Photophysical properties of 4,4'-di-tert-butyl-2,2'-bipyridine supported 6-membered 2,2'-diphenyl-X platinacycles (X = CH2, NMe, O)

The six-membered platinacycle complex, Pt((t)Bu(2)bpy)(C(6)H(4)OC(6)H(4)) (6) ((t)Bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) has been prepared from Pt((t)Bu(2)bpy)Cl(2) and 2,2'-dilithio-diphenyl ether. Platinacycle 6 and its analogs with X = CH(2) (4) and NMe (5) exhibit intense solid-state photoluminescence and nearly identical crystal structures. The photophysical properties of 4-6 in the visible range are dominated by mixed metal-ligand-to-ligand charge transfer (MLL'CT) transitions involving high-lying filled mixed metal-ligand orbitals (ML), composed primarily of platinacyclic ring-based d- and π-orbitals, and a low lying vacant π* orbital (L') of the (t)Bu(2)bpy ligand. Lone pair donation from the bridging oxygen atom and especially the NMe group increases the energy of the mixed metal-ligand orbital (ML) without altering the energy of the (t)Bu(2)bpy π* orbital. As a result, the MLL'CT state energy decreases and the absorption and emission wavelengths are red-shifted. DFT and TD-DFT calculations support the experimental results. Additional calculations on the unknown platinacycles with X = CO (7) and SO(2) (8) predict a blue-shift for the MLL'CT absorption and emission. Two nearly equal energy triplet minima were located on the DFT triplet surface for 4-6. One of these (4T-6T) has a geometry very similar to the ground-state singlet (as represented by 4-6) and is associated with the emissive (3)MLL'CT excited state. The other triplet-state (4T'-6T') has a distorted structure where the platinacycle ring is twisted out of the Pt((t)Bu(2)bpy) plane. Thermal access to this distorted triplet may be responsible for the loss of photoluminescence in room temperature solutions of 4-6.     

“Surface-enhanced Raman spectroscopy studies of the passive layer formation in gold leaching from thiosulfate solutions in the presence of cupric ion”

Complementary electrochemical and spectroscopic techniques were used to characterize the behavior and composition of the passive layer formed at the gold surface in a thiosulfate electrolyte in the presence of cupric ions. Raman studies of three different cationic (calcium, ammonium, and sodium) thiosulfate leaching solutions revealed that the concentrations of thiosulfate, trithionate, sulfate, and tetrathionate remained constant in the bulk solution over a 3-h time period. The initial leaching current densities of these three systems were identical; however, significant differences in the open circuit potentials of these systems were observed. To provide additional information about the nature of the passive layer, gold nanorod array electrodes were fabricated and employed as substrates for studying the species present at the gold–thiosulfate interface using surface-enhanced Raman spectroscopy (SERS). The composition and behavior of the passive layer at the gold–thiosulfate interface greatly differed from those of the bulk solutions. The passive layer consisted primarily of elemental sulfur and sulfide-like species, with thiosulfate and its oxidation products, such as tri- and tetrathionates, as minority components. The nature of the cation (calcium, sodium, or ammonium) of the thiosulfate salt showed no significant effect on the composition of the passive layer at leaching times longer than 100 min. In addition, the presence of cupric ions also had no significant effect on the formation of the passive layer. However, copper is a much better oxidant than oxygen in gold–thiosulfate leaching reactions.     

Physical,Thermal and Biological Properties of Yellow Dyes with Two Azodiphenylether Groups of Anthracene

Two yellow bis-azo dyes containing anthracene and two azodiphenylether groups (BPA and BTA) were prepared, and an extensive investigation of their physical, thermal and biological properties was carried out. The chemical structure was confirmed by the FTIR spectra, while from the UV–Vis spectra, the quantum efficiency of the laser fluorescence at the 476.5 nm was determined to be 0.33 (BPA) and 0.50 (BTA). The possible transitions between the energy levels of the electrons of the chemical elements were established, identifying the energies and the electronic configurations of the levels of transition. Both crystals are anisotropic, the optical phenomenon of double refraction of polarized light (birefringence) taking place. Images of maximum illumination and extinction were recorded when the crystals of the bis-azo compounds rotated by 90° each, which confirms their birefringence. A morphologic study of the thin films deposited onto glass surfaces was performed, proving the good adhesion of both dyes. By thermal analysis and calorimetry, the melting temperatures were determined (~224–225 °C for both of them), as well as their decomposition pathways and thermal effects (enthalpy variations during undergoing processes); thus, good thermal stability was exhibited. The interaction of the two compounds with collagen in the suede was studied, as well as their antioxidant activity, advocating for good chemical stability and potential to be safely used as coloring agents in the food industry.     

