Significant nonlinear‐optical switching capacity in atomic clusters built from silicon and lithium: A combined ab initio and density functional study

Starting from a hypothetical but fundamental charge/discharge sequence, the topic of nonlinear optical switching in atomic clusters built from silicon and alkali metals is opened up. The outcomes presented in this work, obtained with ab initio methods of exceptional predictive capabilities, offer strong evidences that sizable hyperpolarizability contrasts between neutral and charged alkali metal doped cluster forms might be simultaneously accomplished. The observed switching procedure involves redox polyatomic clusters formed by Si atoms. These centers function as electron acceptors at the ground state and as electron donors at the excited states facilitating low energy charge transfer transitions upon electronic excitation. © 2014 Wiley Periodicals, Inc.     

Bovine lactoferrin purification from whey using Yellow HE‐4R as the chromatographic affinity ligand

The worldwide production of whey increases by around 186 million tons each year and it is generally considered as a waste, even when several whey proteins have important economic relevance. For its valorization, inexpensive ligands and integrated chromatography methods need to be developed for specific and low‐cost protein purification. Here, we describe a novel affinity process with the dye Yellow HE‐4R immobilized on Sepharose for bovine lactoferrin purification. This approach based on a low‐cost ligand showed an efficient performance for the recovery and purification of bovine lactoferrin directly from whey, with a yield of 71% and a purification factor of 61.     

High energy scales in the optical self-energy of the cuprate superconductors

Using optical spectroscopy with a derivative technique, we find for the high Tc cuprate Bi2Sr2CaCu2O8+delta (Bi-2212) evidence for a new high energy scale at 900 meV beyond the two previously well-known ones at roughly 50 and 400 meV. The intermediate scale at 400 meV has recently been seen in angle-resolved photoemission spectroscopy experiments along the nodal direction as a large kink. In YBa2Cu3O6.50, the three energy scales are shifted to lower energy relative to Bi-2212 and we observe the emergence of a possible new high energy feature at 600 meV.     

Elucidating dynamic behavior of synthetic supramolecular polymers in water by hydrogen/deuterium exchange mass spectrometry

A comprehensive understanding of the structure, self-assembly mechanism, and dynamics of one-dimensional supramolecular polymers in water is essential for their application as biomaterials. Although a plethora of techniques are available to study the first two properties, there is a paucity in possibilities to study dynamic exchange of monomers between supramolecular polymers in solution. We recently introduced hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize the dynamic nature of synthetic supramolecular polymers with only a minimal perturbation of the chemical structure. To further expand the application of this powerful technique some essential experimental aspects have been reaffirmed and the technique has been applied to a diverse library of assemblies. HDX-MS is widely applicable if there are exchangeable hydrogen atoms protected from direct contact with the solvent and if the monomer concentration is sufficiently high to ensure the presence of supramolecular polymers during dilution. In addition, we demonstrate that the kinetic behavior as probed by HDX-MS is influenced by the internal order within the supramolecular polymers and by the self-assembly mechanism.     

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3-Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated Au^I species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.     

“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.     

Synthesis of star-branched oligomers by reaction of oligobutadienyllithium with diesters and epoxidized soyabean oil

Anionic polymerization can produce branches with low molecular weight and narrow molecular weight distributions. Post polymerization linking involving the still active chain ends can then be done to produce branched oligomers with a predetermined number of arms. These species are then excellent model compounds for testing high molecular weight branches. Here we chose the reaction of oligobutadienyllithium with ethyl acetate, dimethyl adipatc, diethyl adipatc, dimethyl phthalatcand epoxidized soyabean oil. For the last linking agent, we compared the result obtained with a high molecular weight poly(styryl-b-butadienyl)lithium.     

The notion of observable and the moment problem for $$*$$∗-algebras and their GNS representations

Letters in Mathematical Physics - We address some usually overlooked issues concerning the use of $$*$$-algebras in quantum theory and their physical interpretation. If $${\mathfrak {A}}$$ is a...     

Chemical Processes Involving 18-Crown-6-Ether in Activated Noncovalent Complexes with Protonated Peptides

These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes.