Stability and structure of mixed-ligand metal ion complexes that contain Ni2+, Cu2+, or Zn2+, and Histamine, as well as adenosine 5'-triphosphate (ATP4-) or uridine 5'-triphosphate (UTP(4-): an intricate network of equilibria

With a view on protein–nucleic acid interactions in the presence of metal ions we studied the “simple” mixed‐ligand model systems containing histamine (Ha), the metal ions Ni²⁺, Cu²⁺, or Zn²⁺ (M²⁺), and the nucleotides adenosine 5′‐triphosphate (ATP^4?) or uridine 5′‐triphosphate (UTP^4?), which will both be referred to as nucleoside 5′‐triphosphate (NTP^4?) . The stability constants of the ternary M(NTP)(Ha)^2? complexes were determined in aqueous solution by potentiometric pH titrations. We show for both ternary‐complex types, M(ATP)(Ha)^2? and M(UTP)(Ha)^2?, that intramolecular stacking between the nucleobase and the imidazole residue occurs and that the stacking intensity is approximately the same for a given M²⁺ in both types of complexes: The formation degree of the intramolecular stacks is estimated to be 20 to 50 %. Consequently, in protein–nucleic acid interactions imidazole–nucleobase stacks may well be of relevance. Furthermore, the well‐known formation of macrochelates in binary M²⁺ complexes of purine nucleotides, that is, the phosphate‐coordinated M²⁺ interacts with N7, is confirmed for the M(ATP)^2? complexes. It is concluded that upon formation of the mixed‐ligand complexes the M²⁺? N7 bond is broken and the energy needed for this process corresponds to the stability differences determined for the M(UTP)(Ha)^2? and M(ATP)(Ha)^2? complexes. It is, therefore, possible to calculate from these stability differences of the ternary complexes the formation degrees of the binary macrochelates: The closed forms amount to (65±10) %, (75±8) %, and (31±14) % for Ni(ATP)^2?, Cu(ATP)^2?, and Zn(ATP)^2?, respectively, and these percentages agree excellently with previous results obtained by different methods, confirming thus the internal validity of the data and the arguments used in the evaluation processes. Based on the overall results it is suggested that M(ATP)^2? species, when bound to an enzyme, may exist in a closed macrochelated form only, if no enzyme groups coordinate directly to the metal ion.     

Preparation,Characterization and Application of Modified Surfaces with 3,5-Bis(3,5-dinitrobenzoyl-amino) benzoic acid

Summary: The spontaneous adsorption of the dendron 3,5-Bis (3,5-dinitrobenzoylamino) benzoic acid (D-NO₂) onto gold and carbon electrodes produced conductive surfaces with electroactive chemical functions. A comparative electrochemical behavior of both electrodes after dendron immobilization led us to conclude that the self-assembly of D-NO₂ on carbon is faster and stronger. Considering this advantage, the surface of magnetic maghemite nanoparticles (MNPs) was modified using D-NO₂. Firstly, MNPs were modified with APS as silane coupling agent and afterwards, D-NO₂ was covalently attached to the surface, achieving nitro-functionalized MNPs. Subsequently, the immobilization of these modified MNPs onto glassy carbon surfaces was explored to generate a novel platform promising for biosensors development.     

Determination of nitrate with a flow-injection system combining square-wave polarographic detection with on-line deaeration

The combination of a flow-injection system with square-wave polarography and on-line deaeration is applied to the determination of nitrate, utilizing the catalytic reaction between nitrate and uranyl ion. The method is simple, rapid (60 samples h^?1), sensitive and accurate, with a detection limit of 2 μM nitrate. The method has been applied to the determination of nitrate in drinking and river waters.     

The Binary System BaF2/AlF3

The system BaF₂/AlF₃ is investigated by X-ray and D.T.A., and the liquid-solid phase diagram is established. Five ternary fluorides are disclosed: trimorphic BaAlF₅, Ba₃Al₂F₁₂, Ba₅AlF₁₉, polymorphic Ba₃AlF₉ and Ba₅AlF₁₃. Neutron thermodiffractometry experiments are performed to specify some parts of the diagram. The cell parameters of the fluorides are given and the results are discussed and compared with those of the previous works.     

Measurability of semimartingale characteristics with respect to the probability law

Given a càdlàg process X$X$ on a filtered measurable space, we construct a version of its semimartingale characteristics which is measurable with respect to the underlying probability law. More precisely, let _Psem${\mathfrak{P}}_{sem}$ be the set of all probability measures P$P$ under which X$X$ is a semimartingale. We construct processes (B^P,C,ν^P)$(B^P,C,{\nu }^P)$ which are jointly measurable in time, space, and the probability law P$P$, and are versions of the semimartingale characteristics of X$X$ under P$P$ for each P∈_Psem$P\in {\mathfrak{P}}_{sem}$. This result gives a general and unifying answer to measurability questions that arise in the context of quasi-sure analysis and stochastic control under the weak formulation.     

Properties that Four-Dimensional Objects Cannot Have

The paper argues that four-dimensionalism is incompatible with the existence of “additively cumulative” properties, including mass, volume, and electrical charge. These properties add up over disjoint objects: for example, the mass of a whole composed of two disjoint objects is a sum of the individual masses of the objects. The difficulty with such properties for four-dimensionalism stems from the way this theory makes persistence depend on the existence of disjoint objects at disjoint times. I consider various possible responses to this difficulty and conclude that they all fail.     

Error estimates on anisotropic elements for functions in weighted Sobolev spaces

In this paper we prove error estimates for a piecewise average interpolation on anisotropic rectangular elements, i.e., rectangles with sides of different orders, in two and three dimensions.

Our error estimates are valid under the condition that neighboring elements have comparable size. This is a very mild assumption that includes more general meshes than those allowed in previous papers. In particular, strong anisotropic meshes arising naturally in the approximation of problems with boundary layers fall under our hypotheses.

Moreover, we generalize the error estimates allowing on the right-hand side some weighted Sobolev norms. This extension is of interest in singularly perturbed problems.

Finally, we consider the approximation of functions vanishing on the boundary by finite element functions with the same property, a point that was not considered in previous papers on average interpolations for anisotropic elements.

As an application we consider the approximation of a singularly perturbed reaction-diffusion equation and show that, as a consequence of our results, almost optimal order error estimates in the energy norm, valid uniformly in the perturbation parameter, can be obtained.

     

Deformation Techniques for Sparse Systems

We exhibit a probabilistic symbolic algorithm for solving zero-dimensional sparse systems. Our algorithm combines a symbolic homotopy procedure, based on a flat deformation of a certain morphism of affine varieties, with the polyhedral deformation of Huber and Sturmfels. The complexity of our algorithm is cubic in the size of the combinatorial structure of the input system. This size is mainly represented by the cardinality and mixed volume of Newton polytopes of the input polynomials and an arithmetic analogue of the mixed volume associated to the deformations under consideration. Research was partially supported by the following grants: UBACyT X112 (2004–2007), UBACyT X847 (2006–2009), PIP CONICET 2461, PIP CONICET 5852/05, ANPCyT PICT 2005 17-33018, UNGS 30/3005, MTM2004-01167 (2004–2007), MTM2007-62799 and CIC 2007–2008.     

A mathematical model for the first-pass dynamics of antibiotics acting on the cardiovascular system

We present a preliminary first-pass dynamic model for delivery of drug compounds to the lungs and heart. We use a compartmental mass-balance approach to develop a system of nonlinear differential equations for mass accumulated in the heart as a result of intravenous injection. We discuss sensitivity analysis as well as methodology for minimizing mass in the heart while maximizing mass delivered to the lungs on a first circulatory pass.