High-pressure NMR study of water exchange on magnetic resonance imaging contrast agents

Abstract

The knowledge of water exchange reaction mechanism in aqueous solutions of Gd³⁺ polyaminocarboxylates is important for the understanding of the relatively slow water exchange rates measured for these complexes. Variable ressure measurements show a change of mechanism from associatively activated on [Gd(H₂O)₈]³⁺ and [Gd(PDTA)(H₂O₂)₂]^? to probably limiting dissociative on the MRI contrast agents [Gd(DOTA)(H₂O)]^?, [Gd(DTPA)(H₂O)]^2? and [Gd(DTPA-BMA)(H₂O)].     

Polyhydroxy fullerenes

Characterization of C₆₀ polyhydroxyfullerenes (PHF) prepared in alkaline media, preparation facilitated by phase-transfer catalyst, presents challenges in determining the chemical structure resulting from the possibility of multiple isomers or analogs with greater or fewer hydroxyl groups from a single reaction mixture. This paper presents the utilization of analytical methods employed in tandem, especially X-ray photoelectron spectroscopy, nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy for semi-quantitative analysis on the number of hydroxyl groups present in PHF. Capillary Electrophoresis was used for purity estimation of the material. Multiple spectra and electropherograms were analyzed using a new simultaneous curve fitting method. The most accurate estimate of hydroxyl groups for C₆₀ polyhydroxy fullerenes obtained is between 16 and 18 allylic hydroxyl groups by combining analytical methods’ results with 5 % accuracy. High precision (reproducibility) of the experiments is observed. Purity of 98 % is estimated by capillary electrophoresis. The size of PHF nanoparticles or aggregates has been determined by atomic force microscopy to be 7.4–14.2 nm. According to the elemental analysis the average probable empirical formula for the most pure PHF at pH 7.1 is C₆₀O₁₇H₁₂Na₅(NaHCO₃)₃(H₂O)₁₃ and the average formula weight is 1,605.9 g/mol. This is the first thorough characterization of PHF in terms of purity.     

Highly Selective Optical Detection of Fe3+ Ions in Aqueous Solution Using Label‐Free Silicon Nanocrystals

High brightness amine‐terminated silicon nanocrystals (Si NCs) have been utilized in a simple and rapid assay for the highly selective and sensitive detection of Fe³⁺ via quenching of their strong blue luminescence, without the need for analyte‐specific labeling groups. Sensitive detection of Fe³⁺ is successfully demonstrated, with a linear relationship observed between luminescence quenching and Fe³⁺ concentration from 5 × 10^?6 to 900 × 10^?6m and a limit of detection of 1.3 × 10^?6m . The Si NCs show excellent selectivity toward Fe³⁺ ions, with no quenching of the luminescence signal induced by the presence of Fe²⁺ ions, allowing for solution phase discrimination between the ionic species in different charge states.     

Concise Construction of the ACDE Ring System of Calyciphylline A Type Alkaloids by a [5+2] Cycloaddition

A concise route for construction of the ACDE ring skeleton in calyciphylline A type alkaloids was developed using an intramolecular [5+2] cycloaddition reaction of an oxidopyrylium species bearing a tetrasubstituted olefin. Key to the success of this reaction was the combination of acid and base, which accelerated the construction of this skeleton containing a spiro ring and vicinal quaternary carbon centers. The resultant tricyclic ADE ring compound was converted to an ACDE ring model through C−H oxidation and an aza-Wittig reaction.     

Transport properties of ephedrine hydrochloride through poly(vinyl alcohol) matrices—a simple method for enantiomeric differentiation

Equilibrium and transport properties have been investigated of ephedrines, a class of sympathomimetic amines, through cryogel membranes of poly(vinyl alcohol) (PVA). The effect of the PVA (10 to 18 % (w/v)) on the release properties of (1S,2R)-(+)-ephedrine hydrochloride has been discussed on the basis of partition–diffusion and power-law models. The effect of PVA concentration on the swelling degree of PVA–ephedrine matrices have been measured, allowing the estimation of the volume fraction of polymer in the gel. Ephedrine release rate constants, computed by using a first-order kinetics approach, have been modeled by using free-volume and hydrodynamic-scaling models. Differences in the release properties of the ephedrine isomers, (1S,2R)-(+)- and (1R,2S)-(?)-ephedrine as their hydrochlorides, have also been studied at different temperatures. The release kinetic constants and the corresponding activation energies show a marked discrimination between the two ephedrine isomers. This suggests that PVA cryogel membranes possess high potential for enantiomeric differentiation.     

Colouring a graph frugally

We prove that any graph with maximum degree sufficiently large, has a proper vertex colouring using +1 colours such that each colour class appears at most log⁸ times in the neighbourhood of any vertex. We also show that for 1, the minimum number of colours required to colour any such graph so that each vertex appears at most times in the neighbourhood of any vertex is (+^1+1//), showing in particular that when =log/loglog, such a colouring cannot always be achieved with O() colours. We also provide a polynomial time algorithm to find such a colouring. This has applications to the total chromatic number of a graph.The second two authors were supported by NATO Collaborative Research Grant #CRG950235.