Metabolic profiling for the identification of Huntington biomarkers by on‐line solid‐phase extraction capillary electrophoresis mass spectrometry combined with advanced data analysis tools

In this work, an untargeted metabolomic approach based on sensitive analysis by on‐line solid‐phase extraction capillary electrophoresis mass spectrometry (SPE‐CE‐MS) in combination with multivariate data analysis is proposed as an efficient method for the identification of biomarkers of Huntington's disease (HD) progression in plasma. For this purpose, plasma samples from wild‐type (wt) and HD (R6/1) mice of different ages (8, 12, and 30 weeks), were analyzed by C₁₈‐SPE‐CE‐MS in order to obtain the characteristic electrophoretic profiles of low molecular mass compounds. Then, multivariate curve resolution alternating least squares (MCR‐ALS) was applied to the multiple full scan MS datasets. This strategy permitted the resolution of a large number of metabolites being characterized by their electrophoretic peaks and their corresponding mass spectra. A total number of 29 compounds were relevant to discriminate between wt and HD plasma samples, as well as to follow‐up the HD progression. The intracellular signaling was found to be the most affected metabolic pathway in HD mice after 12 weeks of birth, when mice already showed motor coordination deficiencies and cognitive decline. This fact agreed with the atrophy and dysfunction of specific neurons, loss of several types of receptors, and changed expression of neurotransmitters.     

UV Protective,Antioxidant, Antibacterial and Compostable Polylactic Acid Composites Containing Pristine and Chemically Modified Lignin Nanoparticles

Polylactic acid (PLA) films containing 1 wt % and 3 wt % of lignin nanoparticles (pristine (LNP), chemically modified with citric acid (caLNP) and acetylated (aLNP)) were prepared by extrusion and characterized in terms of their overall performance as food packaging materials. Morphological, mechanical, thermal, UV–Vis barrier, antioxidant and antibacterial properties were assayed; appropriate migration values in food simulants and disintegration in simulated composting conditions were also verified. The results obtained indicated that all lignin nanoparticles succeeded in conferring UV-blocking, antioxidant and antibacterial properties to the PLA films, especially at the higher filler loadings assayed. Chemical modification of the fillers partially reduced the UV protection and the antioxidant properties of the resulting composites, but it induced better nanoparticles dispersion, reduced aggregates size, enhanced ductility and improved aesthetic quality of the films through reduction of the characteristic dark color of lignin. Migration tests and disintegration assays of the nanocomposites in simulated composting conditions indicated that, irrespectively of their formulation, the multifunctional nanocomposite films prepared behaved similarly to neat PLA.     

Solid phase extraction of food contaminants using molecular imprinted polymers

Food contamination from natural or anthropogenic sources poses severe risks to human health. It is now largely accepted that continuous exposure to low doses of toxic chemicals can be related to several chronic diseases, including some type of cancer and serious hormonal dysfunctions.Contemporary analytical methods have the sensitivity required for contamination detection and quantification, but direct application of these methods on food samples can be rarely performed. In fact, the matrix introduces severe disturbances, and analysis can be performed only after some clean-up and preconcentration steps. Current sample pre-treatment methods, mostly based on the solid phase extraction technique, are very fast and inexpensive but show a lack of selectivity, while methods based on immunoaffinity extraction are very selective but expensive and not suitable for harsh environments. Thus, inexpensive, rapid and selective clean-up methods, relaying on “intelligent” materials are needed. Recent years have seen a significant increase of the “molecularly imprinted solid phase extraction” (MISPE) technique in the food contaminant analysis. In fact, this technique seems to be particularly suitable for extractive applications where analyte selectivity in the presence of very complex and structured matrices represents the main problem. In this review, several applications of MISPE in food contamination analysis will be discussed, with particular emphasis on the extraction of pesticides, drugs residua, mycotoxins and environmental contaminants.     

The Stabilizing Effects in Gold Carbene Complexes

Bonding and stabilizing effects in gold carbene complexes are investigated by using Kohn–Sham density functional theory (DFT) and the intrinsic bond orbital (IBO) approach. The π‐stabilizing effects of organic substituents at the carbene carbon atom coordinated to the gold atom are evaluated for a series of recently isolated and characterized complexes, as well as intermediates of prototypical 1,6‐enyne cyclization reactions. The results indicate that these effects are of particular importance for gold complexes especially because of the low π‐backbonding contribution from the gold atom.     

Thermal Gaussian molecular dynamics for quantum dynamics simulations of many-body systems: application to liquid para-hydrogen

A new method, here called thermal Gaussian molecular dynamics (TGMD), for simulating the dynamics of quantum many-body systems has recently been introduced [I. Georgescu and V. A. