Solution-State 2D NMR Spectroscopy of Mixtures HyperpolarizedUsing Optically Polarized Crystals

The HYPNOESYS method (Hyperpolarized NOE System), which relies on the dissolution of optically polarized crystals, has recently emerged as a promising approach to enhance the sensitivity of NMR spectroscopy in the solution state. However, HYPNOESYS is a single-shot method that is not generally compatible with multidimensional NMR. Here we show that 2D NMR spectra can be obtained from HYPNOESYS-polarized samples, using single-scan acquisition methods. The approach is illustrated with a mixture of terpene molecules and a benchtop NMR spectrometer, paving the way to a sensitive, information-rich and affordable analytical method.     

Multiple positive solutions for nonlinear eigenvalue problems with the p-Laplacian

In this paper we consider a nonlinear eigenvalue problem driven by the p$p$-Laplacian differential operator and with a nonsmooth potential. Using degree theoretic arguments based on the degree map for certain operators of monotone type, we show that the problem has at least two nontrivial positive solutions as the parameter λ>0$\lambda >0$ varies in a half-line.     

Is gluconate a good model for isosaccharinate in uranyl(VI) chemistry? A DFT study

The geometries, relative energies and spectroscopic properties of a range of α-isosaccharinate complexes of uranyl(VI) are studied computationally using ground state and time-dependent density functional theory. The effect of pH is accommodated by varying the number of water and hydroxide ligands accompanying isosaccharinate in the equatorial plane of the uranyl unit. For 1 : 1 complexes, the calculated uranyl ν(asym) stretching frequency decreases as pH increases, in agreement with previous experimental data. Three different isosaccharinate chelating modes are studied. Their relative energies are found to be pH dependent, although the energetic differences between them are not sufficient to exclude the possibility of multiple speciation. At higher pH, the uranyl-ligand interactions are dominated more by the equatorial OH(-) than by the organic ligands. Calculated electronic excitation energies support experiment in finding the lowest energy transitions to be ligand → metal charge transfer. (13)C NMR chemical shifts are calculated for the coordinated isosaccharinate in the high pH mimics, and show good agreement with experimental data, supporting the experimental conclusion that the five-membered chelate ring is favoured at high pH. The effect of increasing the isosaccharinate concentration is modelled by calculating 1 : 2 and 1 : 3 uranyl : α-isosaccharinate complexes. Comparison of the results of the present study with those from our closely related investigation of uranyl(VI)-D-gluconate complexes (Dalton Transactions 40 (2011) 11248) reveals strong similarities in structure, bonding, coordination geometry and electronic excitations, but also differences in ΔG for key ligand replacement reactions, suggesting that caution should be exercised when using gluconate as a thermodynamic model for isosaccharinate in uranyl(vi) chemistry.     

Flow Potentiometric Injection Analysis of Uric Acid Using Lipid Stabilized Films with Incorporated Uricase on ZnO Nanowires

A novel potentiometric uric acid biosensor was fabricated by immobilization of uricase into stabilized lipid films using zinc oxide (ZnO) nanowires as measuring electrode. Uricase was incorporated into the lipid film prior polymerization on the surface of well aligned ZnO nanowires resulting in a sensitive, selective, stable and reproducible uric acid biosensor. The potentiometric response was twice as large from previously reported values due to the presence of a cationic lipid in the lipid film. The sensor response had no interferences by normal concentrations of ascorbic acid, glucose, urea, proteins and lipids.     

The Moving-Frame Method for the Iterated-Integrals Signature: Orthogonal Invariants

Geometric, robust-to-noise features of curves in Euclidean space are of great interest for various applications such as machine learning and image analysis. We apply Fels–Olver’s moving-frame method (for geometric features) paired with the log-signature transform (for robust features) to construct a set of integral invariants under rigid motions for curves in \({\mathbb {R}}^d\) from the iterated-integrals signature. In particular, we show that one can algorithmically construct a set of invariants that characterize the equivalence class of the truncated iterated-integrals signature under orthogonal transformations, which yields a characterization of a curve in \({\mathbb {R}}^d\) under rigid motions (and tree-like extensions) and an explicit method to compare curves up to these transformations.

     

ChemInform Abstract: Computational Study of Analogues of the Uranyl Ion Containing the —N=U=N— Unit: Density Functional Theory Calculations on UO22+, UON+, UN2, UO(NPH3)3+, U(NPH3)24+, [UCl4{NPR3}2] (R: H,Me), and [UOCl4{NP(C6H5)3}]‐

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Breaking Malus’ law: Highly efficient,broadband, and angular robust asymmetric light transmitting metasurface

High efficiency, broad bandwidth, and robust angular tolerance are key considerations in photonic device design. Here, a few‐layer, asymmetric light transmitting metasurface that simultaneously satisfies all the above requirements is reported. The metasurface consists of coupled metallic sheets. It has a measured transmission efficiency of 80%, extinction ratio of 13.8 dB around 1.5 μm, and a full width half maximum bandwidth of 1.7 μm. It is as thin as 290 nm, has good performance tolerance against the angle of incidence and constituent nano‐structure geometry variations. This work demonstrates a practical asymmetric light transmission device with optimal performance for large scale manufacturing.

     

ChemInform Abstract: Quantum Chemical Calculations on a Selection of Iodine‐Containing Species (IO,OIO, INO3, (IO)2, I2O3, I2O4 and I2O5) of Importance in the Atmosphere.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.