Hexaphyrin(1.0.1.0.0.0). A new colorimetric actinide sensor

Hexaphyrin(1.0.1.0.0.0) (isoamethyrin) undergoes a significant color change in the presence of UO₂²⁺, PuO₂²⁺, and NpO₂²⁺. The complexation of the first of these dioxo actinide cations was studied in semi-quantitative fashion in 1:1 MeOH-CH₂Cl₂. Under these conditions, the detection limit for UO₂²⁺ was found to be ca. 5.8 ppm by naked eye monitoring and <28 ppb by UV-vis spectroscopy. Isoamethyrin does not undergo a color change in the presence of most transition metals or when exposed to Gd(III). Isoamethyrin thus constitutes an attractive alternative to 2,2′(1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo)-bisbenzenarsonic acid (AzIII) and 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (BrPADAP), systems currently used as actinide cation sensors.     

Gallium-boron donor-acceptor bonds

Examples of compounds with gallium-boron donor-acceptor bonds, HC[MeC(2,6-pri2C6H3)N]2Ga-->B(C6F5)3 3 and (eta 5-C5Me5)Ga-->B(C6F5)3 4 have been prepared by treatment of the free gallanediyls with B(C6F5)3; the structures of both compounds were determined by X-ray crystallography.     

Cu(II) 2-quinoxalinol salen catalyzed oxidation of propargylic,benzylic, and allylic alcohols using tert-butyl hydroperoxide in aqueous solutions

The synthesis of carbonyl compounds by oxidation of alcohols is a key reaction in organic synthesis. Such oxidations are typically conducted using catalysts featuring toxic metals and hazardous organic solvents. Considering green and sustainable chemistry, a copper(II) complex of sulfonated 2-quinoxalinol salen (sulfosalqu) has been characterized as an efficient catalyst for the selective oxidation of propargylic, benzylic, and allylic alcohols to the corresponding carbonyl compounds in water when in combination with the oxidant tert-butyl hydroperoxide. The reactions proceed under mild conditions (70 °C in water) to produce yields up to 99% with only 1 mol % of catalyst loading. This reaction constitutes of a rare example of propargylic alcohol oxidation in water, and it makes this process greener by eliminating the use of hazardous organic solvents. Excellent selectivity was achieved with this catalytic protocol for the oxidation of propargylic, benzylic, and allylic alcohols over aliphatic alcohols. The alcohol oxidation is thought to go through a radical pathway.     

Scattering from particles on surfaces: visibility factor and polydispersity

We have developed an experimental method based on the visibility factor of light-scattering minima to obtain size-polydispersity information from contaminants upon a flat substrate. We verify the method by using double-interaction-model calculations and use this technique to examine experimentally the radial variation of a micrometer-sized fiber and the size polydispersity of spherical particles upon a substrate.     

A comparative study in resonant light scattering between spherical and cylindrical dielectric hosts with a metallic inclusion

We show that dielectric spherical and cylindrical particles contaminated with a metallic inclusion have similar spectral resonant behavior. Both geometries show resonance suppression as the position of the inclusion varies. Moreover, it was theoretically observed that the spherical particle suppresses a resonant mode earlier than the cylindrical one. Based on semi-classical arguments, a physical interpretation of this fact is given. In addition, a comment is also made regarding Wiscombe's criteria for estimating the size of the coefficient matrix used to solve the truncated non-homogeneous set of linear equations related to this problem.     

Light scattering computational methods for particles on substrates

Four theoretical and computational methods to describe the scattering from simple particles on substrates are presented and discussed. These methods are based on the extinction theorem, image theory, the double-interaction model, and geometrical optics (ray-tracing). We compare the four methods with measurements of scattered light from gold metallic cylinders resting on a gold metallic substrate. In particular, we analyze the co-polarized (s and p polarization) full-scan and back-scattering intensities in the far field within the plane of incidence. Advantages and disadvantages of each method as a computational and reliable tool are discussed.     

Structural characterization of manganese and iron complexes with methylated derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine reveals unanticipated conformational flexibility

Iron and manganese complexes with derivatives of bis(2-pyridylmethyl)-1,2-ethanediamine (bispicen) have previously been found to be efficient catalysts for hydrocarbon oxygenation. Methylation can potentially impact the conformation of the ligand around the metal center and the electronic character of the bound metal ion; each of these, in turn, impacts reactivity. Reported are mononuclear manganese(II) and iron(II) compounds with bispicen and five increasingly methylated derivatives. The extent and sites of methylation strongly impact the optical and electrochemical properties of the manganese and iron complexes. Increased methylation is correlated with more positive M(III/II) reduction potentials. Structural analysis of the Mn(II) series reveals two ligand conformations that have never been observed for the bispicen framework, cis-β and trans, in addition to the common cis-α conformation. (1)H NMR spectra of the structurally characterized iron compounds are consistent with mixtures of these conformers, suggesting that bispicen coordination is both more flexible and more dynamic than previously thought.     

Light scattering in a finite multi-particle system

We use the discrete dipole approximation (DDA) to perform electromagnetic scattering calculations of particles in a 3D volume. We adjust the spacing between the particles to change the volume densities of the scattering systems from approximately 10% to 100%. For very large volume densities, e.g. >50%, it is difficult to assign unambiguously whether the system is composed of a single heterogeneous particle or of multiple particles. Our calculations demonstrate optical effects attributable to multiple scattering in systems having volume densities as high as ～90%. This suggests that heterogeneities within naturally occurring particle systems can produce multiple-scattering effects. We also see evidence of very deep negative polarization branches (NPBs) (～?6%) that may have implications in interpreting polarization phase curves of cometary circumnuclear halos.