Mechanistic Photodissociation of Glycolaldehyde: Insights from Ab Initio and RRKM Calculations

Herein we report a theoretical study on mechanistic photodissociation of glycolaldehyde, HOCH₂CHO. Equilibrium structures, transition states, and intersection structures for the α‐C? C and ‐C? H bond fissions and the β‐C? O bond fission in the excited states are determined by the complete active space self‐consistent field (CASSCF) method. Based on the CASSCF optimized structures, the potential energy profiles for the dissociations are refined by performing single‐point calculations using the multi‐state multi‐reference CASSCF second order perturbation (MS‐MR‐CASPT2) method. With a low excitation energy of 280–340 nm, the T₁ α‐C? C and β‐C? O bond fissions following intersystem crossing from the S₁ state are the predominant and comparable channels, whereas the α‐C? H bond fissions both in the S₁ and in the T₁ states are nearly prohibited due to the relevant high barriers. The rate constants for the T₁ α‐C? C and β‐C? O bond fissions are also calculated by RRKM theory. Furthermore, the S₀ reactions can occur as a consequence of intersystem crossing via T₁/S₀ intersection points resulting from the T₁ C? C and C? O bond cleavages. This photodissociation mechanism is consistent with recent experimental studies.     

Enzyme entrapped nanoporous scaffolds formed through flow-induced gelation in a microfluidic filter device for sensitive biosensing of organophosphorus compounds

A novel and versatile processing method was developed for the formation of gel scaffolds with in situ AChE-AuNPs immobilization for biosensing of organophosphorus compounds. The biosensor designed by our new approach shows high sensitivity, selectivity and reactivation efficiency. This flow-induced immobilization technique opens up new pathways for designing a simple, fast, biocompatible, and cost-effective process for enhanced sensor performance and on-site monitoring of a variety of toxic organophosphorus compounds.     

Protein‐Directed Solution‐Phase Green Synthesis of BSA‐Conjugated MxSey (M=Ag,Cd, Pb,Cu) Nanomaterials

Bovine serum albumin (BSA)‐conjugated M_xSe_y (M=Ag, Cd, Pb, Cu) nanomaterials with different shapes and sizes were synthesized in water at room temperature by a protein‐directed, solution‐phase, green synthetic method. The method features very low energy consumption and nontoxic reagents with high yields of concentrated nanoparticles. The obtained bioconjugated nanoparticles have good dispersibility, bioactivity, and biocompatibility. In addition, various functional groups of protein on the surface of the nanocrystals are suitable for further biological interactions or couplings, which is very important for further biological applications.     

Microbial transformation of deoxyandrographolide by Alternaria alternata AS 3.4578

Biotransformation of deoxyandrographolide (1) by Alternaria alternata AS 3.4578 gave five derivatives identified by spectral methods including 2D NMR as the known dehydroandrographolide (2) and 9beta-hydroxy-dehydroandrographolide (3) and the new compounds 9beta-hydroxy-deoxyandrographolide (4), 3alpha,17,19-trihydroxy-8,13-ent-labdadien-15,16-olide (5) and 3-oxo-9beta-hydroxy-deoxyandrographolide (6).     

Characterisation of martian soil simulants for the ExoMars rover testbed

The European Space Agency (ESA) ExoMars mission involves landing a rover on the surface of Mars on an exobiology mission to extend the search for life. The locomotion capabilities of the ExoMars rover will enable it to use its scientific instruments in a wide variety of locations. Before it is sent to Mars, this locomotion system must be tested and its performance limitations understood. To test the locomotion performance of the ExoMars rover, three martian regolith simulants were selected: a fine dust analogue, a fine Aeolian sand analogue, and a coarse sand analogue. To predict the performance of the ExoMars rover locomotion system in these three regolith simulants, it is necessary to measure some fundamental macroscopic properties of the materials: cohesion, friction angle, and various bearing capacity constants. This paper presents the tests conducted to determine these properties. During these tests, emphasis was placed on preparing the regolith simulants at different levels of density in order to evaluate its impact on the value of the parameters in particular. It was shown that compaction can influence the Bekker coefficients of pressure-sinkage. The shear properties are consistent with the critical state model at normal stresses similar to those of the ExoMars rover in all but one of the simulants, which showed behaviour more consistent with transitional soil behaviour. It is necessary to give due consideration to these variations to ensure a robust test regime is developed when testing the tractive ability of the ExoMars mobility system.     

Spatial behavior of an epidemic model with migration

It was reported that there are traveling patterns in the spatiotemporal data of epidemics (Cummings et al., Nature 427:344, 2004; Grenfell et al., Nature 414:716, 2001). To well understand the mechanism, we present a spatial epidemic model with migration, which means that the individuals exhibit a correlated motion toward certain direction, and obtain traveling pattern. Our results may be helpful to understand the mechanism of the spatiotemporal epidemics and have potential application of control of the epidemics.     

A note on Poisson stability and controllability

The connection between Poisson stability and controllability is revisited. For the controllability criterion based on weakly positive Poisson stability (WPPS) and Lie algebra rank condition (LARC), it is shown that two natural assumptions about the set of input values are necessary for strictness. By using the relationship between conservative property and WPPS, sufficient conditions for controllability of affine nonlinear systems are further discussed. At last, for systems defined on compact Riemannian manifold, the WPPS is proved to be equivalent to Poisson stability.     

Numerical investigation of the effects of structural geometric and material nonlinearities on limit-cycle oscillation of a cropped delta wing

This article presents numerical simulations of the limit-cycle oscillation (LCO) of a cropped delta wing in order to investigate the effects of structural geometric and material nonlinearities on aeroelastic behavior. In the computational model, the structural part included both the geometric nonlinearity that arises from large deflections, and the material nonlinearity that originates from plasticity. The Euler equations were employed in the fluid part to describe the transonic aerodynamics. Moreover, the load transfer was conducted using a 3-D interpolating procedure, and the interfaces between the structural and aerodynamic domains were constructed in the form of an exact match. The flutter and LCO behaviors of the cropped delta wing were simulated using the coupling model, and the results were compared with existing experimental measurements. For lower dynamic pressures, the geometric nonlinearity provided the proper mechanism for the development of the LCO, and the numerical results correlated with the experimental values. For higher dynamic pressures, the material nonlinearity led to a rapid rise in the LCO amplitude, and the simulated varying trend was consistent with the experimental observation. This study demonstrated that the LCO of the cropped delta wing was not only closely related to geometric nonlinearity, but was also remarkably affected by material nonlinearity.     

一类弱奇异边值问题的大范围收敛算法

该文研究如下的弱奇异边值问题: (p(x)y')'=f(x, y),0b₀g(x), 0≤b₀<1, 边值条件为y(0)=A,αy(1)+β y'(1)=γ 或y'(0)=0,αy(1)+βy'(1)=γ (R.K.Pandey 和 Arvind K.Singh 给出了一种求解此问题的二阶有限差分方法^[1]. 在再生核空间中讨论方程解的存在性, 给出一种新的迭代算法,这种迭代算法是大范围收敛的. 给出数值算例并与R. K. Pandey 和Arvind K.Singh 给出的方法进行比较说明该文方法的有效性.