Alkane/Alcohol mixed monolayers at the solid/liquid interface

In this work, we present the behavior of solid monolayers of binary mixtures of alkanes and alcohols adsorbed on the surface of graphite from their liquid mixtures. We demonstrate that solid monolayers form for all the combinations investigated here. Differential scanning calorimetry (DSC) is used to identify the surface phase behavior of these mixtures, and elastic neutron incoherent scattering has been used to determine the composition of the mixed monolayers inferred by the calorimetry. The mixing behavior of the alcohol/alkane monolayer mixtures is compared quantitatively with alkane/alkane and alcohol/alcohol mixtures using a regular solution approach to model the incomplete mixing in the solid monolayer with preferential adsorption determining the surface composition. This analysis indicates the preferential adsorption of alcohols over alkanes of comparable alkyl chain length and even preferential adsorption of shorter alcohols over longer alkanes, which contrasts strongly with mixtures of alkane/alkane and alcohol/alcohol of different alkyl chain lengths where the longer homologue is always found to preferentially adsorb over the shorter. The alcohol/alkane mixtures are all found to phase separate to a significant extent in the adsorbed layer mixtures even when molecules are of a similar size. Again, this contrasts strongly with alkane/alkane and alcohol/alcohol mixtures where, although phase separation is found for molecules of significantly different size, good mixing is found for similar size species.     

Self-assembly at the liquid/solid interface: STM reveals

The liquid/solid interface provides an ideal environment to investigate self-assembly phenomena, and scanning tunneling microscopy (STM) is the preferred methodology to probe the structure and the properties of physisorbed monolayers on the nanoscale. Physisorbed monolayers are of relevance in areas such as lubrication, patterning of surfaces on the nanoscale, and thin film based organic electronic devices, to name a few. It's important to gain insight in the factors which control the ordering of molecules at the liquid/solid interface in view of the targeted properties. STM provides detailed insight into the importance of molecule-substrate (epitaxy) and molecule-molecule interactions (hydrogen bonding, metal complexation, and fluorophobic/fluorophilic interactions) to direct the ordering of both achiral and chiral molecules on the atomically flat surface. By controlling the location and orientation of functional groups, chemical reactions can be induced at the liquid/solid interface, via external stimuli, such as light, or by controlled manipulation with the STM tip. The electronic properties of the self-assembled physisorbed molecules can be probed by taking advantage of the operation principle of STM, revealing spatially resolved intramolecular differences within these physisorbed molecules.     

Dynamic behaviour of hydrosoluble polymers at a solid/liquid interface

The behaviour of flexible hydrosoluble polymers of high molecular weight: polyacrylamide and two polyacids, poly(α, L-glutamic acid) and a copolymer of maleic acid was investigated in the context of their dynamic behaviour at solid/liquid interfaces. The adsorption rate is related to the structure of the surface in terms of remaining interacting surface sites. The desorption rate was measured by carrying out adsorption with radioactive labelled polymers, followed by exchange with unlabelled polymers. The slow exchange rate observed suggests a metastable equilibrium state owing to strong multisegment adsorption in the potential well of the surface. However, the “diffuse” polymer layer formed by loops which extend in the aqueous phase within distances of several hundred Angstroms “responds” reversibly to a change in the solvent composition. The latter effect was found by recording the hydrodynamic permeability of pores covered by the adsorbed polymer; the permeability to fluid flow is very sensitive to the loop layer thickness.     

Tuning molecular orientation with STM at the solid/liquid interface

Triptycene molecular orientation has been tuned with a STM tip at a Cu(111) surface in solution from flat, to tilt, to vertical. The tuning is completely bias dependent and reversible. The study is important in the fields of nanoscience and technology.     

Dynamic behavior of flexible polymers at a solid/liquid interface

The mean time spent by a macromolecule at a solid/liquid interface is analyzed in the region of adsorption saturation. The method consists of carrying out preliminary adsorption with radioactively labeled high-molecular-weight polyacrylamide and subsequently exposing the surface to a solution of unlabeled polyacrylamide. It was found that, apart from a small fraction of polymers “loosely” attached, the exchange between labeled and unlabeled polymers takes place at the interface at a very slow rate. Furthermore, desorption of surface molecules occurs only in the presence of a solution, and then the rate of desorption increases proportionally to the number of molecules in the solution. A mechanism based on a bimolecular chemical exchange process is proposed.     

