Theoretical kinetic study on the decomposition of 1,5‐diaminotetrazole

1,5‐Daminotetrazole (DAT) is of much interest because of the practical significance and the diversity of characteristics. The study on the decomposition pathway and the kinetics of DAT has been performed based on the quantum chemistry theory. The minimum energy path (MEP) calculation has shown that NH₂N₃ and NH₂CN are the initially detected products of DAT. And the structures of reactant, products and transition state were optimized with MP2 methods using 6‐311G** basis sets, and the energies were refined using CCSD(T)/6‐311G** levels of theory. The calculated rate constants were obtained using the conventional transition‐state theory (TST) and the canonical variational transition‐state theory (CVT) methods. The calculation results indicated that the energy barrier of decomposition reaction is 47.98 kcal mol^?1 and the variational effect is small. In addition, the rate constants and the Arrhenius experience formula of DAT decomposition have been obtained between 200 and 2500 K temperature regions. The fitted three‐parameter expressions calculated using the TST and CVT methods are (TST) and (CVT). This work may provide the theoretical support for further experimental synthesis and testing. Copyright © 2015 John Wiley & Sons, Ltd.     

Effects of carbon contents on morphology and electrical properties of Li2MnSiO4/C prepared by a vacuum solid-state method

To improve the electrochemical performance of Li₂MnSiO₄ with low electric conductivity, the Li₂MnSiO₄/C composite are synthesized by a vacuum solid-state reaction of a mixture of SiO₂, LiCH₃COO, Mn(CH₃COO)₂ and designed mass of C₆H₁₂O₆ · H₂O as carbon sources. The crystalline structure and morphology of products are analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and laser scattering technology (LS) respectively. The tested results show that carbon doping decrease the crystallite sizes of products, but keep the aggregation of the particles and made the impurity increased instead. The results of constant current charge-discharge prove that the mixed carbon improve Li⁺ transmission performance and decrease inner polatization resistance of Li₂MnSiO₄ materials, but can not prevent the collapse of Li₂MnSiO₄ crystal structure. While the galvanostatic intermittent titration technique (GITT) results demonstrate that the primary reason for the improved electrochemical performance can be attributed to increased Li-ion diffusion coefficient $(D_{Li^ + } )$ as a result from carbon doping.     

Synthesis of an adhesion‐enhancing polysiloxane containing epoxy groups for addition‐cure silicone light emitting diodes encapsulant

Addition‐cure silicone resin is considered as a good choice for light emitting diodes (LEDs); however, it has very poor adhesion to the substrate, which limits its practical application. A novel polysiloxane with self‐adhesion ability and higher refractive index for the encapsulating of high‐power LEDs is prepared and characterized. This polysiloxane containing vinyl groups, phenyl groups, and epoxy groups was synthesized by a sol‐gel condensation process from methacryloxy propyl trimethoxyl silane, γ‐(2,3‐epoxypropoxy)propytrimethoxysilane, and diphenylsilanediol under the catalysis of an anion exchange resin. Then, the resin‐type encapsulation material was prepared by hydrosilylation of methylphenyl hydrogen‐containing silicone resin and the newly synthesized polysiloxane material. The novel polysiloxane was characterized by ¹H‐NMR and Fourier transform infrared spectroscopy. On the basis of higher refractive index, higher transparency, excellent thermal stability, and appropriate hardness, as well as good adhesive strength between the encapsulating material and the LED lead frame (polyphthalamide), the curable silicone resin‐type encapsulation material can be used as an encapsulant for LEDs. Copyright © 2014 John Wiley & Sons, Ltd.     

Morphology and mechanical behavior of isotactic polypropylene with different stereo‐defect distribution in injection molding

Large amount of work has been published on the isotacticity–properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of iPP injection molding samples is still not clear. In this study, two different isotactic polypropylene (iPP) resins (PP‐A and PP‐B) with similar average isotacticity but different stereo‐defect distribution were selected to investigate the morphology evolution and mechanical properties (tensile and notching) of their injection molding samples using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), 2D wide angle X‐ray diffraction (2D‐WAXD), and scanning electron microscope (SEM). The results of DMA showed that the molecular movement ability of PP‐A (with less uniform distribution of stereo‐defect) was stronger than that of PP‐B, meanwhile the analysis of DSC and SEM suggested that after injection molding, smaller spherullites, and crystals with higher perfection had formed in the specimens of PP‐A. The resulting of tensile properties of PP‐A were found to be better than that of PP‐B. The results of morphology evolution by SEM observation and 2D‐WAXD showed that PP‐A is more likely to occur interspherulite deformation and can disperse the tensile stress more efficiently, and therefore, its crystal structure can withstand a greater force when tensile stress is applied. On the other hand, PP‐B has larger spherulites and boundaries, and low perfection of lamellaes, and the intraspherulte deformation tend to take place. It is easier for the crystal of PP‐B to be broken up and reoriented along the tensile direction. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of polyaniline/Au composite nanotubes and their high performance in the detection of NADH

