Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Rheology and phase behavior of poly(n-butyl acrylate)-block-poly(acrylic acid) in aqueous solution

The surface activity and the rheological properties of aqueous solutions of the amphiphilic block copolymer poly(n-butyl acrylate)-block-poly(acrylic acid) (PnBA-b-PAA) were studied as a function of the degree of neutralization, alpha, of the poly(acrylic acid) block. Although the block copolymer spontaneously forms spherical micelles having a stretched PAA corona and a collapsed PnBA core in water for alpha > 0.1, the solutions do not exhibit any surface activity at this degree of neutralization. Cryo-TEM micrographs show that the radii of the hydrophobic core of the largest micelles are as long as the length of the hydrophobic chain. The micelles, however, have a broad size distribution, and on average, as shown by SANS, the micelles are only about half as long. At concentrations as low as 1 wt %, the solutions exhibit highly viscoelastic behavior and have a yield stress value depending on alpha. The globular micelles are highly ordered in the bulk phase, and the viscoelastic properties are a result of the dense packing of the micelles. The addition of salt or cationic surfactants dramatically decreases the viscosity of the solution. The observed properties seem to be due to electrostatic interactions between the PAA chains of the micelles.     

Stray field magnetic resonance tomography using ferromagnetic spheres

The methodology for obtaining two- and three-dimensional magnetic resonance images by using azimuthally symmetric dipolar magnetic fields from ferromagnetic spheres is described. We utilize the symmetric property of a geometric sphere in the presence of a large externally applied magnetic field to demonstrate that a complete two- or three-dimensional structured rendering of a sample can be obtained without the motion of the sample relative to the sphere. Sequential positioning of the integrated sample-sphere system in an external magnetic field at various angular orientations provides all the required imaging slices for successful computerized tomographic image reconstruction. The elimination of the requirement to scan the sample relative to the ferromagnetic tip in this imaging protocol is a potentially valuable simplification compared to previous scanning probe magnetic resonance imaging proposals.     

New bounds for codes over finite Frobenius rings

We give further results on the question of code optimality for linear codes over finite Frobenius rings for the homogeneous weight. This article improves on the existing Plotkin bound derived in an earlier paper (Greferath and O’Sullivan, Discr Math 289:11–24, 2004) and suggests a version of a Singleton bound. We also present some families of codes meeting these new bounds.     

Smallest close to regular bipartite graphs without an almost perfect matching

A graph G is close to regular or more precisely a （d, d ＋ k）-graph, if the degree of each vertex of G is between d and d ＋ k. Let d ≥ 2 be an integer, and let G be a connected bipartite （d, d＋k）-graph with partite sets X and Y such that ｜X｜- ｜Y｜＋1. If G is of order n without an almost perfect matching, then we show in this paper that·n ≥ 6d ＋7 when k = 1,·n ≥ 4d＋ 5 when k = 2,·n ≥ 4d＋3 when k≥3.Examples will demonstrate that the given bounds on the order of G are the best possible.     

PCA and Kriging for the efficient exploration of consistency regions in Uncertainty Quantification

For stationary power sources such as utility boilers, it is useful to dispose of parametric models able to describe their behavior in a wide range of operating conditions, to predict some Quantities of Interest (QOIs) that need to be consistent with experimental observations. The development of predictive simulation tools for large scale systems cannot rely on full-order models, as the latter would lead to prohibitive costs when coupled to sampling techniques in the model parameter space. An alternative approach consists of using a Surrogate Model (SM). As the number of QOIs is often high and many SMs need to be trained, Principal Component Analysis (PCA) can be used to encode the set of QOIs in a much smaller set of scalars, called PCA scores. A SM is then built for each PCA score rather than for each QOI. The advantage of reducing the number of variables is twofold: computational costs are reduced (less SMs need to be trained) and information is preserved (correlation among the original variables).The strategy is applied to a CFD model simulating the Alstom 15 MW_th oxy-pilot Boiler Simulation Facility (BSF). In practice, experiments cannot provide full coverage of the pulverized-coal utility boiler due to both practicality and costs. Values of the model’s parameters which guarantee consistency with the experimental data of this test facility for 121 QOIs are found, by training a SM based on the combination of Kriging and PCA, using only 5 latent variables.     

The Avogadro Constant for the Definition and Realization of the Mole

The International System of Units’ (SI) base unit of the quantity “amount of substance” is the mole (symbol: mol). After the revision of the SI to be implemented in 2019, when all SI units will be based solely on constants, the mole will be defined through a fixed value of the Avogadro constant N_A. One mole contains exactly 6.02214076 × 10²³ elementary entities, meaning the mole will no longer be linked to the kilogram. Currently, the mole is defined via the mass of exactly 0.012 kg of the ¹²C isotope which links it to the kilogram prototype. The history, changes, and implications of the revised definition of the mole are discussed here from the chemist's point of view. The ability to count entities such as atoms or molecules (precisely enough to enable a revision of the SI and preserve consistency of previous and future measurements) is crucial. This is achieved with the realization (Mise en Pratique) based on the X‐ray‐crystal density (XRCD) method (counting the atoms in a silicon sphere). The determination of N_A, focusing on the measurement of the molar mass of silicon highly enriched in the ²⁸Si isotope, with the lowest uncertainty so far, is presented.     

Enhancements in full‐field PIXE imaging—Large area elemental mapping with increased lateral resolution devoid of optics artefacts

The combination of a pn‐junction charge‐coupled device‐based pixel detector with a poly‐capillary X‐ray optics was installed and examined at the Helmholtz‐Zentrum Dresden‐Rossendorf. The set‐up is intended for particle‐induced X‐ray emission imaging to survey the trace elemental composition of flat/polished geological samples. In the standard configuration, a straight X‐ray optics (20 μm capillary diameter) is used to guide the emitted photons from the sample towards the detector with nearly 70 000 pixels. Their dimensions of 48 × 48 μm² are the main limitation of the lateral resolution. This limitation can be bypassed by applying a dedicated subpixel algorithm to recalculate the footprint of the photon's electron cloud in the detector. The lateral resolution is then mainly determined by the capillary's diameter. Nevertheless, images are still superimposed by the X‐ray optics pattern. The optics' capillaries are grouped in hexagonal bundles resulting in a reduced transmission of X‐rays in the boundary regions. This influence can be largely suppressed by combining a series of short measurements at slightly shifted positions using a precision stage and correcting the image data for this shifting. The use of a subpixel grid for the image reconstruction allows a further increase of the spatial resolution. This approach of image‐stacking and multiframe super‐resolution in combination with the subpixel correction algorithm is presented and illustrated with experimental data. Additionally, a flat‐field correction is shown to remove the remaining imaging inhomogeneity caused by non‐uniform X‐ray transmission. The described techniques can be used for all X‐ray spectrometry methods using an X‐ray camera to obtain high‐quality elemental images.