Water exchange rates of water-soluble manganese(III) porphyrins of therapeutical potential.

The activation parameters and the rate constants of the water-exchange reactions of Mn(III)TE-2-PyP(5+) (meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin) as cationic, Mn(III)TnHex-2-PyP(5+) (meso-tetrakis(N-n-hexylpyridinium-2-yl)porphyrin) as sterically shielded cationic, and Mn(III)TSPP(3-) (meso-tetrakis(4-sulfonatophenyl)porphyrin) as anionic manganese(iii) porphyrins were determined from the temperature dependence of (17)O NMR relaxation rates. The rate constants at 298 K were obtained as 4.12 x 10(6) s(-1), 5.73 x 10(6) s(-1), and 2.74 x 10(7) s(-1), respectively. On the basis of the determined entropies of activation, an interchange-dissociative mechanism (I(d)) was proposed for the cationic complexes (DeltaS(double dagger) = approximately 0 J mol(-1) K(-1)) whereas a limiting dissociative mechanism (D) was proposed for Mn(III)TSPP(3-) complex (DeltaS(double dagger) = +79 J mol(-1) K(-1)). The obtained water exchange rate of Mn(III)TSPP(3-) corresponded well to the previously assumed value used by Koenig et al. (S. H. Koenig, R. D. Brown and M. Spiller, Magn. Reson. Med., 1987, 4, 52-260) to simulate the (1)H NMRD curves, therefore the measured value supports the theory developed for explaining the anomalous relaxivity of Mn(III)TSPP(3-) complex. A magnitude of the obtained water-exchange rate constants further confirms the suggested inner sphere electron transfer mechanism for the reactions of the two positively charged Mn(iii) porphyrins with the various biologically important oxygen and nitrogen reactive species. Due to the high biological and clinical relevance of the reactions that occur at the metal site of the studied Mn(iii) porphyrins, the determination of water exchange rates advanced our insight into their efficacy and mechanism of action, and in turn should impact their further development for both diagnostic (imaging) and therapeutic purposes.

Adaptive Mixture Modelling Metropolis Methods for Bayesian Analysis of Non-linear State-Space Models.

We describe a strategy for Markov chain Monte Carlo analysis of non-linear, non-Gaussian state-space models involving batch analysis for inference on dynamic, latent state variables and fixed model parameters. The key innovation is a Metropolis-Hastings method for the time series of state variables based on sequential approximation of filtering and smoothing densities using normal mixtures. These mixtures are propagated through the non-linearities using an accurate, local mixture approximation method, and we use a regenerating procedure to deal with potential degeneracy of mixture components. This provides accurate, direct approximations to sequential filtering and retrospective smoothing distributions, and hence a useful construction of global Metropolis proposal distributions for simulation of posteriors for the set of states. This analysis is embedded within a Gibbs sampler to include uncertain fixed parameters. We give an example motivated by an application in systems biology. Supplemental materials provide an example based on a stochastic volatility model as well as MATLAB code.

Genome-wide mRNA expression correlates of viral control in CD4+ T-cells from HIV-1-infected individuals.

There is great interindividual variability in HIV-1 viral setpoint after seroconversion, some of which is known to be due to genetic differences among infected individuals. Here, our focus is on determining, genome-wide, the contribution of variable gene expression to viral control, and to relate it to genomic DNA polymorphism. RNA was extracted from purified CD4+ T-cells from 137 HIV-1 seroconverters, 16 elite controllers, and 3 healthy blood donors. Expression levels of more than 48,000 mRNA transcripts were assessed by the Human-6 v3 Expression BeadChips (Illumina). Genome-wide SNP data was generated from genomic DNA using the HumanHap550 Genotyping BeadChip (Illumina). We observed two distinct profiles with 260 genes differentially expressed depending on HIV-1 viral load. There was significant upregulation of expression of interferon stimulated genes with increasing viral load, including genes of the intrinsic antiretroviral defense. Upon successful antiretroviral treatment, the transcriptome profile of previously viremic individuals reverted to a pattern comparable to that of elite controllers and of uninfected individuals. Genome-wide evaluation of cis-acting SNPs identified genetic variants modulating expression of 190 genes. Those were compared to the genes whose expression was found associated with viral load: expression of one interferon stimulated gene, OAS1, was found to be regulated by a SNP (rs3177979, p = 4.9E-12); however, we could not detect an independent association of the SNP with viral setpoint. Thus, this study represents an attempt to integrate genome-wide SNP signals with genome-wide expression profiles in the search for biological correlates of HIV-1 control. It underscores the paradox of the association between increasing levels of viral load and greater expression of antiviral defense pathways. It also shows that elite controllers do not have a fully distinctive mRNA expression pattern in CD4+ T cells. Overall, changes in global RNA expression reflect responses to viral replication rather than a mechanism that might explain viral control.

