Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc–Air Batteries

The lack of high‐efficient, low‐cost, and durable bifunctional electrocatalysts that act simultaneously for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is currently one of the major obstacles to commercializing the electrical rechargeability of zinc–air batteries. A nanocomposite CoO‐NiO‐NiCo bifunctional electrocatalyst supported by nitrogen‐doped multiwall carbon nanotubes (NCNT/CoO‐NiO‐NiCo) exhibits excellent activity and stability for the ORR/OER in alkaline media. More importantly, real air cathodes made from the bifunctional NCNT/CoO‐NiO‐NiCo catalysts further demonstrated superior performance to state‐of‐the‐art Pt/C or Pt/C+IrO₂ catalysts in primary and rechargeable zinc–air batteries.     

A Versatile Approach Towards Nucleobase‐Modified Aptamers

A novel and versatile method has been developed for modular expansion of the chemical space of nucleic acid libraries, thus enabling the generation of nucleobase‐modified aptamers with unprecedented recognition properties. Reintroduction of the modification after enzymatic replication gives broad access to many chemical modifications. This wide applicability, which is not limited to a single modification, will rapidly advance the application of in vitro selection approaches beyond what is currently feasible and enable the generation of aptamers to many targets that have so far not been addressable.     

Chemical Evolution of a Bacterial Proteome

We have changed the amino acid set of the genetic code of Escherichia coli by evolving cultures capable of growing on the synthetic noncanonical amino acid L ‐β‐(thieno[3,2‐b]pyrrolyl)alanine ([3,2]Tpa) as a sole surrogate for the canonical amino acid L ‐tryptophan (Trp). A long‐term cultivation experiment in defined synthetic media resulted in the evolution of cells capable of surviving Trp→[3,2]Tpa substitutions in their proteomes in response to the 20 899 TGG codons of the E. coli W3110 genome. These evolved bacteria with new‐to‐nature amino acid composition showed robust growth in the complete absence of Trp. Our experimental results illustrate an approach for the evolution of synthetic cells with alternative biochemical building blocks.     

A Bioinspired Molybdenum Complex as a Catalyst for the Photo‐ and Electroreduction of Protons

A molybdenum–dithiolene–oxo complex was prepared as a model of some active sites of Mo/W‐dependent enzymes. The ligand, a quinoxaline–pyran‐fused dithiolene, mimics molybdopterin present in these active sites. For the first time, this type of complex was shown to be active as a catalyst for the photoreduction of protons with excellent turnover numbers (500) and good stability in aqueous/organic media and for the electroreduction of protons in acetonitrile with remarkable rate constants (1030 s^?1 at ?1.3 V versus Ag/AgCl). DFT calculations provided insight into the catalytic cycle of the reaction, suggesting that the oxo ligand plays a key role in proton exchange. These results provide a basis to optimize this new class of H₂‐evolving catalysts.     

Kinetics of microcrack blunting ahead of macrocrack approaching shear wave speed

The fracturing of glass and tearing of rubber both involve the separation of material but their crack growth behavior can be quite different, particularly with reference to the distance of separation of the adjacent planes of material and the speed at which they separate. Relatively speaking, the former and the latter are recognized, respectively, to be fast and slow under normal conditions. Moreover, the crack tip radius of curvature in glass can be very sharp while that in the rubber can be very blunt. These changes in the geometric features of the crack or defect, however, have not been incorporated into the modeling of running cracks because the mathematical treatment makes use of the Galilean transformation where the crack opening distance or the change in the radius of curvature of the crack does not enter into the solution. Change in crack speed is accounted for only via the modulus of elasticity and mass density. For this simple reason, many of the dynamic features of the running crack have remained unexplained although speculations are not lacking. To begin with, the process of energy dissipation due to separation is affected by the microstructure of the material that distinguishes polycrystalline from amorphous form. Energy extracted from macroscopic reaches of a solid will travel to the atomic or smaller regions at different speeds at a given instance. It is not clear how many of the succeeding size scales should be included within a given time interval for an accurate prediction of the macroscopic dynamic crack characteristics. The minimum requirement would therefore necessitate the simultaneous treatment of two scales at the same time. This means that the analysis should capture the change in the macroscopic and microscopic features of a defect as it propagates. The discussion for a dual scale model has been invoked only very recently for a stationary crack. The objective of this work is to extend this effort to a crack running at constant speed beyond that of Rayleigh wave. Developed is a dual scale moving crack model containing microscopic damage ahead of a macroscopic crack with a gradual transition. This transitory region is referred to as the mesoscopic zone where the tractions prevail on the damaged portion of the material ahead of the original crack known as the restraining stresses, the magnitude of which depends on the geometry, material and loading. This damaged or restraining zone is not assumed arbitrarily nor assumed to be intrinsically a constant in the cohesive stress approach; it is determined for each step of crack advancement. For the range of micronotch bluntness with 0 < β < 30° and 0.2 σ_∞/σ₀ 0.5, there prevails a nearly constant restraining zone size as the crack approaches the shear wave speed. Note that β is the half micronotch angle and the applied stress ratio is σ_∞/σ₀ with σ₀ being the maximum of the restraining stress. For σ_∞/σ₀ equal to or less than 0.5, the macrocrack opening displacement COD is nearly constant and starts to decrease more quickly as the crack approaches the shear wave speed. For the present dual scale model where the normalized crack speed v/c_s increases with decreasing with the one-half microcrack tip angle β. There prevails a limit of crack tip bluntness that corresponds to β 36° and v/c_s 0.15. That is a crack cannot be maintained at a constant speed if the bluntness is increased beyond this limiting value. Such a feature is manifestation of the dependency of the restraining stress on crack velocity and the applied stress or the energy pumped into the system to maintain the crack at a constant velocity. More specifically, the transitory character from macro to micro is being determined as part of the unknown solution. Using the energy density function dW/dV as the indicator, plots are made in terms of the macrodistance ahead of the original crack while the microdefect bluntness can vary depending on the tip geometry. Such a generality has not been considered previously. The macro-dW/dV behavior with distance remains as the inverse r relation yielding a perfect hyperbola for the homogeneous material. This behavior is the same as the stationary crack. The micro-dW/dV relations are expressed in terms of a single undetermined parameter. Its evaluation is beyond the scope of this investigation although the qualitative behavior is expected to be similar to that for the stationary crack. To reiterate, what has been achieved as an objective is a model that accounts for the thickness of a running crack since the surface of separation representing damage at the macroscopic and microscopic scale is different. The transitory behavior from micro to macro is described by the state of affairs in the mesoscopic zone.     

