Effects of substituent position on aminobenzoate relaxation pathways in solution.

The negative effects of ultraviolet radiation (UVR) on human skin have led to the widespread use of sunscreens, i.e. skincare products containing UV filters to absorb, reflect or otherwise block UVR. The mechanisms by which UV filters dissipate energy following photoexcitation, i.e. their photodynamics, can crucially determine a molecule's performance as a sunscreen UV filter. In this work, we evaluate the effects of substituent position on the in-solution relaxation pathways of two derivates of methyl anthranilate (an ortho compound that is a precursor to the UV filter meradimate), meta- and para-methyl anthranilate, m-MA and p-MA, respectively. The photodynamics of m-MA were found to be sensitive to solvent polarity: its emission spectra show larger Stokes shifts with increasing polarity, and both the fluorescence quantum yield and lifetimes for m-MA increase in polar solvents. While the Stokes shifts for p-MA are much milder and more independent of solvent environment than those of m-MA, we find its fluorescence quantum yields to be sensitive not only to solvent polarity but to the hydrogen bonding character of the solvent. In both cases (m- and p-MA) we have found common computational methods to be insufficient to appropriately model the observed spectroscopic data, likely due to an inability to account for explicit solvent interactions, a known challenge in computational chemistry. Therefore, apart from providing insight into the photodynamics of anthranilate derivatives, the work presented here also provides a case study that may be of use to theoretical chemists looking to improve and develop explicit solvent computational methods.

Atomic and Molecular Collisions at Liquid Surfaces.

The gas-liquid interface remains one of the least explored, but nevertheless most practically important, environments in which molecular collisions take place. These molecular-level processes underlie many bulk phenomena of fundamental and applied interest, spanning evaporation, respiration, multiphase catalysis, and atmospheric chemistry. We review here the research that has, during the past decade or so, been unraveling the molecular-level mechanisms of inelastic and reactive collisions at the gas-liquid interface. Armed with the knowledge that such collisions with the outer layers of the interfacial region can be unambiguously distinguished, we show that the scattering of gas-phase projectiles is a promising new tool for the interrogation of liquid surfaces with extreme surface sensitivity. Especially for reactive scattering, this method also offers absolute chemical selectivity for the groups that react to produce a specific observed product.

Reactive-Atom Scattering from Liquid Crystals at the Liquid-Vacuum Interface: [C12mim][BF4] and 4-Cyano-4'-Octylbiphenyl (8CB).

Two complementary approaches were used to study the liquid-vacuum interface of the liquid-crystalline ionic liquid 1-dodecyl-3-methylimidazolium tetrafluoroborate ([C12mim][BF4]) in the smectic A (SmA) and isotropic phases. O atoms with two distinct incident translational energies were scattered from the surface of [C12mim][BF4]. Angle-dependent time-of-flight distributions and OH yields, respectively, were recorded from high- and low-energy O atoms. There were no significant changes in the measurements using either approach, nor the properties derived from them, accompanying the transition from the SmA to the isotropic phase. This indicates that the surface structure of [C12mim][BF4] remains essentially unchanged across the phase boundary, implying that the bulk order and surface structure are not strongly correlated for this material. This effect is ascribed to the strong propensity for the outer surfaces of ionic liquids to be dominated by alkyl chains, over an underlying layer rich in anions and cation head groups, whether or not the bulk material is a liquid crystal. In a comparative study, the OH yield from the surface of the liquid crystal, 8CB, was found to be affected by the bulk order, showing a surprising step increase at the SmA-nematic transition temperature, whose origin is the subject of speculation.

Site and bond-specific dynamics of reactions at the gas-liquid interface.

The dynamics of the interfacial reactions of O((3)P) with the hydrocarbon liquids squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and squalene (C30H50, trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene) have been studied experimentally. Laser-induced fluorescence (LIF) was used to detect the nascent gas-phase OH products. The O((3)P) atoms are acutely sensitive to the chemical differences of the squalane and squalene surfaces. The larger exothermicity of abstraction from allylic C-H sites in squalene is reflected in markedly hotter OH rotational and vibrational distributions. There is a more modest increase in translational energy release. A larger fraction of the available energy is deposited in the liquid for squalene than for squalane, consistent with a more extensive geometry change on formation of the allylic radical co-product. Although the dominant reaction mechanism is direct, impulsive scattering, there is some evidence for OH being accommodated at both liquid surfaces, resulting in thermalised translation and rotational distributions. Despite the H-abstraction reaction being strongly favoured energetically for squalene, the yield of OH is substantially lower than for squalane. This is very likely due to competitive addition of O((3)P) to the unsaturated sites in squalene, implying that double bonds are extensively exposed at the liquid surface.

Nanosegregation and Structuring in the Bulk and at the Surface of Ionic-Liquid Mixtures.

Ionic-liquid (IL) mixtures hold great promise, as they allow liquids with a wide range of properties to be formed by mixing two common components rather than by synthesizing a large array of pure ILs with different chemical structures. In addition, these mixtures can exhibit a range of properties and structural organization that depend on their composition, which opens up new possibilities for the composition-dependent control of IL properties for particular applications. However, the fundamental properties, structure, and dynamics of IL mixtures are currently poorly understood, which limits their more widespread application. This article presents the first comprehensive investigation into the bulk and surface properties of IL mixtures formed from two commonly encountered ILs: 1-ethyl-3-methylimidazolium and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N] and [C12mim][Tf2N]). Physical property measurements (viscosity, conductivity, and density) reveal that these IL mixtures are not well described by simple mixing laws, implying that their structure and dynamics are strongly composition dependent. Small-angle X-ray and neutron scattering measurements, alongside molecular dynamics (MD) simulations, show that at low mole fractions of [C12mim][Tf2N], the bulk of the IL is composed of small aggregates of [C12mim]+ ions in a [C2mim][Tf2N] matrix, which is driven by nanosegregation of the long alkyl chains and the polar parts of the IL. As the proportion of [C12mim][Tf2N] in the mixtures increases, the size and number of aggregates increases until the C12 alkyl chains percolate through the system and a bicontinuous network of polar and nonpolar domains is formed. Reactive atom scattering-laser-induced fluorescence experiments, also supported by MD simulations, have been used to probe the surface structure of these mixtures. It is found that the vacuum-IL interface is enriched significantly in C12 alkyl chains, even in mixtures low in the long-chain component. These data show, in contrast to previous suggestions, that the [C12mim]+ ion is surface active in this binary IL mixture. However, the surface does not become saturated in C12 chains as its proportion in the mixtures increases and remains unsaturated in pure [C12mim][Tf2N].