMs fabricated on these surfaces. Static contact angles, θs, formed between the SAM and water, diethylene glycol, and hexadecane showed an odd–even effect irrespective of the solvent properties. The average differences in subsequent SAME and SAMO are Δθs|n  – (n+1)| ≈ 1.7° (n = even) and Δθs|n – (n+1)| ≈ 3.1° (n = odd). A gradual increase in θs with increasing length of the molecule was observed, with values ranging from water 104.7–110.7° (overall Δθs = 6.0° while for the evens ΔθsE = 4.4° and odds ΔθsO = 3.5°) to diethylene glycol 72.9–80.4° (overall Δθs = 7.5° while for the evens ΔθsE = 2.9° and odds ΔθsO= 2.4°) and hexadecane 40.4–49.4° (overall Δθs = 9.0° while for the evens ΔθsE = 3.7° and odds ΔθsO = 2.1°). This article establishes that the gradual increase in θs with increasing molecular size in SAMs is due to asymmetry in the zigzag oscillation in the odd–even effect. Comparison of the magnitude and proportion differences in this asymmetry allows us to establish the reduction in interfacial dispersive forces, due to increasing SAM crystallinity with increasing molecular size, as the origin of this asymmetry. By comparing the dependence of θs on surface roughness we infer that (i) RMS roughness ≈ 1 nm is a theoretical limit beyond which the odd–even effect cannot be observed and (ii) on a hypothetically flat surface the maximum difference in hydrophobicity, as expressed in θs, is ∼3°

Effect of Substrate Morphology on the Odd–Even Effect in Hydrophobicity of Self-Assembled Monolayers

Surface roughness, often captured through root-mean-square roughness (Rrms), has been shown to impact the quality of self-assembled monolayers (SAMs) formed on coinage metals. Understanding the effect of roughness on hydrophobicity of SAMs, however, is complicated by the odd-even effect-a zigzag oscillation in contact angles with changes in molecular length. We recently showed that for surfaces with Rrms \u3e 1 nm, the odd-even effect in hydrophobicitycannot be empirically observed. In this report, we compare wetting properties of SAMs on Ag and Au surfaces of different morphologies across the Rrms similar to 1 nm limit. We prepared surfaces with comparable properties (grain sizes and Rrms) and assessed the wetting properties of resultant SAMs. Substrates with Rrms either below or above the odd-even limit were investigated. With smoother surfaces (lower Rrms), an inverted asymmetric odd-evenzigzag oscillation in static contact angles (?s) was observed with change from Au to Ag. Asymmetry in odd-even oscillation in Au was attributed to a larger change in ?s from odd to even number of carbons in the n-alkanethiol and vice versa for Ag. For rougher surfaces, no odd-even effect was observed; however, a gradual increase in the static contact angle was observed. Increase in the average grain sizes (\u3e3 times larger) on rough surfaces did not lead to significant difference in the wetting properties, suggesting that surface roughness significantly dominated the nature of the SAMs. We therefore infer that the predicted roughness-dependent limit to the observation of the odd-even effect in wetting properties of n-alkanethiols cannot be overcome by creating surfaces with large grain sizes for surfaces with Rrms \u3e 1 nm. We also observed that the differences between Au and Ag surfaces are dominated by differences in the even-numbered SAMs, but this difference vanishes with shorter molecular chain length (=C3)

Assembled Monolayers Depends upon the Roughness of the Substrate and the Orientation of the Terminal Moiety

The origin of the odd even effect in properties of self-assembled monolayers (SAMs) and/or technologies derived from them is poorly understood. We report that hydrophobicity and, hence, surface wetting of SAMs are dominated by the nature of the substrate (surface roughness and identity) and SAM tilt angle, which influences surface dipoles/orientation of the terminal moiety. We measured static contact angles (theta(s)) made by water droplets on n-alkanethiolate SAMs with an odd (SAM(O)) or even (SAM(E)) number of carbons (average theta(s) range of 105.8-112.1 degrees). When SAMs were fabricated on smooth template-stripped metal (M-TS) surfaces [root-mean-square (rms) roughness = 0.36 +/- 0.01 nm for Au-TS and 0.60 +/- 0.04 nm for Ag-TS], the odd-even effect, characterized by a zigzag oscillation in values of theta(s), was observed. We, however, did not observe the same effect with rougher as-deposited (M-AD) surfaces (rms roughness = 2.27 +/- 0.16 nm for Au-AD and 5.13 +/- 0.22 nm for Ag-AD). The odd-even effect in hydrophobicity inverts when the substrate changes from Au-TS (higher theta(s) for SAM(E) than SAM(O), with average Delta theta(s) (vertical bar n - (n + 1)vertical bar) approximate to 3 degrees) to Ag-TS (higher theta(s) for SAM(O) than SAM(E), with average Delta theta(s) (vertical bar n - (n + 1)vertical bar) approximate to 2 degrees). A comparison of hydrophobicity across Ag-TS and Au-TS showed a statistically significant difference (Student\u27s t test) between SAM(E) (Delta theta(s) (vertical bar Ag evens - Au evens vertical bar) approximate to 5 degrees; P \u3c 0.01) but failed to show statistically significant differences on SAM(O) (Delta theta(s) (vertical bar Ag odds) (- Au odds vertical bar) approximate to 1 degrees; p \u3e 0.1). From these results, we deduce that the roughness of the metal substrate (from comparison of M-AD versus M-TS) and orientation of the terminal -CH2CH3 (by comparing SAM(E) and SAM(O) on Au-TS versus Ag-TS) play major roles in the hydrophobicity and, by extension, general wetting properties of n-alkanethiolate SAMs

