A Framework for Characterizing Structural Uncertainty in Large-Eddy Simulation Closures

Motivated by the sizable increase of available computing resources, large-eddy simulation of complex turbulent flow is becoming increasingly popular. The underlying filtering operation of this approach enables to represent only large-scale motions. However, the small-scale fluctuations and their effects on the resolved flow field require additional modeling. As a consequence, the assumptions made in the closure formulations become potential sources of incertitude that can impact the quantities of interest. The objective of this work is to introduce a framework for the systematic estimation of structural uncertainty in large-eddy simulation closures. In particular, the methodology proposed is independent of the initial model form, computationally efficient, and suitable to general flow solvers. The approach is based on introducing controlled perturbations to the turbulent stress tensor in terms of magnitude, shape and orientation, such that propagation of their effects can be assessed. The framework is rigorously described, and physically plausible bounds for the perturbations are proposed. As a means to test its performance, a comprehensive set of numerical experiments are reported for which physical interpretation of the deviations in the quantities of interest are discussed.     

Multi-scale Fractured Coal Gas–Solid Coupling Model and Its Applications in Engineering Projects

With coal mining entering the geological environment of “high stress, rich gas, strong adsorption and low permeability,” the difficulty of joint coal and gas extraction clearly augments, the risk of solid–gas coupling dynamic disasters greatly increases, and the underlying mechanisms become more complex. In this paper, based on the characteristics of coal’s multi-scale structure and spatiotemporal variation, the multi-scale fractured coal gas–solid coupling model (MSFM) was built. In this model, the interaction between coal matrix and its fractures and the mechanical characteristics of gas-bearing coal were considered, as well as their coupling relationship. By MATLAB software, the stress–damage–seepage numerical computation programs were developed, which were applied into Comsol Multiphysics to simulate gas flow caused by coal mining. The simulation results showed the spatial variability of coal elastic modulus and cross-flow behaviors of coal seam gas, which were superior to the results of traditional gas–solid coupling model. And the numerical results obtained from MSFM were closer to the measured results in field, while the computation results of traditional model were slightly higher than the measured results. Furthermore, the MSFM in a large scale was verified by field engineering project.     

An Object-Based Shale Permeability Model: Non-Darcy Gas Flow,Sorption, and Surface Diffusion Effects

Shale samples consist of two major components: organic matter (OM) and inorganic mineral component (iOM). Each component has its distinct pore network topology and morphology, which necessitates generating a model capable of distinguishing the two media. We constructed an object-based model using the OM and iOM composition of shale samples. In the model, we integrated information such as OM population and size distribution, as well as its associated pore-size distribution. For the iOM part, we used mineralogy and pore-size information derived from X-ray diffraction, scanning electron microscopy, and nitrogen sorption measurements. Our proposed model results in millimeter-scale 2D realizations of shale samples by honoring OM and mineral types, their compositions, shapes, and size distributions. The model can capture heterogeneities smaller than 1 mm. We studied the effects of different gas flow processes and found that Knudsen diffusion and gas slippage dominate the flow, but surface diffusion has little impact on total gas flow.     

Semiconducting Polymer Dots with Dual-Enhanced NIR-IIa Fluorescence for Through-Skull Mouse-Brain Imaging

Fluorescence probes in the NIR-IIa region show drastically improved imaging owing to the reduced photon scattering and autofluorescence in biological tissues. Now, NIR-IIa polymer dots (Pdots) are developed with a dual fluorescence enhancement mechanism. First, the aggregation induced emission of phenothiazine was used to reduce the nonradiative decay pathways of the polymers in condensed states. Second, fluorescence quenching was minimized by different levels of steric hindrance to further boost the fluorescence. The resulting Pdots displayed a fluorescence QY of ca. 1.7 % in aqueous solution, suggesting an enhancement of ca. 21 times in comparison with the original polymer in tetrahydrofuran (THF) solution. Small-animal imaging by using the NIR-IIa Pdots exhibited a remarkable improvement in penetration depth and signal to background ratio, as confirmed by through-skull and through-scalp fluorescent imaging of the cerebral vasculature of live mice.     

