Water-Assisted Concerted Proton-Electron Transfer at Co(II)-Aquo Sites in Polyoxotungstates With Photogenerated RuIII(bpy)33+ Oxidant

The cobalt substituted polyoxotungstate [Co₆(H₂O)₂(α-B-PW₉O₃₄)₂(PW₆O₂₆)]¹⁷⁻ ( Co6 ) displays fast electron transfer (ET) kinetics to photogenerated Ru^III(bpy)₃³⁺, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II) −OH ₂ and Co6(II) −OH, respectively, whose speciation in aqueous solution is associated to a pK_a of 7.6), and generates a Co(III)−OH moiety ( Co6(III) −OH), as proven by transient absorption spectroscopy; (ii) at pH>pK_a, the Co6(II) −OH→Ru^III(bpy)₃³⁺ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH <pK_a, the process involves Co6(II) − OH₂ → Co6(III)−OH transformation and proceeds via a multiple-site, concerted proton electron transfer (CPET) where water assists the transfer of the proton, as proven by the absence of effect of buffer base concentrations on the rate of the ET and by a H/D kinetic isotope in a range of 1.2–1.4. The reactivity of water is ascribed to its organization on the surface of the polyanionic scaffold through hydrogen bond networking involving the Co(II)−OH₂ group.     

Thermodynamic properties of xanthone: Heat capacities,phase-transition properties,and thermodynamic-consistency analyses using computational results

Heat capacities and phase-transition properties for xanthone (IUPAC name 9H-xanthen-9-one and Chemical Abstracts registry number [90-47-1]) are reported for the temperature range 5 < T/K < 524. Statistical calculations were performed and thermodynamic properties for the ideal gas were derived based on molecular geometry optimization and vibrational frequencies calculated at the B3LYP/6-31+G(d,p) level of theory. These results are combined with sublimation pressures from the literature to allow critical evaluation of inconsistent enthalpies of sublimation for xanthone, also reported in the literature. Literature values for the enthalpy of combustion of xanthone are re-assessed, a revision is recommended for one result, and a new value for the enthalpy of formation of the ideal gas is derived. Comparisons with thermophysical properties reported in the literature are made for all other reported and derived properties, where possible.     

Measurement of interdiffusion in polymeric materials by applying Raman spectroscopy

Raman spectroscopy was evaluated regarding its specific value in terms of detection of interdiffusion in two-component injection molded parts. Two-component injection molded parts made of four material combinations chosen from polypropylene, styrene based thermoplastic elastomer, polycarbonate, polystyrene and polymethyl methacrylate produced by varying melt temperatures of the second component T_M2 were investigated.In principle, Raman spectroscopy was found to be a powerful tool to detect interdiffusion. However, some restrictions arise. These include spatial resolution limit and detection limit. Interdiffusion lengths ranging from below 1 μm–3 μm were determined. Either an increase, a decrease or no change of the interdiffusion length for increasing T_M2 was detected. The interdiffusion lengths were compared with the stress and elongation at break obtained by tensile tests. No distinct correlation of interdiffusion length and the mechanical properties was found. However, a high T_M2 provoked an increase in the stress and elongation at break.     

Structural and Functional Implications of the Interaction between Macrolide Antibiotics and Bile Acids

Macrolide antibiotics, such as azithromycin and erythromycin, are in widespread use for the treatment of bacterial infections. Macrolides are taken up and excreted mainly by bile. Additionally, they have been implicated in biliary system diseases and to modify the excretion of other drugs through bile. Despite mounting evidence for the interplay between macrolide antibiotics and bile acids, the molecular details of this interaction remain unknown. Herein, we show by NMR measurements that macrolides directly bind to bile acid micelles. The topology of this interaction has been determined by solvent paramagnetic relaxation enhancements (solvent PREs). The macrolides were found to be bound close to the surface of the micelle. Increasing hydrophobicity of both the macrolide and the bile acid strengthen this interaction. Both bile acid and macrolide molecules show similar solvent PREs across their whole structures, indicating that there are no preferred orientations of them in the bile micelle aggregates. The binding to bile aggregates does not impede macrolide antibiotics from targeting bacteria. In fact, the toxicity of azithromycin towards enterotoxic E. coli (ETEC) is even slightly increased in the presence of bile, as was shown by effective concentration (EC₅₀) values.     

