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)].     

A recyclable, self-supported organocatalyst based on a poly(N-heterocyclic carbene)

We report the synthesis and catalytic activity of a polymeric imidazolium salt. In contrast to the well-known resin-supported N-heterocyclic carbenes (NHCs), the material described herein affords a polymer with NHCs orthogonally positioned along a main chain upon generation in situ. The unique structural characteristics of the corresponding poly(NHC)s enabled the materials to display catalytic activities that were similar or superior to those displayed by monomeric analogues. Moreover, the new catalyst was successfully recovered and reused with minimal loss of performance over several cycles.     

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3+3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution.     

Post-lactonization of vinyl polymers containing pendent ester and hydroxymethyl groups

Copolymers of methyl methacrylate with methyl and ethyl α-hydroxymethylacrylate and with α-hydroxymethylstyrene have been prepared with free-radical initiators at temperatures below 80°C. At higher reaction temperatures or under extrusion conditions, alcohol was eliminated and the free hydroxyl content was greatly decreased. All evidence indicates the formation of six-membered lactone groups in this post-polymerization reaction: direct evidence for their formation is lacking, however, since neither infrared nor nuclear magnetic resonance spectra could be used to detect lactonization in this system. The loss of activity from ¹⁴C ester-labeled methyl methacrylate copolymer on heating could be correlated with the extent of lactonization. The degree of lactonization is relatively less with copolymers containing higher amounts of hydroxymethyl groups. The resulting polymers exhibit higher heat distortion temperatures and decreased impact resistance when compared to poly(methyl methacrylate). Attempts were made to incorporate similar lactone structures by cyclocopolymerization with methyl methacrylate of α-methacryloxymethylstyrene or ethyl α-methacryloxymethylacrylate, but only crosslinked polymers or polymers with pendent unsaturation were found.     

Quadratic termination properties of Davidon's new variable metric algorithm

Davidon [1] provides a variable metric algorithm for minimization calculations that achieves quadratic termination without any line searches by a method that uses positive definite second derivative approximations. We give a new and elementary proof of these termination properties. It shows the great freedom allowed by the algorithm in the choice of search directions and it explains the effect of a restart procedure.     

On the global convergence of trust region algorithms for unconstrained minimization

Many trust region algorithms for unconstrained minimization have excellent global convergence properties if their second derivative approximations are not too large [2]. We consider how large these approximations have to be, if they prevent convergence when the objective function is bounded below and continuously differentiable. Thus we obtain a useful convergence result in the case when there is a bound on the second derivative approximations that depends linearly on the iteration number.     

The Balian-Low theorem and regularity of Gabor systems

For any positive real numbers A, B, and d satisfying the conditions , d>2, we construct a Gabor orthonormal basis for L²(ℝ), such that the generating function g∈L²(ℝ) satisfies the condition:∫_ℝ|g(x)|²(1+|x| ^A )/log ^d (2+|x|)dx < ∞ and .     

DNA Origami Rotaxanes: Tailored Synthesis and Controlled Structure Switching

Mechanically interlocked supramolecular assemblies are appealing building blocks for creating functional nanodevices. Herein, we describe the multistep assembly of large DNA origami rotaxanes that are capable of programmable structural switching. We validated the topology and structural integrity of these rotaxanes by analyzing the intermediate and final products of various assembly routes by electrophoresis and electron microscopy. We further analyzed two structure‐switching behaviors of our rotaxanes, which are both mediated by DNA hybridization. In the first mechanism, the translational motion of the macrocycle can be triggered or halted at either terminus. In the second mechanism, the macrocycle can be elongated after completion of the rotaxane assembly, giving rise to a unique structure that is otherwise difficult to access.     

Improved experimental tracking techniques for validating discrete element method simulations of tumbling mills

We report on further developments in the three-dimensional tracking of a particle deep within the tumbling ball charge of an experimental mill. The experimental X-ray program employing the use of bi-planar X-ray angiography now includes the tracking of a typical 6 mm bulk charge particle in three dimensions with a spatial resolution that is accurate to within 0.15 mm. The improved experimental tracking techniques presented were developed for the purpose of generating accurate three-dimensional particle trajectory data against which to validate a numerical method for the simulation of discrete media, namely the discrete element method (DEM). These improvements are complimented with techniques for comparing charge profiles between numerical DEM simulations and three-dimensional experimental trajectory data.