Static electrification of solid oxide in liquid metal and electrical double layer at the interface

Static electrification of a solid oxide, say a semiconducting oxide in liquid metal, is mainly due to electron transfer between two phases. Excess electrons in the liquid metal phase provided by the oxide give rise to an electrical double layer at the interface. The electrical double layer may be divided into three parts, an immobile inner layer, a compressed diffuse layer, and a flat layer extending into the bulk liquid metal. Differential potential analysis and the induced emf method were used to measure the potential of the compressed diffuse layer and the excess electron density of the flat layer, respectively. Results show that most oxides in liquid metals carry positive charges on their surfaces and the potentials of the compressed diffuse layer are in the range of 3 to 42 microV. Such a low potential implies that the diffuse layer is considerably compressed. The excess electron densities of the flat layer are on the order of 10(22) electrons/m(3) of Hg and their contributions to surface charges of oxide are in the range of 10(17) to 10(18) charges/m(2) for the oxide/mercury systems with a solid density of 0.3 wt% at room temperature.     

Molecular patterning at a liquid/solid interface: the foldamer approach

Molecular patterning has received a lot of attention in the past decade; however, the functionalization of these surface-confined 2D patterns on the nanoscale level remains a challenge. Assembling 2D patterns from oligomeric foldamers turns out to be an interesting approach to accomplishing the controlled positioning of functional elements. We designed a family of peptidomimetic foldamers bearing a 2D turn element folding at the liquid/solid interface. The turning element was developed while studying derivatives with one turning unit. Furthermore, folding was found to be induced by the confinement of the surface. This achievement paves the way for the design of foldamers with multiple turns, providing a higher versatility in the functionalization of nanopatterns.     

X-ray reflectivity measurements of layer-by-layer films at the solid/liquid interface

In this Letter, we present a method for the decoration of layer-by-layer (LbL) structures by heavy metal ions, which allows X-ray reflectivity (XRR) measurements at the solid/water interface. The improved contrast has allowed us to obtain well-structured X-ray reflectivity curves from samples at the liquid/solid interface that can be used for the film structure modeling. The developed technique was also used to follow the formation of complexes between DNA and the LbL multilayer. The XRR data are confirmed by independent null-ellipsometric measurements at the solid/liquid interface on the very same architectures.     

Two-dimensional self-assembly of linear molecular rods at the liquid/solid interface

We report on the synthesis and scanning tunneling microscopy (STM) studies of a series of linear molecular rods (1-5) comprising different numbers and/or spatial arrangements of perfluorinated benzene and benzene subunits interlinked with diacetylenes in the para position and decorated with or without terminal dodecyl chains. The molecules organize themselves into well-ordered 2D crystal structures at the liquid/solid interface through intermolecular and molecule-substrate interactions. Whereas the molecules substituted by dodecyl chains form the lamellar structures with alternating rigid core rows and alkyl chain rows, the unsubstituted ones change the orientation of the rigid backbones with respect to the lamellar axis. The molecular arrangement is not influenced by fluoro substituents on any phenyl ring of the backbone, which suggests that the interactions between the π-conjugated backbones are dominated by close packing rather than by the dipole moments of the rods or fluorine-based intermolecular interactions.     

Supramolecular nanopatterns self-assembled by adenine-thymine quartets at the liquid/solid interface

By means of scanning tunneling microscopy (STM), we have observed for the first time well-ordered supramolecular nanopatterns formed by mixing two complementary DNA bases: adenine (A) and thymine (T), respectively, at the liquid/solid interface. By mixing A and T at a specific mixing molar ratio, cyclic structures that were distinctly different from the structures observed by the individual base molecules separately were formed. From an interplay between the STM findings and self-consistent charge density-functional based tight-binding (SCC-DFTB) calculation method, we suggest formation of A-T-A-T quartets constructed on the basis of A-T base pairing. The formation of the A-T-A-T quartets opens new avenues to use DNA base pairing as a way to form nanoscale surface architecture and biocompatible patterned surfaces particularly via host-guest complexation that might be suitable for drug design, where the target can be trapped inside the cavities of the molecular containers.     

Formation of a non-crystalline bimolecular porous network at a liquid/solid interface

An equimolar mixture of two structurally related molecular building blocks self-assembles into a 2D non-crystalline bimolecular porous pattern at a liquid-solid interface as revealed by scanning tunneling microscopy.     

Vermiculite-aliphatic amine interactions at the solid/liquid interface: a thermodynamic approach

Polar n-alkylmonoamines of general formula H₃C(CH₂) _n NH₂ (n = 1, 3, 5) interacted with layered silicate vermiculite at the solid/liquid interface. The maximum amount of amine intercalated (N _f ) inside the interlamellar space were 0.62, 0.46, and 0.38 mmol g⁻¹, to give the following order of intercalation ethyl → butyl → hexylamines. The layered vermiculite solid was suspended in deionized water and calorimetrically titrated with this series of amines, to give favorable thermodynamic data, such as exothermic enthalpy, negative Gibbs free energy and positive entropy data.     

