Dissociation Kinetics of Open‐Chain and Macrocyclic Gadolinium(III)‐Aminopolycarboxylate Complexes Related to Magnetic Resonance Imaging: Catalytic Effect of Endogenous Ligands

The kinetics of the metal exchange reactions between open‐chain Gd(DTPA)^2? and Gd(DTPA‐BMA), macrocyclic Gd(DOTA)^? and Gd(HP‐DO3A) complexes, and Cu²⁺ ions were investigated in the presence of endogenous citrate, phosphate, carbonate and histidinate ligands in the pH range 6–8 in NaCl (0.15 M ) at 25 °C. The rates of the exchange reactions of Gd(DTPA)^2? and Gd(DTPA‐BMA) are independent of the Cu²⁺ concentration in the presence of citrate and the reactions occur via the dissociation of Gd³⁺ complexes catalyzed by the citrate ions. The HCO₃^?/CO₃^2? and H₂PO₄^? ions also catalyze the dissociation of complexes. The rates of the dissociation of Gd(DTPA‐BMA), catalyzed by the endogenous ligands, are about two orders of magnitude higher than those of the Gd(DTPA)^2?. In fact near to physiological conditions the bicarbonate and carbonate ions show the largest catalytic effect, that significantly increase the dissociation rate of Gd(DTPA‐BMA) and make the higher pH values (when the carbonate ion concentration is higher) a risk‐factor for the dissociation of complexes in body fluids. The exchange reactions of Gd(DOTA)^? and Gd(HP‐DO3A) with Cu²⁺ occur through the proton assisted dissociation of complexes in the pH range 3.5–5 and the endogenous ligands do not affect the dissociation rates of complexes. More insights into the interaction scheme between Gd(DTPA‐BMA) and Gd(DTPA)^2? and endogenous ligands have been obtained by acquiring the ¹³C NMR spectra of the corresponding diamagnetic Y(III)‐complexes, indicating the increase of the rates of the intramolecular rearrangements in the presence of carbonate and citrate ions. The herein reported results may have implications in the understanding of the etiology of nephrogenic systemic fibrosis, a rare disease that has been associated to the administration of Gd‐containing agents to patients with impaired renal function.     

Nonlinear Analysis of a Cantilever Pipe Containing Pulsatile Flow

In this paper we investigate the nonlinear dynamics of a cantilever elastic pipe that contains pulsatile flow. The equation of motion was derived by using Hamiltonian action function. We use Galerkin's technique to include only finite number of spatial modes in the solution.The stability chart of the time-varying system was computed in the space of the relative perturbation amplitude of the flow velocity and dimensionless forcing frequency using an efficient numerical method based on Chebyshev polynomials. In the near of some critical regions bifurcation diagrams were also computed which show secondary Hopf bifurcations and phase locking followed by chaotic motion.     

Lanthanide‐Based Functional Misfit‐Layered Nanotubes

The synthesis of nanotubes from layered compounds has generated substantial scientific interest. “Misfit” layered compounds (MLCs) of the general formula [(MX)_1+x]_m[TX₂]_n, where M can include Pb, Sb, rare earths; T=Cr, Nb, and X=S, Se can form layered structures, even though each sub‐system alone is not necessarily a layered or a stable compound. A simple chemical method is used to synthesize these complex nanotubes from lanthanide‐based misfit compounds. Quaternary nanotubular structures formed by partial substitution of the lanthanide atom in nanotubes by other elements are also confirmed. The driving force and mechanism of formation of these nanotubes is investigated by systematic temperature and time‐dependent studies. A stress‐inducement mechanism is proposed to explain the formation of the nanotubes. The resulting materials may find applications in fields that include thermoelectrics, light emitters, and catalysis and address fundamental physical issues in low dimensions.     

Optimisation of solid-state urea clathrate formation as a chemical separation method coupled to compound-specific stable carbon isotope analysis

Solid-state urea clathrate formation (SSUCF) as a chemical separation method prior to stable carbon isotope fingerprinting of diesel fuel contaminations was studied. The stable carbon isotope ratios (δ¹³C) of n-alkanes in diesel fuel can be used to trace the origin of a contamination. The accurate measurement of the stable isotopic composition of individual compounds requires baseline separation from any other co-eluting compounds. For this purpose silica gel column chromatography (SGCC) and SSUCF were applied. Detailed optimisation of SSUCF was performed: different activators, clathrate formation temperatures, activator volumes, clathrate formation times and sample capacity were investigated. The main benefits of the developed method are reduced clathrate formation time and increased recoveries for lower molecular weight n-alkanes. The recoveries of the developed SSUCF method ranged between 63 and 100% for C10–C24 n-alkanes with relative standard deviation no more than 7%. The precision of the gas chromatography-isotope ratio mass spectrometry measurement was acceptable with a standard deviation of the δ¹³C values ranging between 0.08 and 0.15‰. The absence of isotopic fractionation was also investigated.

The robustness of the method was tested within a model experiment. Nine different water samples including distilled water, tap water, river water, industrial wastewaters and groundwater samples were spiked with the same diesel fuel. The water samples were extracted with n-hexane and after purification with both SGCC and SSUCF n-alkanes were measured. The δ¹³C values of n-alkanes were found to be similar for all samples. The importance of sample purification prior to compound-specific isotope analysis (CSIA) was also demonstrated within this model experiment by analysing samples from different stages of the sample preparation.

Our results show that the proposed method can remarkably improve the precision of compound-specific stable carbon isotope analysis of n-alkanes originating from diesel contamination of the aquatic environment.     

Phosphetes via Transition Metal Free Ring Closure – Taking the Proper Turn at a Thermodynamic Crossing

A transition metal free route to phosphetes featuring an exocyclic alkene unit is presented. In this approach phosphanides are added to a variety of diynes generating phosphaallylic intermediates which depending on the reaction conditions transform either to phosphetes or the corresponding phospholes. Investigation of the reaction mechanism by combined quantum chemical and experimental means identifies phosphole formation as thermodynamically controlled reaction path, whereas kinetic control furnishes the corresponding phosphetes. Structural and luminescence properties of the rare class of phosphetes are explored, as well as for selected key intermediates.     

The Chromatic Spectrum of Mixed Hypergraphs

 A mixed hypergraph is a triple ℋ=(X, ?, ?), where X is the vertex set, and each of ?, ? is a list of subsets of X. A strict k-coloring of ℋ is a surjection c:X→{1,…,k} such that each member of ? has two vertices assigned a common value and each member of ? has two vertices assigned distinct values. The feasible set of H is {k: H has a strict k-coloring}. Among other results, we prove that a finite set of positive integers is the feasible set of some mixed hypergraph if and only if it omits the number 1 or is an interval starting with 1. For the set {s,t} with 2≤s≤t−2, the smallest realization has 2t−s vertices. When every member of ?∪? is a single interval in an underlying linear order on the vertices, the feasible set is also a single interval of integers. Received: May 24, 1999 Final version received: August 31, 2000