The effects of the interphase and strain gradients on the elasticity of layer by layer (LBL) polymer/clay nanocomposites

A synergistic stiffening effect observed in the elastic mechanical properties of LBL assembled polymer/clay nanocomposites is studied via two continuum mechanics approaches. The nanostructure of the representative volume element (RVE) includes an effective interphase layer that is assumed to be perfectly bonded to the particle and matrix phases. An inverse method to determine the effective thickness and stiffness of the interphase layer using finite element (FE) simulations and experimental data previously published in Kaushik et al. (2009), is first illustrated. Next, a size-dependent strain gradient Mori–Tanaka (M–T) model (SGMT) is developed by applying strain gradient elasticity to the classical M–T method. Both approaches are applied to LBL-assembled polyurethane–montmorillonite (PU–MTM) clay nanocomposites. Both two-dimensional (2D) and three-dimensional (3D) FE models used in the first approach are shown to be able to accurately predict the stiffness of the PU–MTM specimens with various volume fractions. The SGMT model also accurately predicts the experimentally observed increase in stiffness of the PU–MTM nanocomposite with increasing volume fraction of clay. An analogy between the strain gradient effect and the role of an interphase in accounting for the synergistic elastic stiffening in nanocomposites is provided.     

IRMPD and ECD fragmentation of intermolecular cross-linked peptides

Despite the increasing number of studies using mass spectrometry for three dimensional analyses of proteins (MS3D), the identification of cross-linked peptides remains a bottleneck of the method. One of the main reasons for this is the lack of knowledge about the fragmentation of these species. Intermolecular cross-linked peptides are considered the most informative species present in MS3D experiment, since different peptides are connected by a cross-linker, the peptides chain can be either from a single protein, providing information about protein folding, or from two different proteins in a complex, providing information about binding partners, complex topology and interaction sites. These species tend to be large and highly charged in ESI, making comprehensive fragmentation by CID MS/MS problematic. On the other hand, these highly charged peptides are very suitable for dissociation using both infrared multiphoton dissociation (IRMPD) and electron capture dissociation (ECD). Herein, we report the fragmentation study of intermolecular cross-linked peptides using IRMPD and ECD. Using synthetic peptides and different commercial cross-linkers, a series of intermolecular cross-linked peptides were generate, and subsequently fragmented by IRMPD and ECD in a FT-ICR-MS instrument. Due to the high mass accuracy and resolution of the FT-ICR, the fragment ions could be attributed with high confidence. The peptides sequence coverage and fragmentation features obtained from IRMPD and ECD were compared for all charge states.     

Evaluation of cytoprotective effects of compounds isolated from Copaifera langsdorffii Desf. against induced cytotoxicity by exposure to methylmercury and lead

Abstract

Copaifera langsdorffii L. is one of the most known medicinal species in Brazil. Its leaves are rich in phenolic compounds with potential biological activities as an antioxidant and chelating agent. This paper reports the isolation of four compounds from the hydroalcoholic extract of the leaves of C. langsdorffii and the investigation of their possible cytoprotective effects against heavy metal poisoning. Quercitrin (1), afzelin (2), 3,5-di-O-(3-O-methyl galloyl) quinic acid (3) and 4,5-di-O-(3-O-methyl galloyl) quinic acid (4), were associated with toxic doses of methylmercury and lead and evaluated by Alamar blue cell viability assays in HepG2 and PC12. The compounds displayed significant cytoprotective effect for the HepG2 cell line against both metals. Compounds 1–4 did not protect PC12 cells against methylmercury induced-cytotoxicity, but at lower concentrations, they protected against lead induced-cytotoxicity. The evaluated compounds showed a promising cytoprotection effect against exposure to heavy metals and should be further investigated as protective agents.     

Neural Approach for Solving Several Types of Optimization Problems

Neural networks consist of highly interconnected and parallel nonlinear processing elements that are shown to be extremely effective in computation. This paper presents an architecture of recurrent neural net-works that can be used to solve several classes of optimization problems. More specifically, a modified Hopfield network is developed and its inter-nal parameters are computed explicitly using the valid-subspace technique. These parameters guarantee the convergence of the network to the equilibrium points, which represent a solution of the problem considered. The problems that can be treated by the proposed approach include combinatorial optimiza-tion problems, dynamic programming problems, and nonlinear optimization problems.Communicated by L. C. W. Dixon     

Arithmetical and geometrical means of generalized logarithmic and exponential functions: Generalized sum and product operators

One-parameter generalizations of the logarithmic and exponential functions have been obtained as well as algebraic operators to retrieve extensivity. Analytical expressions for the successive applications of the sum or product operators on several values of a variable are obtained here. Applications of the above formalism are considered.     