Cambios en el régimen de temperaturas mínimas de la ciudad de Buenos Aires (período 1906 - 1992)

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La importancia del razonamiento inductivo en la formación inicial de profesores

En este trabajo mostramos la importancia del razonamiento inductivo en la enseñanza y aprendizaje de las matemáticas en el nivel de Secundaria y, como consecuencia, la necesidad que tienen los futuros profesores de realizar tareas que fomenten el uso, y por tanto el conocimiento, de este tipo de razonamiento. Pensamos que la reflexión sobre una metodología en la que el razonamiento inductivo esté presente, se debe hacer desde la formación inicial de profesores, y más concretamente desde la didáctica de las matemáticas. Con este planteamiento, presentamos los objetivos que se pueden contemplar desde esta disciplina en la formación de profesores de matemáticas.

Método gráfico para resolver sistemas de ecuaciones lineales 2x2

El presente documento corresponde al trabajo final de la concentración en Educación Matemática de la Maestría en Educación de la Universidad de los Andes. El trabajo fue elaborado por cuatro profesores licenciados en matemáticas que ejercen en instituciones educativas públicas y privadas en la ciudad de Bogotá y en el departamento de Cundinamarca. Este informe describe el diseño fundamentado y justificado, la implementación y el balance estratégico de la unidad didáctica titulada “Método gráfico para resolver sistemas de ecuaciones lineales 2x2”. El diseño de la unidad didáctica surgió de la selección de un tema matemático que a su vez hace parte de los contenidos incluidos en el currículo oficial para los grados octavo y noveno de educación básica como lo establece el documento de Estándares Básicos de Competencias (Ministerio de Educación Nacional [MEN], 2006a). El diseño se fundamenta a partir del procedimiento de análisis didáctico que constituyó el contenido central de la maestría. Dicho procedimiento permitió concretar elementos previos a la aplicación y la descripción junto con el balance estratégico de la implementación de la unidad didáctica.

Comparison of finite element and finite volume methods application in geometrically nonlinear stress analysis

A novel three-dimensional finite volume (FV) procedure is described in detail for the analysis of geometrically nonlinear problems. The FV procedure is compared with the conventional finite element (FE) Galerkin approach. FV can be considered to be a particular case of the weighted residual method with a unit weighting function, where in the FE Galerkin method we use the shape function as weighting function. A Fortran code has been developed based on the finite volume cell vertex formulation. The formulation is tested on a number of geometrically nonlinear problems. In comparison with FE, the results reveal that FV can reach the FE results in a higher mesh density.

Applications of Feller-Reuter-Riley transition functions

A Feller–Reuter–Riley function is a Markov transition function whose corresponding semigroup maps the set of the real-valued continuous functions vanishing at infinity into itself. The aim of this paper is to investigate applications of such functions in the dual problem, Markov branching processes, and the Williams-matrix. The remarkable property of a Feller–Reuter–Riley function is that it is a Feller minimal transition function with a stable q-matrix. By using this property we are able to prove that, in the theory of branching processes, the branching property is equivalent to the requirement that the corresponding transition function satisfies the Kolmogorov forward equations associated with a stable q-matrix. It follows that the probabilistic definition and the analytic definition for Markov branching processes are actually equivalent. Also, by using this property, together with the Resolvent Decomposition Theorem, a simple analytical proof of the Williams' existence theorem with respect to the Williams-matrix is obtained. The close link between the dual problem and the Feller–Reuter–Riley transition functions is revealed. It enables us to prove that a dual transition function must satisfy the Kolmogorov forward equations. A necessary and sufficient condition for a dual transition function satisfying the Kolmogorov backward equations is also provided.

A framework for historical case-based reasoning

This paper presents a framework for Historical Case-Based Reasoning (HCBR) which allows the expression of both relative and absolute temporal knowledge, representing case histories in the real world. The formalism is founded on a general temporal theory that accommodates both points and intervals as primitive time elements. A case history is formally defined as a collection of (time-independent) elemental cases, together with its corresponding temporal reference. Case history matching is two-fold, i.e., there are two similarity values need to be computed: the non-temporal similarity degree and the temporal similarity degree. On the one hand, based on elemental case matching, the non-temporal similarity degree between case histories is defined by means of computing the unions and intersections of the involved elemental cases. On the other hand, by means of the graphical presentation of temporal references, the temporal similarity degree in case history matching is transformed into conventional graph similarity measurement.

The effect of reflow process on the contact resistance and reliability of anisotropic conductive film interconnection for flip chip on flex applications

The work presented in this paper focuses on the effect of reflow process on the contact resistance and reliability of anisotropic conductive film (ACF) interconnection. The contact resistance of ACF interconnection increases after reflow process due to the decrease in contact area of the conducting particles between the mating I/O pads. However, the relationship between the contact resistance and bonding parameters of the ACF interconnection with reflow treatment follows the similar trend to that of the as-bonded (i.e. without reflow) ACF interconnection. The contact resistance increases as the peak temperature of reflow profile increases. Nearly 40% of the joints were found to be open after reflow with 260 °C peak temperature. During the reflow process, the entrapped (between the chip and substrate) adhesive matrix tries to expand much more than the tiny conductive particles because of the higher coefficient of thermal expansion, the induced thermal stress will try to lift the bump from the pad and decrease the contact area of the conductive path and eventually, leading to a complete loss of electrical contact. In addition, the environmental effect on contact resistance such as high temperature/humidity aging test was also investigated. Compared with the ACF interconnections with Ni/Au bump, higher thermal stress in the Z-direction is accumulated in the ACF interconnections with Au bump during the reflow process owing to the higher bump height, thus greater loss of contact area between the particles and I/O pads leads to an increase of contact resistance and poorer reliability after reflow.

Experimental and modeling analysis of the reliability of the anisotropic conductive films

Experiments as well as computer modeling methods have been used to investigate the effect of the solder reflow process on the electrical characteristics and reliability of anisotropic conductive film (ACF) interconnections. In the experiments, the contact resistance of the ACF interconnections was found to increase after a subsequent reflow and the magnitude of this increase was strongly correlated to the peak temperature of the reflow profile. In fact, nearly 40 percent of the joints were opened (i.e. lifted away from the pad) after the reflow with a peak temperature of 260 OC while no openings was observed when the peak temperature was 210 "C. It is believed that the CTE mismatch between the polymer particle and the adhesive matrix is the main cause of this contact degradation. To understand this phenomenon better, a 3-D model of an ACF joint structure was built and Finite Element Analysis was used to predict the stress distrihution in the conductive particles, adhesive matrix and metal pads during the reflow process. The effects of the peak temperature, the CTE of the adhesive matrix and the bump height on the reliability of the ACF interconnections were discussed.

Effects of reflow process on the reliability of flip chip on flex interconnections using anisotropic conductive adhesives

In this paper, the effects of the solder reflow process on the reliability of anisotropic conductive film (ACF) interconnections for flip chip on flex (FCOF) applications are investigated. Experiments as well as computer modeling methods have been used. In the experiments, it was found that the contact resistance of ACF joints increased after the subsequent reflow process, and the magnitude of this increase was strongly correlated to the peak temperature of the reflow profile. Nearly 40% of the joints were opened (i.e. lifted away from the pad) after the reflow process with 260 °C peak temperature while no opening was observed when the peak temperature was 210 °C. It is believed that the CTE mismatch between the polymer particle and the adhesive matrix is the main cause of this contact degradation. It was also found that the ACF joints after the reflow process with 210 °C peak temperature showed a high ability to resist water absorption under steady state 85 °C/85%RH conditions, probably because the curing degree of the ACF was improved during the reflow process. To give a good understanding, a 3D model of an ACF joint structure was built and finite element analysis was used to predict the stress distribution in the conductive particles, adhesive matrix and metal pads during the reflow process.

Low temperature X-ray crystallographic structures of two lamotrigine analogues: (I) 2-methyl,3-amino, 5-imino-6-(2,3-dichlorophenyl)-1,2,4-triazine water solvate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine isethionate, hemi-hydrate

The X-ray crystal structures of two lamotrigine derivatives (I) 2-methyl, 3-amino, 5-imino-6-(2, 3-dichlorophenyl)-1,2,4-triazine, C10H9Cl2N5, as the hemi hydrate and (II) 2-methyl,3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine, C10H10Cl2N5, as the isethionate-water solvate, have been carried out at liquid nitrogen temperature. A detailed comparison of the two structures is given. Both are monoclinic and centrosymmetric, with (I) in space group C2/c, and (II) in space group P2(1)/n. For (I) the unit cell dimensions are a = 19.5466(10), b = 7.5483(4), c = 15.7861(8) angstrom, beta = 91.458(3)degrees, volume = 2328.4(2) angstrom(3), Z = 8, density = 1.590 Mg/m(3); for (II). For (II) the unit cell dimensions are a = 6.0566(2), b = 11.0084(4) c = 23.9973(9) angstrom, beta = 92.587(3)degrees, volume = 1598.35(10) angstrom(3), Z = 4, density = 1.597 Mg/m(3). For (I) final R indices [I > 2sigma(I)] are R1 = 0.0356, wR2 = 0.0782 and R indices (all data) are R1 = 0.0424, wR2 = 0.0817. For (II) final R indices [I > 2sigma(I)] are R1 = 0.0380, wR2 = 0.0871 and R indices (all data) R1 = 0.0558, wR2 = 0.0949. Both structures have a molecule of water of crystallization and (II) also includes a solvated CH3SO3. Comparisons are made between the two structures. Structure (I) is very unusual in having a = NH group at position C5' on the triazine ring. No other examples of this particular substitution, which is usually -NH2, have been reported.