Sustainable poly(ether amide)s from lignin-derived precursors

In recent years, there have been concerted efforts to replace petrochemical products with those from renewable sources due to the unsustainability of petroleum feedstock, and the continued volatility in the price. This work describes the synthesis and thermal properties of two new lignin-derived poly(ether-amide)s as alternative thermoplastics to petroleum-based commodities. Poly-4-(2-aminoethoxy)benzoate (PEAB) and poly-4-(2-aminoethoxy)-3-methoxybenzoate (PEAV) are synthesized by a melt polycondensation and characterized by ¹H NMR spectroscopy and thermal analysis. The number average molecular weight (M_n) of the polymers are estimated from the ¹H NMR spectroscopy analysis, and were shown to be 4100 and 12,000 g/mol for PEAB and PEAV respectively. The PEAB had a higher decomposition temperature (T_d) as well as glass transition temperature (T_g) compared to PEAV; albeit, with a lower molecular weight. The polymers’ T_d were in the range of 330 °C–380 °C and the T_g were between 100 °C and 120 °C. The thermal properties of the polymers are in the desirable range for thermoplastic materials used in the packaging, storage, and coating industries. Furthermore, the polymers are susceptible to degradation under acidic conditions in a short period; a property that is highly desirable for degradable polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2154–2160     

Third-order statistics and the dynamics of strongly anisotropic turbulent flows

Anisotropy is induced by body forces and/or mean large-scale gradients in turbulent flows. For flows without energy production, the dynamics of second-order velocity or second-order vorticity statistics are essentially governed by triple correlations, which are at the origin of the anisotropy that penetrates towards the inertial range, deeply altering the cascade and the eventual dissipation process, with a series of consequences on the evolution of homogeneous turbulence statistics: in the case of rotating turbulence, the anisotropic spectral transfer slaves the multiscale anisotropic energy distribution; nonlinear dynamics are responsible for the linear growth in terms of Ωt of axial integral length-scales; third-order structure functions, derived from velocity triple correlations, exhibit a significant departure from the 4/5 Kolmogorov law. We describe all these implications in detail, starting from the dynamical equations of velocity statistics in Fourier space, which yield third-order correlations at three points (triads) and allow the explicit removal of pressure fluctuations. We first extend the formalism to anisotropic rotating turbulence with ‘production’, in the presence of mean velocity gradients in the rotating frame. Second, we compare the spectral approach at three points to the two-point approach directly performed in physical space, in which we consider the transport of the scalar second-order structure function ?(δq)²?. This calls into play componental third-order correlations ?(δq)²δu?(r) in axisymmetric turbulence. This permits to discuss inhomogeneous anisotropic effects from spatial decay, shear, or production, as in the central region of a rotating round jet. We show that the above-mentioned important statistical quantities can be estimated from experimental planar particle image velocimetry, and that explicit passage relations systematically exist between one- and two-point statistics in physical and spectral space for second-order tensors, but also sometimes for third-order tensors that are involved in the dynamics.     

Use of a microelectromechanical mirror for adaptive optics in the human eye

Ophthalmic instrumentation equipped with adaptive optics offers the possibility of rapid and automated correction of the eye's optics for improving vision and for improving images of the retina. One factor that limits the widespread implementation of adaptive optics is the cost of the wave-front corrector, such as a deformable mirror. In addition, the large apertures of these elements require high pupil magnification, and hence the systems tend to be physically large. We present what are believed to be the first closed-loop results when a compact, low-cost, surface micromachined, microelectromechanical mirror is used in a vision adaptive-optics system. The correction performance of the mirror is shown to be comparable to that of a Xinetics mirror for a 4.6-mm pupil size. Furthermore, for a pupil diameter of 6.0-mm, the residual rms error is reduced from 0.36 to 0.12 microm and individual photoreceptors are resolved at a pupil eccentricity of 1 degrees from the fovea.     

Quadratic geometric programming with application to machining economics

Geometric Programming is extended to include convex quadratic functions. Generalized Geometric Programming is applied to this class of programs to obtain a convex dual program. Machining economics problems fall into this class. Such problems are studied by applying this duality to a nested set of three problems. One problem is zero degree of difficulty and the solution is obtained by solving a simple system of equations. The inclusion of a constraint restricting the force on the tool to be less than or equal to the breaking force provides a more realistic solution. This model is solved as a program with one degree of difficulty. Finally the behavior of the machining cost per part is studied parametrically as a function of axial depth. This research was supported by the Air Force Office of Scientific Research Grant AFOSR-83-0234     

Size-dependent oxidation of Pdn (n 13) on alumina/NiAl(110): Correlation with Pd core level binding energies

Small Pd clusters Pd_n (n = 1, 4, 7, 10, 13) deposited on alumina/NiAl(110) at room temperature were examined by X-ray photoelectron spectroscopy (XPS), as-deposited and after exposure to O₂ at temperatures ranging from 100 to 500 K. After O₂ exposure at 100 K, the Pd clusters showed XPS shifts indicative of oxidation. The exception was Pd₄, which did not oxidize under any conditions. The inertness of Pd₄/alumina/NiAl(110) appears to be correlated with a significantly higher-than-expected Pd 3d binding energy, which we attribute to a particularly stable valence shell. None of the clusters examined oxidized during O₂ exposures at 300 K or above, but He⁺ scattering showed that oxygen was bound on the cluster surfaces. Upon heating, all the oxygen associated with these small clusters appeared to spill over and react with the alumina/NiAl(110) support.     