Effective elastic moduli of two dimensional solids with distributed cohesive microcracks

Effective elastic properties of a defected solid with distributed cohesive micro-cracks are estimated based on homogenization of the Dugdale–Bilby–Cottrell–Swinden (Dugdale–BCS) type micro-cracks in a two dimensional elastic representative volume element (RVE).Since the cohesive micro-crack model mimics various realistic bond forces at micro-scale, a statistical average of cohesive defects can effectively represent the overall properties of the material due to bond breaking or crack surface separation in small scale. The newly proposed model is distinctive in the fact that the resulting effective moduli are found to be pressure sensitive.     

自紧身管临界裂纹尺寸的概率断裂力学研究

基于概率断裂力学理论和Mome Caflo模拟方法，本文进行了自紧身管临界裂纹尺寸的可靠性研究。自紧身管内表面的疲劳裂纹考虑为半椭圆形式。裂纹尖端处的应力强度因子由内压和自紧残余应力共同产生。自紧残余应力采用了符合身管材料具有强化和包辛格效应性能推导的公式计算，它产生的应力强度因子通过权函数方法得到。根据断裂准则，可计算出自紧身管的临界裂纹尺寸。实例分析表明，对数正态分布为临界裂纹尺寸的最佳分布，同时给出了在各种置信度和可靠度下自紧身管的临界裂纹尺寸。     

Refinement of the plastic-zone boundary in the vicinity of a crack tip for the quasiviscous and viscous types of fracture

A refined solution of the elastoplastic problem of an insulated mode I crack in a thin plate of reasonably large dimensions is obtained. Estimates of the plastic zone in the vicinity of the crack tip are given for quasiviscous and viscous types of fracture.Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 46, No. 1, pp. 126–132, January–February, 2005     

The scattering of harmonic elastic anti-plane shear waves by two collinear cracks in the piezoelectric plate by using the non-local theory

In this paper, the dynamic interaction between two collinear cracks in a piezoelectric material plate under anti-plane shear waves is investigated by using the non-local theory for impermeable crack surface conditions. By using the Fourier transform, the problem can be solved with the help of two pairs of triple integral equations. These equations are solved using the Schmidt method. This method is more reasonable and more appropriate. Unlike the classical elasticity solution, it is found that no stress and electric displacement singularity is present at the crack tip. The non-local dynamic elastic solutions yield a finite hoop stress at the crack tip, thus allowing for a fracture criterion based on the maximum dynamic stress hypothesis. The project supported by the Natural Science Foundation of Heilongjiang Province and the National Natural Science Foundation of China(10172030, 50232030)     

高应变率大变形下的聚丙烯/尼龙共混高聚物损伤型本构特性

对两种采用不同相容剂的聚丙烯（PP）和尼龙（PA）共混高聚物材料在大变形下的粘弹性力学行为进行研究,着重考察应变率效应和损伤的演化,从而分析不同的界面分子设计对共混体系材料宏观性能的作用。在准静态及冲击实验研究的基础上,基于ZWT非线性粘弹性模型,并结合了遗传算法,分别得到了能有效描述两种共混高聚物大变形阶段计及损伤的非线性粘弹性本构关系。两种材料在不同加载条件下表现出明显不一致的性能,原因在于其损伤演化的率相关性,且两种材料的大变形机制存在一定的差别,能用ZWT方程进行描述的范围也不一样。