Synthesis of the enantiomers of the dual function 2‐nitroimidazole radiation sensitizer RB 6145

Short, efficient pathways are described for the synthesis of racemic 2‐nitroimidazole radiation sensitizer RB‐6145 ( 2a ) and each of its corresponding (R)‐ and (S)‐enantiomers ( 2b and 2c , respectively). The synthesis of each enantiomer commences with the appropriate chiral epichlorohydrin and utilizes a novel application of 3‐trimethylsilyl‐2‐oxazolidinone ( 3b ) as a mild, safe surrogate for highly toxic aziridine. The synthesis of the (R)‐enantiomer ( 2b ) has been successfully scaled up to provide multi‐kilo quantities of material for early stage preclinical evaluation.     

1JCH correlates with alcohol hydrogen bond strength

The strength of the H-bond donation by alcohols is reflected in the carbon-hydrogen bond of the H-C-O-H functional group. The one-bond 13C-1H spin-spin coupling constant of hexafluoroisopropanol (HFIP) correlates with the strength of the H-bond in various HFIP-amine complexes with a slope of approximately -0.2 Hz in 1JCH per approximately 1 kJ mol(-1) increase in the H-bond enthalpy. The decrease in 1JCH is attributed to an increased overlap of the H-bonding sigma orbital with the antibonding sigma orbitals of the vicinal C-H bonds.     

Scattering of plane guided waves obliquely incident on a straight feature with uniform cross-section

A frequency-domain finite element (FE) method is presented for modeling the scattering of plane guided waves incident on an infinitely-long, straight feature with uniform cross-section in a planar host waveguide. The method utilizes a mesh of 2-dimensional finite elements with harmonic shape functions in the perpendicular direction. The model domain comprises a cross-section through the feature and short lengths of the adjoining host waveguide. A spatial frequency equal to the wavenumber of the desired incident mode multiplied by the sine of the desired incidence angle is prescribed for the element shape functions. An integral representation of the incident mode is used to determine a suitable system of harmonic forces to uniquely excite that mode. These are applied at nodes through the thickness of the host waveguide on one side of the feature. The displacement field is measured at nodes through the thickness of the host waveguide on either side of the feature and decomposed into reflected and transmitted modes. The cases of guided wave transmission in a featureless waveguide and the reflection of guided waves from a free-edge are examined as validation cases. Finally, the results for transmission at an adhesively-bonded stiffener are presented and compared with experimental measurements.     

Bicoherence analysis of model-scale jet noise

Bicoherence analysis has been used to characterize nonlinear effects in the propagation of noise from a model-scale, Mach-2.0, unheated jet. Nonlinear propagation effects are predominantly limited to regions near the peak directivity angle for this jet source and propagation range. The analysis also examines the practice of identifying nonlinear propagation by comparing spectra measured at two different distances and assuming far-field, linear propagation between them. This spectral comparison method can lead to erroneous conclusions regarding the role of nonlinearity when the observations are made in the geometric near field of an extended, directional radiator, such as a jet.     

Shape distortions induced by convective effect on hot object in visible, near infrared and infrared bands

The goal of this study is to examine the perturbation induced by the convective effect (or mirage effect) on shape measurement and to give an estimation of the error induced. This work explores the mirage effect in different spectral bands and single wavelengths. A numerical approach is adopted and an original setup has been developed in order to investigate easily all the spectral bands of interest with the help of a CCD camera (Si, 0.35–1.1 μm), a near infrared camera (VisGaAs, 0.8–1.7 μm) or infrared cameras (8–12 μm). Displacements due to the perturbation for each spectral band are measured and finally some hints about how to correct them are given.     

A Study of Microscale Gas Trapping Using Etched Silicon Micromodels

Immobilization and trapping of carbon dioxide (CO₂) enhances the security of geological storage. Trapping mechanisms have been characterized in four groups: structural, residual, dissolution, and mineralization. While structural trapping acts immediately when injection starts and is well investigated, the contribution of residual and dissolution trapping increases over storage time and these contributions need to be better understood for better predictions. This paper focuses on an experimental pore-scale investigation of residual and capillary trapping. CO₂?Cwater imbibition experiments were conducted in micromodels whose homogenous pore space is geometrically and topologically similar to Berea sandstone. Microvisual data, photographs and video footage, describes the trapping mechanism and, especially, the disconnection and shrinkage of the CO₂ phase. Results show that depending on the flow rate of the imbibing water different trapping mechanisms are observed. Lower flow rates, comparable to the trailing edge of a CO₂ plume, lead to more snap-off events and greater trapped residual saturation, whereas rates comparable to the near wellbore area during enhanced sequestration showed displacement of gas bubbles and greater dissolution that ultimately leads to very low or zero gas saturations. Furthermore, complete dissolution events showed that homogenous as well as heterogeneous dissolution occurs. Whereas the latter is subdivided into microbubble formation and dissolution on crevices or pore roughness, the former occurs without the influence of pore walls. Based on the observations we suggest that the type of rock and its roughness as well as the fines present at the CO₂ brine interface are important factors determining the dissolution mechanism.     

