A bird nest-like manganese dioxide and its application as electrode in supercapacitors

A novel bird nest-like nanostructured MnO2(BNNS-MnO2) was prepared by a facile and cost-effective strategy. Their structures and morphologies were characterized by field emission scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction. Capacitive behaviors were investigated by cyclic voltammetry and galvanostatic charge-discharge. The obtained nano-MnO2 possesses a well designed loose-assembled hierarchical nanoarchitecture with an appropriate crystallinity which gives rise to excellent performances as an electrode material for supercapacitors. A maximum specific capacitance of 917 F/g has been obtained at a current density of 5 mA/cm2 in 6 mol/L KOH aqueous solution, and a specific capacitance of 210 F/g has been maintained for 500 cycles. As the low cost of MnSO4 and KCr2O7 and the low reaction temperature, the present method avoids the requirements for complicated operations, time/energy-consuming and expensive reagents, and perhaps is ready for the industrialization of nano-MnO2 production.     

Palladium‐catalyzed selective decarboxylative coupling reaction versus direct C―H arylation for arylation of heteroaromatics

Conditions for selective palladium‐catalyzed decarboxylative 2‐arylation of 3‐substituted thiophene and furan derivatives bearing an ester at C2 position have been established. By using 2 mol% phosphine‐free Pd(OAc)₂ as the catalyst and a mixture of KOH and K₂CO₃ as the bases, in dimethylacetamide, moderate to good yields of the desired 2‐arylated products were obtained. A range of functional groups such as nitrile, nitro, formyl or acetyl on the aryl bromides was tolerated. This method allows us to employ in some cases more convenient reactants in terms of cost or physical properties (boiling point) for arylations. Copyright © 2013 John Wiley & Sons, Ltd.     

Palladium‐catalyzed Suzuki–Miyaura coupling with aryl and heteroaryl bromides using N,N,N′,N′‐tetra(diphenylphosphinomethyl)‐1,2‐ethylenediamine

An easily prepared tetraphosphine N,N,N′,N′‐tetra(diphenylphosphinomethyl)‐1,2‐ethylenediamine (1) combined with PdCl₂ affords an efficient catalytic system for Suzuki cross‐coupling of aryl and heteroaryl bromides. A high turnover number of 750 000 is obtained with the catalyst loading as low as 1 ppm. This catalyst system exhibits good stability and longevity. In this study, a broad scope of substrates is investigated and satisfactory yields are obtained. Copyright © 2012 John Wiley & Sons, Ltd.     

Ethylene polymerization with long‐lifetime monopendant thienyl‐substituted group 4 metallocenes

A series of group 4 metallocenes (RCp)[Cp―(bridge)―(2‐C₄H₃S)]MCl₂ [M = Ti ( C1 , C2 , C3 , C4 ); M = Zr ( C5 , C6 , C7 , C8 )] bearing a pendant thiophene group on a cyclopentadienyl ring have been synthesized, characterized and tested as catalyst precursors for ethylene polymerization. The molecular structures of representative titanocenes C2 and C4 were confirmed by single‐crystal X‐ray diffraction and revealed that both complexes exist in an expected coordination environment for a monomeric bent metallocene. No intramolecular coordination between the thiophene group and the titanium center could be observed in the solid state. Upon activation by methylaluminoxane (MAO), titanocenes C1 , C2 , C3 , C4 showed moderate catalytic activities and produced high‐ or ultra‐high‐molecular‐weight polyethylene (M_v 70.5–227.1 × 10⁴ g mol^?1). Titanocene C3 is more active and long‐lived, with a lifetime of nearly 9 h at 30 °C. At elevated temperatures of 80–110 °C, zirconocenes C5 , C6 , C7 , C8 displayed high catalytic activities (up to 27.6 × 10⁵ g PE (mol Zr)^?1 h^?1), giving high‐molecular‐weight polyethylene (M_v 11.2–53.7 × 10⁴ g mol^?1). Even at 80 °C, a long lifetime of at least 2 h was observed for the C8/MAO catalyst system. Copyright © 2014 John Wiley & Sons, Ltd.     

