Assignment of complex species by affinity capillary electrophoresis: The case of Th(IV)-desferrioxamine B

The electrophoretic mobility change of desferrioxamine B (DFO) was monitored by UV absorption spectrophotometry upon increasing the thorium(IV) concentration in the background electrolyte at two acidities ([HClO₄]_Tot = 0.0316 and 0.0100 M). These data enabled to assess the speciation model and to determine the equilibrium constant of [Th(DFO)H₂]³⁺ at fixed ionic strength (I = 0.1 M (H,Na)ClO₄). Affinity capillary electrophoresis (ACE) turned out to be most helpful in identifying the complexed species by ascertaining its charge and protonation state. The assignment of the correct stoichiometry relied on the reliable estimation of the electrophoretic mobility by assuming similar hydrodynamic radii for (DFO)H₄⁺ and the chelate. The value of the apparent equilibrium constant (log β₁₁₂ = 38.7 ± 0.4) obtained by ACE compares favorably well with those reported in the literature for thorium and a range of other metal ions, according to a linear free-energy relationship. This method is useful for studying metal-ligand binding equilibria and provides valuable information for further modelling the behavior of tetravalent actinides under environmental conditions. Structural information about the prevalent solution species in acidic conditions was gained by DFT calculations, confirming the bishydroxamato coordination mode of Th⁴⁺ by the diprotonated ligand.     

Intrinsic relaxation rates of polarized Cs vapor in miniaturized cells

The intrinsic relaxation rates of the vector magnetization of cesium vapor enclosed in microfabricated atomic magnetometer cells are investigated. Two methods—the optically detected magnetic resonance and the ground-state Hanle effect—are used to carry out automated measurements in dependence on cell temperature and nitrogen buffer gas pressure. The experimental results are compared with expected contributions of the different relaxation processes and in this way allow the discrimination between them to help further optimization of cell design. The methods are compared in terms of basic features, data quality, and practical applicability.     

Cubic C8: An Observable Allotrope of Carbon?

Ab initio and DFT calculations are used to investigate the structure, electronic properties, spectra and reactivity of cubic C₈, which is predicted to be aromatic according to Hirsch′s rule. Although highly strained and with a small amount of diradical character, the carbon cube represents a surprisingly deep minimum and should therefore be observable as an isolated molecule. It is, however, predicted to be very reactive, both with itself and triplet oxygen. Calculated IR, Raman, and UV/Vis spectra are provided to aid identification of cubic C₈ should it be synthesized.     

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility**

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives ( 1 and 2 ) as subunits of 8-AGNR , with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR . The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm² V⁻¹ s⁻¹ for the 8-AGNR .