Importance of Outer‐Sphere and Aggregation Phenomena in the Relaxation Properties of Phosphonated Gadolinium Complexes with Potential Applications as MRI Contrast Agents

A series composed of a tetra‐, a tris‐ and a bisphosphonated ligand based on a pyridine scaffold ( L⁴ , L³ and L² , respectively) was studied within the frame of lanthanide (Ln) coordination. The stability constants of the complexes formed with lanthanide cations (Ln=La, Nd, Eu, Gd, Tb, Er and Lu) were determined by potentiometry in aqueous solutions (25.0 °C, 0.1 M NaClO₄), showing that the tetraphosphonated complexes are among the most stable Ln^III complexes reported in the literature. The complexation of L⁴ was further studied by different titration experiments using mass spectrometry and various spectroscopic techniques including UV/Vis absorption, and steady state and time‐resolved luminescence (Ln=Eu and Tb). Titration experiments confirmed the formation of highly stable [Ln L⁴ ] complexes. ³¹P NMR experiments of the Lu L⁴ complex revealed an intramolecular interconversion process which was studied at different temperatures and was rationalized by DFT modelling. The relaxivity properties of the Gd^III complexes were studied by recording their ¹H NMRD profiles at various temperatures, by temperature dependent ¹⁷O NMR experiments (Gd L⁴ ) and by pH dependent relaxivity measurements at 0.47 T (Gd L³ and Gd L² ). In addition to the high relaxivity values observed for all complexes, the results showed an important second‐sphere contribution to relaxivity and pH dependent variations associated with the formation of aggregates for Gd L² and Gd L³ . Finally, intravenous injection of Gd L⁴ to a mouse was followed by dynamic MRI imaging at 1.5 T, which showed that the complex can be immediately found in the blood stream and rapidly eliminated through the liver and in large part through the kidneys.     

Hydrolysis of mefenpyrdiethyl: an analytical and DFT investigation

The hydrolysis of the herbicide safener mefenpyrdiethyl (1-(2, 4-dichlorophenyl)-4, 5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylic acid diethyl ester) was investigated in aqueous solutions in the pH range from 2 to 9 and the temperature range from 298 to 323 K. The kinetics of hydrolysis were pseudo first order and were found to be strongly pH and temperature dependent. While near-constant in acidic medium, the hydrolysis rates strongly increased in alkaline pH, and total hydrolysis was observed at pH 11. Two main hydrolysis products, mefenpyrethyl (monoester) and mefenpyr (dicarboxylic acid) were isolated by ultrahigh-pressure liquid chromatography (UHPLC) and characterized using high-resolution Fourier transform ion cyclotron resonance mass spectroscopy (ICR-FT/MS) as well as ¹H, ¹³C and 2D NMR analyses. Additionally, a density functional theory (DFT) investigation explained the stability of the pesticide at pH 7 and the high reactivity of the pesticide in alkaline medium. The key nucleophilic reaction partner is hydroxyl ions instead of neutral water molecules. Furthermore, the calculated activation barrier for hydrolysis in alkaline medium is in agreement with the extrapolated and experimentally determined activation barrier at pH 14.     

Effect of some physical and chemical parameters on fluoride removal by nanofiltration

In natural waters, fluoride ions are necessary and beneficial for the human being. At higher level of F⁻ in water, it is toxic and detrimental to human health, leading to serious problems such as dental and skeleton fluorosis. According to the World Health Organization, the acceptable concentrations of fluoride in potable water are in the range of 0.7–1.5 mg L⁻¹. Various treatment technologies for fluoride removal from water have been used such as ion exchange, adsorption and membrane processes. In the present study, removal of fluoride ions from aqueous solutions was investigated using a polyamide thin film composite nanofiltration membrane denoted as HL 2514 T from Osmonics Company. Through this membrane, the mechanism of transport was investigated. The Kedem–Katchelsky model was applied in order to determine phenomenological parameters σ and P _s, respectively, the reflection coefficient of the membrane and the solute permeability of ions. The convective and diffusive parts of the mass transfer were quantified. The retention of monovalent and bivalent salts by this membrane shows that it is negatively charged. In the second part, retention of fluoride anions was investigated. Results show that the retention of fluoride by HL membrane exceeds 80%. The influence of the chemical parameters (feed concentration and ionic strength) and the physical parameters (applied pressure and recovery) on the elimination of fluoride was studied.     