Variations in T(2)* and fat content of murine brown and white adipose tissues by chemical-shift MRI

Purpose

The purpose was to compare T₂* relaxation times and proton density fat-fraction (PDFF) values between brown (BAT) and white (WAT) adipose tissue in lean and ob/ob mice.

Materials and Methods

A group of lean male mice (n=6) and two groups of ob/ob male mice placed on similar 4-week (n=6) and 8-week (n=8) ad libitum diets were utilized. The animals were imaged at 3 T using a T₂*-corrected chemical-shift-based water–fat magnetic resonance imaging (MRI) method that provides simultaneous estimation of T₂* and PDFF on a voxel-wise basis. Regions of interest were drawn within the interscapular BAT and gonadal WAT depots on co-registered T₂* and PDFF maps. Measurements were assessed using analysis of variance, Bonferroni-adjusted t test for multigroup comparisons and the Tukey post hoc test.

Results

Significant differences (P<.01) in BAT T₂* and PDFF were observed between the lean and ob/ob groups. The ob/ob animals exhibited longer BAT T₂* and greater PDFF than lean animals. However, only BAT PDFF was significantly different (P<.01) between the two ob/ob groups. When comparing BAT to WAT within each group, T₂* and PDFF values were consistently lower in BAT than WAT (P<.01). The difference was most prominent in the lean animals. In both ob/ob groups, BAT exhibited very WAT-like appearances and properties on the MRI images.

Conclusion

T₂* and PDFF are lower in BAT than WAT. This is likely due to variations in tissue composition. The values were consistently lower in lean mice than in ob/ob mice, suggestive of the former's greater demand for BAT thermogenesis and reflective of leptin hormone deficiencies and diminished BAT metabolic activity in the latter.     

Tensor Decomposition With Generalized Lasso Penalties

We present an approach for penalized tensor decomposition (PTD) that estimates smoothly varying latent factors in multiway data. This generalizes existing work on sparse tensor decomposition and penalized matrix decompositions, in a manner parallel to the generalized lasso for regression and smoothing problems. Our approach presents many nontrivial challenges at the intersection of modeling and computation, which are studied in detail. An efficient coordinate-wise optimization algorithm for PTD is presented, and its convergence properties are characterized. The method is applied both to simulated data and real data on flu hospitalizations in Texas and motion-capture data from video cameras. These results show that our penalized tensor decomposition can offer major improvements on existing methods for analyzing multiway data that exhibit smooth spatial or temporal features.     

Evaluating continuous chirality measure as a 3D descriptor in chemoinformatics applied to asymmetric catalysis

Continuous Chirality Measure (CCM) is a computational metric by which to quantify the chirality of a compound. In enantioselective catalysis, prior work has postulated that CCM is correlated to selectivity and can be used to understand which structural features dictate catalyst efficacy. Herein, the investigation of CCM as a metric capable of guiding catalyst optimization is explored. Conformer-dependent CCM is also explored. Finally, CCM is used with Sterimol parameters to significantly improve the performance of Random Forest models.     

New Explanation for Ligand Bending in Transition Metal Tris(dithiolate) Complexes

The results of Fenske-Hall molecular orbital calculations are reported for the trigonal prismatic complexes Mo(S(2)C(2)H(2))(3) and Mo(S(2)C(6)H(4))(3). Both complexes exhibit a bend of the S-C-C-S ligand plane away from the S-Mo-S plane. A series of calculations which systematically follow the changes in electronic structure as the bend angle alpha is varied between 0 and 30 degrees indicates that the bend can be attributed to a second order Jahn-Teller distortion. The driving force for this distortion, which allows mixing between a set of ligand pi orbitals and the metal d(z)()()2 orbital, should be greatest for d(0) systems. In these systems the bent geometry leads to the stabilization of the doubly occupied HOMO. The driving force for ligand bending should be lower in systems having more or fewer electrons (e.g. Re(S(2)C(2)Ph(2))(3) or V(S(2)C(2)Ph(2))(3), respectively). While the steric bulk of the dithiolate ligands in the latter complexes may also influence the degree of ligand bending, this is probably a secondary effect.     

Key Word Index for Volume 11

Other Index

Key Word Index for Volume 11