High-order Large Eddy Simulations of Confined Rotor-Stator Flows

In many engineering and industrial applications, the investigation of rotating turbulent flow is of great interest. In rotor-stator cavities, the centrifugal and Coriolis forces have a strong influence on the turbulence by producing a secondary flow in the meridian plane composed of two thin boundary layers along the disks separated by a non-viscous geostrophic core. Most numerical simulations have been performed using RANS and URANS modelling, and very few investigations have been performed using LES. This paper reports on quantitative comparisons of two high-order LES methods to predict a turbulent rotor-stator flow at the rotational Reynolds number Re(=?Ωb ²/ν)?=4 × 10⁵. The classical dynamic Smagorinsky model for the subgrid-scale stress (Germano et al., Phys Fluids A 3(7):1760–1765, 1991) is compared to a spectral vanishing viscosity technique (Séverac & Serre, J Comp Phys 226(2):1234–1255, 2007). Numerical results include both instantaneous data and post-processed statistics. The results show that both LES methods are able to accurately describe the unsteady flow structures and to satisfactorily predict mean velocities as well as Reynolds stress tensor components. A slight advantage is given to the spectral SVV approach in terms of accuracy and CPU cost. The strong improvements obtained in the present results with respect to RANS results confirm that LES is the appropriate level of modelling for flows in which fully turbulent and transition regimes are involved.     

Electrophoresis of sheared polyelectrolytes

ABSTRACT

A shear flow breaks the spherical symmetry of a flexible polymer, which has some interesting consequences for the electrophoresis of polyelectrolytes. In addition to introducing a chain-length dependence of the electrophoretic velocity, there is also the possibility of migration of the molecule perpendicular to the direction of coaxial gradients in pressure and electric potential. This has been shown to produce a rapid and highly localised concentration of DNA within a microfluidic capillary, with a number of potential applications to on-chip preparation and analysis of genomic DNA. In this paper, dedicated to Prof. Daan Frenkel, I will describe a calculation of the electrophoretic motion of a long polyelectrolyte under a coaxial flow and electric field.     

Ultrafast X‐ray imaging of laser–metal additive manufacturing processes

The high‐speed synchrotron X‐ray imaging technique was synchronized with a custom‐built laser‐melting setup to capture the dynamics of laser powder‐bed fusion processes in situ. Various significant phenomena, including vapor‐depression and melt‐pool dynamics and powder‐spatter ejection, were captured with high spatial and temporal resolution. Imaging frame rates of up to 10 MHz were used to capture the rapid changes in these highly dynamic phenomena. At the same time, relatively slow frame rates were employed to capture large‐scale changes during the process. This experimental platform will be vital in the further understanding of laser additive manufacturing processes and will be particularly helpful in guiding efforts to reduce or eliminate microstructural defects in additively manufactured parts.     

Elucidation of the Mechanism of Enhanced Insulin Uptake and Release from pH Responsive Hydrogels

Summary: Environmentally responsive hydrogels composed of poly(methacrylic acid-g-ethylene glycol) (P(MAA-g-EG)) have shown promise for oral insulin delivery due to their pH responsive complexation behavior. A series of hydrogel formulations were polymerized with varying amounts of crosslinker and varying monomer volume fraction. The mesh size of the network depended primarily on pH, varying from 8.0 to 27.2 nm. Insulin loading efficiency varied directly with crosslink density, ranging from 42.7 to 84.9% of available insulin loaded into the hydrogels. The release of insulin was performed with each polymer formulation at 5 pH levels ranging from 2.7 to 6.8. Insulin release was less than 20% for all formulations tested with insulin for the duration of the 3 hour release study for all pH levels considered except when the pH was 6.8, at which point the release occurred as a burst. Loading studies performed with insulin glargine, an insulin analog with an increased pI, showed the same trends as native insulin. However, the release of insulin glargine only occurred at a pH level above that of the pI of the protein. These results indicate that hydrogen bonds and ionic interactions between the protein and P(MAA-g-EG) may strongly influence its loading and release behavior in vitro.