Design of a dinuclear nickel(II) bioinspired hydrolase to bind covalently to silica surfaces: synthesis, magnetism, and reactivity studies

Presented herein is the design of a dinuclear Ni(II) synthetic hydrolase [Ni(2)(HBPPAMFF)(μ-OAc)(2)(H(2)O)]BPh(4) (1) (H(2)BPPAMFF = 2-[(N-benzyl-N-2-pyridylmethylamine)]-4-methyl-6-[N-(2-pyridylmethyl)aminomethyl)])-4-methyl-6-formylphenol) to be covalently attached to silica surfaces, while maintaining its catalytic activity. An aldehyde-containing ligand (H(2)BPPAMFF) provides a reactive functional group that can serve as a cross-linking group to bind the complex to an organoalkoxysilane and later to the silica surfaces or directly to amino-modified surfaces. The dinuclear Ni(II) complex covalently attached to the silica surfaces was fully characterized by different techniques. The catalytic turnover number (k(cat)) of the immobilized Ni(II)Ni(II) catalyst in the hydrolysis of 2,4-bis(dinitrophenyl)phosphate is comparable to the homogeneous reaction; however, the catalyst interaction with the support enhanced the substrate to complex association constant, and consequently, the catalytic efficiency (E = k(cat)/K(M)) and the supported catalyst can be reused for subsequent diester hydrolysis reactions.     

Differentiation of aminomethyl corrole isomers by mass spectrometry

Two new isomeric aminomethyl corrole derivatives of [5,10,15‐tris(pentafluorophenyl)corrolato]gallium(III) were synthesized with pyridine (py) molecules as axial ligands. When investigated by electrospray ionization mass spectrometry, in the positive and the negative ion modes, these compounds showed an unusual gas‐phase behavior that could be used for their differentiation. In the positive ion mode, the differentiation was achieved through the formation of diagnostic fragment ions formed from [M‐py + H]⁺ precursors, by (CH₃)₂NH and HF losses. An unusual addition of water to the main fragment ions provides an alternative route for isomer identification. Semi‐empirical calculations were performed to elucidate the structures and stabilities of the main ionic species formed in the positive ion mode. In the negative ion mode isomer discrimination is accomplished via the fragmentation of the methoxide adduct ions [M‐py + CH₃O]^‐ through (CH₃)₂ N^. and HF losses. Copyright © 2012 John Wiley & Sons, Ltd.     

An immune-inspired instance selection mechanism for supervised classification

One issue in data classification problems is to find an optimal subset of instances to train a classifier. Training sets that represent well the characteristics of each class have better chances to build a successful predictor. There are cases where data are redundant or take large amounts of computing time in the learning process. To overcome this issue, instance selection techniques have been proposed. These techniques remove examples from the data set so that classifiers are built faster and, in some cases, with better accuracy. Some of these techniques are based on nearest neighbors, ordered removal, random sampling and evolutionary methods. The weaknesses of these methods generally involve lack of accuracy, overfitting, lack of robustness when the data set size increases and high complexity. This work proposes a simple and fast immune-inspired suppressive algorithm for instance selection, called SeleSup. According to self-regulation mechanisms, those cells unable to neutralize danger tend to disappear from the organism. Therefore, by analogy, data not relevant to the learning of a classifier are eliminated from the training process. The proposed method was compared with three important instance selection algorithms on a number of data sets. The experiments showed that our mechanism substantially reduces the data set size and is accurate and robust, specially on larger data sets.     

Phase Space Transformations of Gaussian Diffusions

It is shown that for Gaussian diffusions, the transformation back to Brownian motion, usually accomplished via the Girsanov (or Feynman–Kac) formula and time-shift, can be obtained by a classical canonical, i.e. symplectic, transformation in phase space. The method is based on constants of motion, in this case the Wronskian. Similar transformations for general diffusions are briefly discussed.     

Effects of Prenatal Exposure to Aflatoxin B1: A Review

Aflatoxins are mycotoxins produced as secondary fungal metabolites. Among them, aflatoxin B1 (AFB1) stands out due to its genotoxic and mutagenic potential, being a potent initiator of carcinogenesis. In this review, the outcomes from the published literature in the past 10 years on the effects of AFB1 pathophysiological mechanisms on embryological and fetal development are discussed. In several animal species, including humans, AFB1 has a teratogenic effect_, resulting in bone malformations, visceral anomalies, lesions in several organs, and behavioral and reproductive changes, in addition to low birth weight. The mutagenic capacity of AFB1 in prenatal life is greater than in adults, indicating that when exposure occurs in the womb, the risk of the development of neoplasms is higher. Studies conducted in humans indicate that the exposure to this mycotoxin during pregnancy is associated with low birth weight, decreased head circumference, and DNA hypermethylation. However, as the actual impacts on humans are still unclear, the importance of this issue cannot be overemphasized and studies on the matter are essential.     

Localized modulated wave solution of diffusive FitzHugh–Nagumo cardiac networks under magnetic flow effect

Nonlinear Dynamics - Motivated by often non-observance clinical effects attributed to some pathological heart diseases, we obtain in this paper the analytical solutions describing localized...     

Stepwise Adsorption of Alkoxy-Pyrene Derivatives onto a Lamellar,Non-Porous Naphthalenediimide-Template on HOPG

The development of new strategies for the preparation of multicomponent supramolecular assemblies is a major challenge on the road to complex functional molecular systems. Here we present the use of a non-porous self-assembled monolayer from uC₃₃-NDI-uC₃₃ , a naphthalenediimide symmetrically functionalized with unsaturated 33 carbon-atom-chains, to prepare bicomponent supramolecular surface systems with a series of alkoxy-pyrene ( PyrOR ) derivatives at the liquid/HOPG interface. While previous attempts at directly depositing many of these PyrOR units at the liquid/HOPG interface failed, the multicomponent approach through the uC₃₃-NDI-uC₃₃ template enabled control over molecular interactions and facilitated adsorption. The PyrOR deposition restructured the initial uC₃₃-NDI-uC₃₃ monolayer, causing an expansion in two dimensions to accommodate the guests. As far as we know, this represents the first example of a non-porous or non-metal complex-bearing monolayer that allows the stepwise formation of multicomponent supramolecular architectures on surfaces.     

Variants of Kato’s inequality and removable singularities

An inequality reminiscent of Kato’s inequality is presented. Motivated by this, we discuss some criteria to decide whether a singularity of the equation Δu=g in Ω/K comes from a Radon measure or not. As an application, we extend a lemma of H. Brezis and P. L. Lions on isolated singularities to the case where the singularity lies on a compact manifold. this author was supported by CAPES, Brazil, under the grant BEX 1187/99-6.     

Infinite symmetry algebras of extended supergravity theories

When extended supergravity theories with noncompact symmetry groups are written in a physical gauge, the noncompact symmetries join with the supersymmetries to generate an infinite-dimensional algebra. The details are worked out explicitly for a two-dimensional theory with an SU(1, 1) internal symmetry. Our analysis confirms the observation of Ellis et al. that the infinite rigid superalgebra should be obtained from the finite-dimensional local superalgebra by replacing scalar fields with their asymptotic values at infinity. The infinite algebra is described by extending the super-Poincaré generators to functions on the coset space defined by the scalar fields at infinity. While mathematically nontrivial, this result is, in a certain sense, trivial from a physical point of view.