Centred TVD schemes for hyperbolic conservation laws

New first- and high-order centred methods for conservation lawsare presented. Convenient TVD conditions for constructing centredTVD schemes are then formulated and some useful results areproved. Two families of centred TVD schemes are constructedand extended to nonlinear systems. Some numerical results arealso presented.     

Stability and optimality of a multi-product production and storage system under demand uncertainty

This work develops a discrete event model for a multi-product multi-stage production and storage (P&S) problem subject to random demand. The intervention problem consists of three types of possible decisions made at the end of one stage, which depend on the observed demand (or lack of) for each item: (i) to proceed further with the production of the same product, (ii) to proceed with the production of another product or (iii) to halt the production. The intervention problem is formulated in terms of dynamic programming (DP) operators and each possible solution induces an homogeneous Markov chain that characterizes the dynamics. However, solving directly the DP problem is not a viable task in situations involving a moderately large number of products with many production stages, and the idea of the paper is to detach from strict optimality with monitored precision, and rely on stability. The notion of stochastic stability brought to bear requires a finite set of positive recurrent states and the paper derives necessary and sufficient conditions for a policy to induce such a set in the studied P&S problem. An approximate value iteration algorithm is proposed, which applies to the broader class of control problems described by homogeneous Markov chains that satisfy a structural condition pointed out in the paper. This procedure iterates in a finite subset of the state space, circumventing the computational burden of standard dynamic programming. To benchmark the approach, the proposed algorithm is applied to a simple two-product P&S system.     

Compensation of the Schlieren effect in flow-injection analysis by using dual-wavelength spectrophotometry

The Schlieren effect in flow-injection analysis is critically examined. Effects of sample constitution, injection volume, coil lengths, flow-rates, confluent stream addition and temperature are studied and practical implications in flow-injection design with and without the stopped-flow approach are discussed. For Schlieren compensation, a diode-array spectrophotometer is used and non-specific absorbance subtraction is exploited: the incident light passes through the flowing sample, the emergent light is dispersed, the intensities of two selected monochromatic beams are measured simultaneously by separate detectors and real-time subtraction of the wavelength-independent noise is achieved. The sensitivity and measurement precision improve after application of the subtraction algorithm. The potential, limitations and practical applications of the method are discussed.     

Two-dimensional difference gel electrophoresis applied for analytical proteomics: fundamentals and applications to the study of plant proteomics

The present review reports the principles, fundamentals and some applications of two-dimensional difference gel electrophoresis for analytical proteomics based on plant proteome analysis, also emphasizing some advantages of 2-D DIGE over 2-D PAGE techniques. Some fluorescent protein labeling reagents, methods of protein labeling, models of 2-D DIGE experiments, and some limitations of this technique are presented and discussed in terms of 2-D DIGE plant proteomes. Finally, some practical applications of this technique are pointed out, emphasizing its potentialities in plant proteomics.     

Quantitation of drugs via molecularly imprinted polymer solid phase extraction and electrospray ionization mass spectrometry: benzodiazepines in human plasma

The association of solid phase extraction with molecularly imprinted polymers (MIP) and electrospray ionization mass spectrometry (ESI-MS) is applied to the direct extraction and quantitation of benzodiazepines in human plasma. The target analytes are sequestered by MIP and directly analyzed by ESI-MS. Due to the MIP highly selective extraction, ionic suppression during ESI is minimized; hence no separation is necessary prior to ESI-MS, which greatly increases analytical speed. Benzodiazepines (medazepam, nitrazepam, diazepam, chlordiazepoxide, clonazepam and midazolam) in human plasma were chosen as a proof-of-principle case of drug analyses by MIP-ESI-MS in a complex matrix. MIP-ESI-MS displayed good figures of merits for medazepam, nitrazepam, diazepam, chlordiazepoxide and midazolam, with analytical calibration curves ranging from 10 to 250 μg L(-1) (r > 0.98) with limit of quantification <10 μg L(-1) and acceptable within-day and between-day precision and accuracy.