Effect of TiMn1.5 alloying on the structure,hydrogen storage properties and electrochemical properties of LaNi3.8Co1.1Mn0.1 hydrogen storage alloys

A series of experiments were performed to investigate the effect of TiMn_1.5 alloying on the structure, hydrogen storage properties and electrochemical properties of LaNi_3.8Co_1.1Mn_0.1 hydrogen storage alloys at 303 K. For simple, A, B, and C are used to represent alloys (x = 0 wt %, x = 4 wt % and x = 8 wt %) respectively. The results of XRD and SEM show that LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloys have LaNi₅ phase and (NiCo)₃Ti phase. Based on the results of PCT curves, the hydrogen storage capacities of LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloys are about 1.28 wt % (A), 1.16 wt % (B) and 1.01 wt % (C) at 303 K. And the released pressure platform and the pressure hysteresis decrease with the increase of TiMn_1.5 content. Meanwhile the activation curves show that LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloy electrodes can be activated in three times and the maximum discharge capacity is 343.74 mA h/g at 303 K. In addition, with the increase of TiMn_1.5 content, the cyclic stability of the hydrogen storage alloy electrodes decreases obviously and the capacity retention decreases from 76.70% to 70.00% when TiMn_1.5 content increases from A to C. It also can be seen that LaNi_3.8Co_1.1Mn_0.1?xTiMn_1.5 hydrogen storage alloy electrode C and B have the best self-discharge ability and the best high-rate discharge ability from self-discharge curves and high-rate discharge curves.     

Microwave absorbing properties of Fe3O4–poly(3, 4‐ethylenedioxythiophene) hybrids in low‐frequency band

A facile method is proposed to obtain microwave absorbing materials (MAMs), which possess strong microwave absorption properties in low‐frequency range. By simply mechanical mixing, the obtained Fe₃O₄–poly (3,4‐ethylenedioxythiophene) (PEDOT) hybrids exhibit more excellent microwave absorbing properties than that of Fe₃O₄ or PEDOT individually. The analysis on the microwave absorbing properties of the Fe₃O₄–PEDOT hybrids indicates that the excellent microwave absorbing properties are ascribed to several factors, like the dielectric loss, the interface polarization, eddy current effect, natural ferromagnetic resonance, and the impedance as well as the thickness of the coating. The Fe₃O₄–PEDOT hybrids with appropriate mass ratios of PEDOT to Fe₃O₄ (represented by (PEDOT)/(Fe₃O₄)) show superior microwave absorbing property at low frequency. When the thickness is 4 mm, the reflection loss of the sample reached ?15.8 dB at 3.2 GHz with (PEDOT)/(Fe₃O₄) of 3 and ?31.4 dB at 4.5 GHz with (PEDOT)/(Fe₃O₄) of 2, respectively. The obtained Fe₃O₄–PEDOT MAMs will have a promising application in the practical industry and commerce affairs. Copyright © 2013 John Wiley & Sons, Ltd.     

Label Scrambling During CID of Covalently Labeled Peptide Ions

Covalent labeling along with mass spectrometry is finding more use as a means of studying the higher order structure of proteins and protein complexes. Diethylpyrocarbonate (DEPC) is an increasingly used reagent for these labeling experiments because it is capable of modifying multiple residues at the same time. Pinpointing DEPC-labeled sites on proteins is typically needed to obtain more resolved structural information, and tandem mass spectrometry after protein proteolysis is often used for this purpose. In this work, we demonstrate that in certain instances, scrambling of the DEPC label from one residue to another can occur during collision-induced dissociation (CID) of labeled peptide ions, resulting in ambiguity in label site identity. From a preliminary study of over 30 labeled peptides, we find that scrambling occurs in about 25% of the peptides and most commonly occurs when histidine residues are labeled. Moreover, this scrambling appears to occur more readily under non-mobile proton conditions, meaning that low charge-state peptide ions are more prone to this reaction. For all peptides, we find that scrambling does not occur during electron transfer dissociation, which suggests that this dissociation technique is a safe alternative to CID for correct label site identification. Graphical Abstract

?     

Morphological transformations of nonequilibrium assemblies of amphiphilic diblock copolymer

Amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-PEO) assembled into nonequilibrium bicontinuous structures or mixture of vesicles, bilayers and nanorods upon rapid micellization induced by rapid addition of selective solvent (water) into the PS-PEO solutions in a common solvent (dimethyl formamide) with different concentrations. These kinetically trapped assemblies were unstable and slowly evolved into thermodynamically favorable spheres and vesicles. The addition of non-ionic surfactant Pluronic P123 upon rapid micellization generated novel nanocages and flower-like vesicles. The nanocages spontaneously transformed into tubules capped with vesicles. These novel assemblies are beyond the classic phase diagram of block copolymer self-assemblies, especially for those primarily based on thermodynamics.     

Novel 1D Mn(II) complexes containing aromatic dicarboxylic acids

Three Mn(II) complexes of [MnL(Bipy)(H₂O)] _n (I), [Mn₃(Phen)₂(HL)₂(L)₂]n (II), and [Mn(Phen)₂(HL)(OH)] (III), where L = 4,4′-(2-acetylpropane-1,3-diyl)dibenzoic acid, Bipy = 2,2′-bipyridine, and Phen = 1,10-phenanthroline, were hydrothermally synthesized and characterized by single crystal X-ray diffractions, infrared spectroscopy, thermogravimetric analyses, and magnetic analyses. Complexes I and II are one dimensional (1D) coordination polymers which can form the supramolecules with the help of the intermolecular hydrogen bond interactions. Finally, the landé factors are simulated by magentochemical analysis to be 2.15 and 1.80 for I and II with S = 5/2, respectively.     