Quantitative selenium speciation in human urine by using liquid chromatography–electrospray tandem mass spectrometry

A liquid chromatography–electrospray-tandem mass spectrometry (ES-MS/MS) method was developed for the speciation analysis of four organic selenium species of relevance to human urinary metabolism, namely trimethylselenomium ion (TMSe⁺), selenomethionine (SeMet) and the two selenosugars, methyl 2-acetamido-2-deoxy-1-seleno-β-d-galactos/-glucos-amine (SeGalNAc and SeGluNAc, respectively). Their chromatographic separation was achieved by using a cation exchange pre-column coupled in-series with a reversed-phase high-performance liquid chromatography column, along with an isocratic mobile phase. Online detection was performed using ES-MS/MS in selective reaction monitoring mode. SeGalNAc was detected as the major human urinary metabolite of selenium in the samples analysed, whereas TMSe⁺ was detected in the urine of one volunteer before and after receiving a selenium supplement. SeMet was not detected as a urine excretory metabolite in this study. Spiking experiments performed with the urine samples revealed significant signal suppression caused by coeluting matrix constituents. To overcome such interferences, isotopically labelled ¹³CD₃⁸²SeGalNAc was used as an internal standard, whereas in the absence of an isotopically labelled internal standard for TMSe⁺, the standard addition method was applied. Quality control for the accurate quantitation of TMSe⁺ and SeGalNAc was carried out by analysing spiked human urine samples with appropriate selenium standards over a concentration range of 10–50 μg Se L⁻¹. The method has achieved a limit of detection in the presence of urine matrix comparable to that of HPLC-inductively coupled plasma-mass spectrometry for the four selenium species: 1.0 μg Se L⁻¹ for TMSe⁺, 5.6 μg Se L⁻¹ for SeMet, and 0.1 μg Se L⁻¹ for both SeGalNAc and SeGluNAc.     

Comparison of irradiated foil measurements with activation calculations and HPGe simulations

Theoretical activation calculations for Fe, Ni, and stainless steel foils were compared against irradiated foil measurements from a critical assembly. Calculated/experiment values spanning 0.62–1.31 showed that the restricted approach used here is insufficient for experiment planning, with the collapsed cross-section being the primary source of error. The effect of decay time on gamma-ray spectroscopy measurement reliability was investigated using a Monte Carlo HPGe detector model. Simulations showed no correlation with decay time, absent interferences. Specific interferences for Fe-59 (Ni) and Co-60 (stainless steel) activation product ratios suggested optimal measurement windows having respective decay times of 9–11 days and 4–7 days.     

Optimizing Antimicrobial Peptide Dendrimers in Chemical Space

We used nearest‐neighbor searches in chemical space to improve the activity of the antimicrobial peptide dendrimer (AMPD) G3KL and identified dendrimer T7 , which has an expanded activity range against Gram‐negative pathogenic bacteria including Klebsiellae pneumoniae, increased serum stability, and promising activity in an in vivo infection model against a multidrug‐resistant strain of Acinetobacter baumannii. Imaging, spectroscopic studies, and a structural model from molecular dynamics simulations suggest that T7 acts through membrane disruption. These experiments provide the first example of using virtual screening in the field of dendrimers and show that dendrimer size does not limit the activity of AMPDs.     

Preparation and Properties of Elastomer Composites Containing “Graphene”-Based Fillers: A Review

Elastomers are materials showing exceptional elasticity and are used for numerous applications. However, their low stiffness as well as their insulating behavior can be limiting so the incorporation of graphene-based materials can help and improve drastically their properties. With high Young's modulus, high electrical and thermal conductivities, graphene and graphene-like fillers seem ideal fillers to effectively tune elastomers properties. With low graphene-like loadings, most elasticity properties of elastomers could be preserved while increasing or adding new properties to the composites to enable new applications. Herein, we focus on the effects of “graphene” incorporation into elastomers and we will highlight the key parameters to effectively monitor the changes.