Optical spectra of protected diamine 10-bond-bridged intervalence radical cations related to N,N,N'N'-tetraalkylbenzidine

The optical absorption spectra of the delocalized intervalence radical cations of seven o,o'-linked benzidine derivatives that have the nitrogens protected as 9-(9-aza-bicyclo[3.3.1]nonan-3-one) derivatives are discussed and compared with that of the p-phenylene radical cation. The linking units are CH2, CH2CH2, NMe, S, SO2, and C=O, and we also studied H,H (the unlinked benzidine). The lowest-energy absorption band is assigned as the transition from the antibonding combination of symmetrical N and aromatic orbitals to the antibonding combination of the antisymmetric N and aromatic orbitals using TD-DFT calculations, and a good correlation between the observed transition energies and those calculated using the simple Koopmans theorem-based "neutral in-cation geometry" calculations on the UB3LYP/6-31G* structures is found. The use of the two-state model that equates the electronic interaction through the bridge between the amino groups with half of the lowest transition energy is seriously incorrect for these and other delocalized intervalence compounds. The problem of extracting the electronic interactions that actually are involved from calculated transition energies is discussed.     

A STEM/EELS method for mapping iron valence ratios in oxide minerals

The valence state of iron in minerals has useful applications in the geosciences for estimating redox conditions during mineral formation or re-equilibration. STEM/EELS techniques offer the advantage over other methods of being able to measure Fe valence with very high spatial resolution across mineral grains and grain boundaries. We have modified an EELS method for point analyses of iron valence ratios (Fe(3+)/SigmaFe) making it possible to generate line scans and maps of Fe valence. We demonstrate this method with measurements at an interface between iron-bearing oxides in a finely intergrown sample of magnetite and ilmenite. The STEM/EELS method is based on a calibrated relationship between Fe(3+)/SigmaFe and the relative intensities of the Fe L(3) and L(2) white lines in core energy-loss spectra for oxide and silicate minerals. Our method overcomes problems of energy drift in spectrum images by aligning energy-loss edges at a fixed energy position prior to background removal. An automated routine for batch processing of core loss spectra, including additional background removal and calculation of Fe L(3)/L(2) intensity ratios, allows for rapid Fe(3+)/SigmaFe determinations of multiple point analyses or spectrum images and the preparation of Fe valence maps, with an analytical error of +/-0.05 to +/-0.09 in the Fe(3+)/SigmaFe measurements.     

Catalytic enantioselective protonation of nitronates utilizing an organocatalyst chiral only at sulfur

The highly enantioselective protonation of nitronates formed upon the addition of α-substituted Meldrum's acids to terminally unsubstituted nitroalkenes is described. This work represents the first enantioselective catalytic addition of any type of nucleophile to this class of nitroalkenes. Moreover, for the successful implementation of this method, a new type of N-sulfinyl urea catalyst with chirality residing only at the sulfinyl group was developed, thereby enabling the incorporation of a diverse range of achiral diamine motifs. Finally, the Meldrum's acid addition products were readily converted to pharmaceutically relevant 3,5-disubstituted pyrrolidinones in high yield.     

One-pot, single-component synthesis of functional emulsion-templated hybrid inorganic-organic polymer capsules

Multi-purpose amphiphilic branched copolymer surfactants can be used to simultaneously stabilise and cross-link emulsion droplets to produce encapsulated spheres and hollow capsules.     

Poly[2-(methacryloyloxy)ethylphosphorylcholine]-coated iron oxide nanoparticles: synthesis, colloidal stability and evaluation for stem cell labelling

Poly[2-(methacryloyloxy)ethylphosphorylcholine]-coated SPIONs were prepared through ATRP and amidation coupling reactions. The coated SPIONs exhibited high stability and re-dispersability in phosphate buffered saline and uptake in a stem cell line, with high T(2) relaxivity.     

Dispersion-corrected density functional theory calculations of the molecular binding of n-alkanes on Pd(111) and PdO(101)

We investigated the molecular binding of n-alkanes on Pd(111) and PdO(101) using conventional density functional theory (DFT) and the dispersion-corrected DFT-D3 method. In agreement with experimental findings, DFT-D3 predicts that the n-alkane desorption energies scale linearly with the molecule chain length on both surfaces, and that n-alkanes bind more strongly on PdO(101) than on Pd(111). The desorption energies computed using DFT-D3 are slightly higher than the measured values for n-alkanes on Pd(111), though the agreement between computation and experiment is a significant improvement over conventional DFT. The measured desorption energies of n-alkanes on PdO(101) and the energies computed using DFT-D3 agree to within better than 2.5 kJ/mol (< 5%) for chain lengths up to n-butane. The DFT-D3 calculations predict that the molecule-surface dispersion energy for a given n-alkane is similar in magnitude on Pd(111) and PdO(101), and that dative bonding between the alkanes and coordinatively unsaturated Pd atoms is primarily responsible for the enhanced binding of n-alkanes on PdO(101). From analysis of the DFT-D3 results, we estimate that the strength of an alkane η(2)(H, H) interaction on PdO(101) is ~16 kJ/mol, while a single η(1) H-Pd dative bond is worth about 10 kJ/mol.     