Structural transitions under high-pressure in a langasite-type multiferroic Ba3TaFe3Si2O14

The iron containing langasite family compound Ba₃Ta⁵⁷Fe₃Si₂O₁₄ was studied at high pressure up to 30 GPa at room temperature by means of in situ X-ray diffraction, Raman and Mössbauer spectroscopies in diamond anvil cell. Two structural transitions at pressures ∼5 and ∼20 GPa are observed. At ∼5 GPa, the low-pressure trigonal P321 phase undergoes phase transition to the most likely P3 structure as manifested by slight increase in the c/a ratio and by anomalies of the Mössbauer and Raman spectra parameters. At ∼20 GPa, the first order phase transition to monoclinic structure occurred with a drop of unit cell volume by 9%. The appearance of the ferroelectric state at such transitions is discussed in connection with the multiferroic properties.     

High Ethene/Ethane Selectivity in 2,2′‐Bipyridine‐Based Silver(I) Complexes by Removal of Coordinated Solvent

Following removal of coordinated CH₃CN, the resulting complexes [Ag^I(2,2′‐bipyridine)][BF₄] ( 1 ) and [Ag^I(6,6′‐dimethyl‐2,2′‐bipyridine)][OTf] ( 2 ) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g^?1 when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2 , ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes.     

Electronic Olfactory Sensor Based on A. mellifera Odorant‐Binding Protein 14 on a Reduced Graphene Oxide Field‐Effect Transistor

An olfactory biosensor based on a reduced graphene oxide (rGO) field‐effect transistor (FET), functionalized by the odorant‐binding protein 14 (OBP14) from the honey bee (Apis mellifera) has been designed for the in situ and real‐time monitoring of a broad spectrum of odorants in aqueous solutions known to be attractants for bees. The electrical measurements of the binding of all tested odorants are shown to follow the Langmuir model for ligand–receptor interactions. The results demonstrate that OBP14 is able to bind odorants even after immobilization on rGO and can discriminate between ligands binding within a range of dissociation constants from K_d=4 μM to K_d=3.3 mM . The strongest ligands, such as homovanillic acid, eugenol, and methyl vanillate all contain a hydroxy group which is apparently important for the strong interaction with the protein.     

The reduction of skin friction by riblets under the influence of an adverse pressure gradient

In this paper we address the effectiveness of riblets on skin friction reduction under the influence of an adverse pressure gradient. The measurements were taken in a wind tunnel. Skin friction was observed with a drag balance which has a reproducibility of better than 1%. The accuracy of the balance is estimated to be less than 1% for the case of zero-pressure gradient and at most 3% for a pressure gradient. The data on skin friction reduction at zero pressure gradient were consistent with previous results and amount to 5% at dimensionless riblet width of s ⁺ = 13. We find that at all adverse pressure gradients the skin friction reduction by riblets persists. At moderate pressure gradients the reduction increases somewhat to 7%. The velocity profile which is also measured, exhibits the characteristic shape for a boundary layer with an adverse pressure gradient and agrees well with theory. From the velocity profiles measured at two stations we estimated with the help of a momentum balance the skin friction and skin friction reduction. The results differ from the drag-balance data. Due to the poor accuracy of the momentum balance method which we estimate in our case, we conclude that the results obtained with this method are less reliable than those obtained with the drag balance. This throws some doubt on previous results on drag reduction under the influence of a pressure gradient which were based on the momentum balance method.     

A fluorescence technique for measurement of slot injected fluid concentration profiles in a turbulent boundary layer

A technique for measuring near instantaneous concentration profiles of a fluid injected through a narrow inclined slot at the wall into a high unit Reynolds number flat plate turbulent boundary layer is discussed. The concentration profiles are determined by measuring the light intensity emitted from a fluorescent dye, premixed into the injectant flow, as the injectant convects through an excitation laser beam. The fluorescence intensity is quantified by an electronically shuttered single stage microchannel plate image intensifier coupled to a linear photodiode array. This instrumentation provided the high spatial and temporal resolution required for these boundary layer concentration profile measurements. The laser induced fluorescence technique is being used to study the diffusion of injected polymer solutions away from the near wall region of the boundary layer where these solutions are effective in reducing drag. The diffusion of slot injected water has also been examined and the present results are in excellent agreement with previous studies.     

Point force in a MHB rotating fluid

We consider the steady flow of an inviscid, rotating fluid confined in a cylinder under the influence of a uniform axial magnetic field, in the presence of an isolated point force. It is found that, the wave-like terms, infinite in number, occurring on the downstream side are not persistent and decay at far distances, in contrast to the non-magnetic case. Also the presence of a uniform magnetic field induces an additional finite number of decaying modes on the upstream side and an infinite number of similar modes on the downstream side, which reduce to the geostrophic terms, in the corresponding non-magnetic case. The downstream solution reveals that discontinuities occur in the velocity gradients inside the fluid region.