In Situ Formation of a MoS2‐Based Inorganic–Organic Nanocomposite by Directed Thermal Decomposition

Nanocomposites based on molybdenum disulfide (MoS₂) and different carbon modifications are intensively investigated in several areas of applications due to their intriguing optical and electrical properties. Addition of a third element may enhance the functionality and application areas of such nanocomposites. Herein, we present a facile synthetic approach based on directed thermal decomposition of (Ph₄P)₂MoS₄ generating MoS₂ nanocomposites containing carbon and phosphorous. Decomposition at 250 °C yields a composite material with significantly enlarged MoS₂ interlayer distances caused by in situ formation of Ph₃PS bonded to the MoS₂ slabs through Mo?S bonds and (Ph₄P)₂S molecules in the van der Waals gap, as was evidenced by ³¹P solid‐state NMR spectroscopy. Visible‐light‐driven hydrogen generation demonstrates a high catalytic performance of the materials.     

Surface-enhanced Raman scattering on molecular self-assembly in nanoparticle-hydrogel composite

Surface-enhanced Raman scattering has been applied to study weak intermolecular interactions between small organic gelling molecules involved in the silver nanoparticle-hydrogel composite formation. Assembly and disassembly of the gelator molecules in close vicinity to embedded silver nanoparticles were followed by changes in Raman intensity of the amide II and carboxyl vibrational bands, whereas the strength of the bands related to benzene modes remained constant. This implied that the gelator molecules were strongly attached to the silver particles through the benzene units, while participating in gel structure organization by intermolecular hydrogen bonding between oxalyl amide and carboxyl groups.     

3D Oriented Projective Geometry Through Versors of $${\mathbb{R}^{3,3}}$$

It is possible to set up a correspondence between 3D space and \({\mathbb{R}^{3,3}}\), interpretable as the space of oriented lines (and screws), such that special projective collineations of the 3D space become represented as rotors in the geometric algebra of \({\mathbb{R}^{3,3}}\). We show explicitly how various primitive projective transformations (translations, rotations, scalings, perspectivities, Lorentz transformations) are represented, in geometrically meaningful parameterizations of the rotors by their bivectors. Odd versors of this representation represent projective correlations, so (oriented) reflections can only be represented in a non-versor manner. Specifically, we show how a new and useful ‘oriented reflection’ can be defined directly on lines. We compare the resulting framework to the unoriented \({\mathbb{R}^{3,3}}\) approach of Klawitter (Adv Appl Clifford Algebra, 24:713–736, 2014), and the \({\mathbb{R}^{4,4}}\) rotor-based approach by Goldman et al. (Adv Appl Clifford Algebra, 25(1):113–149, 2015) in terms of expressiveness and efficiency.     

Single-Phase Polymer Alloys of Polyvinyl Chloride and New Polymers

Polymer alloying is acquiring ever increasing significance for the modification of polymeric materials. Polymer alloys are defined by their phase character, which in turn is determined by the mutual compatibility or incompatibility of the components. Suitable techniques for the analysis of the phase character include, inter alia, dynamic-mechanical methods, according to which a polymer alloy may be considered in a simplified manner as single-phase when only one glass transition is observed, even if it extends over a broader temperature range than in the case of the pure components. Aliphatic (polyester)-polycarbonates and tetramethylbisphenol-A polycarbonate are new, PVC-compatible, polymer modifiers. The (polyester)-polycarbonates (from adipic acid, hexane-1,6-diol, neopentanediol, and diphenyl carbonate) yield with PVC single-phase alloys that at temperatures above the glass transitions of the mixture display the characteristics of soft PVC and that are tough far below this temperature. The special high-temperature properties of the resin-like tetramethylbisphenol-A polycarbonate permits the preparation of alloys with increased dimensional stability under heat (higher deflection temperatures under load).     

