Alkane Surface Research Articles

Effect of molecular branching and surface wettability on solid-liquid surface tension and line-tension of liquid alkane surface nanodroplets

HypothesisSurface nanodroplets have important technological applications. Previous experiments and simulations have shown that their contact angle deviates from Young's equation. A modified version of Young's equation considering the three-phase line tension (τ) has been widely used in literature, and a wide range of values for τ are reported. We have recently shown that molecular branching affects the liquid–vapour surface tension γlv of liquid alkanes. Therefore, the wetting behaviour of surface nanodroplets should be affected by molecular branching. This study conducted molecular dynamics (MD) simulations to gain insight into the wetting behaviour of linear and branched alkane nanodroplets on oleophilic and oleophobic surfaces. We aim to examine the Young equation's validity and branching's effect on fundamental properties, including solid–liquid surface tension γsl and line tension τ. SimulationsThe simulations were performed on a linear alkane, triacontane (C30H62), as well as four of its branched isomers: 2,6,13,17-tetrapropyloctadecane,2,6,9,10,13,17-hexaethyloctadecane, 2,5,7,8,11,12,15-heptaethylhexadecane and 2,3,6,7,10,11-hexapropyldodecane. Nanodroplets with a diameter of approximately 15 nm were released onto the surfaces, and their contact angles were measured. Additionally, using a novel approach, the solid–liquid surface tension (γsl), the validity of Young's equation and line tension for all alkane and surface combinations are determined. FindingsIt was discovered that the calculated γsl, deviated from the theoretical γsl,Young predicted from Young's equation for all alkanes on oleophilic surfaces. However, this deviation was minimal for branched alkanes on the oleophobic surfaces but more significant for the linear alkane. The findings indicated that γsl < 0 for oleophilic surfaces and γsl > 0 for oleophobic surfaces. Moreover, it was observed that |γsl| was lower for branched molecules and decreased as branching increased. Line tension values were then determined through a novel method, showing τ was positive for oleophilic surfaces ranging from 1.30 × 10-10 to 6.27 × 10-11N. On an oleophobic surface, linear alkane shows a negative line tension of −1.15 × 10-10N and branched alkanes up to two orders of magnitude lower values ranging from −2.09 × 10-12 to 2.43 × 10-11N. Line tension values between −1.15 × 10-10 and + 1.1 × 10-10N are calculated for various linear alkane and surface combinations. These findings show the dependence of line tension on the contact angle and branching, demonstrating that for linear alkanes, τ is significant, whereas, for branched alkanes, line tension is smaller or negligible for large contact angles.

Adsorption Characteristics of Alkanes with Different Carbon Numbers in Kaolinite Slits

Shale oil is of interest for unconventional oil and gas exploration and development and has abundant geological reserves. Shale reservoirs contain numerous nanopores. Understanding the adsorption state of shale oil in the nanopores of shale is beneficial to improve the recovery of shale oil. In this study, the adsorption properties of shale oil in kaolinite slit pores were investigated by molecular dynamics simulation. In order to study the adsorption characteristics of shale oil with different components, a single-component model from n-C8 to n-C15 was established, and a mixed model of n-C8 and n-C15 with different mass ratios represented different crude oil components. The results show that the adsorption capacity per unit area increases with the increase of the alkane carbon number. The adsorption capacity of alkanes on the surface of silicon-oxygen tetrahedron is greater than that on the surface of aluminium-oxygen octahedron. The interaction force between kaolinite and alkane surface increases with the increase of alkane carbon number. The alkane adsorption capacity of silicon-oxygen tetrahedron is stronger than that of aluminium-oxygen octahedron. Competitive adsorption also exists between alkane molecules. Alkanes with higher carbon numbers are more easily adsorbed on the surface of kaolinite. Light alkanes are more likely to exist in free form than heavy alkanes. Based on molecular simulations, we studied the adsorption capacity of alkanes with different carbon numbers and calculated the adsorption capacity per unit area in the pores. It provides a theoretical basis for the calculation of shale oil geological reserves.

An experimental investigation of light emission produced in the process of positronium formation in matter.

