Coordination of imidazoles by Cu(II) and Zn(II) as studied by NMR relaxometry, EPR, far-FTIR vibrational spectroscopy and ab initio calculations: effect of methyl substitution

Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position.     

Tverberg’s Theorem and Graph Coloring

The topological Tverberg theorem has been generalized in several directions by setting extra restrictions on the Tverberg partitions. Restricted Tverberg partitions, defined by the idea that certain points cannot be in the same part, are encoded with graphs. When two points are adjacent in the graph, they are not in the same part. If the restrictions are too harsh, then the topological Tverberg theorem fails. The colored Tverberg theorem corresponds to graphs constructed as disjoint unions of small complete graphs. Hell studied the case of paths and cycles. In graph theory these partitions are usually viewed as graph colorings. As explored by Aharoni, Haxell, Meshulam and others there are fundamental connections between several notions of graph colorings and topological combinatorics. For ordinary graph colorings it is enough to require that the number of colors q satisfy q>Δ, where Δ is the maximal degree of the graph. It was proven by the first author using equivariant topology that if q>Δ ² then the topological Tverberg theorem still works. It is conjectured that q>KΔ is also enough for some constant K, and in this paper we prove a fixed-parameter version of that conjecture. The required topological connectivity results are proven with shellability, which also strengthens some previous partial results where the topological connectivity was proven with the nerve lemma.     

An isoindigo-based low band gap polymer for efficient polymer solar cells with high photo-voltage

A new low band gap polymer (E(g) = 1.6 eV) with alternating thiophene and isoindigo units was synthesized and characterized. A PCE of 3.0% and high open-circuit voltage of 0.89 V were realized in polymer solar cells, which demonstrated the promise of isoindigo as an electron deficient unit in the design of donor-acceptor conjugated polymers for polymer solar cells.     

Photofragmentation and photoabsorption cross sections for mass selected argon cluster ions,n=3 to 108

A tandem time-of-flight mass spectrometer is used to measure photofragmentation mass spectra and optical absorption spectra of mass selected argon cluster ions in then=3 to 108 atoms per cluster range.     

Baryon production in the string fragmentation picture

An improved version of the “pop-corn” model for baryon production in quark and gluon jets is presented. With a reduced number of parameters the model reproduces well both production rates for different baryon species and baryon momentum distributions. Predictions are presented for a set of baryon-antibaryon correlations.     

Sensitive detection and separation of fluorescent derivatives using capillary electrophoresis with laser-induced fluorescence detection with 532 nm Nd:YAG laser

Capillary electrophoresis with laser-induced fluorescence detection (CELIF) is a powerful tool for separation and sensitive determination of fluorescent species. Biologically active compounds, such as amino acids, peptides and proteins may exhibit native fluorescence, which is however often low and/or an expensive laser is required for excitation in UV. Therefore, labelling of the analytes with a fluorescent dye is usually necessary.In this work, a home-built CELIF instrument with diode pumped frequency-doubled continuous wave Nd:YAG excitation laser with feedback power regulation (532 nm) was constructed. The suitability of this type of laser for LIF detection in a separation method was found excellent. A limit of detection (LOD) (S/N=3) of 2×10⁻¹³ mol/l was achieved with rhodamine B, which is comparable to those obtained using similar instruments with Ar⁺ laser [Y.F. Cheng, N.J. Dovichi, Science 242 (1988) 562, E.S. Yeung et al., J. Chromatogr. 608 (1992) 73]. LOD of a protein derivatized according to modified procedures [M.J. Little et al., Anal. Chim. Acta 339 (1997) 279, A. Chersi et al., Biochim. Biophys. Acta 1336 (1997) 83] was determined. Detection of the derivatives was found to be limited by insufficient reaction recovery at low analyte concentration, chemical noise, separation efficiency and quality of the derivatizing reagent rather than by the detector performance. As a consequence, a huge gap between the detection ability of CELIF instruments and LOD determined in real samples is revealed.     

The Quest for Polysulfides in Lithium–Sulfur Battery Electrolytes: An Operando Confocal Raman Spectroscopy Study

Confocal Raman spectra of a lithium–sulfur battery electrolyte are recorded operando in a depth‐of‐discharge resolved manner for an electrochemical cell with a realistic electrolyte/sulfur loading ratio. The evolution of various possible polysulfides is unambiguously identified by combining Raman spectroscopy data with DFT simulations.