The structure,composition, and dimensions of TiO<Subscript>2</Subscript> and ZnO nanomaterials in commercial sunscreens

TiO₂ and ZnO nanomaterials are widely used to block ultraviolet radiation in many skin care products, yet product labels do not specify their dimensions, shape, or composition. The absence of this basic information creates a data gap for both researchers and consumers alike. Here, we investigate the structural similarity of pigments derived from actual sunscreen products to nanocrystals which have been the subject of intense scrutiny in the nanotoxicity literature. TiO₂ and ZnO particles were isolated from eight out of nine commercial suncare products using three extraction methods. Their dimension, shape, crystal phase, surface area, and elemental composition were examined using transmission and scanning electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller (BET) specific surface area analysis, energy dispersive X-ray and inductively coupled plasma optical emission spectroscopy. TiO₂ pigments were generally rutile nanocrystals (dimensions ~25 nm) with needle-like or near-spherical shapes. ZnO pigments were wurtzite rods with a short axes less than 40 nm and longer dimensions often in excess of 100 nm. We identify two commercial sources of TiO₂ and ZnO nanocrystals whose physical and chemical features are similar to the pigments found in sunscreens. These particular materials would be effective surrogates for the commercial product and could be used in studies of the health and environmental impacts of engineered nanomaterials contained in sunscreens.     

Substituted 3-phenylpropenoates and related analogs: electron ionization mass spectral fragmentation and density functional theory calculations

Analysis of ethyl 3-(2-chlorophenyl)propenoate by electron ionization mass spectrometry showed the distinct loss of an ortho chlorine. To characterize the structural requisites for the observed mass fragmentation, a series of 30 halogen-substituted 3-phenylpropenoate-related structures were examined. All ester-containing alkene derivatives exhibited loss of the distinctive chlorine from the 2-position of the phenyl ring. Analogous derivatives with the halogen (chlorine or bromine) in the para position did not evidence selective halogen loss. Results demonstrated that substituted 3-phenylpropenoates and their analogs fragment via the formation of a previously reported benzopyrylium intermediate. To understand the correlation between the intramolecular radical substitution and the abundance and selectivity of the chlorine (or other halogen) displacement, density functional theory calculations were performed to determine the charge on the principal cation involved in the chlorine loss (in the ortho, meta, and para positions), the charge for the neutral radical (noncation), the excess alpha-electron density on the relevant atom and the energy to form the cation from the neutral atom (ionization energy). Results showed that the selectivity and extent of halogen displacement correlated highly to the electrophilicity of the radical cation as well as the neutral radical. These data further support the proposed fragmentation mechanism involving intramolecular radical elimination.     

Role of bridge energetics on the preference for hole or electron transfer leading to charge recombination in donor-bridge-acceptor molecules

The impact of donor-acceptor electronic coupling and bridge energetics on the preference for hole or electron transfer leading to charge recombination in a series of donor-bridge-acceptor (D-B-A) molecules was examined. In these systems, the donor is 3,5-dimethyl-4-(9-anthracenyl)-julolidine (DMJ-An) and acceptor is naphthalene-1,8:4,5-bis(dicarboximide) (NI), while the bridges are either oligo(p-phenyleneethynylene) (PE(n)P, where n = 1-3) 1-3 or oligo(2,7-fluorenone) (FN(n), where n = 1-3) 4-6. Photoexcitation of 1-3 and 4-6 produces DMJ(+?)-An-PE(n)P-NI(-?) and DMJ(+?)-An-FN(n)-NI(-?), respectively, which undergo radical pair intersystem crossing followed by charge recombination to yield both (3*)An and (3*)NI, which are observed by time-resolved electron paramagnetic resonance (TREPR) spectroscopy. (3*)NI is produced by hole transfer from DMJ(+?) to NI(-?), while (3*)An is produced by electron transfer from NI(-?) to DMJ(+?), using the agency of the bridge HOMOs and LUMOs, respectively. By monitoring the initial population of (3*)NI and (3*)An in 1-6, the data show that charge recombination occurs preferentially by selective hole transfer when the bridge is PE(n)P, while it occurs by preferential electron transfer when the bridge is FN(n). Over time, the initial population of (3*)NI decreases, while that of (3*)An increases, indicating that triplet-triplet energy transfer (TEnT) occurs. The observed distance dependence of TEnT from (3*)NI to An is weakly exponential with a decay parameter β = 0.08 ?(-1) for the PE(n)P series and β = 0.03 ?(-1) for the FN(n) series. In the PE(n)P series, this weak distance dependence is attributed to a transition from the superexchange regime to hopping transport as the energy gap for triplet energy injection onto the bridge becomes significantly smaller as n increases, while in the FN(n) series the corresponding energy gap is small for all n resulting in triplet energy transport by the hopping mechanism.     

