On the reversibility of anode supported proton conducting solid oxide cells

Reversible proton conducting solid oxide cells (SOCs) off a highly efficient route to matching supply from intermittent, renewable resources, with power demand by consumers. The cells would store excess electrical energy as chemical fuel during times of peak production, and operate in reverse during times of peak demand. In this study we examine the operation of anode supported proton conducting SOCs in electrolysis mode. The required overpotential for a given current density decreases with increasing humidity at the anode and increasing temperature. All of the V-I curves show distinct curvature. The electrode polarization resistance increases and electrolyte ohmic resistance decreases with increasing current density. This is accompanied by a deviation below the theoretical rate of hydrogen production. We interpret these changes as resulting from deviation away from pure proton conduction in the cell with increasing polarization.     

Fabrication of superhydrophobic polyaniline films with rapidly switchable wettability

A superhydrophobic polyaniline (PANI) film has been fabricated by using a facile one-step spraying method. The PANI was synthesized via in situ doping polymerization in the presence of perfluorooctanoic acid (PFOA) as the dopant. The water contact angle of this superhydrophobic surface reaches to 156°. Both the surface chemical compositions and morphological structures were analyzed. A granular morphology of PANI with a moderate amount of nanofibers was obtained. Moreover, a rapid surface wettability transition between superhydrophobicity and superhydrophilicity can be observed when it is doped with PFOA and de-doped with base. The mechanism for this tunable wettability has been discussed in detail.     

An investigation of the deprotonation of hydrazone-based receptors on interaction with anion: develop a colorimetric system distinguishing cyanide from anions

Hydrazone-based receptors, containing fluorene-skeleton substituents, in a THF solution, in the presence of fluoride or cyanide, do not only form H-bond complexes, but mainly undergo deprotonation of the N–H fragments, an event, which is signaled by the color change, the ability of the deprotonation is associated with the fluorene skeleton. The deprotonation process is also reversible by the addition of metal ions, while cyanide from fluoride could be distinguished by the addition of copper (II).     

Nanostructured thermoresponsive quantum dot/PNIPAM assemblies

Synthesis, characterization, and applications of novel thermoresponsive polymeric coatings for quantum dots (QDs) are presented. Comb-copolymers featuring hydrophobic alkyl groups, carboxylic groups and poly(N-isopropylacrylamide) (PNIPAM) side chains with molar masses ranging from 1000 g/mol to 25,400 g/mol were obtained. The amphiphilic comb-copolymers were shown to efficiently transfer the QDs to aqueous media. The PNIPAM-coated QD materials display a lower critical solution temperature (LCST). The absorbance, luminescence emission, size of the assemblies, and electrophoretic mobility were followed as a function of temperature and the reversibility of the temperature induced changes is demonstrated by cyclic heating and cooling.     

Geometric approach to Fletcher's ideal penalty function

In this note, we derive a geometric formulation of an ideal penalty function for equality constrained problems. This differentiable penalty function requires no parameter estimation or adjustment, has numerical conditioning similar to that of the target function from which it is constructed, and also has the desirable property that the strict second-order constrained minima of the target function are precisely those strict second-order unconstrained minima of the penalty function which satisfy the constraints. Such a penalty function can be used to establish termination properties for algorithms which avoid ill-conditioned steps. Numerical values for the penalty function and its derivatives can be calculated efficiently using automatic differentiation techniques.     

2D water layer enclathrated between Mn(II)-Ni(CN)4 coordination frameworks

A [Ni(CN)₄]²⁻-based two-dimensional Mn(II) coordination polymer {Mn(H₂O)₂[NiCN]₄·4H₂O}, in which the coordination layers are stacked on top of each other sandwiching 2D water layer of boat-shaped hexagonal water clusters has been synthesized. The complex exhibits high thermal decomposition temperature and reversible water absorption, which were clearly demonstrated by thermal and PXRD studies on the parent and rehydrated complex after dehydration.     

回转体局部空泡绕流的非线性分析

基于面元法, 通过在回转体和空泡壁面放置源汇,对回转体定长局部空泡的绕流问题进行了分析和讨论,并提出了求解回转体局部空泡绕流“正问题”的方法。计算结果表明：所给出的方法具有快速收敛的特征,第1次迭代和最终收敛时空泡壁面切向速度的误差不超过5％;随着回转体面元总数N的增加,局部空泡的空泡数σ趋于稳定;通过比较可知,该方法得到的理论估算值与实测值的一致性较好。     

Branched Polymers via ROMP of Termimers

Today's olefin metathesis catalysts show high reactivity, selectivity, and functional group tolerance and allow the design of new syntheses of precisely functionalized polymers. Here the synthesis of a new end‐capping reagent is investigated allowing the introduction of a highly reactive activated ester end‐group at the polymer chain end as well as its prefunctionalization to directly introduce functional moieties. The versatility of this new end‐capping reagent is demonstrated by utilizing it to synthesize a so‐called termimer (a monomer with termination capabilities). Copolymerization of a norbornene derivative with the termimer leads to hyperbranched ring‐opening metathesis polymerization polymers as proven by gel permeation chromatography and MALDI‐ToF‐(matrix‐assisted laser desorption/ionization time of flight) mass spectrometry.

     

Reactivity of N-nitrosoamides in confined spaces

The thermal rearrangement of several N-nitrosoamides was studied by ¹H NMR in the context of reversible encapsulation. The N-nitrosoamide guests were isolated from the bulk solvent in a hydrogen-bonded dimeric host capsule which prevented their rearrangement. The guests appear to be preserved in their ground state conformations by the pressure exerted by the host. The conformations of the free and bound N-nitrosoamides are of comparable relative energies as determined by DFT calculations.