Platinum/carbon black composites as counter electrodes for high-performance dye-sensitized solar cells

Journal of Solid State Electrochemistry - Low-cost counter electrodes for dye-sensitized solar cells (DSSCs) are prepared using platinum/carbon black (Pt/CB) composites via a spin-coating process....     

Accuracy of high‐order density‐based compressible methods in low Mach vortical flows

At low Mach numbers, Godunov‐type approaches, based on the method of lines, suffer from an accuracy problem. This paper shows the importance of using the low Mach number correction in Godunov‐type methods for simulations involving low Mach numbers by utilising a new, well‐posed, two‐dimensional, two‐mode Kelvin–Helmholtz test case. Four independent codes have been used, enabling the examination of several numerical schemes. The second‐order and fifth‐order accurate Godunov‐type methods show that the vortex‐pairing process can be captured on a low resolution with the low Mach number correction applied down to 0.002. The results are compared without the low Mach number correction and also three other methods, a Lagrange‐remap method, a fifth‐order accurate in space and time finite difference type method based on the wave propagation algorithm, and fifth‐order spatial and third‐order temporal accurate finite volume Monotone Upwind Scheme for Conservation Laws (MUSCL) approach based on the Godunov method and Simple Low Dissipation Advection Upstream Splitting Method (SLAU) numerical flux with low Mach capture property. The ability of the compressible flow solver of the commercial software, ANSYS FLUENT , in solving low Mach flows is also demonstrated for the two time‐stepping methods provided in the compressible flow solver, implicit and explicit. Results demonstrate clearly that a low Mach correction is required for all algorithms except the Lagrange‐remap approach, where dissipation is independent of Mach number. © 2013 Crown copyright. International Journal for Numerical Methods in Fluids. © 2013 John Wiley & Sons, Ltd.     

Thermodynamics of ionization of some substituted 4-methyl-thioanilines

Ionization constants of chloro, iodo and nitro substituted 4-methyl-thioanilines were determined over the range 30° to 50° using a spectro-photometric method. The results were analyzed in terms of the Harned-Robinson equation and values of heat, free energy and entropy of ionization were calculated. The free energies are additive, except in the case of 3, 5-diiodo-4-methylthioaniline, while the heats and the entropies are not.     

Nickel and palladium complexes of enolatefunctionalised N-heterocyclic carbenes

The reaction of chloroethyltrimethylsilylether with 1-methylimidazole furnishes an ionic liquid that undergoes methanolysis to crystalline 2-hydroxyethylimidazolium chloride (crystal structure presented). Conversion to defined hydroxyethylimidazol-2-ylidene nickel complexes failed, but was accomplished with 1-methyl-3-acetophenyl-imidazolium bromide. The bis(NHC^⋂O⁻) nickel(II) chelate is formed, rather than a methallylnickel monochelate, but with nickelocene a monochelate NiCp complex was detected. The bulky 1-(2,6-diisopropylphenyl)-3-(2’-phenyl-enolato)-imidazol-2-ylidene allylpalladium chloride was obtained in pure form. Attempts to generate catalysts for ethylene oligomerization by in situ techniques have failed so far whereas P^⋂O⁻ ligands, comparable by the P-C diagonal relationship, provide active catalysts.      

Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography

A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields.     

Vibrational resonance in a time-delayed genetic toggle switch

Biological oscillators can respond in a surprising way when they are perturbed by two external periodic forcing signals of very different frequencies. The response of the system to a low-frequency signal can be enhanced or depressed when a high-frequency signal is acting. This is what is known as vibrational resonance (VR). Here we study this phenomenon in a simple time-delayed genetic toggle switch, which is a synthetic gene-regulatory network. We have found out how the low-frequency signal changes the range of the response, while the high-frequency signal influences the amplitude at which the resonance occurs. The delay of the toggle switch has also a strong effect on the resonance since it can also induce autonomous oscillations.     

Hybrid system of nickel<Emphasis Type="Bold">–</Emphasis>cobalt hydroxide on carbonised natural cellulose materials for supercapacitors

Advanced carbon materials formed from abundant biomass are an exciting and promising class for energy devices due to the clear advantages of low cost, sustainability and good physical and electrochemical properties. However, these materials typically do not compete well with their metal functionalised counterparts. In this work, we demonstrate that xCo(OH)₂–(1?x)Ni(OH)₂ with various Ni:Co ratios can be deposited onto biomass-derived carbon to make a hybrid inorganic-carbon electrode with tuneable physical features and electrochemical performance. These features were tuned by adjusting the Ni:Co ratio within precursor solutions. The electrodes had shown a capacitance ranging from 780.7 to 2041 F g^?1, which is very close to the theoretical value for Ni(OH)₂ (2365 F g^?1). A hypothesis is presented to help explain this performance for a modified, biomass-derived carbon electrode.     

A Ferroelectric Aminophosphonium Cyanoferrate with a Large Electrostrictive Coefficient as a Piezoelectric Nanogenerator

Hybrid materials possessing piezo- and ferroelectric properties emerge as excellent alternatives to conventional piezoceramics due to their merits of facile synthesis, lightweight nature, ease of fabrication and mechanical flexibility. Inspired by the structural stability of aminophosphonium compounds, here we report the first A₃BX₆ type cyanometallate [Ph₂(ⁱPrNH)₂P]₃[Fe(CN)₆] ( 1 ), which shows a ferroelectric saturation polarization (P_s) of 3.71 μC cm⁻². Compound 1 exhibits a high electrostrictive coefficient (Q₃₃) of 0.73 m⁴ C⁻², far exceeding those of piezoceramics (0.034–0.096 m⁴ C⁻²). Piezoresponse force microscopy (PFM) analysis demonstrates the polarization switching and domain structure of 1 further confirming its ferroelectric nature. Furthermore, thermoplastic polyurethane (TPU) polymer composite films of 1 were prepared and employed as piezoelectric nanogenerators. Notably, the 15 wt % 1 -TPU device gave a maximum output voltage of 13.57 V and a power density of 6.03 μW cm⁻².     

Antivitamin B12 Inhibition of the Human B12-Processing Enzyme CblC: Crystal Structure of an Inactive Ternary Complex with Glutathione as the Cosubstrate

B₁₂ antivitamins are important and robust tools for investigating the biological roles of vitamin B₁₂. Here, the potential antivitamin B₁₂ 2,4-difluorophenylethynylcobalamin (F2PhEtyCbl) was prepared, and its 3D structure was studied in solution and in the crystal. Chemically inert F2PhEtyCbl resisted thermolysis of its Co−C bond at 100 °C, was stable in bright daylight, and also remained intact upon prolonged storage in aqueous solution at room temperature. It binds to the human B₁₂-processing enzyme CblC with high affinity (K_D=130 nm ) in the presence of the cosubstrate glutathione (GSH). F2PhEtyCbl withstood tailoring by CblC, and it also stabilized the ternary complex with GSH. The crystal structure of this inactivated assembly provides first insight into the binding interactions between an antivitamin B₁₂ and CblC, as well as into the organization of GSH and a base-off cobalamin in the active site of this enzyme.