Structures, electronic properties and solid state luminescence of Cu(I) iodide complexes with 2,9-dimethyl-1,10-phenanthroline and aliphatic aminomethylphosphines or triphenylphosphine

The luminescent complexes of triphenylphosphine and two interesting aminomethylphosphines: P(CH(2)N(CH(2)CH(2))(2)NCH(3))(3) and P(CH(2)N(CH(2)CH(2))(2)O)(3) with copper(I) iodide and 2,9-dimethyl-1,10-phenanthroline (dmp): [CuI(dmp)PPh(3)], [CuI(dmp)P(CH(2)N(CH(2)CH(2))(2)NCH(3))(3)] and [CuI(phen)P(CH(2)N(CH(2)CH(2))(2)O)(3)] are presented in this work. These complexes were characterized in solution by means of NMR spectroscopy and their structures were crystallographically determined in the solid state. All complexes crystallize as the discrete dimers bound by π-stacking interactions between dmp rings. The coordination geometry about the Cu(I) centre is pseudo-tetrahedral showing small flattening and large rocking distortions. The investigated compounds exhibit intense orange photoluminescence in the solid state (emission peaks at r.t.: λ(max) = 588-592 nm; τ = 1.7-2.2 and 6.4-10.0 μs; at 77 K: λ(max) = 605-612 nm; τ = 4.8-6.5 and 32-47 μs), which is several orders higher than the luminescence of the analogous complexes with 1,10-phenanthroline (phen). Electronic and structural properties of the [CuI(dmp/phen)PR(3)] complexes were characterized using DFT methods to interpret their photophysics. On the basis of TDDFT calculations the broad CT bands observed in UV-Vis spectra are interpreted as the two mixed transitions from σ(CuI) bond with a small admixture of σ(CuP) bond to π* phen or dmp ligand: (MX,MPR(3))LCT, while the emissions most probably occur from two triplet states which are in thermal equilibrium.     

On the points realizing the distance to a definable set

We prove a definable/subanalytic version of a useful lemma, presumably due to John Nash, concerning the points realizing the Euclidean distance to an analytic submanifold of Rn. We present a parameter version of the main result and we discuss the properties of the multifunction obtained.     

Quantification of changes in oxygen release from red blood cells as a function of age based on magnetic susceptibility measurements

This study extends the in vitro understanding of the RBC storage lesion by serially analyzing the RBC's magneophoretic mobility, a property dependent on the content and oxygenation or oxidation state of hemoglobin (Hb) iron, during storage. Four prestorage leukoreduced, AS-5 preserved RBC units were stored between 1 and 6 °C for 42 days. Weekly starting on storage day 7, each unit was sampled, divided into 3 aliquots, each subjected to different reactions: one aliquot was exposed to room air to produce oxyhemoglobin (oxyHb), another aliquot was mixed with sodium nitrite to produce methemoglobin (metHb), while the third aliquot was desaturated of oxygen (deoxyhemoglobin, deoxyHb) using nitrogen gas. These aliquots were placed into a cell tracking velocimetry (CTV) apparatus which measured both the settling velocity (u(s)) of the RBCs as well as their magnetically induced velocity (u(m)). The u(m)/u(s) ratio depends on the oxygenation state of the hemoglobin and the quantity of iron within the RBC. The RBC density was measured by percoll centrifugation. There was a significant reduction in the u(m)/u(s) ratio for the deoxyHb RBC aliquot as storage time elapsed, with a smaller but still significant reduction in the u(m)/u(s) ratio for the metHb aliquot. The average RBC density decreased very slightly during storage, as determined by the percoll centrifugation technique, although the average settling velocity (another measure of cell density) seemed to fluctuate during storage. The decrease in magnetophoretic mobility of the deoxyHb portion is explicable either by Hb's increased affinity for oxygen during storage, or else a loss of iron from the cells.     