Application of Ionic Liquids in Pot-in-Pot Reactions

Pot-in-pot reactions are designed such that two reaction media (solvents, catalysts and reagents) are isolated from each other by a polymeric membrane similar to matryoshka dolls (Russian nesting dolls). The first reaction is allowed to progress to completion before triggering the second reaction in which all necessary solvents, reactants, or catalysts are placed except for the starting reagent for the target reaction. With the appropriate trigger, in most cases unidirectional flux, the product of the first reaction is introduced to the second medium allowing a second transformation in the same glass reaction pot—albeit separated by a polymeric membrane. The basis of these reaction systems is the controlled selective flux of one reagent over the other components of the first reaction while maintaining steady-state catalyst concentration in the first “pot”. The use of ionic liquids as tools to control chemical potential across the polymeric membranes making the first pot is discussed based on standard diffusion models—Fickian and Payne’s models. Besides chemical potential, use of ionic liquids as delivery agent for a small amount of a solvent that slightly swells the polymeric membrane, hence increasing flux, is highlighted. This review highlights the critical role ionic liquids play in site-isolation of multiple catalyzed reactions in a standard pot-in-pot reaction

Role of Molecular Dipoles in Charge Transport across Large Area Molecular Junctions Delineated Using Isomorphic Self-Assembled Monolayers

Delineating the role of dipoles in large area junctions that are based on self-assembled monolayers (SAMs) is challenging due to molecular tilt, surface defects, and interchain coupling among other features. To mitigate SAM-based effects in study of dipoles, we investigated tunneling rates across carboranesisostructural molecules that orient along the surface normal on Au (but bear different dipole moments) without changing the thickness, packing density, or morphology of the SAM. Using the Au-SAM//Ga₂O₃-EGaIn junction (where “//” = physisorption, “–” = chemisorption, and EGaIn is eutectic gallium–indium), we observe that molecules with dipole moments oriented along the surface normal (with dipole moment, <i>p</i> = 4.1D for both M9 and 1O2) gave lower currents than when the dipole is orthogonal (<i>p</i> = 1.1 D, M1) at ±0.5 V applied bias. Similarly, from transition voltage spectroscopy, the transition voltages, <i>V</i>_T (volt), are significantly different. (0.5, 0.43, and 0.4 V for M1, M9, and 1O2, respectively). We infer that the magnitude and direction of a dipole moments significantly affect the rate of charge transport across large area junctions with Δ log|J| ≅ 0.4 per Debye. This difference is largely due to effect of the dipole moment on the molecule-electrode coupling strength, Γ, hence effect of dipoles is likely to manifest in the contact resistance, <i>J</i>_o, although in conformational flexible molecules field-induced effects are expected

Limits to the Effect of Substrate Roughness or Smoothness on the Odd–Even Effect in Wetting Properties of n-Alkanethiolate Monolayers

This study investigates the effect of roughness on interfacial properties of an n-alkanethiolate self-assembled monolayer (SAM) and uses hydrophobicity to demonstrate the existence of upper and lower limits. This article also sheds light on the origin of the previously unexplained gradual increase in contact angles with increases in the size of the molecule making the SAM. We prepared Au surfaces with a root-mean-square (RMS) roughness of ∼0.2–0.5 nm and compared the wetting properties of n-alkanethiolate (C10–C16) SAMs fabricated on these surfaces. Static contact angles, θs, formed between the SAM and water, diethylene glycol, and hexadecane showed an odd–even effect irrespective of the solvent properties. The average differences in subsequent SAME and SAMO are Δθs|n  – (n+1)| ≈ 1.7° (n = even) and Δθs|n – (n+1)| ≈ 3.1° (n = odd). A gradual increase in θs with increasing length of the molecule was observed, with values ranging from water 104.7–110.7° (overall Δθs = 6.0° while for the evens ΔθsE = 4.4° and odds ΔθsO = 3.5°) to diethylene glycol 72.9–80.4° (overall Δθs = 7.5° while for the evens ΔθsE = 2.9° and odds ΔθsO= 2.4°) and hexadecane 40.4–49.4° (overall Δθs = 9.0° while for the evens ΔθsE = 3.7° and odds ΔθsO = 2.1°). This article establishes that the gradual increase in θs with increasing molecular size in SAMs is due to asymmetry in the zigzag oscillation in the odd–even effect. Comparison of the magnitude and proportion differences in this asymmetry allows us to establish the reduction in interfacial dispersive forces, due to increasing SAM crystallinity with increasing molecular size, as the origin of this asymmetry. By comparing the dependence of θs on surface roughness we infer that (i) RMS roughness ≈ 1 nm is a theoretical limit beyond which the odd–even effect cannot be observed and (ii) on a hypothetically flat surface the maximum difference in hydrophobicity, as expressed in θs, is ∼3°.Reprinted with permission from Chen, Jiahao, Zhengjia Wang, Stephanie Oyola-Reynoso, Symon M. Gathiaka, and Martin Thuo. "Limits to the effect of substrate roughness or smoothness on the odd–even effect in wetting properties of n-alkanethiolate monolayers." Langmuir 31, no. 25 (2015): 7047-7054,doi:10.1021/acs.langmuir.5b01662. Posted with permission.</p

