Synthesis and crystallization behavior of rigid copolyesters with biphenyl‐4,4′‐dicarboxylate and 2,6‐naphthalenedicarboxylate in the main chain

Structurally rigid copolyester thermoplastics were synthesized from 1,4‐cyclohexanedimethanol and the diesters dimethyl biphenyl‐4,4′‐dicarboxylate and dimethyl 2,6‐naphthalenedicarboxylate (DMN) via conventional melt transesterification. Conventional differential scanning calorimetry (CDSC) showed all compositions to exhibit multiple endotherms upon heating. Wide‐angle X‐ray diffraction analysis showed copolyester compositions to exhibit the crystalline structure of either the homopolyester Poly(1,4‐cyclohexylenedimethylene 2,6‐naphthalate) (PCN) or the homopolyester Poly(1,4‐cyclohexylenedimethylene 4,4′‐bibenzoate) (PCB), but not both simultaneously. Further thermal analysis using CDSC and fast DSC investigated the origin of the multiple endotherm behavior. While three endotherms are observed for low heating rates, the upper two endotherms appear to merge at heating rates about 1–5 °C s^?1 and a single endotherm remains above heating rates about 10–50 °C s^?1. While the behavior of the upper two endotherms is undeniably consistent with the mechanism of melting–recrystallization–remelting (MRR), we suggest that the low endotherm is likely associated with the melting of constrained secondary crystals, although MRR effects cannot be ruled out. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 973–980     

Spherically symmetric axial Gaussian lobe 3d and 4f orbitals

The axial Gaussian lobe orbital (AGLO ) representations of 3d and 4f orbitals proposed by LeRouzo and Silvi have been angularly optimized to ensure spherical symmetry of filled 3d and 4f shells. The functions have been tested on the hydrogen atom in the presence of high quality s and p basis sets and found to provide excellent minimal Gaussian representations of polarization functions. Exact orbital degeneracy is not obtained within each shell, however. Tabulated values are given to allow arbitrary scaling of the 3d and 4f lobe mimic orbitals.     

Oxidation of tertiary amines by hexachloroacetone

Triethylamine and ethyldiisopropylamine are oxidized by hexachloroacetone. The vinyldialkylamines are acylated by hexachloroacetone, a discussion of the mechanism is presented.     

Poly[tetrakis(n‐propylammonium) [octa‐μ‐chlorido‐dichloridotrinickelate(II)]]: a hybrid organic–inorganic layer compound in the Cs4Mg3F10 structure type

The title compound, {(C₃H₁₀N)₄[Ni₃Cl₁₀]}_n, contains zigzag layers of tri‐μ‐chlorido‐bridged linear 2/m‐symmetric Ni₃Cl₁₂ segments, linked by mono‐μ‐chlorido quasi‐linear bridges to two other segments at each end. These inorganic layers are interleaved with interdigitated bilayers of mirror‐symmetric n‐propylammonium cations, the ammonium head groups of which are directed into the inorganic layers to form multiple N—H...Cl hydrogen bonds, while the propyl tail groups pack together in a tongue‐and‐groove manner in the center of the bilayer. The propyl groups are ordered at 100 K but disordered with opposite conformations on the mirror plane at 240 K.     

Synthesis, characterization, and tunable optical properties of hollow gold nanospheres

Nearly monodisperse hollow gold nanospheres (HGNs) with tunable interior and exterior diameters have been synthesized by sacrificial galvanic replacement of cobalt nanoparticles. It is possible to tune the peak of the surface plasmon band absorption between 550 and 820 nm by carefully controlling particle size and wall thickness. Cobalt particle size is tunable by simultaneously changing the concentration of sodium borohydride and sodium citrate, the reducing and capping agent, respectively. The thickness of the gold shell can be varied by carefully controlling the addition of gold salt. With successful demonstration of ensemble as well as single HGN surface-enhanced Raman scattering, these HGNs have shown great potential for chemical and biological sensing applications, especially those requiring nanostructures with near-IR absorption.     

Development and Infrared Applications of Chalcogenide Glass Optical Fibers

Chalcogenide glass fibers based on sulphide, selenide, telluride, and their rare earth doped compositions are being actively pursued both at the Naval Research Laboratory in Washington, D.C. (NRL) and worldwide. Great strides have been made in reducing optical losses using improved chem ical purification techniques, but further improvements are needed in both purification and fiberization technology to attain the theoretical optical losses. Despite this, current singlemode and multimode chalcogenide glass fibers are enabling numerous applications. Some of these applications include laser power delivery, chemical sensing, imaging, scanning near field microscopy spectroscopy, fiber infrared (IR) sources lasers, amplifiers, and optical switches. The authors assert that the research and development of chalcogenide glasses will grow in the foreseeable future, especially with respect to improvements the optical quality of the fibers and the performance of the fibers in existing future applications.     

Generation of candidate ligands for nicotinic acetylcholine receptors via in situ click chemistry with a soluble acetylcholine binding protein template

Nicotinic acetylcholine receptors (nAChRs), which are responsible for mediating key physiological functions, are ubiquitous in the central and peripheral nervous systems. As members of the Cys loop ligand-gated ion channel family, neuronal nAChRs are pentameric, composed of various permutations of α (α2 to α10) and β (β2 to β4) subunits forming functional heteromeric or homomeric receptors. Diversity in nAChR subunit composition complicates the development of selective ligands for specific subtypes, since the five binding sites reside at the subunit interfaces. The acetylcholine binding protein (AChBP), a soluble extracellular domain homologue secreted by mollusks, serves as a general structural surrogate for the nAChRs. In this work, homomeric AChBPs from Lymnaea and Aplysia snails were used as in situ templates for the generation of novel and potent ligands that selectively bind to these proteins. The cycloaddition reaction between building-block azides and alkynes to form stable 1,2,3-triazoles was used to generate the leads. The extent of triazole formation on the AChBP template correlated with the affinity of the triazole product for the nicotinic ligand binding site. Instead of the in situ protein-templated azide-alkyne cycloaddition reaction occurring at a localized, sequestered enzyme active center as previously shown, we demonstrate that the in situ reaction can take place at the subunit interfaces of an oligomeric protein and can thus be used as a tool for identifying novel candidate nAChR ligands. The crystal structure of one of the in situ-formed triazole-AChBP complexes shows binding poses and molecular determinants of interactions predicted from structures of known agonists and antagonists. Hence, the click chemistry approach with an in situ template of a receptor provides a novel synthetic avenue for generating candidate agonists and antagonists for ligand-gated ion channels.     

The determination of chromium in water-soluble polymers by gas chromatography

Water-soluble polymers have found increasing use in the areas of water treatment, paper production and oil recovery, and the determination of heavy metals in such materials is important from an environmental standpoint. Heavy metal contamination could result from redox catalysts in the polymerization system, raw materials or stainless steel storage facilities.