化学蒸气发生-电感耦合等离子体原子发射光谱法测定地质样品中痕量金

地质样品经盐酸-硝酸(3+1)混合酸溶解,活性炭分离富集后,于90℃用12g.L-1硼氢化钠溶液(溶于0.5g.L-1氢氧化钠溶液中)作还原剂,用化学蒸气发生-电感耦合等离子体原子发射光谱法测定其中痕量的金。金的质量浓度在1 500μg.L-1以内与其发射强度呈线性关系,方法的检出限(3s)为0.59μg.L-1。方法用于测定2个标准物质(GBW 07289和GBW 07291)中金含量,测定值与认定值相符。     

A cation trap for anodic stripping voltammetry: NH3–plasma treated carbon nanotubes for adsorption and detection of metal ions

NH₃–plasma treated multi-walled carbon nanotubes (pn-MWCNTs) with cation traps for the detection of ultratrace quantities of Zn(II), Cd(II), Cu(II), and Hg(II) using square wave anodic stripping voltammetry (SWASV) is described. The pn-MWCNTs use their adsorption performance to enhance the sensitivity. It is found that under optimized conditions Zn(II), Cd(II), Cu(II) and Hg(II) were individually detected at potentials of −1.16, −0.78, −0.268 and 0.108 V, respectively. The detection limit (3σ method) of 0.314, 0.0272, 0.2263, and 0.1439 nM toward Zn(II), Cd(II), Cu(II), and Hg(II) is achievable, respectively. No interference could be seen during the simultaneous detection of Zn(II), Cd(II), Cu(II), and Hg(II). The pn-MWCNTs exhibit excellent selectivity owing to the different ability of adsorption. A study of the ability of pn-MWCNTs in practical application is carried out using a sample of water collected from Dongpu Reservoir in Hefei City, Anhui, China. It is found that the results were favorable when compared against inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis.     

Metal-Organic Frameworks with Novel Catenane-like Interlocking: Metal-Determined Photoresponse and Uranyl Sensing

The assembly of two tripyridinium-tricarboxylate ligands and different metal ions leads to seven isostructural MOFs, which show novel 2D→2D supramolecular entanglement featuring catenane-like interlocking of tricyclic cages. The MOFs show tripyridinium-afforded and metal-modulated photoresponsive properties. The MOFs with d¹⁰ metal centers ( 1-Cd , 1-Zn , 2-Cd , 2-Zn ) show fast and reversible photochromism and concomitant fluorescence quenching, 1-Ni displays slower photochromism but does not fluoresce, and 1-Co and 2-Co are neither photochromic nor fluorescent. It is shown here that the network entanglement dictates donor-acceptor close contacts, which enable fluorescence originated from interligand charge transfer. The contacts also allow photoinduced electron transfer, which underlies photochromism and concomitant fluorescence response. The metal dependence in fluorescence and photochromism can be related to energy transfer through metal-centered d-d transitions. In addition, 1-Cd is demonstrated to be a potential fluorescence sensor for sensitive and selective detection of UO₂²⁺ in water.     

Design,synthesis and biological evaluation of pyridyl substituted benzoxazepinones as potent and selective inhibitors of aldosterone synthase

Exorbitant aldosterone is closely associated with various severe diseases, including congestive heart failure and chronic kidney disease. As aldosterone synthase is the pivotal enzyme in aldosterone biosynthesis, its inhibition constitutes a promising treatment for these diseases. Via a structure-based approach, a series of pyridyl substituted 3,4-dihydrobenzo[f][1,4]oxazepin-5(2H)-ones were designed as inhibitors of aldosterone synthase. Six compounds (5j, 5l, 5m 5w, 5x and 5y) distinguished themselves with potent inhibition (IC₅₀ <100 nmol/L) and high selectivity over homogenous 11β-hydroxylase. As the most promising compound, 5x exhibited an IC₅₀ of 12 nmol/L and an excellent selectivity factor (SF) of 157, which are both superior to those of the reference fadrazole (IC₅₀ = 21 nmol/L, SF = 7). Importantly, 5x showed no inhibition against steroidogenic CYP17, CYP19 and a panel of hepatic CYP enzymes indicating an outstanding safety profile. As it manifested satisfactory pharmacokinetic properties in rats, compound 5x was considered as a drug candidate for further development.