The rates of the exchange reactions between [Gd(DTPA)]2- and the endogenous ions Cu2+ and Zn2+: a kinetic model for the prediction of the in vivo stability of [Gd(DTPA)]2-, used as a contrast agent in magnetic resonance imaging

The kinetic stability of the complex [Gd(DTPA)]2- (H5DTPA = diethylenetriamine-N,N,N',N",N"-pentaacetic acid), used as a contrast-enhancing agent in magnetic resonance imaging (MRI), is characterised by the rates of the exchange reactions that take place with the endogenous ions Cu2+ and Zn2+. The reactions predominantly occur through the direct attack of Cu2+ and Zn2+ on the complex (rate constants are 0.93+/-0.17 M(-1) s(-1) and (5.6+/-0.4) x 10(-2)M(-1) S(-1), respectively). The proton-assisted dissociation of [Gd(DTPA)]2- is relatively slow (k1 = 0.58+/-0.22 M(-1) s(-1)), and under physiological conditions the release of Gd3+ predominantly occurs through the reactions of the complex with the Cu2+ and Zn2+ ions. To interpret the rate data, the rate-controlling role of a dinuclear intermediate was assumed in which a glycinate fragment of DTPA is coordinated to Cu2+ or Zn2+. In the exchange reactions between [Gd-(DTPA)]2- and Eu3+, smaller amounts of Cu2+ and Zn2+ and their complexes with the amino acids glycine and cysteine have a catalytic effect. In a model of the fate of the complex in the body fluids, the excretion and the "dissociation" of [Gd(DTPA)]2- are regarded as parallel first-order processes, and by 10 h after the intravenous administration the ratio of the amounts of "dissociated" and excreted [Gd(DTPA)]2- is constant. From about this time, 1.71% of the injected dose of [Gd(DTPA)]2- is "dissociated". The results of equilibrium calculations indicate that the Gd3+ released from the complex is in the form of Gd3+-citrate.     

Local–Global Minimum Property in Unconstrained Minimization Problems

The main goal of this paper is to prove some new results and extend some earlier ones about functions, which possess the so-called local–global minimum property. In the last section, we show an application of these in the theory of calculus of variations.     

HPLC separation of diastereomers of Ln(III)-ethylenepropylene-triamine-pentaacetate complexes. Direct assessment of their water exchange rate

The diastereomers of two Ln(III)-EPTPA derivatives have been separated by reversed-phase HPLC, and the water exchange rate on their Gd(III) complexes has been directly determined by 17O NMR (H5EPTPA = ethylenepropylene-triamine-pentaacetic acid).     

Phase boundaries as agents of structural change in macromolecules

We model long rod-like molecules, such as DNA and coiled-coil proteins, as one-dimensional continua with a multi-well stored energy function. These molecules suffer a structural change in response to large forces, characterized by highly typical force-extension behavior. We assume that the structural change proceeds via a moving folded/unfolded interface, or phase boundary, that represents a jump in strain and is governed by the Abeyaratne–Knowles theory of phase transitions. We solve the governing equations using a finite difference method with moving nodes to represent phase boundaries. Our model can reproduce the experimental observations on the overstretching transition in DNA and coiled-coils and makes predictions for the speed at which the interface moves. We employ different types of kinetic relations to describe the mobility of the interface and show that this leads to different classes of experimentally observed force-extension curves. We make connections with several existing theories, experiments and simulation studies, thus demonstrating the effectiveness of the phase transitions-based approach in a biological setting.     

Characterization of quasi-arithmetic means without regularity condition

Acta Mathematica Hungarica - We show that bisymmetry, which is an algebraic property, has a regularity improving feature. More precisely, we prove that every bisymmetric, partially strictly...     

Study of translational,librational and intra-molecular motion of adsorbed liquid water monolayers at various TiO2 interfaces

Equilibrium classical molecular dynamics (MD) simulations have been performed to investigate the vibrational motion of water in contact with rutile-(110), rutile-(100), rutile-(001), anatase-(101) and anatase-(001) surfaces at room temperature (300?K). The vibrational density of states (VDOS) of the first adsorbed monolayer of liquid water has been analysed for each surface. These have been compared with reported experimental INS values involving rutile and anatase polymorph surfaces, along with ab initio MD results. It is observed that good qualitative agreement is obtained for the rutile-(110) and the anatase-(101) surfaces with the corresponding experimental VDOS. A significant contribution from librational dynamics is found for planar rutile surfaces, but no such demarcation is seen in the experimental VDOS.     

Hydrogen bond dynamical properties of adsorbed liquid water monolayers with various TiO2 interfaces

Equilibrium classical molecular dynamics (MD) simulations have been performed to investigate the hydrogen-bonding kinetics of water in contact with rutile-(110), rutile-(101), rutile-(100), and anatase-(101) surfaces at room temperature (300?K). It was observed that anatase-(101) exhibits the longest-lived hydrogen bonds in terms of overall persistence, followed closely by rutile-(110). The relaxation times, defined as the integral of the autocorrelation of the hydrogen bond persistence function, were also longer for these two cases, while decay of the autocorrelation function was slower. The increased number and overall persistence of hydrogen bonds in the adsorbed water monolayers at these surfaces, particularly for anatase-(101), may serve to promote possible water photolysis activity thereon.     

Large Hecke eigenvalues and an Omega result for non-Saito–Kurokawa lifts

The Ramanujan Journal - We prove a result on the distribution of Hecke eigenvalues, $$\mu _F(p^r)$$ (for $$r=1,2$$ or 3) of a non-Saito–Kurokawa lift F of degree 2. As a consequence, we...     

The equality problem in the class of conjugate means

Let ${I\subset\mathbb{R}}$ be a nonempty open interval and let ${L:I^2\to I}$ be a fixed strict mean. A function ${M:I^2\to I}$ is said to be an L-conjugate mean on I if there exist ${p,q\in{]}0,1]}$ and a strictly monotone and continuous function φ such that $$M(x,y):=\varphi^{-1}(p\varphi(x)+q\varphi(y)+(1-p-q)\varphi(L(x,y)))=:L_\varphi^{(p,q)}(x,y),$$ for all ${x,y\in I}$ . Here L(x, y) is a fixed quasi-arithmetic mean. We will solve the equality problem in this class of means.