Electrochemical behaviour of nickel-based electrodes for oxygen evolution reaction in alkaline water electrolysis

NiZnS electrode has been investigated for use in oxygen evolution reaction in alkaline media. Nickel mesh electrode was coated with the ternary composition of NiZnS by four methods, viz., direct current electrodeposition, pulse electrodeposition, sonoassisted direct current electrodeposition and sonoassisted pulse electrodeposition. The oxygen evolution studies carried out using these electrodes resulted in higher current density for the electrode prepared by sonoassisted pulse electrodeposition compared to those prepared by other methods. Effect of plating current density, pulse duty cycle and temperature on the electrochemical parameters of the alloy coating has been studied. Surface morphologies of the various coating were studied using scanning electron microscopy. Long-term stability of the electrodes prepared was studied in alkaline medium. Exchange current density (j _o) was found to increase with the increase in temperature and was the highest for sonoassisted pulse electrodeposited electrode.     

Effects of Thermal Radiation on a 3D Sisko Fluid over a Porous Medium Using Cattaneo-Christov Heat Flux Model

This paper investigates the three-dimensional flow of a Sisko fluid over a bidirectional stretching sheet, in a porous medium. By using the effect of Cattaneo-Christov heat flux model, heat transfer analysis is illustrated. Using similarity transformation the governing partial differential equations are transferred into a system of ordinary differential equations that are solved numerically by applying Nachtsheim-Swigert shooting iteration technique along with the 6-th order Runge-Kutta integration scheme. The effect of various physical parameters such as Sisko fluid, ratio parameter,thermal conductivity, porous medium, radiation parameter, Brownian motion, thermophoresis, Prandtl number, and Lewis number are graphically represented.     

Robust reliable L2 – L∞ control for continuous‐time systems with nonlinear actuator failures

This article examines the reliable L₂ – L_∞ control design problem for a class of continuous‐time linear systems subject to external disturbances and mixed actuator failures via input delay approach. Also, due to the occurrence of nonlinear circumstances in the control input, a more generalized and practical actuator fault model containing both linear and nonlinear terms is constructed to the addressed control system. Our attention is focused on the design of the robust state feedback reliable sampled‐data controller that guarantees the robust asymptotic stability of the resulting closed‐loop system with an L₂ – L_∞ prescribed performance level γ > 0, for all the possible actuator failure cases. For this purpose, by constructing an appropriate Lyapunov–Krasovskii functional (LKF) and utilizing few integral inequality techniques, some novel sufficient stabilization conditions in terms of linear matrix inequalities (LMIs) are established for the considered system. Moreover, the established stabilizability conditions pave the way for designing the robust reliable sampled‐data controller as the solution to a set of LMIs. Finally, as an example, a wheeled mobile robot trailer model is considered to illustrate the effectiveness of the proposed control design scheme. © 2016 Wiley Periodicals, Inc. Complexity 21: 309–319, 2016     

A Simple and Efficient Approach for Estimating Recovery of a Preparative Reversed Phase HPLC Purification

The widely applied reversed phase high-performance liquid chromatography (RP-HPLC) is an indispensable purification technique in drug discovery. During drug discovery, recovery was usually calculated based on the weight of the purified product after drying over the weight of the crude material multiplied by the assumed purity from HPLC/UV area percent of the product. Such a purity assumption can be off significantly when the crude material contains water, solvents, other UV-inactive impurities and inorganic salts. In this paper, we report a simple and efficient way to estimate recovery of preparative HPLC purification process. It is based on the ratio of the HPLC/UV peak area measured for the product in the crude solution and that in the final collected fraction with both accounted for their volumes. This approach eliminates not only the need for drying of the collected fraction to calculate recovery but also the inaccuracy associated with the true content in the crude sample using the traditional method. A systematic study was conducted to verify this method using caffeine mixed with various UV-active and -inactive impurities. The calculated recoveries using this approach were found to be consistent within 4% with the true recoveries based on dry weight estimation. The approach has been successfully applied for our in-house purifications. Furthermore, the approach was extended to library purifications, where in many cases heart-cutting the desired peaks is used to meet the purity requirements.

     

Choice of Reference Electrode is Critical for Potentiometric Whole Cell‐based Sensor

Cells have a net negative outer charge which gives rise to a potential difference in a potentiometric set up. Here, Triton X‐100 was used as a model toxin and the cell death was monitored by the potential change, noticed as decrease in negativity. Hence, cytotoxicity can be tested in vitro and real‐time using potentiometry. However, silver ions (Ag⁺) and/or silver chloride ions (AgCl₂)^?1 lead to cell death when we used the standard Ag/AgCl reference electrode with 3 M NaCl as filling solution. Our further experimentation showed that PBS as filling solution was biocompatible and also gave stable potentiometric profiles.     