Polyaniline (PANI)/Au composite nanotubes were synthesized and developed as an electrode material for a nicotinamide adenine dinucleotide (NADH) sensor. A MnO₂ self-degradable template method was used to prepare the tube-like PANI nanomaterial. By introducing PANI nanotubes into Au colloid, Au nanoparticles (NPs) were successfully decorated onto the surface of PANI nanotubes through electrostatic effects. The morphology, composition, and optical properties of the resulting products were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-vis) absorption spectra, and thermogravimetric analysis (TGA). In addition, the obtained PANI/Au composites were used as catalysts for the electrochemical oxidation of NADH. Cyclic voltammogram (CV) experiments indicated that PANI/Au-modified glassy carbon electrode showed a higher electrocatalytic activity towards the oxidation of NADH in a neutral environment. Differential pulse voltammogram (DPV) results illustrated that the fabricated NADH sensor had excellent anti-interference ability and displayed a wide linear range from 4?×?10^?4 to 8?×?10^?3 M with a detection limit of 0.5?×?10^?7 M.     

Multi‐Colored Fibers by Self‐Assembly of DNA,Histone Proteins,and Cationic Conjugated Polymers

The development of biomolecular fiber materials with imaging ability has become more and more useful for biological applications. In this work, cationic conjugated polymers (CCPs) were used to construct inherent fluorescent microfibers with natural biological macromolecules (DNA and histone proteins) through the interfacial polyelectrolyte complexation (IPC) procedure. Isothermal titration microcalorimetry results show that the driving forces for fiber formation are electrostatic and hydrophobic interactions, as well as the release of counterions and bound water molecules. Color‐encoded IPC fibers were also obtained based on the co‐assembly of DNA, histone proteins, and blue‐, green‐, or red‐ (RGB‐) emissive CCPs by tuning the fluorescence resonance energy‐transfer among the CCPs at a single excitation wavelength. The fibers could encapsulate GFP‐coded Escherichia coli BL21, and the expression of GFP proteins was successfully regulated by the external environment of the fibers. These multi‐colored fibers show a great potential in biomedical applications, such as biosensor, delivery, and release of biological molecules and tissue engineering.     

An Effective Pd–Ni2P/C Anode Catalyst for Direct Formic Acid Fuel Cells

The direct formic acid fuel cell is an emerging energy conversion device for which palladium is considered as the state‐of‐the‐art anode catalyst. In this communication, we show that the activity and stability of palladium for formic acid oxidation can be significantly enhanced using nickel phosphide (Ni₂P) nanoparticles as a cocatalyst. X‐ray photoelectron spectroscopy (XPS) reveals a strong electronic interaction between Ni₂P and Pd. A direct formic acid fuel cell incorporating the best Pd–Ni₂P anode catalyst exhibits a power density of 550 mW cm^?2, which is 3.5 times of that of an analogous device using a commercial Pd anode catalyst.     

An Antibody with a Variable‐Region Coiled‐Coil “Knob” Domain

The X‐ray crystal structure of a bovine antibody (BLV1H12) revealed a unique structure in its ultralong heavy chain complementarity determining region 3 (CDR3H) that folds into a solvent‐exposed β‐strand “stalk” fused to a disulfide crosslinked “knob” domain. We have substituted an antiparallel heterodimeric coiled‐coil motif for the β‐strand stalk in this antibody. The resulting antibody (Ab‐coil) expresses in mammalian cells and has a stability similar to that of the parent bovine antibody. MS analysis of H–D exchange supports the coiled‐coil structure of the substituted peptides. Substitution of the knob‐domain of Ab‐coil with bovine granulocyte colony‐stimulating factor (bGCSF) results in a stably expressed chimeric antibody, which proliferates mouse NFS‐60 cells with a potency comparable to that of bGCSF. This work demonstrates the utility of this novel coiled‐coil CDR3 motif as a means for generating stable, potent antibody fusion proteins with useful pharmacological properties.     

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.