Light driven reactions of single physisorbed azobenzenes

We present a successful attempt of decoupling a dye molecule from a metallic surface via physisorption for enabling direct photoisomerization. Effective switching between the isomers is possible by exposure to UV light via the rotation pathway.     

A Rapid Gas-Chromatography/Mass-Spectrometry Technique for Determining Odour Activity Values of Volatile Compounds in Plant Proteins: Soy,and Allergen-Free Pea and Brown Rice Protein

Plant-based protein sources have a characteristic aroma that limits their usage in various meat-alternative formulations. Despite being the most popular plant-based protein, the allergenicity of soy protein severely restricts the potential adoption of soy protein as an animal substitute. Thereby, allergen-free plant-protein sources need to be characterized. Herein, we demonstrate a rapid solid-phase-microextraction gas-chromatography/mass-spectrometry (SPME-GC/MS) technique for comparing the volatile aroma profile concentration of two different allergen-free plant-protein sources (brown rice and pea) and comparing them with soy protein. The extraction procedure consisted of making a 1:7 w/v aqueous plant protein slurry, and then absorbing the volatile compounds on an SPME fibre under agitation for 10 min at 40 °C, which was subsequently injected onto a GC column coupled to an MS system. Observed volatile concentrations were used in conjunction with odour threshold values to generate a Total Volatile Aroma Score for each protein sample. A total of 76 volatile compounds were identified. Aldehydes and furans were determined to be the most dominant volatiles present in the plant proteins. Both brown rice protein and pea protein contained 64% aldehydes and 18% furans, with minor contents of alcohols, ketones and other compounds. On the other hand, soy protein consisted of fewer aldehydes (46%), but a more significant proportion of furans (42%). However, in terms of total concentration, brown rice protein contained the highest intensity and number of volatile compounds. Based on the calculated odour activity values of the detected compounds, our study concludes that pea proteins could be used as a suitable alternative to soy proteins in applications for allergen-free vegan protein products without interfering with the taste or flavour of the product.     

Twistor Geometry of a Pair of Second Order ODEs

We discuss the twistor correspondence between path geometries in three dimensions with vanishing Wilczynski invariants and anti-self-dual conformal structures of signature (2, 2). We show how to reconstruct a system of ODEs with vanishing invariants for a given conformal structure, highlighting the Ricci-flat case in particular. Using this framework, we give a new derivation of the Wilczynski invariants for a system of ODEs whose solution space is endowed with a conformal structure. We explain how to reconstruct the conformal structure directly from the integral curves, and present new examples of systems of ODEs with point symmetry algebra of dimension four and greater which give rise to anti–self–dual structures with conformal symmetry algebra of the same dimension. Some of these examples are (2, 2) analogues of plane wave space–times in General Relativity. Finally we discuss a variational principle for twistor curves arising from the Finsler structures with scalar flag curvature.     

Microwave assisted sulfopropylation of N-heterocycles using 1,3-propane sultone

Dramatic rate acceleration was observed for N-sulfopropylation of heterocyclic compounds (1a-h) using 1,3-propane sultone(2) under microwave irradiation affording the N-sulfopropylated compounds (3a-h) in 68–95% yield.     

Highly conducting solid electrolytes based on poly (ethylene oxide-co-propylene oxide)

The conducting properties of solid electrolytes comprising random poly(ethylene oxide-co-propylene oxide) (of 84 : 16 monomer units mole ratio) and lithium, sodium, potassium, cesium, and rubidium salts have been studied. The systems containing some lithium or sodium salts achieved conductivity levels as high as 10^?5–10^?4 S/cm at ambient temperature and greater than 10^?3 S/cm at 100°C. However, the systems with rubidium and cesium salts exhibit conductivities a few orders of magnitude smaller. DSC studies show that the electrolytes studied are characterized by a high content of an amorphous phase (95–100%). It is suggested that the copolymer exhibits lower complexing abilities than that of poly(ethylene oxide), which results in a higher flexibility of electrolytes containing small cations and poor dissociation of the salts having large cations. © 1995 John Wiley & Sons, Inc.