One-step 9-stage Hermite–Birkhoff–Taylor DAE solver of order 10

The HBT(10)9 method for ODEs is expanded into HBT(10)9DAE for solving nonstiff and moderately stiff systems of fully implicit differential algebraic equations (DAEs) of arbitrarily high fixed index. A scheme to generate first-order derivatives at off-step points is combined with Pryce scheme which generates high order derivatives at step points. The stepsize is controlled by a local error estimator. HBT(10)9DAE uses only the first four derivatives of y instead of the first 10 required by Taylor’s series method T10DAE of order 10. Dormand–Prince’s DP(8,7)13M for ODEs is extended to DP(8,7)DAE for DAEs. HBT(10)9DAE wins over DP(8,7)DAE on several test problems on the basis of CPU time as a function of relative error at the end of the interval of integration. An index-5 problem is equally well solved by HBT(10)9DAE and T10DAE. On this problem, the error in the solution by DP(8,7)DAE increases as time increases.     

Nonlinear variants of the TR/BDF2 method for thermal radiative diffusion

We apply the Trapezoidal/BDF2 (TR/BDF2) temporal discretization scheme to nonlinear grey radiative diffusion. This is a scheme that is not well-known within the radiation transport community, but we show that it offers many desirable characteristics relative to other second-order schemes. Several nonlinear variants of the TR/BDF2 scheme are defined and computationally compared with the Crank–Nicholson scheme. It is found for our test problems that the most accurate TR/BDF2 schemes are those that are fully iterated to nonlinear convergence, but the most efficient TR/BDF2 scheme is one based upon a single Newton iteration. It is also shown that neglecting the contributions to the Jacobian matrix from the cross-sections, which is often done due to a lack of smooth interpolations for tabular cross-section data, has a significant impact upon efficiency.     

Therapeutic Targeting of Oncogenic K‐Ras by a Covalent Catalytic Site Inhibitor

We report the synthesis of a GDP analogue, SML‐8‐73‐1, and a prodrug derivative, SML‐10‐70‐1, which are selective, direct‐acting covalent inhibitors of the K‐Ras G12C mutant relative to wild‐type Ras. Biochemical and biophysical measurements suggest that modification of K‐Ras with SML‐8‐73‐1 renders the protein in an inactive state. These first‐in‐class covalent K‐Ras inhibitors demonstrate that irreversible targeting of the K‐Ras guanine‐nucleotide binding site is potentially a viable therapeutic strategy for inhibition of Ras signaling.     

Zeolite-like metal-organic frameworks as platforms for applications: on metalloporphyrin-based catalysts

The extra-large cavities of zeolite-like metal-organic frameworks (ZMOFs) offer great potential for their exploration in applications pertinent to larger molecules, like porphyrins. The anionic nature of the framework allowed for facile in situ encapsulation of a cationic free-base porphyrin, and the alpha-cage of our (In-imidazoledicarboxylate)-based rho-ZMOF is ideally suited to the isolation of one porphyrin molecule per cage, which prevents the oxidative self-degradation associated with self-dimerization common in homogeneous catalysis and upon aggregation in solid supports like mesoporous silicates or polymers. The encapsulation of a free-base porphyrin [5,10,15,20-tetrakis(1-methyl-4- pyridinio)porphyrin] and the stability of the rho-ZMOF to metalation conditions, allows for the preparation of a variety of metalloporphyrins (i.e., Mn, Cu, Co, Zn ions) with the ZMOF serving as a platform. The Mn-metallated porphyrin encapsulated in rho-ZMOF shows catalytic activity toward the oxidation of cyclohexane, with turn-over numbers, to the best of our knowledge, higher than reported for similar heterogeneous systems, and our system can be recycled up to 11 cycles, which represents a longer lifetime than reported for any other system.     

Quest for zeolite-like metal-organic frameworks: on pyrimidinecarboxylate bis-chelating bridging ligands

Two novel porous zeolitelike metal-organic frameworks (ZMOFs) were constructed via the single metal ion-based molecular building block approach from rigid and directional tetrahedral building units and pyrimidinecarboxylate bridging ligands; their ion exchange and hydrogen sorption properties were evaluated.     

Using low-E resonators to reduce RF heating in biological samples for static solid-state NMR up to 900 MHz

RF heating of solid-state biological samples is known to be a destabilizing factor in high-field NMR experiments that shortens the sample lifetime by continuous dehydration during the high-power cross-polarization and decoupling pulses. In this work, we describe specially designed, large volume, low-E 15N-1H solid-state NMR probes developed for 600 and 900 MHz PISEMA studies of dilute membrane proteins oriented in hydrated and dielectrically lossy lipid bilayers. The probes use an orthogonal coil design in which separate resonators pursue their own aims at the respective frequencies, resulting in a simplified and more efficient matching network. Sample heating at the 1H frequency is minimized by a loop-gap resonator which produces a homogeneous magnetic field B1 with low electric field E. Within the loop-gap resonator, a multi-turn solenoid closely matching the shape of the sample serves as an efficient observe coil. We compare power dissipation in a typical lossy bilayer sample in the new low-E probe and in a previously reported 15N-1H probe which uses a double-tuned 4-turn solenoid. RF loss in the sample is measured in each probe by observing changes in the 1H 360 degrees pulse lengths. For the same values of 1H B1 field, sample heating in the new probe was found to be smaller by an order of magnitude. Applications of the low-E design to the PISEMA study of membrane proteins in their native hydrated bilayer environment are demonstrated at 600 and 900 MHz.     

Stability of exact solutions of the cubic-quintic nonlinear Schrödinger equation with periodic potential

The nonlinear Schr?dinger equation with attractive quintic nonlinearity in periodic potential in 1D, modeling a dilute-gas Bose–Einstein condensate in a lattice potential, is considered and one family of exact stationary solutions is discussed. Some of these solutions have an analog neither in the linear Schr?dinger equation nor in the integrable nonlinear Schr?dinger equation. Their stability is examined analytically and numerically.     

Millimeter wave rheometry: theory and experiment

A novel millimeter wave (MMW) rheometry is developed to determine the viscosity of fluids based on an unsteady film flow on an inclined plane. The method measures fringes due to MMW interference between the front and back surfaces of a fluid flowing across the field of view of a ceramic wave guide coupled to a MMW receiver operating at 137 GHz. With knowledge of the dielectric constant, the interference fringe spacing is used to calculate the thickness of the fluid layer. This thickness is then transformed into the viscosity by means of a simple hydrodynamic theory. Our results show that the MMW rheometry can practically distinguish between the 30, 100, and 200 Pa·s silicone oils. The geometry of the method allows for potential industrial applications such as measuring viscosity of the flowing slag down the walls of coal gasifiers. The MMW rheometry with simple modifications can be easily extended to measure important non-Newtonian fluid characteristics such as yield stress.     

A strategy for the late-stage divergent syntheses of scyphostatin analogues

This account details the synthesis of two scyphostatin analogues exhibiting a reactive polar epoxycyclohexenone core and various amide side chains outfitted for late-stage chemical derivatization into the desirable lipophilic tails. Our efforts highlight a key ipso-dearomatization process and provide new insights regarding the incompatibility and orthogonal reactivity of scyphostatin's functional groups. We further showcase the utility of resorcinol derived 2,5-cyclohexadienones as synthetic platforms capable of participating in selective chemical reactivity, and we further demonstrate their potential for rapid elaboration into complex structural motifs.