硫化镉反蛋白石光子晶体制备及光解水制氢

对硫化镉反蛋白石结构光子晶体薄膜进行了可控合成,用巯基乙酸修饰的纳米晶和P(St-MMA-SPMAP)高分子小球共组装,成功地构筑了反蛋白石结构并用于可见光光解水产氢。结果表明,在可见光(λ≥420 nm)照射下,Cd S-310反蛋白石结构薄膜的光解水产氢性能比硫化镉纳米颗粒提高了一倍。这主要是因为等级孔结构反蛋白石光子晶体特性对催化剂的光催化性能的提升:首先,反蛋白石的周期性结构增加了光子在材料中的传播,提高了催化剂对太阳光的利用率;同时,大孔孔壁是由纳米颗粒堆积而成的,在反应中提供了更多的反应活性位点;此外,孔结构有利于物质的传输和分子的吸附。     

The designing strategies of graphene-based peroxidase mimetic materials

Natural enzymes have been praised highly as ideal catalysts, presumably owing to their remarkable advantages of high efficiency, high selectivity, and mild reaction conditions. The reports of chemical simulation and systematic synthesis of natural enzymes such as peroxidase (POD) are rare because of their complex biological structures. POD represents a large family of oxidoreductases and offers a wide range of applications in many fields of science. Recent advance in the fusion of nanomaterial, catalysis, and biochemistry has inspired the development of artificial enzymes implemented with desired catalytic features of natural enzymes. Herein, we review the redox chemistry of POD and compare its catalytic performance to graphene-based nanomaterials (G-NMs) as POD mimetic nanoenzymes bases on catalytic center, binding site, and carrier function. Based on the viewpoints of stereo chemistry and molecular kinetic and dynamics in heterogeneous system, we evaluate and compare the suitability of different NMs as artificial enzyme constituent. We propose that reevaluates design strategies of graphene-based peroxidase (G-POD) mimetic materials and emphasizes on their selectivity (role as catalytic center, binding site, or carrier) is of uttermost.     

Inference for a change-point problem under a generalised Ornstein–Uhlenbeck setting

Determining accurately when regime and structural changes occur in various time-series data is critical in many social and natural sciences. We develop and show further the equivalence of two consistent estimation techniques in locating the change point under the framework of a generalised version of the one-dimensional Ornstein–Uhlenbeck process. Our methods are based on the least sum of squared error and the maximum log-likelihood approaches. The case where both the existence and the location of the change point are unknown is investigated and an informational methodology is employed to address these issues. Numerical illustrations are presented to assess the methods’ performance.     

Multi-emissive 1D Cd(II) polymers with a biphenyl bridged bisazamacrocycle for ratiometric discrimination of nitroaromatics and selective visual detection of picric acid

Three one-dimensional ladder-like coordination polymers consisting of Cd₆ metalloring as the building unit, {[Cd₄LCl₄]·3H₂O}_n ( 1 ), {[Cd₃L(ClO₄)(H₂O)]ClO₄·3H₂O}_n ( 2 ), and {[Cd₆(L)₂(NO₃)₂(CH₃OH)(H₂O)](NO₃)₂·2CH₃OH·5H₂O}_n ( 3 ), were solvothermally constructed from a carboxylic functionalized bisazamacrocyclic ligand 4,4′-bis((4,7-bis(2-carboxyethyl)-1,4,7-triazacyclonon-1-yl)methyl)-1,1′-biphenyl (H₄L). These compounds dispersed in ethanol show the multiple emissions originating from the monomeric and intramolecularly overlapping biphenyl moieties which could be sensitively quenched by picric acid (PA) and 4-nitrophenol (4-NP) through the effective fluorescence resonance energy transfer process. The differential fluorescent responses of each compound on exposure to PA and 4-NP individually make the convenient ratiometric discrimination of two analytes based on the fluorescent intensity ratio (I₃₂₀/I₃₆₀) attainable, and 1 and 2 as ratiometric chemosensors for PA present a broad linear detection range from 4 to 300 μM with detection limits of 0.84 and 0.93 μM, respectively. Furthermore, the blue light emission of 1 under an ultraviolet lamp could be selectively quenched by PA even in the presence of all other interfering nitroaromatic pollutants, which empowers the fast visual detection of PA by naked eye.