The excess energy emitted during the positronium (Ps) formation in condensed matter may be released as light. Spectroscopic analysis of this light can be a new method of studying the electronic properties of materials. We report the first experimental attempt, according to our knowledge, to verify the existence of this emission process. As a result, the possibility of the emission of photons during Ps formation is within the experimental uncertainty in two different solids: an n-alkane and porous silica. However, it seems that the Ps formation on the alkane surface is not accompanied by the emission of photons with energy in the detection range of 1.6-3.8 eV. Various processes that can influence the energy of the photon emitted during the Ps formation are discussed to elucidate this issue. To aid future experiments, equations were developed to estimate the expected ratio of light emission events to annihilation events with the presence or absence of a photon during the Ps formation.

Influence of Semifluorinated Alkane Surface Domains on Phase Behavior and Linear and Nonlinear Viscoelasticity of Phospholipid Monolayers.

Semifluorinated alkanes self-assemble into 30-40 nm-large surface domains (hemimicelles) at the air/water interface. They have been drawing increasing attention to stabilize microbubbles coated with lipids, which are used for enhancing the contrast in sonographic imaging. Although previous studies suggested that semifluorinated alkanes increase the stability of phospholipid membranes, little is known about how semifluorinated alkanes influence phase behaviors and mechanical properties of lipid-coated microbubbles. As a well-defined model of microbubble surfaces, we prepared monolayers consisting of a mixture of phospholipids and semifluorinated alkanes at the air/water interface and investigated the influence of hemimicelles of semifluorinated alkanes on the phase behavior and interfacial viscoelastic properties of phospholipid monolayers. Hemimicelles are phase-separated from phospholipids and accumulate at the phase boundary, which strongly modulates the correlation between solid phospholipid domains. Intringuingly, we found that the mixed monolayer of semifluorinated alkanes and phospholipids possesses linear and nonlinear viscoelastic properties comparable to those of phospholipid monolayers. Since the mixing of semifluorinated alkanes and phospholipids enables one to overcome the intrinsically low stability of pure semifluorinated alkanes against the change in the surface area of microbubbles through the partial dissolution of gas into the aqueous phase, this is a promising strategy for the stable coating of microbubbles in ultrasound diagnosis.

Toward prediction of surface tension of branched n-alkanes using ANN technique

This study features the application of artificial neural network for prediction of surface tension of branched alkanes. Surface and interfacial tensions of alkanes show a specific interaction between adjacent molecules of the higher n-alkanes which results in an anisotropic dispersion force component of the surface energy. The surface tension of branched alkanes was studied for temperatures between 283.15 and 448.15 K. Two intelligent models named multilayer perceptron model (MLP) and radial basis function (RBF) model were developed and the accuracy of two models was examined by different graphical and statistical methods. Results showed that the both models are accurate and effective in prediction of surface tension of branched alkanes. However, the results were compared with experimental data and it was found that the estimated surface tension by multi-layer perceptron neural network is more accurate than radial basis function network.

Formation of Alkanethiol Supported Hybrid Membranes Revisited.

A phospholipid monolayer supported on an alkanethiol self-assembled monolayer (SAM) constitutes a supported hybrid membrane, a model of biological membranes optimized for electronic access through the underlying metal support surface. It is believed that phospholipids, when deposited from aqueous liposome suspension, spontaneously cover the alkanethiol-modified surface, owing to the reduction of surface free energy of the hydrophobic alkane surface exposed to the solution. However, the formation of the hybrid layer has to overcome significant energy barriers in rupturing the vesicle and "unzipping" the membrane leaflets; hence drivers of the spontaneous hybrid membrane formation are unclear. In this work, the authors studied the efficiency of the liposome deposition method to form hybrid membranes on octanethiol and hexadecanethiol SAMs in aqueous environment. Using quartz crystal microbalance to monitor the deposition process it was found that the hybrid membrane did not form spontaneously; the deposit was dominated by hemi-fused liposomes that can only be removed by applying osmotic stress. However, osmotic stress yielded a reproducible layer characterized by ≈-5Hz frequency change that is also confirmed by fluorescence microscopy imaging, irrespective of lipid concentration and the chain length of the SAMs. The frequency change is ≈20% of the frequency change expected for a tightly bound bilayer membrane, or 40% of a single leaflet, suggesting that the lipid layer is in a different conformation compared to a bilayer membrane: the acyl chains are most likely parallel to the SAM surface, likely due to strong hydrophobic interaction. Comparing these results to the literature it appears that the initial formation of hybrid membranes is inhibited by the ionic environment, while osmotic stress leads to the observed unique layer conformation.