Molecular adsorption and growth of n-butane adlayers on Pt(1 1 1)

The molecular adsorption of n-butane and the growth of n-butane adlayers on Pt(1 1 1) was investigated using molecular beam techniques, temperature-programmed desorption (TPD) and low-energy electron diffraction (LEED). It is found that as the surface coverage of n-butane increases, structural changes occur in the adlayer at surface temperatures near 98 K that are accompanied by changes in the binding energy and mobility of the adsorbed species. The film growth process can be divided into four distinct coverage regimes. At low coverages (θ<0.14 ML, where 1 ML is defined as one butane molecule per Pt atom) a disordered monolayer forms in which the butane molecules prefer to lie parallel to the surface in order to minimize their binding energy. At coverages from 0.14 to 0.20 ML, ordered regions develop within the monolayer in which the butane molecules also lie parallel to the surface. The binding energy in the ordered phase is lower than that in the disordered phase due to repulsive intermolecular interactions. A more densely-packed ordered phase begins to form at 98 K after the low-coverage ordered phase saturates at 0.20 ML. The experimental results suggest that the n-butane molecules tilt away from the surface in the high-coverage ordered phase. Finally, a disordered second layer phase forms after the high coverage ordered phase saturates at 0.35 ML. The molecules in the second layer are very mobile at 98 K and rapidly diffuse to the edges of the beam spot. Interchange of molecules between the second layer and ordered monolayer is found to govern the net rate of second layer diffusion at surface temperatures less than 133 K. The adsorption probability of n-butane on Pt(1 1 1) continuously increases with increasing coverage, with no significant dependencies on the structure of the n-butane adlayer. This finding indicates that the long-range arrangements and molecular orientations of a mobile alkane adlayer have a negligible influence on the intrinsic adsorption dynamics, suggesting that the energy transfer processes that facilitate adsorption are highly localized.     

A Stereocontrolled Total Synthesis of Lipoxin B4 and its Biological Activity as a Pro-Resolving Lipid Mediator of Neuroinflammation

Two stereocontrolled, efficient, and modular syntheses of eicosanoid lipoxin B4 (LXB₄) are reported. One features a stereoselective reduction followed by an asymmetric epoxidation sequence to set the vicinal diol stereocentres. The dienyne was installed via a one-pot Wittig olefination and base-mediated epoxide ring opening cascade. The other approach installed the diol through an asymmetric dihydroxylation reaction followed by a Horner-Wadsworth-Emmons olefination to afford the common dienyne intermediate. Finally, a Sonogashira coupling and an alkyne hydrosilylation/proto-desilylation protocol furnished LXB₄ in 25 % overall yield in just 10 steps. For the first time, LXB₄ has been fully characterized spectroscopically with its structure confirmed as previously reported. We have demonstrated that the synthesized LXB₄ showed similar biological activity to commercial sources in a cellular neuroprotection model. This synthetic route can be employed to synthesize large quantities of LXB₄, enable synthesis of new analogs, and chemical probes for receptor and pathway characterization.     

How acidic are corroles and why?

The pH-dependent absorption and emission spectra of the water-soluble 2,17-disulphonato-5,10,15-tris(pentafluorophenyl)corrole revealed that its inner-core nitrogen atoms can be both protonated and deprotonated, with acidity constants of 2.5 and 5.2, respectively. An analysis of the structural features of free-base corroles suggests that the quite limited pH range at which corroles remain neutral is reminiscent of the instability of mono-protonated porphyrins.     

Coverage dependence of neopentane trapping dynamics on Pt(111)

Adsorption probabilities for neopentane on Pt(111) were measured directly using supersonic molecular-beam techniques at coverages ranging from zero to monolayer saturation, incident translational energies between 18 and 110 kJ mol⁻¹ and incident angles between 0° and 60° at a surface temperature of 105 K. The adsorption probability was found to increase with coverage up to near monolayer saturation at all incident translational energies and incident angles. The coverage dependence of the adsorption probability predicted by a modified Kisliuk model with enhanced trapping into the second layer exhibits good quantitative agreement with the experimental values. The angular dependence of the adsorption probability decreases with increasing coverage, suggesting that the effective corrugation of the gas–surface interaction potential increases with the adsorbate coverage. The initial adsorption probability into the second layer onto the covered surface decreases from 0.95 to 0.75 with increasing energy over the energy range studied, and exhibits total energy scaling. A comparison with second-layer trapping data of simpler molecules onto covered Pt(111) indicates that the structural complexity of adsorbed neopentane molecules facilitates collisional energy transfer during adsorption.