Chemisorption and physisorption of alcohols on iron(III) oxide-terminated surfaces from nonpolar solvents.

Hypothesis: The adsorption isotherm of alkanols at the haematite|hydrocarbon interface should reflect both chemisorption (chemically bonded fraction) and physisorption (hydrogen bonded fraction).

Experiments And Model: Quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS) have been used for characterization of FeO|hydrocarbon interfaces with absorbed alcohol. A range of FeO-terminated surfaces, alkanols, hydrocarbons and temperatures have been investigated.

RAFT Dispersion Polymerization of 2-Hydroxyethyl Methacrylate in Non-polar Media.

We report the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of 2-hydroxyethyl methacrylate (HEMA) in -dodecane using a poly(lauryl methacrylate) (PLMA) precursor at 90 °C. This formulation is an example of polymerization-induced self-assembly (PISA), which leads to the formation of a colloidal dispersion of spherical PLMA-PHEMA nanoparticles at 10-20% w/w solids. PISA syntheses involving polar monomers in non-polar media have been previously reported but this particular system offers some unexpected and interesting challenges in terms of both synthesis and characterization.

Facile Synthesis of Functionalised Hyperbranched Polymers for Application as Novel, Low Viscosity Lubricant Formulation Components.

A novel, previously unreported, method for synthesising hyperbranched (HB) materials is detailed. Their use as additives to produce lubricant formulations that exhibit enhanced levels of wear protection and improved low-temperature oil viscosity and flow is also reported. The lubricant formulations containing HB additives were found to exhibit both significantly lower viscosities and improved in-use film-forming properties than the current industry standard formulations.

Role of Iron Speciation in Oxidation and Deposition at the Hexadecane-Iron Interface.

Interactions between iron surfaces and hydrocarbons are the basis for a wide range of materials synthesis processes and novel applications, including sensing. However, in diesel engines these interactions can lead to deposit formation that reduces performance, lowers efficiency, and increases emissions. Here, we present a global study to understand deposition at iron-hexadecane interfaces.

Adsorption of 4--Nonylphenol, Carvacrol, and Ethanol onto Iron Oxide from Nonaqueous Hydrocarbon Solvents.

The adsorption of 4--nonylphenol (4NP), carvacrol, and ethanol onto the surface of iron oxide from nonaqueous solutions is presented. It is found that adsorption of 4NP from alkanes is strong and proceeds to monolayer formation, where the molecules are essentially "upright". However, at high relative concentrations, ethanol successfully out-competes 4NP for the iron oxide surface.

Competitive Adsorption of a Multifunctional Amine and Phenol Surfactant with Ethanol on Hematite from Nonaqueous Solution.

Surfactants, which contain phenol and amine groups, are commonly used in industries to protect metallic surfaces, and their efficiency depends strongly on factors such as pressure and temperature, solvent properties, and the presence of other surfactants in the system. In this work, we present a molecular simulation study of the competitive adsorption between a multifunctional phenol and amine surfactant model and ethanol at the oil/solid interface formed between iso-octane and a model hematite (α-FeO) slab. We show that the surfactant strongly adsorbs at the iso-octane/hematite interface in the absence of ethanol at moderate temperatures.

Modeling study of the anti-knock tendency of substituted phenols as additives: an application of the reaction mechanism generator (RMG).

This work presents kinetic modeling efforts to evaluate the anti-knock tendency of several substituted phenols if used as gasoline additives. They are p-cresol, m-cresol, o-cresol, 2,4-xylenol, 2-ethylphenol, and guaiacol. A detailed kinetic model was constructed to predict the ignition of blends of the phenols in n-butane with the help of reaction mechanism generator (RMG), an open-source software package.

Liquid Adsorption of Organic Compounds on Hematite α-FeO Using ReaxFF.

ReaxFF-based molecular dynamics simulations are used in this work to study the effect of the polarity of adsorbed molecules in the liquid phase on the structure and polarization of hematite (α-FeO). We compared the adsorption of organic molecules with different polarities on a rigid hematite surface and on a flexible and polarizable surface. We show that the displacements of surface atoms and surface polarization in a flexible hematite model are proportional to the adsorbed molecule's polarity.

Aromatic donor-acceptor interactions in non-polar environments.

We have evaluated the strength of aromatic donor-acceptor interactions between dialkyl naphthalenediimide and dialkoxynaphthalene in non-polar environments. (1)H NMR, UV-vis spectroscopy and isothermal titration calorimetry were used to characterise this interaction. We concluded that the strength of donor-acceptor interactions in heptane is sufficient to drive supramolecular assemblies in this and other aliphatic solvents.

Pressure-induced conformation transition of o-phenylene solvated in bulk hydrocarbons.

The conformational behavior of o-phenylene 8-mers and 10-mers solvated in a series of linear alkane solvents by means of classical molecular dynamics and first-principles calculations was studied. Irrespective of the solvent used, we find that at ambient pressure the molecule sits in the well-defined close-helical arrangement previously observed in light polar solvents. However, for pressures greater than 50 atm, and for tetradecane or larger solvent molecules, our simulations predict that o-phenylene undergoes a conformational transition to an uncoiled, extended geometry with a 35% longer head-to-tail distance and a much larger overlap between its lateral aromatic ring groups.

A contribution to the nomenclature of depsipeptides.

Depsipeptides, also called peptolides, are a class of peptidic compounds in which an amide bond has been replaced with an ester bond. The literature does not clearly display rules for the nomenclature of such compounds. Here a method is proposed to transcribe drawn depsipeptide structures in one-line text.