Continuous and Segmented Semiconducting Fiber-like Nanostructures with Spatially Selective Functionalization by Living Crystallization-Driven Self-Assembly

Fiber-like π-conjugated nanostructures are important components of flexible organic electronic and optoelectronic devices. To broaden the range of potential applications, one needs to control not only the length of these nanostructures, but the introduction of diverse functionality with spatially selective control. Here we report the synthesis of a crystalline-coil block copolymer of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV₅-b-P2VP₄₄), in which the basicity and coordinating/chelating ability of the P2VP segment provide a landscape for the incorporation of a variety of functional inorganic NPs. Through a self-seeding strategy, we were able to prepare monodisperse fiber-like micelles of OPV₅-b-P2VP₄₄ with lengths ranging from 50 to 800 nm. Significantly, the exposed two ends of OPV core of these fiber-like micelles remained active toward further epitaxial deposition of OPV₅-b-PNIPAM₄₉ and OPV₅-b-P2VP₄₄ to generate uniform A-B-A and B-A-B-A-B segmented block comicelles with tunable lengths for each block. The P2VP domains in these (co-)micelles can be selectively decorated with inorganic and polymeric nanoparticles as well as metal oxide coatings, to afford hybrid fiber-like nanostructures. This work provides a versatile strategy toward the fabrication of narrow length dispersity continuous and segmented π-conjugated OPV-containing fiber-like micelles with the capacity to be decorated in a spatially selective way with varying functionalities.     

A rapid dissolution procedure to aid initial nuclear forensics investigations of chemically refractory compounds and particles prior to gamma spectrometry

A rapid and effective preparative procedure has been evaluated for the accurate determination of low-energy (40–200 keV) gamma-emitting radionuclides (²¹⁰Pb, ²³⁴Th, ²²⁶Ra, ²³⁵U) in uranium ores and uranium ore concentrates (UOCs) using high-resolution gamma ray spectrometry. The measurement of low-energy gamma photons is complicated in heterogeneous samples containing high-density mineral phases and in such situations activity concentrations will be underestimated. This is because attenuation corrections, calculated based on sample mean density, do not properly correct where dense grains are dispersed within a less dense matrix (analogous to a nugget effect). The current method overcomes these problems using a lithium tetraborate fusion that readily dissolves all components including high-density, self-attenuating minerals/compounds. This is the ideal method for dissolving complex, non-volatile components in soils, rocks, mineral concentrates, and other materials where density reduction is required. Lithium borate fusion avoids the need for theoretical efficiency corrections or measurement of matrix matched calibration standards. The resulting homogeneous quenched glass produced can be quickly dissolved in nitric acid producing low-density solutions that can be counted by gamma spectrometry. The effectiveness of the technique is demonstrated using uranium-bearing Certified Reference Materials and provides accurate activity concentration determinations compared to the underestimated activity concentrations derived from direct measurements of a bulk sample. The procedure offers an effective solution for initial nuclear forensic studies where complex refractory minerals or matrices exist. It is also significantly faster, safer and simpler than alternative approaches.     

Self‐assembled polyurea macromer nanodispersion and resulting hybrid polyurea‐acrylic emulsions and films

A polyurea macromer (PUM) was synthesized and dispersed in basic conditions to form self‐assembled nanoparticles (<20 nm dispersions, up to 30 wt % aq. soln.). These nanoparticles enabled surfactant‐free emulsion polymerization to form hybrid polyurea‐acrylic particles despite the absence of a measureable water‐soluble fraction. The T_g of the starting PUM material was a strong function of the PUM's extent of neutralization and hydration (varying between 100 °C and >175 °C) due to changes in hydrogen and ionic bonding. Two separate hybrid polyurea‐acrylic emulsion systems were prepared: one by direct polymerization of (meth)acrylic monomers in the presence of the nanodispersion and a second by a physical blend of PUM nanodispersion with an acrylic latex control. The direct polymerization method resulted in a hybrid emulsion particle size that developed by a mechanism resembling conventional emulsion polymerization and was unlike that described for seeded polyurethane dispersion systems. Film hardness was shown to increase with increasing coating thickness for the hybrid film prepared by direct polymerization. The resulting mechanical properties could be explained by applying mechanical models for a composite foam structure. These results were unprecedented for normal elastomer films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1373–1388     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Estimation,dependence and stability of solutions of an iterative equation

Aequationes mathematicae - In this paper we study estimation, continuous dependence and Hyers–Ulam stability for continuous solutions of a second order iterative equation. First we give an...     

On the Optimal Design of Wall-to-Wall Heat Transport

We consider the problem of optimizing heat transport through an incompressible fluid layer. Modeling passive scalar transport by advection-diffusion, we maximize the mean rate of total transport by a divergence-free velocity field. Subject to various boundary conditions and intensity constraints, we prove that the maximal rate of transport scales linearly in the r.m.s. kinetic energy and, up to possible logarithmic corrections, as the one-third power of the mean enstrophy in the advective regime. This makes rigorous a previous prediction on the near optimality of convection rolls for energy-constrained transport. On the other hand, optimal designs for enstrophy-constrained transport are significantly more difficult to describe: we introduce a “branching” flow design with an unbounded number of degrees of freedom and prove it achieves nearly optimal transport. The main technical tool behind these results is a variational principle for evaluating the transport of candidate designs. The principle admits dual formulations for bounding transport from above and below. While the upper bound is closely related to the “background method,” the lower bound reveals a connection between the optimal design problems considered herein and other apparently related model problems from mathematical materials science. These connections serve to motivate designs. © 2019 Wiley Periodicals, Inc.