Ultrahigh Photocatalytic Rate at a Single‐Metal‐Atom‐Oxide

Metal oxides, as one of the mostly abundant and widely utilized materials, are extensively investigated and applied in environmental remediation and protection, and in energy conversion and storage. Most of these diverse applications are the result of a large diversity of the electronic states of metal oxides. Noticeably, however, many metal oxides present obstacles for applications in catalysis, mainly due to the lack of efficient active sites with desired electronic states. Here, the fabrication of single‐tungsten‐atom‐oxide (STAO) is demonstrated, in which the metal oxide's volume reaches its minimum as a unit cell. The catalytic mechanism in the STAO is determined by a new single‐site physics mechanism, named as quasi‐atom physics. The photogenerated electron transfer process is enabled by an electron in the spin‐up channel excited from the highest occupied molecular orbital to the lowest unoccupied molecular orbital +1 state, which can only occur in STAO with W⁵⁺. STAO results in a record‐high and stable sunlight photocatalytic degradation rate of 0.24 s^?1, which exceeds the rates of available photocatalysts by two orders of magnitude. The fabrication of STAO and its unique quasi‐atom photocatalytic mechanism lays new ground for achieving novel physical and chemical properties using single‐metal‐atom oxides (SMAO).     

Analysis of a rotation‐free 4‐node shell element

In this paper, a shell element for small and large deformations is presented based on the extension of the methodology to derive triangular shell element without rotational degrees of freedom (so‐called rotation‐free). As in our original triangular S3 element, the curvatures are computed resorting to the surrounding elements. However, the extension to a quadrilateral element requires internal curvatures in order to avoid singular bending stiffness. The quadrilateral area co‐ordinates interpolation is used to establish the required expressions between the rigid‐body modes of normal nodal translations and the normal through thickness bending strains at mid‐side. In order to propose an attractive low‐cost shell element, the one‐point quadrature is achieved at the centre for the membrane strains, which are superposed to the bending strains in the centred co‐rotational local frame. The membrane hourglass control is obtained by the perturbation stabilization procedure. Free, simply supported and clamped edges are considered without introducing virtual nodes or elements. Several numerical examples with regular and irregular meshes are performed to show the convergence, accuracy and the reasonable little sensitivity to geometric distortion. Based on an updated Lagrangian formulation and Newton iterations, the large displacements of the pinched hemispherical shell show the effectiveness of the proposed simplified element (S4). Finally, the deep drawing of a square box including large plastic strains with contact and friction completes the ability of the rotation‐free quadrilateral element for sheet‐metal‐forming simulations. Copyright © 2005 John Wiley & Sons, Ltd.     

Biomechanical Strain Exacerbates Inflammation on a Progeria‐on‐a‐Chip Model

Organ‐on‐a‐chip platforms seek to recapitulate the complex microenvironment of human organs using miniaturized microfluidic devices. Besides modeling healthy organs, these devices have been used to model diseases, yielding new insights into pathophysiology. Hutchinson‐Gilford progeria syndrome (HGPS) is a premature aging disease showing accelerated vascular aging, leading to the death of patients due to cardiovascular diseases. HGPS targets primarily vascular cells, which reside in mechanically active tissues. Here, a progeria‐on‐a‐chip model is developed and the effects of biomechanical strain are examined in the context of vascular aging and disease. Physiological strain induces a contractile phenotype in primary smooth muscle cells (SMCs), while a pathological strain induces a hypertensive phenotype similar to that of angiotensin II treatment. Interestingly, SMCs derived from human induced pluripotent stem cells of HGPS donors (HGPS iPS‐SMCs), but not from healthy donors, show an exacerbated inflammatory response to strain. In particular, increased levels of inflammation markers as well as DNA damage are observed. Pharmacological intervention reverses the strain‐induced damage by shifting gene expression profile away from inflammation. The progeria‐on‐a‐chip is a relevant platform to study biomechanics in vascular biology, particularly in the setting of vascular disease and aging, while simultaneously facilitating the discovery of new drugs and/or therapeutic targets.     