A fast simulated annealing method for batching precedence-constrained customer orders in a warehouse

Batching customer orders in a warehouse can result in considerable savings in order pickers’ travel distances. Many picker-to-parts warehouses have precedence constraints in picking a customer order. In this paper a joint order-batching and picker routing method is introduced to solve this combined precedence-constrained routing and order-batching problem. It consists of two sub-algorithms: an optimal A^∗-algorithm for the routing; and a simulated annealing algorithm for the batching which estimates the savings gained from batching more than two customer orders to avoid unnecessary routing. For batches of three customer orders, the introduced algorithm produces results with an error of less than 1.2% compared to the optimal solution. It also compares well to other heuristics from literature. A data set from a large Finnish order picking warehouse is rerouted and rebatched resulting in savings of over 5000 kilometres or 16% in travel distance in 3 months compared to the current method.     

Universal elasticity and fluctuations of nematic gels

We study elasticity of spontaneously orientationally ordered amorphous solids, characterized by a vanishing transverse shear modulus, as realized by nematic elastomers and gels. We show that local heterogeneities and elastic nonlinearities conspire to lead to anomalous nonlocal universal elasticity controlled by a nontrivial infrared fixed point. Namely, such solids are characterized by universal shear and bending moduli that, respectively, vanish and diverge at long scales, are universally incompressible, and exhibit a universal negative Poisson ratio and a non-Hookean elasticity down to arbitrarily low strains. Based on expansion about five dimensions, we argue that the nematic order is stable to thermal fluctuation and local heterogeneities down to d(lc)<3.     

On sets of subspaces with two intersection dimensions and a geometrical junta bound

Designs, Codes and Cryptography - In this article, constant dimension subspace codes whose codewords have subspace distance in a prescribed set of integers, are considered. The easiest example of...     

A Tumor-Targeting Dual-Stimuli-Activatable Photodynamic Molecular Beacon for Precise Photodynamic Therapy

A multifunctional photodynamic molecular beacon (PMB) has been designed and synthesized which contains an epidermal growth factor receptor (EGFR)-targeting cyclic peptide and a trimeric phthalocyanine skeleton in which the three zinc(II) phthalocyanine units are each substituted with a glutathione (GSH)-responsive 2,4-dinitrobenzenesulfonate (DNBS) quencher and are linked via two cathepsin B-cleavable GFLG peptide chains. This tailor-made conjugate is fully quenched in the native form due to the photoinduced electron transfer effect of the DNBS moieties and the self-quenching of the phthalocyanine units. It can target the EGFR overexpressed in cancer cells, and after receptor-mediated endocytosis, it can be activated selectively by the co-existence of intracellular GSH and cathepsin B, both of which are also overproduced in cancer cells, in terms of fluorescence emission and singlet oxygen generation. The cell-selective behavior of this PMB has been demonstrated using a range of cancer cells with different expression levels of EGFR, while the stimuli-responsive properties have been studied both in vitro and in various aqueous media. The overall results show that this advanced PMB, which exhibits several levels of control of the tumor specificity, is a promising photosensitizer for precise antitumoral photodynamic therapy.     

Synthesis and characterization of imidized poly(styrene‐maleic anhydride) nanoparticles in stable aqueous dispersion

Organic nanoparticles are synthesized by partial imidization of high‐molecular weight styrene(maleic‐anhydride) with 26 to 34 mol% maleic anhydride, in aqueous environment and presence of ammonium hydroxide. The nanoparticle dispersions have a maximum solid content of 35 wt% and good stability that critically depends on the ratio of imidized and ammonolyzed maleic anhydride moieties. The deprotonated residual maleic anhydride moieties provide dispersion stability at pH > 4, while protonation at pH < 4 causes nanoparticle sedimentation. After presentation of the synthesis conditions, the imidization reaction is characterized by FT‐IR and Raman spectroscopy, followed by thermal analysis (TGA, DSC), and morphological characterization (DLS, SEM, TEM, AFM). The reaction conditions were optimized by physical characterization of various dispersions, and finally nanoparticles could be obtained with a maximum degree of imidization of 77% in dispersed conditions, or 90 to 95% after drying that are favorable for coating applications. Copyright © 2010 John Wiley & Sons, Ltd.