Structure of adsorption layers of ionic surfactants at the solid/liquid interface

A large number of experimental results of different surfactant adsorption systems (mainly on the silicas) obtained from both equilibrium and kinetic studies under different conditions are interpreted by a model of small individual surface aggregates. The adsorption model is contrasted with the influences of various factors, including electrostatic interaction, hydrophobic interaction, concentrations, types of coions, types of counterions, surfactant structure, alkyl chain length, types of head groups, neutral electrolytes, pH, adsorbent structure, porosity, surface charge density, and surface polarity.Dedicated to Frau Professor Dr. Elsa Ullmann on the occasion of her 80th birthday     

Coexistence of homochiral and heterochiral adenine domains at the liquid/solid interface

In this work, the self-assembly of the DNA base molecule adenine (A) is imaged with high-resolution scanning tunneling microscopy (STM) at the liquid (1-octanol)/solid (HOPG) interface at room temperature. Rather surprisingly, the STM results reveal, for the first time, the spontaneous formation of two coexisting distinct (homo- and heterochiral) domains of adenine, which are formed at the liquid/solid interface without changing any experimental conditions. Ab initio density functional theory (DFT) calculations support our STM findings and suggest the existence of various A networks of nearly similar stability that all are constructed from the most stable A dimer.     

Hybridization of graphene oxide and carbon nanotubes at the liquid/air interface

The liquid/air interface provides an ideal platform for the uniform hybridization of multi-components in a thin graphene-based membrane through self-assembly. This study presents the first example for such a hybrid membrane which combines chemically active GO layers with highly conductive carbon nanotubes.     

Adsorption and mixing behavior of ethers and alkanes at the solid/liquid interface

The behavior of binary mixtures of linear symmetrical ethers and alkanes adsorbed to a graphite surface from the bulk liquid mixtures is described on the basis of differential scanning calorimetry (DSC) data. Both the ethers and the alkanes are found to form solid monolayers when adsorbed from the liquid. In addition, the monolayer mixing behavior is addressed. The results indicate that there is good, essentially ideal, mixing in the monolayers for ethers and alkanes of the same overall chain length, where the chain length is equal to the total number of carbon and oxygen atoms in the molecule. However, a difference in chain length of more than one atom results in a variation of mixing behavior from nonideal mixing (for long pairs) to phase separation (for short pairs) on the graphite surface. Hence, we conclude that it is the relative chain lengths that control mixing behavior. The results are quantified using a regular solution model with a correction for preferential adsorption. The phase behavior of the mixed monolayers is also compared to the behavior of the bulk. Interestingly, we observe mixtures where the bulk and monolayer behavior are quite different, for example, phase separation in the bulk but essentially ideal mixing in the monolayer for mixtures of ethers and alkanes with the same chain lengths. At present, we attribute this mixing in the monolayer to dilution of the unfavorable ether oxygen-ether oxygen lone pair interactions by the coadsorbed alkanes. In addition, we find evidence for the preferential adsorption of the alkane over the ether. For example, heptane is preferentially adsorbed over dibutyl ether even though it contains two fewer atoms in the molecular chain. This contrasts with the preferential adsorption of alcohols over alkanes reported previously (Messe, L.; Perdigon, A.; Clarke, S. M.; Inaba, A.; Arnold, T. Langmuir 2005, 21, 5085-5093).     

Flow microcalorimetry of adsorption of anionic alkyl surfactants at the solid/liquid interface

Flow microcalorimetry was used to study the adsoption of anionic alkyl surfactants from aque--ous solutions onto silica. It is found that for alkyl sulfate systems the strength of adsorption interactionincreases with increases of the alkyl chain length and decreases as temperature rises. The adsorptiondepends only on monomer concentration of the solution even above the critical micelle concentration(cmc). The assumption is made that the adsorption involves only a transfer of monomers from bulkto surface phase. A different adsorption mechanism is operative for the alkyl carboxylate.     

Role of pseudopolymorphism on concentration dependent competitive adsorption at a liquid/solid interface

We present for the first time a peculiar concentration effect on competitive adsorption of a binary mixture at the liquid/solid interface, which we attribute to the existence of pseudopolymorphism and its concentration dependence. These results are helpful for the understanding of phase behavior of multi-component systems at the interface.     

Local Freedericksz transitions at a nematic liquid crystal/thin film oxide ferroelectric interface

The electro-optical properties of a novel device comprising nematic liquid crystals and a thin film oxide ferroelectric (OFE) substrate are reported. The OFE was the lead zirconate-lead titanate, PZT, system with the molar composition 30:70, respectively. The first evidence of the interaction of nematic liquid crystals with the spontaneous polarisation ( Ps ) of an OFE is presented. Coupling of the ferroelectric Ps from poled grains (5-10mum in diameter) with the liquid crystal results in local Freedericksz transitions, allowing the grain structure of the substrate to be visualized. Further, this novel device structure allows the director tilt and anchoring energy of commercially available nematic materials to be quantified.