Phosphorus‐Mediated MoS2 Nanowires as a High‐Performance Electrode Material for Quasi‐Solid‐State Sodium‐Ion Intercalation Supercapacitors

Molybdenum disulfide (MoS₂) is a promising electrode material for electrochemical energy storage owing to its high theoretical specific capacity and fascinating 2D layered structure. However, its sluggish kinetics for ionic diffusion and charge transfer limits its practical applications. Here, a promising strategy is reported for enhancing the Na⁺‐ion charge storage kinetics of MoS₂ for supercapacitors. In this strategy, electrical conductivity is enhanced and the diffusion barrier of Na⁺ ion is lowered by a facile phosphorus‐doping treatment. Density functional theory results reveal that the lowest energy barrier of dilute Na‐vacancy diffusion on P‐doped MoS₂ (0.11 eV) is considerably lower than that on pure MoS₂ (0.19 eV), thereby signifying a prominent rate performance at high Na intercalation stages upon P‐doping. Moreover, the Na‐vacancy diffusion coefficient of the P‐doped MoS₂ at room temperatures can be enhanced substantially by approximately two orders of magnitude (10^?6–10^?4 cm² s^?1) compared with pure MoS₂. Finally, the quasi‐solid‐state asymmetrical supercapacitor assembled with P‐doped MoS₂ and MnO₂, as the positive and negative electrode materials, respectively, exhibits an ultrahigh energy density of 67.4 W h kg^?1 at 850 W kg^?1 and excellent cycling stability with 93.4% capacitance retention after 5000 cycles at 8 A g^?1.     

Metal Ion‐Induced Self‐Assembly of a Multi‐Responsive Block Copolypeptide into Well‐Defined Nanocapsules

Protein cages are an interesting class of biomaterials with potential applications in bionanotechnology. Therefore, substantial effort is spent on the development of capsule‐forming designer polypeptides with a tailor‐made assembly profile. The expanded assembly profile of a triblock copolypeptide consisting of a metal ion chelating hexahistidine‐tag, a stimulus‐responsive elastin‐like polypeptide block, and a pH‐responsive morphology‐controlling viral capsid protein is presented. The self‐assembly of this multi‐responsive protein‐based block copolymer is triggered by the addition of divalent metal ions. This assembly process yields monodisperse nanocapsules with a 20 nm diameter composed of 60 polypeptides. The well‐defined nanoparticles are the result of the emergent properties of all the blocks of the polypeptide. These results demonstrate the feasibility of hexahistidine‐tags to function as supramolecular cross‐linkers. Furthermore, their potential for the metal ion‐mediated encapsulation of hexahistidine‐tagged proteins is shown.     

In‐plane and out‐of‐plane constraint parameters along a three‐dimensional crack‐front stress field under creep loading

Full‐field three‐dimensional (3D) numerical analyses was performed to determine in‐plane and out‐of‐plane constraint effect on crack‐front stress fields under creep conditions of finite thickness boundary layer models and different specimen geometries. Several parameters are used to characterize constraint effects including the non‐singular T‐stresses, the local triaxiality parameter, the T_z ‐factor of the stress‐state in a 3D cracked body and the second‐order‐term amplitude factor. The constraint parameters are determined for centre‐cracked plate, three‐point bend specimen and compact tension specimen. Discrepancies in constraint parameter distribution on the line of crack extension and along crack front depending on the thickness of the specimens have been observed under different loading conditions of creeping power law hardening material for various configurations of specimens.     

A Droplet‐Based High‐Throughput SERS Platform on a Droplet‐Guiding‐Track‐Engraved Superhydrophobic Substrate

A novel droplet‐based surface‐enhanced Raman scattering (SERS) sensor for high‐throughput real‐time SERS monitoring is presented. The developed sensors are based on a droplet‐guiding‐track‐engraved superhydrophobic substrate covered with hierarchical SERS‐active Ag dendrites. The droplet‐guiding track with a droplet stopper is designed to manipulate the movement of a droplet on the superhydrophobic substrate. The superhydrophobic Ag dendritic substrates are fabricated through a galvanic displacement reaction and subsequent self‐assembled monolayer coating. The optimal galvanic reaction time to fabricate a SERS‐active Ag dendritic substrate for effective SERS detection is determined, with the optimized substrate exhibiting an enhancement factor of 6.3 × 10⁵. The height of the droplet stopper is optimized to control droplet motion, including moving and stopping. Based on the manipulation of individual droplets, the optimized droplet‐based real‐time SERS sensor shows high resistance to surface contaminants, and droplets containing rhodamine 6G, Nile blue A, and malachite green are successively controlled and detected without spectral interference. This noble droplet‐based SERS sensor reduces sample preparation time to a few seconds and increased detection rate to 0.5 µ L s^?1 through the simple operation mechanism of the sensor. Accordingly, our sensor enables high‐throughput real‐time molecular detection of various target analytes for real‐time chemical and biological monitoring.     