Computational Analysis of Mixing and Scale-Up in Emulsion Polymerization Reactors

Summary: A hybrid multi-zonal/computational fluid dynamics (CFD) framework is currently being developed to aid in the scale-up of high solid content latex production and processing. Poly3D, a commercial laminar CFD code tailored to modelling the mixing of non-Newtonian fluids, has been coupled to a population balance model via a customized interface. CFD is used to generate flow fields inside a series of reactors; this information is then transferred to a multi-zone population balance model to assess the impact of non-homogenous mixing on the evolution of the latex particle size distribution (PSD) when concentrated latex suspension is altered via the addition of a coagulant. The rheological properties of high solid content latexes are sensitive to changes in the PSD, so the flow field is periodically updated if significant changes in the rheological properties of the latex are detected in any of the zones. The details of the models comprising the framework are presented and the utility of the framework is demonstrated.     

Stability estimate for an inverse wave equation and a multidimensional Borg-Levinson theorem

We consider the stability in an inverse problem of determining the potential q entering the wave equation in a bounded smooth domain of Rd from boundary observations. The observation is given by a hyperbolic (dynamic) Dirichlet to Neumann map associated to a wave equation. We prove a log-type stability estimate in determining q from a partial Dirichlet to Neumann map provided that q is a priori known in a neighbourhood of the boundary of the spatial domain and satisfies an additional condition. Next, we use this result to establish a stability estimate related to the multidimensional Borg-Levinson theorem.     

1,3,4‐Thiadiazole, 1,3,4‐thiadiazine, 1,3,6‐thiadiazepane and quinoxaline derivatives from symmetrical hydrazine‐1,2‐dicarbothioamide as well as N,N″‐ethane‐1,2‐diylbis(thiourea) derivatives

Reactions of N,N′‐disubstituted hydrazine‐1,2‐carbothioamides 8a‐c and substituted N,N″‐ethane‐1,2‐diylbis(thioureas) 9a‐c with 2,3,5,6‐tetrachloro‐1,4‐benzoquinone (chloranil, 10a ) and 2,3,5,6‐tetrabromo‐1,4‐benzoquinone (bromanil, 10b ) to form N,N′‐disubstituted 1,3,4‐thiadiazole‐2,5‐diamines 11a‐c , substituted 3‐amino‐6,7‐dichloro‐2,3‐dihydro‐1H‐4,2,1‐benzothiadiazine‐5,8‐diones 12a‐c , 2,3,7,8‐tetrahalothianthrene‐1,4,6,9‐tetrones 13a,b , substituted 5,6,8‐trihalo‐7‐oxo‐3,7‐dihydroquinoxaline‐2H‐carbothioamides 14a‐c, 15a‐c and 7‐substituted imino‐1,3,6‐thiadiazepane‐2‐thiones 16a‐c are reported.     

Accurate measurement of the cutoff wavelength in a microstructured optical fiber by means of an azimuthal filtering technique

A simple self-referenced nondestructive method is proposed for measuring the cutoff wavelength of microstructured optical fibers (MOFs). It is based on the analysis of the time-dependent optical power transmitted through a bow-tie slit rotating in the far-field pattern of the fiber under test. As a first demonstration, the cutoff wavelength of a 2 m MOF sample is found to be close to that provided by numerical predictions (approximately 25 nm higher). Because of the high dynamics of the measurement, the uncertainty is limited to Dlambda= +/-10 nm.     

Shape-induced frustration of hexagonal order in polyhedral colloids

The effect of a nonspherical particle shape and shape polydispersity on the structure of densely packed hard colloidal particles was studied in real space by confocal microscopy. We show that the first layer at the wall of concentrated size-monodisperse but shape-polydisperse polyhedral colloids exhibits significant deviations from a hexagonal lattice. These deviations are identified as bond-orientational fluctuations which lead to percolating "mismatch lines." While the shape-induced geometrical frustration of the hexagonal symmetry suppresses translational order, bond-orientational order is clearly retained, indicating a hexaticlike structure of the polyhedral colloids.     

Multivariate holomorphic Hermite polynomials

The Ramanujan Journal - We introduce holomorphic Hermite polynomials in n complex variables that generalize the Hermite polynomials in n real variables introduced by Hermite in the late 19th...     

Sparsest cut in planar graphs,maximum concurrent flows and their connections with the max-cut problem

We study the sparsest cut problem when the “capacity-demand” graph is planar, and give a combinatorial polynomial algorithm. In this type of graphs there is an edge for each positive capacity and also an edge for each positive demand. We extend this result to graphs with no \(K_5\) minor. We also show how to find a maximum concurrent flow in these two cases. We also prove that the sparsest cut problem is NP-hard if we only impose that the “capacity-demand” graph has no \(K_6\) minor. We use ideas that had been developed for the max-cut problem, and show how to exploit the connections among these problems.