Phase‐controlled crystallization of amorphous calcium carbonate in ethanol‐water binary solvents

The evolution of amorphous calcium carbonate (ACC) into crystals in ethanol/water binary solvents under ambient temperature was investigated, and it was found to depend on the volume ratio of ethanol to water (R). Calcite remained dominant when the amount of water was high (R = 1/3). A slight change in the amount of ethanol (R = 3/1) could lead to a dramatic change in the polymorph from calcite to aragonite. However, when poly (allylamine hydrochloride) (PAH) was added at R = 3/1, almost pure vaterite could be obtained, which has a specific morphological variation (from hollow microspheres to cloud‐like). This study provides an alternative polymorphic route for the CaCO₃ mineral by using the evolution of ACC in different solvent environments, which provides some useful clues for understanding the importance of kinetic control of the morphologies and polymorphs of a wide range of inorganic materials. In addition, this simple mild phase‐controlled synthetic method could be scaled up as a green chemistry route for the industrial production of different polymorphs of CaCO₃.     

Asymmetric NH Insertion of Secondary and Primary Anilines under the Catalysis of Palladium and Chiral Guanidine Derivatives

Efficient enantioselective N? H insertion reactions of secondary and primary anilines were catalyzed by palladium(0) in combination with chiral guanidine derivatives. A broad range of substituted anilines were tolerated, and the corresponding products were obtained in high yield (up to 99 %) with good enantioselectivity (up to 94 % ee) under mild reaction conditions. The N? H insertion mechanism was examined by the study of kinetic isotope effects, control experiments, HRMS, and spectroscopic analysis.     

Activated nitrogen-doped carbons from polyvinyl chloride for high-performance electrochemical capacitors

Activated nitrogen-doped carbons (ANCs) were prepared by carbonization/activation approach using aminated polyvinyl chloride (PVC) as precursor. ANCs exhibit larger porosities and higher specific surface areas than those of their nitrogen-free counterparts for the same KOH/carbon ratio. The specific surface area of ANC-1 is up to 1,398 m² g^?1 even at a low KOH/carbon ratio of 1:1. Fourier transform infrared spectroscopy investigation of the nitrogen-enriched resin precursor indicates the efficient dehydrochlorination of PVC by ethylenediamine at a low temperature. The nitrogen content and the population of nitrogen functionalities strongly depend on the KOH/carbon ratios and decrease drastically after KOH activation as seen from the elemental and X-ray photoelectron spectroscopy analysis. The surface concentration of N-6 and N-Q almost disappears and the dominant nitrogen groups become N-5 after KOH activation. The highest specific capacitance of ANCs is up to 345 F g^?1 at a current density of 50 mA g^?1 in 6 M KOH electrolyte. ANCs also exhibit a good capacitive behavior at a high scan rate of 200 mV s^?1 and an excellent cyclability with a capacitance retention ratio as high as ～93 % at a current density of 2,000 mA g^?1 for 5,000 cycles.     

Large Hexagonal Bi‐ and Trilayer Graphene Single Crystals with Varied Interlayer Rotations

Bi‐ and trilayer graphene have attracted intensive interest due to their rich electronic and optical properties, which are dependent on interlayer rotations. However, the synthesis of high‐quality large‐size bi‐ and trilayer graphene single crystals still remains a challenge. Here, the synthesis of 100 μm pyramid‐like hexagonal bi‐ and trilayer graphene single‐crystal domains on Cu foils using chemical vapor deposition is reported. The as‐produced graphene domains show almost exclusively either 0° or 30° interlayer rotations. Raman spectroscopy, transmission electron microscopy, and Fourier‐transformed infrared spectroscopy were used to demonstrate that bilayer graphene domains with 0° interlayer stacking angles were Bernal stacked. Based on first‐principle calculations, it is proposed that rotations originate from the graphene nucleation at the Cu step, which explains the origin of the interlayer rotations and agrees well with the experimental observations.     

Effect of Cu content on structure,hydrogen storage properties and electrode performance of LaNi4.1-x Co0.6Mn0.3Cu x alloys

The effect of Cu content on structure, hydrogen storage, and electrochemical properties of LaNi_4.1-x Co_0.6Mn_0.3Cu _x alloys has been investigated. For sample, A, B, C, and D are used to represent alloys (x?=?0, 0.15, 0.3, and 0.45), respectively. The results indicate that the four alloys are all single-phase alloy with LaNi₅ phase of CaCu₅ hexagonal structure, the hydrogen storage capacities of the alloy are about 1.49 wt% (A), 1.48 wt% (B), 1.43 wt% (C), and 1.25 wt% (D) at 303 K. With the increase of Cu content (x) from A to D, hydrogen desorption plateau pressure and pressure hysteresis decrease. Alloy electrode A shows better activation property and higher capacity (334.44 mAh/g). The addition of Cu improves the cyclic stability of the alloy electrodes when x?=?0?~?0.45. However, their self-discharge properties and high-rate dischargeability (HRD) decrease with the increase of x. Further, electrochemical kinetics and electrochemical impedance spectroscopy (EIS) analysis show that the reaction of alloy electrode is controlled by charge transfer step, and the adding of Cu benefits the electrode properties in alkaline solution.