Efficient CO2 Removal for Ultra‐Pure CO Production by Two Hybrid Ultramicroporous Materials

Removal of CO₂ from CO gas mixtures is a necessary but challenging step during production of ultra‐pure CO as processed from either steam reforming of hydrocarbons or CO₂ reduction. Herein, two hybrid ultramicroporous materials (HUMs), SIFSIX‐3‐Ni and TIFSIX‐2‐Cu‐i , which are known to exhibit strong affinity for CO₂, were examined with respect to their performance for this separation. The single‐gas CO sorption isotherms of these HUMs were measured for the first time and are indicative of weak affinity for CO and benchmark CO₂/CO selectivity (>4000 for SIFSIX‐3‐Ni ). This prompted us to conduct dynamic breakthrough experiments and compare performance with other porous materials. Ultra‐pure CO (99.99 %) was thereby obtained from CO gas mixtures containing both trace (1 %) and bulk (50 %) levels of CO₂ in a one‐step physisorption‐based separation process.     

Plasmonic Hotspots in Air: An Omnidirectional Three‐Dimensional Platform for Stand‐Off In‐Air SERS Sensing of Airborne Species

Molecular‐level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface‐enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS‐active depth. “Aerosolized plasmonic colloidosomes” (APCs) are introduced as airborne plasmonic hotspots for direct in‐air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100‐fold higher tolerance to laser misalignment along the z‐axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in‐air SERS detection is demonstrated in stand‐off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas.     

Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment

A combination of nuclear resonance vibrational spectroscopy (NRVS), FTIR spectroscopy, and DFT calculations was used to observe and characterize Fe?H/D bending modes in CrHydA1 [FeFe]‐hydrogenase Cys‐to‐Ser variant C169S. Mutagenesis of cysteine to serine at position 169 changes the functional group adjacent to the H‐cluster from a ‐SH to ‐OH, thus altering the proton transfer pathway. The catalytic activity of C169S is significantly reduced compared to that of native CrHydA1, presumably owing to less efficient proton transfer to the H‐cluster. This mutation enabled effective capture of a hydride/deuteride intermediate and facilitated direct detection of the Fe?H/D normal modes. We observed a significant shift to higher frequency in an Fe?H bending mode of the C169S variant, as compared to previous findings with reconstituted native and oxadithiolate (ODT)‐substituted CrHydA1. On the basis of DFT calculations, we propose that this shift is caused by the stronger interaction of the ‐OH group of C169S with the bridgehead ‐NH‐ moiety of the active site, as compared to that of the ‐SH group of C169 in the native enzyme.     

On exponential stability of nonlinear Volterra difference equations in phase spaces

Using a novel approach, we present some new explicit criteria for global exponential stability of the zero solution of general nonlinear Volterra difference equations in phase spaces. In particular, this gives a solution to an open problem posed very recently by E. Braverman and I. M. Karabash in Journal of Difference Equations and Applications 18 , 909–939 (2012). As an application, we apply the obtained results to study asymptotic behavior of equilibriums of discrete time neural networks.     

Randomized filtering and Bellman equation in Wasserstein space for partial observation control problem

We study a stochastic optimal control problem for a partially observed diffusion. By using the control randomization method in Bandini et al. (2018), we prove a corresponding randomized dynamic programming principle (DPP) for the value function, which is obtained from a flow property of an associated filter process. This DPP is the key step towards our main result: a characterization of the value function of the partial observation control problem as the unique viscosity solution to the corresponding dynamic programming Hamilton–Jacobi–Bellman (HJB) equation. The latter is formulated as a new, fully non linear partial differential equation on the Wasserstein space of probability measures. An important feature of our approach is that it does not require any non-degeneracy condition on the diffusion coefficient, and no condition is imposed to guarantee existence of a density for the filter process solution to the controlled Zakai equation. Finally, we give an explicit solution to our HJB equation in the case of a partially observed non Gaussian linear–quadratic model.     

Necessary and Sufficient Conditions for Qualitative Properties of Infinite Dimensional Linear Programming Problems

Necessary and sufficient conditions for qualitative properties of infinite dimensional linear programing problems such as solvability, duality, and complementary slackness conditions are studied in this article. As illustrations for the results, we investigate the parametric version of Gale’s example.     

Preconditioners for pseudodifferential equations on the sphere with radial basis functions

In a previous paper a preconditioning strategy based on overlapping domain decomposition was applied to the Galerkin approximation of elliptic partial differential equations on the sphere. In this paper the methods are extended to more general pseudodifferential equations on the sphere, using as before spherical radial basis functions for the approximation space, and again preconditioning the ill-conditioned linear systems of the Galerkin approximation by the additive Schwarz method. Numerical results are presented for the case of hypersingular and weakly singular integral operators on the sphere \mathbbS²{\mathbb{S}^2} .     

Upper semicontinuity result for the solution mapping of a mixed parametric generalized vector quasiequilibrium problem with moving cones

In this paper, we give sufficient conditions for the upper semicontinuity property of the solution mapping of a parametric generalized vector quasiequilibrium problem with mixed relations and moving cones. The main result is proven under the assumption that moving cones have local openness/local closedness properties and set-valued maps are cone-semicontinuous in a sense weaker than the usual sense of semicontinuity. The nonemptiness and the compactness of the solution set are also investigated.     

An overlapping additive Schwarz preconditioner for interpolation on the unit sphere with spherical radial basis functions

The problem of interpolation of scattered data on the unit sphere has many applications in geodesy and Earth science in which the sphere is taken as a model for the Earth. Spherical radial basis functions provide a convenient tool for constructing the interpolant. However, the underlying linear systems tend to be ill-conditioned. In this paper, we present an additive Schwarz preconditioner for accelerating the solution process. An estimate for the condition number of the preconditioned system will be discussed. Numerical experiments using MAGSAT satellite data will be presented.