Precise Control of Molecular Self-Diffusion in Isoreticular and Multivariate Metal-Organic Frameworks

Understanding the factors that affect self-diffusion in isoreticular and multivariate (MTV) MOFs is key to their application in drug delivery, separations, and heterogeneous catalysis. Here, we measure the apparent self-diffusion of solvents saturated within the pores of large single crystals of MOF-5, IRMOF-3 (amino-functionalized MOF-5), and 17 MTV-MOF-5/IRMOF-3 materials at various mole fractions. We find that the apparent self-diffusion coefficient of N,N-dimethylformamide (DMF) may be tuned linearly between the diffusion coefficients of MOF-5 and IRMOF-3 as a function of the linker mole fraction. We compare a series of solvents at saturation in MOF-5 and IRMOF-3 to elucidate the mechanism by which the linker amino groups tune molecular diffusion. The ratio of the self-diffusion coefficients for solvents in MOF-5 to those in IRMOF-3 is similar across all solvents tested, regardless of solvent polarity. We conclude that average pore aperture, not solvent-linker chemical interactions, is the primary factor responsible for the different diffusion dynamics upon introduction of an amino group to the linker.     

A Facile Method for the Separation of Methionine Sulfoxide Diastereomers,Structural Assignment,and DFT Analysis

Methionine (Met) oxidation is an important biological redox node, with hundreds if not thousands of protein targets. The process yields methionine oxide (MetO). It renders the sulfur chiral, producing two distinct, diastereomerically related products. Despite the biological significance of Met oxidation, a reliable protocol to separate the resultant MetO diastereomers is currently lacking. This hampers our ability to make peptides and proteins that contain stereochemically defined MetO to then study their structural and functional properties. We have developed a facile method that uses supercritical CO₂ chromatography and allows obtaining both diastereomers in purities exceeding 99 %. ¹H NMR spectra were correlated with X-ray structural information. The stereochemical interconversion barrier at sulfur was calculated as 45.2 kcal mol⁻¹, highlighting the remarkable stereochemical stability of MetO sulfur chirality. Our protocol should open the road to synthesis and study of a wide variety of stereochemically defined MetO-containing proteins and peptides.     

Catalytically Active Hollow Fiber Membranes with Enzyme-Embedded Metal–Organic Framework Coating

Metal–organic frameworks (MOFs) are suitable enzyme immobilization matrices. Reported here is the in situ biomineralization of glucose oxidase (GOD) into MOF crystals (ZIF-8) by interfacial crystallization. This method is effective for the selective coating of porous polyethersulfone microfiltration hollow fibers on the shell side in a straightforward one-step process. MOF layers with a thickness of 8 μm were synthesized, and fluorescence microscopy and a colorimetric protein assay revealed the successful inclusion of GOD into the ZIF-8 layer with an enzyme concentration of 29±3 μg cm⁻². Enzymatic activity tests revealed that 50 % of the enzyme activity is preserved. Continuous enzymatic reactions, by the permeation of β-d -glucose through the GOD@ZIF-8 membranes, showed a 50 % increased activity compared to batch experiments, emphasizing the importance of the convective transport of educts and products to and from the enzymatic active centers.     

Determination of nitrate with a flow-injection system combining square-wave polarographic detection with on-line deaeration

The combination of a flow-injection system with square-wave polarography and on-line deaeration is applied to the determination of nitrate, utilizing the catalytic reaction between nitrate and uranyl ion. The method is simple, rapid (60 samples h^?1), sensitive and accurate, with a detection limit of 2 μM nitrate. The method has been applied to the determination of nitrate in drinking and river waters.     

Radial equivalence for the two basic nonlinear degenerate diffusion equations

In this paper we prove that there exists an explicit correspondence between the radially symmetric solutions of two well-known models of nonlinear diffusion, the porous medium equation and the p-Laplacian equation. We establish exact correspondence formulas between these solutions. We also study in detail the application of the results in the important case of self-similar solutions. In particular, we derive the existence of new self-similar solutions for the evolution p-Laplacian equation.     

Verbenanone,an octahydro-5H-chromen-5-one from a Hawaiian-plant associated fungus FT431

Verbenanone (1), a new secondary metabolite with a unique (4aS,8aS)-octahydro-5H-chromen-5-one moiety has been obtained from the endophytic fungus FT431, which was isolated from the native Hawaiian plant Verbena sp. The structure of compound 1 was characterized based on NMR and MS spectroscopic analysis. The absolute configuration (AC) of compound 1 was determined by Mosher acids. Compound 1 was tested against A2780 and A2780cisR, but it was inactive.     

Spherical and non-spherical bubbles in cosmological phase transitions

The cosmological remnants of a first-order phase transition generally depend on the perturbations that the walls of expanding bubbles originate in the plasma. Several of the formation mechanisms occur when bubbles collide and lose their spherical symmetry. However, spherical bubbles are often considered in the literature, in particular for the calculation of gravitational waves. We study the steady state motion of bubble walls for different bubble symmetries. Using the bag equation of state, we discuss the propagation of phase transition fronts as detonations and subsonic or supersonic deflagrations. We consider the cases of spherical, cylindrical and planar walls, and compare the energy transferred to bulk motions of the relativistic fluid. We find that the different wall geometries give similar perturbations of the plasma. For the case of planar walls, we obtain analytical expressions for the kinetic energy in the bulk motions. As an application, we discuss the generation of gravitational waves.     

Measurability of semimartingale characteristics with respect to the probability law

Given a càdlàg process X$X$ on a filtered measurable space, we construct a version of its semimartingale characteristics which is measurable with respect to the underlying probability law. More precisely, let _Psem${\mathfrak{P}}_{sem}$ be the set of all probability measures P$P$ under which X$X$ is a semimartingale. We construct processes (B^P,C,ν^P)$(B^P,C,{\nu }^P)$ which are jointly measurable in time, space, and the probability law P$P$, and are versions of the semimartingale characteristics of X$X$ under P$P$ for each P∈_Psem$P\in {\mathfrak{P}}_{sem}$. This result gives a general and unifying answer to measurability questions that arise in the context of quasi-sure analysis and stochastic control under the weak formulation.