A potentiometric method for the determination of uranium by stannous chloride reduction

A potentiometric method has been developed for the determination of uranium using stannous chloride as reductant. The oxidation of excess stannous chloride was accomplished with an excess of sodium nitrite, the excess of which was destroyed by sulfamic acid. The U(IV) was then determined by potentiometric titration with standard potassium dichromate. For 3–5 mg amounts of uranium the precision obtained was better than 0.3%.     

Molecular and electronic structure of square-planar nickel II, nickel III and nickel III pi-cation radical complexes with a tetradentate o-phenylenedioxamidate redox-active ligand

The molecular and electronic structures of the electron transfer series of four-coordinate square-planar nickel complexes with the ligand o-phenylenebis(N'-methyloxamidate), [NiL]z (z = 2-, 1-, 0), have been evaluated by DFT and TDDFT calculations, and most of their experimentally available structural and spectroscopic properties (X. Ottenwaelder et al., Dalton Trans., 2005, DOI: 10.1039/b502478a) have been reasonably reproduced at the B3LYP level of theory. The anionic species [NiL]2- and [NiL]- are genuine low-spin nickel II and nickel III complexes with diamagnetic singlet (S = 0) and paramagnetic doublet (S = 1/2) states, respectively. The nickel III complex presents shorter Ni-N(amidate) bond distances (1.85-1.90 A) than the parent nickel II complex (1.88-1.93 A) and characteristic LMCT bands in the NIR region (lambda max = 794 and 829 nm) while the analogous MLCT bands for the nickel(II) complex are in the UV region (lambda max = 346 and 349 nm). The neutral species [NiL] is a nickel III o-benzosemiquinonediimine pi-cation radical complex with a diamagnetic singlet (S = 0) and a paramagnetic triplet (S = 1) states fairly close in energy but fundamentally different in orbital configuration. The singlet metal-radical ground state results from the antiferromagnetic coupling between the 3d(yz) orbital of the Ni III ion (S(M) = 1/2) and the pi(b) orbital of the benzosemiquinone-type radical ligand (S(L) = 1/2), which have a large overlap and thus strong covalent bonding. The triplet metal-radical excited state involves the ferromagnetic coupling between the Ni III 3d(zx) orbital and the benzosemiquinone-type pi(b) orbital, which are orthogonal to each other. The singlet and triplet states of the nickel III pi-cation radical complex possess characteristic quinoid-type short-long-short alternating sequence of C-C bonds in the benzene ring, as well as intense MLCT transitions in the VIS (lambda max = 664 nm) and NIR (lambda max = 884 nm) regions, respectively.     

Polynuclear and 1-D derivatives of 1,3-bis(dimethylamino)-2-propanolato ligand. Structure and magnetic characterization

Several new Cu(II) derivatives of the 1,3-bis(dimethylamino)-2-propanolato (bdmap) ligand with formula [Cu(2)(bdmap)(acac)(NH(3))(3)(MeOH)](ClO(4))(2), [Cu(2)(bdmap)(NO(2))(3)(H(2)O)](4) and [Cu(2)(bdmap)(OH)(ox)(0.5)(H(2)O)(2)](n)(ClO(4))(n)xnH(2)O were synthesized and characterized both structurally and magnetically. Dinuclear compound crystallizes in the monoclinic system, space group P2(1)/c, octanuclear compound crystallizes in the triclinic space group P1 and the 1-D alternating system crystallizes in the monoclinic system, space group P2/n. Magnetic analysis indicates strong antiferromagnetic coupling for all derivatives, mainly due to the interaction through the alkoxo O-atom of the bdmap ligand. The effect on the magnetic behaviour of the additional bridging ligands is analysed.     

Simulation of the photodissociation of Ar 3 +

A simulation of the photodissociation of Ar ₃ ⁺ is performed in the range 200–650nm. The approach relies on Diatomic in Molecules electronic modelling, Molecular Dynamics and the Hemiquantal method. The results are used to interpret the experimental abundance of slow ions in terms of the various absorption bands. Kinetic energy distributions of all fragments are analysed at 530 and 280nm for two internal energies. The time evolution of the cluster is discussed and a concerted one-step mechanism emerges involving charge fluctuations. The simulation only yields fast-fast and fastslow photoneutral-photoneutral coincidences.     

New light on quantum dot cytotoxicity

As quantum dots are beginning to be used for in vivo imaging, the question of their long-term effect on cell viability is becoming critical. In this issue of Chemistry & Biology, Lovri? and colleagues examine the likely role of reactive oxygen species in quantum dot cytotoxicity .     

Light induced gradient refractive index materials

Controlled and patterned variation of refractive index (wavefront) across a lens surface was obtained via the use of “phase mask”. Gradient interpenetrating network was selected to screen the acrylate and epoxy monomer to obtain necessary refractive index change over the lens surface. The best photoinitiator system was determined to give a stable and transparent wavefront as a mixture of 2 wt% Irgacure 250 (I 250), 1 wt% Isopropylthoxanthone (ITX) and 0.5 wt Irgacure 184 (I 184). It is found that a dipropylene glycol diacrylate (SR 508) and a triethylene glycol dimethacrylate (TGDM) improved the stability of the transparent wavefront because of higher Tg of the network. Haze problem, a consequence of diffusion of one monomer to other network because of the rate differences, was eliminated with IPN composed of TGDM (an acrylate with slow polymerization rate) and bis (3,4‐epoxy cyclohexylmethyl)adipate (BECMA, an epoxy with fast polymerization rate). A high refractive index additive, bromonaphthalene, resulted the best wavefront with lens power when incorporated into BECMA and TGDM IPN. Copyright © 2015 John Wiley & Sons, Ltd.     

Highly Enantioselective Iridium‐Catalyzed Hydrogenation of Cyclic Enamides

The MaxPHOX–Ir catalyst system provided the highest selectivity ever reported for the reduction of cyclic enamides derived from α‐ and β‐tetralones. This result indicates that iridium catalysts are also proficient in reducing alkenes bearing metal‐coordinating groups. In the present system, selectivity was pressure‐dependent: In most cases, a decrease in the H₂ pressure to 3 bar resulted in an increase in enantioselectivity. Moreover, the process can be carried out in environmentally friendly solvents, such as methanol and ethyl acetate, with no loss of selectivity.     

Reducing complexity of algebraic multigrid by aggregation

A typical approach to decrease computational costs and memory requirements of classical algebraic multigrid methods is to replace a conservative coarsening algorithm and short‐distance interpolation on a fixed number of fine levels by an aggressive coarsening with a long‐distance interpolation. Although the quality of the resulting algebraic multigrid grid preconditioner often deteriorates in terms of convergence rates and iteration counts of the preconditioned iterative solver, the overall performance can improve substantially. We investigate here, as an alternative, a possibility to replace the classical aggressive coarsening by aggregation, which is motivated by the fact that the convergence of aggregation methods can be independent of the problem size provided that the number of levels is fixed. The relative simplicity of aggregation can lead to improved solution and setup costs. The numerical experiments show the relevance of the proposed combination on both academic and benchmark problems in reservoir simulation from oil industry. Copyright © 2016 John Wiley & Sons, Ltd.