Bioinspired Solid Organogel Materials with a Regenerable Sacrificial Alkane Surface Layer.

In nature, lifetime-long functionalities of land plant leaves rely on the regenerability as well as the solid feature of the epicuticular wax layer. Inspired by the regenerable solid epicuticular wax on land plant leaf surfaces, herein a type of solid organogel material with regenerable sacrificial alkane surface layer is reported. This type of surface material is demonstrated to be of great practical importance for tackling solid deposition, such as anti-icing, antigraffiti, and antifouling, since the deposited foreign materials can be easily removed together with the alkane surface layer. Significantly, the solid alkane layer does not contaminate nearby surfaces due to its solid nature in both working and stand-by conditions, which is completely different to liquid-infused materials.

On the determination of the crystal-vapor surface free energy, and why a Gaussian expression can be accurate for a system far from Gaussian

The crystal-vapor surface free energy γ is an important physical parameter governing physical processes, such as wetting and adhesion. We explore exact and approximate routes to calculate γ based on cleaving an intact crystal into non-interacting sub-systems with crystal-vapor interfaces. We do this by turning off the interactions, ΔV, between the sub-systems. Using the soft-core scheme for turning off ΔV, we find that the free energy varies smoothly with the coupling parameter λ, and a single thermodynamic integration yields the exact γ. We generate another exact method, and a cumulant expansion for γ by expressing the surface free energy in terms of an average of e(-βΔV) in the intact crystal. The second cumulant, or Gaussian approximation for γ is surprisingly accurate in most situations, even though we find that the underlying probability distribution for ΔV is clearly not Gaussian. We account for this fact by developing a non-Gaussian theory for γ and find that the difference between the non-Gaussian and Gaussian expressions for γ consist of terms that are negligible in many situations. Exact and approximate methods are applied to the (111) surface of a Lennard-Jones crystal and are also tested for more complex molecular solids, the surface of octane and nonadecane. Alkane surfaces were chosen for study because their crystal-vapor surface free energy has been of particular interest for understanding surface freezing in these systems.

Quadruply Hydrogen Bonding Modules as Highly Selective Nanoscale Adhesive Agents

Covalently linking DNA base analogues DAN, DeUG, or UPy to glass slides led to functional surfaces that could be glued together using a functionalized polystyrene displaying the complementary recognition unit. Nonspecific adhesion was minimized with fluorinated alkane (Teflon-like or Scotchgard-like) surfaces.

Theoretical study of the dynamics of F+alkanethiol self-assembled monolayer hydrogen-abstraction reactions

The dynamics of the reactions of F atoms with octanethiol self-assembled monolayers (SAMs) has been studied using theoretical methods. F+SAM classical trajectories have been propagated directly using a quantum-mechanics (QM)/molecular-mechanics scheme in which the QM portion is described using a specific-reaction-parameters (SRP) semiempirical Hamiltonian. This SRP Hamiltonian has been derived using ab initio information of model gas-phase F+alkane reactions and its accuracy has been calibrated via comparison of the result of direct-dynamics calculations with available experiments on the F+CH(4)-->HF+CH(3) and F+C(2)H(6)-->HF+C(2)H(5) reactions. The F+SAM calculations are used to analyze HF product-energy distributions at collision energies ranging from 0.80 to 11.53 kcal mol(-1) and 0 degrees, 30 degrees, and 60 degrees incident angles with respect to the surface normal. The calculations show that while the HF product is vibrationally excited, it desorbs translationally and rotationally cold at all collision energies and incident angles explored. The calculated results shed light into recent experiments of F-atom reactions with liquid alkane surfaces by providing mechanistic understanding of the factors that govern the amount of energy deposited into the various degrees of freedom of the HF product. Specifically, examination of the dynamics of postreaction HF collisions with the surface shows the role that secondary collisions play in quenching rotational and translational excitation of HF before desorption from the surface.

Heterogeneous reactions of H and O2 with solid alkanes

The paper describes a new source of surface organic radicals whose special feature is a low rate of the initiation of alkyl radicals in reactions of H atoms with the surface of alkanes. A special reactor design was used to accumulate radicals at room temperature and observe alkoxyl radicals RO by the EPR method. For this purpose, alkanes were deposited on aerosil and placed into an EPR cavity. Thanks to the large area of aerosil loads (∼103 cm2), we were able to obtain a stable signal corresponding to a ∼1017 total amount of alkoxyl radicals (the degree of surface coverage ∼0.1%). When O2 was introduced into the reactor in concentrations of 1015–1016 cm−3, a sharp decrease in the signal from surface organic radicals was observed. The process was described as the first-order (RO)s + O2 → HO2 + ketone reaction with a 1.7 × 10−17 cm3 s−1 rate constant.