Scaled boundary finite‐element analysis of a non‐homogeneous elastic half‐space

As a result of stresses experienced during and after the deposition phase, a soil strata of uniform material generally exhibits an increase in elastic stiffness with depth. The immediate settlement of foundations on deep soil deposits and the resultant stress state within the soil mass may be most accurately calculated if this increase in stiffness with depth is taken into account. This paper presents an axisymmetric formulation of the scaled boundary finite‐element method and incorporates non‐homogeneous elasticity into the method. The variation of Young's modulus (E) with depth (z) is assumed to take the form E=m_Ez^α, where m_E is a constant and αis the non‐homogeneity parameter. Results are presented and compared to analytical solutions for the settlement profiles of rigid and flexible circular footings on an elastic half‐space, under pure vertical load with αvarying between zero and one, and an example demonstrating the versatility and practicality of the method is also presented. Known analytical solutions are accurately represented and new insight regarding displacement fields in a non‐homogeneous elastic half‐space is gained. Copyright © 2003 John Wiley & Sons, Ltd.     

Threshold Identification for Micro‐Tomographic Damage Characterisation in a Short‐Fibre‐Reinforced Polymer

The micro‐tomographic technique represents an important tool for the analysis of the internal structure in short‐fibre‐reinforced polymers samples. For the investigation of damage mechanisms, detection of the micro‐voids within the matrix can be facilitated by applying a tensile load in‐situ during the scan. The investigations here described started from two micro‐CT acquisitions, at different strain levels, of the same PA6.6GF10 sample. An original procedure for micro‐voids identification is proposed, based on the statistical elaboration of the matrix grey‐tone range. In order to validate the suggested procedure beyond visual inspection, an independent method based on an optimisation approach, which puts to use the two available micro‐tomographic sets, was developed and applied. The effect of the tensile load, which can induce a progression of the damage within the specimen, was investigated, and the relations among strain, fibre distribution and micro‐voids volumetric fraction were studied. Our findings point out that the mechanisms of damage progression, even under static loading as in this case, appear to be more complex than those related to the fibre‐density‐induced stress concentrations alone and require further investigation.     

Crack face contact in X‐FEM using a segment‐to‐segment approach

In this study, we propose a segment‐to‐segment contact formulation (mortar‐based) that uses Lagrange's multipliers to establish the contact between crack faces when modeled with the extended finite element method (X‐FEM) in 2D problems. It is shown that, in general, inaccuracies arise when the contact is formulated following a point‐to‐point approach. This is due to the non‐linear character of the X‐FEM interpolation along the crack faces that leads to crack face interpenetration. However, the segment‐to‐segment approach optimizes the fulfilment of the contact constraints along the whole crack segment, and in practice the contact is modeled precisely. Convergence studies for mesh sequences have been performed, showing the advantages of the proposed methodology. Copyright © 2009 John Wiley & Sons, Ltd.     

High‐Responsivity Photodetection by a Self‐Catalyzed Phase‐Pure p‐GaAs Nanowire

Defects are detrimental for optoelectronics devices, such as stacking faults can form carrier‐transportation barriers, and foreign impurities (Au) with deep‐energy levels can form carrier traps and nonradiative recombination centers. Here, self‐catalyzed p‐type GaAs nanowires (NWs) with a pure zinc blende (ZB) structure are first developed, and then a photodetector made from these NWs is fabricated. Due to the absence of stacking faults and suppression of large amount of defects with deep energy levels, the photodetector exhibits room‐temperature high photoresponsivity of 1.45 × 10⁵ A W^?1 and excellent specific detectivity (D*) up to 1.48 × 10¹⁴ Jones for a low‐intensity light signal of wavelength 632.8 nm, which outperforms previously reported NW‐based photodetectors. These results demonstrate these self‐catalyzed pure‐ZB GaAs NWs to be promising candidates for optoelectronics applications.