Chemical tuning by 5-Methyl and N-Methyl-substitution in heptanuclear complexes effects multistability investigated by Mössbauer spectroscopy

The precursors [Fe^(III)(^N???R???L)Cl] (^N???R???LH₂=N,N′-bis(2′-hydroxy- 5′-methyl-benzyliden)-1,7-diamino-4-R-4-azaheptane, R ?=? H, methyl(Me)) are high-spin (S?=?5/2) complexes. The Lewis-acidic precursors are combined with Lewis- Base-bridging-units [M(CN) _x ] ^y??? (M = Fe^(II), Ru^(II), Co^(III)) to form heptanuclear star-shaped [M{CN-Fe^(III)(^N???R???L)} _x ]Cl _y molecular switches. The star-shaped compounds are high-spin systems at room temperature. On cooling to 20 K some of the compounds exhibit multistability, i.e. several iron(III) centers within a molecule switch to the low-spin state as shown by Mössbauer spectroscopy.     

Influence of vehicle color on loudness judgments

This experiment investigates the effect of images of differently colored sports cars on the loudness of a simultaneously perceived car sound. Still images of a sports car, colored in red, light green, blue, and dark green, were displayed to subjects during a magnitude estimation task. The sound of an accelerating sports car was used as a stimulus. Statistical analysis suggests that the color of the visual stimulus may have a small influence on loudness judgments. The observed loudness differences are generally equivalent to a change in sound level of about 1 dB, with maximum individual differences of up to 3 dB.     

Helical Ullazine-Quinoxaline-Based Polycyclic Aromatic Hydrocarbons

Polycyclic aromatic azomethine ylides (PAMYs) are powerful building blocks in the bottom-up synthesis of internally nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs) through 1,3-cycloaddition reactions. In this work, the cycloaddition reaction of PAMYs to asymmetric ortho-quinones is presented, which, in contrast to the addition to symmetric para-quinones, facilitates subsequent condensation reactions and allows the synthesis of three helical N-PAHs with ullazine-quinoxaline ( UQ - 1 – 3 ) backbones. UQ - 1 and UQ - 2 possess two helical centers; however, single-crystal X-ray analysis together with the computational modeling of UQ - 3 elucidate the formation of only the thermodynamically most stable geometry with four helical centers in a (P,P,M,M) configuration. For the series UQ - 1 – 3 , the number of redox steps is directly correlated with the number of ullazine or quinoxaline units incorporated into the targeted molecular backbones. A detailed investigation of the spectroscopic and magnetic properties of the radical cation and anion as well as the dication and dianion species by in situ EPR/UV/Vis-NIR spectroelectrochemistry is provided. The excellent optical and redox properties combined with helical geometries render them possibly applicable as chiral emitter or ambipolar charge transport material in organic electronics.     

Anion‐Mediated Effects on the Size and Mechanical Properties of Enzymatically Crosslinked Suckerin Hydrogels

The suckerin family of proteins, identified from the squid sucker ring teeth assembly, offers unique mechanical properties and potential advantages over other natural biomaterials. In this study, a small suckerin isoform, suckerin‐12, is used to create enzymatically crosslinked, macro‐scale hydrogels. Upon exposure to specific salt conditions, suckerin‐12 hydrogels contracted into a condensed state where mechanical properties are found to be modulated by the salt anion present. The rate of contraction is found to correlate well with the kosmotropic arm of the Hofmeister anion series. However, the observed changes in hydrogel mechanical properties are better explained by the ability of the salt to neutralize charges in suckerin‐12 by deprotonization or charge screening. Thus, by altering the anions in the condensing salt solution, it is possible to tune the mechanical properties of suckerin‐12 hydrogels. The potential for suckerins to add new properties to materials based on naturally‐derived proteins is highlighted.     

Octaboraneyl Complexes of Nickel: Monomers for Redox-Active Coordination Polymers

Herein, we establish the preparation, characterization, and reactivity of a new diphosphine ligand, 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane (P₂B^Cy₄), a scaffold that contains four pendant boranes. An entryway into the coordination chemistry of P₂B^Cy₄ is established by using nickel, providing the octaboraneyl complex [Ni(P₂B^Cy₄)₂]—this species contains a boron-rich secondary coordination sphere that reacts readily with Lewis bases. In the case of 4,4′-bipyridine, an air-sensitive coordination polymer is obtained. Characterization of this material by solid-state NMR and EPR spectroscopy reveals the presence of a charge-transfer polymer, which forms as a function of intramolecular Ni→4,4′-bpy electron transfer (ET), providing an array of oxidized nickel sites and reduced 4,4′-bpy radical anion sites. Notably, the related intermolecular reaction between the model fragments [Ni(dnppe)₂] (dnppe=1,2-bis(di-n-propylphosphino)ethane) and a bis(boraneyl)-protected 4,4′-bpy, provides no ET. Overall, the P₂B^Cy₄ fragment provides a unique opportunity for Lewis base activation, in one case allowing for the facile construction of monomers for incorporation into redox-active macromolecules.     

A liquid chromatography coupled to quadrupole–time-of-flight–mass spectrometry (LC–QTOF–MS) method for identification analysis of saponins from Quillaja saponaria bark extracts in foot-and-mouth disease vaccines: Development,validation and applicability

Saponins from Quillaja saponaria have been commonly used as immunomodulatory adjuvants in foot-and-mouth disease vaccines (FMDVs). However, due to the lack of consensus over the possible exacerbation of local inflammatory responses in cattle and its economic impacts, their use has been discouraged by Brazilian authorities. A qualitative method intended to determine the presence of saponins from Q. saponaria bark extracts in FMDVs was developed and validated. Instrumental analysis was performed using an liquid chromatography (LC) coupled to a quadrupole–time-of-flight–mass spectrometry (TOF-MS) system. The method was validated according to the International Conference on Harmonization Harmonized Tripartite Guideline Q2 (R1) and Brazilian Ministry of Agriculture, Livestock and Food Supply Analytical Quality Assurance Guidelines. Validation parameters were determined and considered suitable to the established criteria. The validated method has been applied in routine analysis in the National Agricultural Laboratory at Rio Grande do Sul (LANAGRO-RS). All results obtained were in agreement with the vaccine's composition described by the manufacturer. The method is easy and adequate for analysis in routine laboratories. To the best of the authors' knowledge, this is the first report of a method which intends to investigate the presence of saponins from Q. saponaria bark extracts in veterinary vaccines.     

Di- and Tetracyano-Substituted Pyrene-Fused Pyrazaacenes: Aggregation in the Solid State

Five di- and tetracyano-substituted pyrene-fused pyrazaacenes were synthesized and studied as potential electron acceptors in the solid state. Single crystals of all compounds were grown and the crystal packing studied by DFT calculations (transfer integrals and reorganization energies) to get insight into possible use for semiconducting charge transport.     

Steady oscillatory states of a finite Josephson junction

Under the assumption that solutions have traveling-wave form, time-periodic solutions are found for the Josephson phase equation for a finite-length tunnel junction with uniform current feed and linear loss term. Exact current-voltage characteristics are found and compared with simple approximations. The complete current-velocity and mean-width-velocity curves for isolated fluxons are found. Comparison with characteristics for a finite junction shows that end effects obtained from analysis of a circuit model of the junction shows that end effects introduce lower- and upper-current thresholds.