Molecular shape-selective detection by tin oxide film sensor modified with chemical vapor deposition of molecular-sieving silica overlayer using organic template

A film (several hundred micrometers in thickness) made of tin oxide powder was loaded on an insulator plate, and the particle surface was covered with a molecular-sieving silica overlayer by a chemical vapor deposition method using a molecular template. Electrical response as a chemical sensor was then examined to hexane isomers. The SiO 2/SnO 2 sensor prepared using benzaldehyde as a template showed a high response to linear hexane, while quite low responses were observed to branched isomers (2-methylpentane and 2,2-dimethylbutane). It is suggested that the branched isomers could not react with the tin oxide surface because they could not penetrate into the cavities in the silica overlayer templated by the pre-adsorbed molecules. SiO 2/SnO 2 prepared using a butanal template also showed quite low responses to the branched alkanes, and in addition, the response to hexane was slow. Use of a 1-naphthaldehyde template allowed the reactions of all the examined isomers. These are in agreement with molecular models, showing that the response was controlled by the shapes of alkane molecules and surface cavities; the latter had been controlled by the molecular shape of the template. Thus, clear shape selectivity was demonstrated for the sensing of hydrocarbons. The selectivity was low on a bulky pellet sensor (5 mm thickness and 10 mm diameter), where the branched alkanes showed relatively high responses even in the case that benzaldehyde was used as a template. X-ray photoelectron spectroscopy showed that the concentrations of the template and silica were low inside the pellet, resulting in the high responses to the branched alkanes of the pellet. The high selectivity was obtained by changing the sensor morphology from the pellet to the film.

Magnetic and microstructural analysis of palladium nanoparticles with different capping systems

Palladium nanoparticles capped with different protective systems in a size range between 1.2 and 2.4 nm have been obtained by varying the preparation chemical method. Magnetization curves for all the samples show hysteresis loops, evidencing a ferromagnetic or a permanent magnetism in the nanoparticles. The microstructure of the nanoparticles has been analyzed by x-ray absorption and transmission electron microscopy. The nature of the magnetic behavior found for all these Pd nanoparticles (NPs) is different depending on their sizes and structural features and is explained on the basis of two different suggested mechanisms. The particles protected by means of a surfactant (tetralkylammonium salts), present a ferromagnetic order related to the factors increasing the density of states just below the Fermi level. Whereas, when the nanoparticles are stabilized by covalent bonds with protective species (thiol derivatized alkane chains or surface oxidized Pd NPs), the increase of the $4d$ density of holes, localized by the bonded atoms (S or O), is giving rise to the observed ferromagneticlike behavior.

Catalytic autoignition of higher alkane partial oxidation on Rh-coated foams

Through online mass spectrometry it is demonstrated that steady-state production of syngas (CO and H 2) can be attained within 5 s after admitting large alkanes ( i-octane, n-octane, n-decane, or n-hexadecane) and air into a short-contact-time reactor by using an automotive fuel injector and initially preheating the Rh-coated catalyst above the respective catalytic autoignition temperature for each fuel. Minimum catalytic autoignition temperatures on Rh were ∼260 °C for n-octane and 240 °C for i-octane and n-decane. In contrast, catalytic autoignition of n-hexadecane indirectly occurred at temperatures (>220 °C) lower than those of the other fuels investigated because of exothermic homogeneous chemistry that preheated the catalyst (30–60 °C) to a temperature (∼280 °C) sufficient for surface lightoff. Additionally, the ignition kinetics for the large alkanes were determined and compared with those of methane. The step controlling surface ignition possessed an apparent activation energy of ∼78 kJ/mol that was not significantly different between fuels ( p > 0.05). However, a significant difference was found between the ignition preexponential for methane, O(10 4 s −1), and the other large alkanes, O(10 6 −1). The dominant energetic step for large alkane surface ignition is hypothesized to be oxygen desorption at saturation coverage as has been suggested for methane.

Intermolecular Potential To Represent Collisions of Protonated Peptide Ions with Fluorinated Alkane Surfaces

The MP2/6-311++G(2df,2pd) level of theory was used to calculate intermolecular potential curves between CF(4), as a model for the C and F atoms of a fluorinated alkane surface, and CH(4), NH(3), NH(4)(+), H(2)CO, and H(2)O as models for different types of atoms and functional groups comprising protonated peptide ions. This level of theory was tested by comparisons with the MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ theories. Explicit-atom (EA) analytic potential energy functions were then derived by fitting these potential energy curves with two-body potentials between the atoms of the two interacting molecules. An intermolecular potential for the interaction of a protonated peptide ion with a fluorinated alkane surface may be constructed from these two-body potentials. Intermolecular potentials, for which CF(4) is treated as a united atom (UA), were developed by isotropically averaging the CF(4) orientation for each of the EA potential energy curves. The intermolecular potential energy curves calculated for CF(4) are compared with curves calculated previously for CH(4) interacting with the same molecules, to consider the relative efficiency of energy transfer for protonated peptide ion collisions with hydrogenated and fluorinated alkane surfaces.

An ab Initio Study on the Torsional Surface of Alkanes and Its Effect on Molecular Simulations of Alkanes and a DPPC Bilayer

Energies of 119 conformations of normal alkanes from butane to heptane were calculated at approximately the CCSD(T)/cc-pVQZ level. Energies of gauche (g) conformers relative to trans (t) decrease as chain length increases. In what is termed the "positive pentane effect", adjacent gauche conformers of the same sign are stabilized compared to nonadjacent conformers; e.g., for hexane the energies of tgt, tgg, and gtg are 0.600, 0.930, and 1.18 kcal/mol, respectively. Torsional terms in the CHARMM27 (C27) force field were fit to the calculated QM energies to yield a revised potential, C27r. Molecular dynamics simulations of normal alkanes (heptane, decane, tridecane, and pentadecane) with C27r yield higher populations of gauche states, increased transition rates, and improved agreement with experiment as compared to C27. In addition, C27r simulations of a hydrated DPPC lipid bilayer yield improved agreement with the experimental NMR deuterium order parameters for the aliphatic chain ends.

The hydrophobicity of nanostructured alkane and perfluoro alkane surfaces: A comparison by molecular dynamics simulation

In this contribution we investigate the differences in the hydrophobicity of a perfluoro-n-eicosane crystal and the n-eicosane crystal by molecular dynamics simulation. The results were analysed in terms of density of water at the interface, the chemical potential of water at the interface and the orientational ordering of water at the interface. The perfluoro-n-eicosane crystal-water interface is found to have a less density, higher chemical potential and a weaker orientational ordering at the interface than the corresponding n-eicosane crystal.

Atmospheric evolution of organic aerosol

We report here results of an experimental study of the OH‐initiated oxidation of solid organics in the presence of O2, NOx and H2O, using two kinds of self‐assembled organic monolayers (alkane and aromatic), paraffin and pyrene films as proxies for organic aerosol. We show that the OH‐initiated oxidation of the alkane surfaces leads to rapid volatilization. The gas‐phase products detected include HO2, H2O2, CO, CO2, HCO, CH2O, CH3CHO, CH3OH, and HCOOH. We conclude that volatilization is at least as efficient as wet deposition as a removal process for aliphatic particulates, whereas aromatic particulates show higher stability towards volatilization.

Prediction of Molecular Volume and Surface of Alkanes by Molecular Topology.

Molecular volume and molecular surface are expressed as a function of topological degree in alkane graphs. This allows not only a straightforward approach to calculate such physicochemical magnitudes but also an interpretation of the role of the local vertex invariant (LOVI) or valence degree, delta, as well as the connectivity indices in the prediction of physicochemical properties. The interpretation is based on the concept of molecular accessibility (as introduced by Estrada, J. Phys. Chem. A 2002, 106, 9085) for which precise mathematical definitions are provided.

Prediction of molecular volume and surface of alkanes by molecular topology.

Molecular volume and molecular surface are expressed as a function of topological degree in alkane graphs. This allows not only a straightforward approach to calculate such physicochemical magnitudes but also an interpretation of the role of the local vertex invariant (LOVI) or valence degree, delta, as well as the connectivity indices in the prediction of physicochemical properties. The interpretation is based on the concept of molecular accessibility (as introduced by Estrada, J. Phys. Chem. A 2002, 106, 9085) for which precise mathematical definitions are provided.