Characterization of PfTrxR inhibitors using antimalarial assays and in silico techniques

BACKGROUND: The compounds 1,4-napthoquinone (1,4-NQ), bis-(2,4-dinitrophenyl)sulfide (2,4-DNPS), 4-nitrobenzothiadiazole (4-NBT), 3-dimethylaminopropiophenone (3-DAP) and menadione (MD) were tested for antimalarial activity against both chloroquine (CQ)-sensitive (D6) and chloroquine (CQ)-resistant (W2) strains of Plasmodium falciparum through an in vitro assay and also for analysis of non-covalent interactions with P. falciparum thioredoxin reductase (PfTrxR) through in silico docking studies. RESULTS: The inhibitors of PfTrxR namely, 1,4-NQ, 4-NBT and MD displayed significant antimalarial activity with IC(50) values of < 20 μM and toxicity against 3T3 cell line. 2,4-DNPS was only moderately active. In silico docking analysis of these compounds with PfTrxR revealed that 2,4-DNPS, 4-NBT and MD interact non-covalently with the intersubunit region of the enzyme. CONCLUSIONS: In this study, tools for the identification of PfTrxR inhibitors using phenotyphic screening and docking studies have been validated for their potential use for antimalarial drug discovery project

Effect of Substrate Morphology on the Odd–Even Effect in Hydrophobicity of Self-Assembled Monolayers

Surface roughness, often captured through root-mean-square roughness (Rrms), has been shown to impact the quality of self-assembled monolayers (SAMs) formed on coinage metals. Understanding the effect of roughness on hydrophobicity of SAMs, however, is complicated by the odd-even effect-a zigzag oscillation in contact angles with changes in molecular length. We recently showed that for surfaces with Rrms > 1 nm, the odd-even effect in hydrophobicitycannot be empirically observed. In this report, we compare wetting properties of SAMs on Ag and Au surfaces of different morphologies across the Rrms similar to 1 nm limit. We prepared surfaces with comparable properties (grain sizes and Rrms) and assessed the wetting properties of resultant SAMs. Substrates with Rrms either below or above the odd-even limit were investigated. With smoother surfaces (lower Rrms), an inverted asymmetric odd-evenzigzag oscillation in static contact angles (?s) was observed with change from Au to Ag. Asymmetry in odd-even oscillation in Au was attributed to a larger change in ?s from odd to even number of carbons in the n-alkanethiol and vice versa for Ag. For rougher surfaces, no odd-even effect was observed; however, a gradual increase in the static contact angle was observed. Increase in the average grain sizes (>3 times larger) on rough surfaces did not lead to significant difference in the wetting properties, suggesting that surface roughness significantly dominated the nature of the SAMs. We therefore infer that the predicted roughness-dependent limit to the observation of the odd-even effect in wetting properties of n-alkanethiols cannot be overcome by creating surfaces with large grain sizes for surfaces with Rrms > 1 nm. We also observed that the differences between Au and Ag surfaces are dominated by differences in the even-numbered SAMs, but this difference vanishes with shorter molecular chain length (=C3).Reprinted with permission from Wang, Zhengjia, Jiahao Chen, Symon M. Gathiaka, Stephanie Oyola-Reynoso, and Martin Thuo. "Effect of Substrate Morphology on the Odd–Even Effect in Hydrophobicity of Self-Assembled Monolayers." Langmuir 32, no. 40 (2016): 10358-10367, doi:10.1021/acs.langmuir.6b01681. Copyright 2016 American Chemical Society.</p

Determination of antiplasmodial activity and binding affinity of curcumin and demethoxycurcumin towards PfTrxR

In our study, the inhibitory activity of curcuminoids towards Plasmodium falciparum thioredoxin reductase (PfTrxR) was determined using LC-MS-based functional assay and showed that only demethoxycurcumin (DMC) inhibited PfTrxR (IC 50 : 2 μM). In silico molecular modelling was used to ascertain and further confirm that the binding affinities of curcumin and DMC are towards the dimer interface of PfTrxR. The in vitro antiplasmodial activities of curcumin and DMC were evaluated and shown to be active against chloroquine (CQ)-sensitive (D6 clone) and moderately active against CQ-resistant (W2 clone) strains of Plasmodium falciparum while no cytotoxicity was observed against Vero cells