Colloidal CsPbBr3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots

Traditional CdSe‐based colloidal quantum dots (cQDs) have interesting photoluminescence (PL) properties. Herein we highlight the advantages in both ensemble and single‐nanocrystal PL of colloidal CsPbBr₃ nanocrystals (NCs) over the traditional cQDs. An ensemble of colloidal CsPbBr₃ NCs (11 nm) exhibits ca. 90 % PL quantum yield with narrow (FWHM=86 meV) spectral width. Interestingly, the spectral width of a single‐NC and an ensemble are almost identical, ruling out the problem of size‐distribution in PL broadening. Eliminating this problem leads to a negligible influence of self‐absorption and Förster resonance energy transfer, along with batch‐to‐batch reproducibility of NCs exhibiting PL peaks within ±1 nm. Also, PL peak positions do not alter with measurement temperature in the range of 25 to 100 °C. Importantly, CsPbBr₃ NCs exhibit suppressed PL blinking with ca. 90 % of the individual NCs remain mostly emissive (on‐time >85 %), without much influence of excitation power.     

Raman spectra of vibrational and librational modes in methane clathrate hydrates using density functional theory

The sI type methane clathrate hydrate lattice is formed during the process of nucleation where methane gas molecules are encapsulated in the form of dodecahedron (5(12)CH(4)) and tetrakaidecahedron (5(12)6(2)CH(4)) water cages. The characterization of change in the vibrational modes which occur on the encapsulation of CH(4) in these cages plays a key role in understanding the formation of these cages and subsequent growth to form the hydrate lattice. In this present work, we have chosen the density functional theory (DFT) using the dispersion corrected B97-D functional to characterize the Raman frequency vibrational modes of CH(4) and surrounding water molecules in these cages. The symmetric and asymmetric C-H stretch in the 5(12)CH(4) cage is found to shift to higher frequency due to dispersion interaction of the encapsulated CH(4) molecule with the water molecules of the cages. However, the symmetric and asymmetric O-H stretch of water molecules in 5(12)CH(4) and 5(12)6(2)CH(4) cages are shifted towards lower frequency due to hydrogen bonding, and interactions with the encapsulated CH(4) molecules. The CH(4) bending modes in the 5(12)CH(4) and 5(12)6(2)CH(4) cages are blueshifted, though the magnitude of the shifts is lower compared to modes in the high frequency region which suggests bending modes are less affected on encapsulation of CH(4). The low frequency librational modes which are collective motion of the water molecules and CH(4) in these cages show a broad range of frequencies which suggests that these modes largely contribute to the formation of the hydrate lattice.     

Screening rhodium metallopeptide libraries "on bead": asymmetric cyclopropanation and a solution to the enantiomer problem

Searching with a beady eye: A high-throughput, on-bead screen of rhodium metallopeptide catalysts was developed in a 96-well format for asymmetric cyclopropanation. Different sequences of natural L-amino acids have been identified that produce opposite product enantiomers. In addition to styrene derivatives, high enantioselectivity is observed for vinyl ether and vinyl amine derivatives.     

Highly Luminescent and Thermally Stable Lanthanide Coordination Polymers Designed from 4-(Dipyridin-2-yl)aminobenzoate: Efficient Energy Transfer from Tb(3+) to Eu(3+) in a Mixed Lanthanide Coordination Compound

Herein, a new aromatic carboxylate ligand, namely, 4-(dipyridin-2-yl)aminobenzoic acid (HL), has been designed and employed for the construction of a series of lanthanide complexes (Eu(3+) = 1, Tb(3+) = 2, and Gd(3+) = 3). Complexes of 1 and 2 were structurally authenticated by single-crystal X-ray diffraction and were found to exist as infinite 1D coordination polymers with the general formulas {[Eu(L)(3)(H(2)O)(2)]}(n) (1) and {[Tb(L)(3)(H(2)O)].(H(2)O)}(n) (2). Both compounds crystallize in monoclinic space group C2/c. The photophysical properties demonstrated that the developed 4-(dipyridin-2-yl)aminobenzoate ligand is well suited for the sensitization of Tb(3+) emission (Φ(overall) = 64%) thanks to the favorable position of the triplet state ((3)ππ*) of the ligand [the energy difference between the triplet state of the ligand and the excited state of Tb(3+) (ΔE) = (3)ππ* - (5)D(4) = 3197 cm(-1)], as investigated in the Gd(3+) complex. On the other hand, the corresponding Eu(3+) complex shows weak luminescence efficiency (Φ(overall) = 7%) due to poor matching of the triplet state of the ligand with that of the emissive excited states of the metal ion (ΔE = (3)ππ* - (5)D(0) = 6447 cm(-1)). Furthermore, in the present work, a mixed lanthanide system featuring Eu(3+) and Tb(3+) ions with the general formula {[Eu(0.5)Tb(0.5)(L)(3)(H(2)O)(2)]}(n) (4) was also synthesized, and the luminescent properties were evaluated and compared with those of the analogous single-lanthanide-ion systems (1 and 2). The lifetime measurements for 4 strongly support the premise that efficient energy transfer occurs between Tb(3+) and Eu(3+) in a mixed lanthanide system (η = 86%).