Rational Design of a Uranyl Metal–Organic Framework for the Capture and Colorimetric Detection of Organic Dyes

A new uranyl containing metal–organic framework, RPL-1 : [(UO₂)₂(C₂₈H₁₈O₈)] ^. H₂O (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid-state photoluminescence properties explored. Single crystal X-ray diffraction data reveals the structure of RPL - 1 consists of two crystallographically unique three dimensional, interpenetrating nets with a 4,3-connected tbo topology. Each net contains large pores with an average width of 22.8 Å and is formed from monomeric, hexagonal bipyramidal uranyl nodes that are linked via 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB) ligands. The thermal and photophysical properties of RPL-1 were investigated using thermogravimetric analysis and absorbance, fluorescence, and lifetime spectroscopies. The material displays excellent thermal stability and temperature dependent uranyl and TCPB luminescence. The framework is stable in aqueous media and due to the large void space (constituting 76 % of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.     

Hydrogenation of acetylene into ethane–ethene mixtures over modified Pd–alumina catalysts

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Highly Conjugated π-Systems Arising from Cannibalistic Hexadehydro-Diels–Alder Couplings: Cleavage of C−C Single and Triple Bonds

We have investigated the cannibalistic self-trapping reaction of an ortho-benzyne derivative generated from 1,11-bis(p-tolyl)undeca-1,3,8,10-tetrayne in an HDDA reaction. Without adding any specific trapping agent, the highly reactive benzyne is trapped by another bisdiyne molecule in at least three different modes. We have isolated and characterized the resulting products and performed high-level calculations concerning the reaction mechanism. During the cannibalistic self-trapping process, either a C≡C triple bond or an sp–sp³ C−C single bond is cleaved. Up to seven rings and nine C−C bonds are formed starting from two 1,11-bis(p-tolyl)undeca-1,3,8,10-tetrayne molecules. Our experiments and calculations provide considerable insight into the variety of reaction pathways which the ortho-benzyne derivative, generated from a bisdiyne, can take when reacting with another bisdiyne molecule.     

Nonlinear obstacle problems with double phase in the borderline case

In this paper we study a double phase problem with an irregular obstacle. The energy functional under consideration is characterized by the fact that both ellipticity and growth switch between a type of polynomial and a type of logarithm, which can be regarded as a borderline case of the double phase functional with $(p,q)$-growth. We obtain an optimal global Calderón–Zygmund type estimate for the obstacle problem with double phase in the borderline case.     

Polyoxometalate‐Mediated One‐Pot Synthesis of Pd Nanocrystals with Controlled Morphologies for Efficient Chemical and Electrochemical Catalysis

Polyoxometalates (POMs), as inorganic ligands, can endow metal nanocrystals (NCs) with unique reactivities on account of their characteristic redox properties. In the present work, we present a facile POM‐mediated one‐pot aqueous synthesis method for the production of single‐crystalline Pd NCs with controlled shapes and sizes. The POMs could function as both reducing and stabilizing agents in the formation of NCs, and thus gave a fine control over the nucleation and growth kinetics of NCs. The prepared POM‐stabilized Pd NCs exhibited excellent catalytic activity and stability for electrocatalytic (formic acid oxidation) and catalytic (Suzuki coupling) reactions compared to Pd NCs prepared without the POMs. This shows that the POMs play a pivotal role in determining the catalytic performance, as well as the growth, of NCs. We envision that the present approach can offer a convenient way to develop efficient NC‐based catalyst systems.     

Advancements in subsea riser analysis using quasi-rotations and the Newton–Raphson method

Beam structures undergoing finite deflections and rotations in space have extensive application in the subsea industry particularly for the analysis of holistic systems with larger numbers of mooring and riser components. In using the finite element analysis approach, there is an increasing requirement for large element sizes which preserve accuracy with regard to the coupling of axial, bending and torsion response.The authors outline a method for improving the current state of practice for the analysis of riser systems. The approach draws on the convected coordinates method, Euler–Bernoulli beam theory, the principle of virtual work and the finite element method. Two quasi-rotation measures are developed including a quasi-material rotation definition for rotational deformation relative to the convected axis of a beam and a quasi-space rotation definition to deal with the path dependent nature of rotations in three dimensions.The novel aspect of this work is to relate the rate of change of the quasi-material rotation vector along the beam axis to a linear transformation of the beam axis rate-of-rotation vector through utilising the convected coordinates axes system. In this way, incremental values of quasi-material rotation are directly linked to incremental values of nodal quasi-space rotation and a global Newton–Raphson solution technique for interconnecting beam elements is straightforward to assemble.Furthermore, this leads to accurate definitions of coupled axial, bending and torque response for beams with significant deflection. The approach has particular advantages in the analysis of subsea riser sections. Also, the accuracy of the solution is preserved for a fewer number of elements compared to alternative solutions for computationally sensitive load cases with highly non-linear loading regimes.     

Multiferroicity in La1/2Nd1/2FeO3 nanoparticles

Nano-sized La_1/2Nd_1/2FeO₃ (LNF) powder is synthesized by the sol–gel citrate method. The Rietveld refinement of the X-ray diffraction profile of the sample at room temperature (303 K) shows the orthorhombic phase with Pbnm symmetry. The particle size is obtained by transmission electron microscope. The antiferromagnetic nature of the sample is explained using zero field cooled and field cooled magnetisation and the corresponding hysteresis loop. A signature of weak ferromagnetic phase is observed in LNF at low temperature which is explained on the basis of spin glass like behaviour of surface spins. The dielectric relaxation of the sample has been investigated using impedance spectroscopy in the frequency range from 42 Hz to 1 MHz and in the temperature range from 303 K to 513 K. The Cole–Cole model is used to analyse the dielectric relaxation of LNF. The frequency dependent conductivity spectra follow the power law. The magneto capacitance measurement of the sample confirms its multiferroic behaviour.     

An evaluation of semidefinite programming based approaches for discrete lot-sizing problems

The present work is intended as a first step towards applying semidefinite programming models and tools to discrete lot-sizing problems including sequence-dependent changeover costs and times. Such problems can be formulated as quadratically constrained quadratic binary programs. We investigate several semidefinite relaxations by combining known reformulation techniques recently proposed for generic quadratic binary problems with problem-specific strengthening procedures developed for lot-sizing problems. Our computational results show that the semidefinite relaxations consistently provide lower bounds of significantly improved quality as compared with those provided by the best previously published linear relaxations. In particular, the gap between the semidefinite relaxation and the optimal integer solution value can be closed for a significant proportion of the small-size instances, thus avoiding to resort to a tree search procedure. The reported computation times are significant. However improvements in SDP technology can still be expected in the future, making SDP based approaches to discrete lot-sizing more competitive.     

Self-affinity and nonextensivity of sunspots

In this paper we study the time series of sunspots by using two different approaches, analyzing its self-affine behavior and studying its distribution. The long-range correlation exponent α has been calculated via Detrended Fluctuation Analysis and the power law vanishes to values greater than 11 years. On the other hand, the distribution of the sunspots obeys a q-exponential decay that suggests a non-extensive behavior. This observed characteristic seems to take an alternative interpretation of the sunspots dynamics. The present findings suggest us to propose a dynamic model of sunspots formation based on a nonlinear Fokker–Planck equation. Therefore its dynamic process follows the generalized thermostatistical formalism.