Adsorption of cadmium on anatase nanoparticles-effect of crystal size and pH

The adsorption and desorption of Cd(2+) to large and nanometer-scale anatase crystals have been studied to determine the relationship between heavy metal adsorption properties and anatase particle size. A solvothermal method was used to synthesize very fine anatase nanocrystals with average grain sizes ranging from 8 to 20 nm. On a surface area basis, it was found that large and nanometer-scale anatase particles had similar maximum Cd(2+) adsorption capacities, while their adsorption slopes differed by more than 1 order of magnitude. The particle-size effect on adsorption is constant over a pH range of 4-7.5. The desorption of Cd(2+) from both particle sizes is completely reversible. The adsorption data have been modeled by the Basic Stern model using three monodentate surface complexes. It is proposed that intraparticle electrostatic repulsion may reduce the adsorption free energy significantly for nanometer-sized particles.     

Identity proton-transfer reactions from C-H, N-H, and O-H acids. An ab initio, DFT, and CPCM-B3LYP aqueous solvent model study

Identity proton-transfer reactions between 21 acids, Y-X-H, and their conjugate bases, (-)X-Y, were studied according to the reaction scheme, Y-X-H + (-)X-Y --> (Y-X-H...(-)X-Y)(cx) --> [Y-X...H...X-Y](ts) --> (Y-X..H-X-Y)(cx) --> Y-X(-) + H-X-Y, where cx indicates an ion-molecule complex and ts indicates the proton-transfer transition state. All species were optimized at the MP2/6-311+G level, and these geometries were used for single-point calculations by other methods: coupled-cluster, DFT (gas phase), and a polarizable continuum aqueous solvent model (COSMO). All methods gave enthalpies of deprotonation which correlate well with experimental measurements of deltaH(ACID) (gas) or pK(a) (aq). Calculated gas-phase enthalpies of deprotonation (deltaH(ACID)) and enthalpies of activation (deltaH(#)) are poorly correlated except for small, carefully selected sets. This result stands in contrast to the many aqueous phase Br?nsted correlations of kinetic and equilibrium acid strength. On the other hand, gas-phase enthalpies of complexation and deltaH(#) are well correlated, indicating that factors which stabilize the transition state are at work in the bimolecular ion-molecule complex although to a smaller degree. We infer that intermoiety electrostatic and other interactions, similar within the complex and the transition state, but absent in the separated reactants (products), cause the lack of correlation between deltaH(ACID) and the other two quantities. Such differences are strongly attenuated in water because reactants and products do interact with polar/polarizable matter (the solvent) if not with each other. Charge distributions (NPA) were computed, allowing calculation of Bernasconi's "transition state imbalance parameter". Such measures provide intuitively satisfactory trends, but only if the reaction termini, X, are kept the same. As X is made more electronegative, the magnitude of the apparent imbalance increases, a result of greater negative charge on X in the transition state. This result gives additional support for the importance of the ion-triplet structure, [YX(-)...H(+)...(-)XY], to the stability of the transition state. Additional qualitative support for this conclusion is provided by the inverse relationship between the activation barrier and the charge on the in-flight hydrogen in the transition state, and by the dominance of polar over resonance substituent effects on the stability of the transition state. Calculations also show that the "nitroalkane anomaly", well established in solution, does not exist in the gas phase. The COSMO model partly reproduces this anomaly and performs adequately except when strong, specific intermolecular forces such as hydrogen bonding between solvent and anions are important.     

Identification and Partial Structural Characterization of Mass Isolated Valsartan and Its Metabolite with Messenger Tagging Vibrational Spectroscopy

Recent advances in the coupling of vibrational spectroscopy with mass spectrometry create new opportunities for the structural characterization of metabolites with great sensitivity. Previous studies have demonstrated this scheme on 300 K ions using very high power free electron lasers in the fingerprint region of the infrared. Here we extend the scope of this approach to a single investigator scale as well as extend the spectral range to include the OH stretching fundamentals. This is accomplished by detecting the IR absorptions in a linear action regime by photodissociation of weakly bound N₂ molecules, which are attached to the target ions in a cryogenically cooled, rf ion trap. We consider the specific case of the widely used drug Valsartan and two isomeric forms of its metabolite. Advantages and challenges of the cold ion approach are discussed, including disentangling the role of conformers and the strategic choices involved in the selection of the charging mechanism that optimize spectral differentiation among candidate structural isomers. In this case, the Na⁺ complexes are observed to yield sharp resonances in the high frequency NH and OH stretching regions, which can be used to easily differentiate between two isomers of the metabolite.

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A model for plasticity kinetics and its role in simulating the dynamic behavior of Fe at high strain rates

The recent diagnostic capability of the Omega laser to study solid-solid phase transitions at pressures greater than 10 GPa and at strain rates exceeding 10⁷ s⁻¹ has also provided valuable information on the dynamic elastic-plastic behavior of materials. We have found, for example, that plasticity kinetics modifies the effective loading and thermodynamic paths of the material. In this paper we derive a kinetics equation for the time-dependent plastic response of the material to dynamic loading, and describe the model’s implementation in a radiation-hydrodynamics computer code. This model for plasticity kinetics incorporates the Gilman model for dislocation multiplication and saturation. We discuss the application of this model to the simulation of experimental velocity interferometry data for experiments on Omega in which Fe was shock compressed to pressures beyond the α-to-ε phase transition pressure. The kinetics model is shown to fit the data reasonably well in this high strain rate regime and further allows quantification of the relative contributions of dislocation multiplication and drag. The sensitivity of the observed signatures to the kinetics model parameters is presented.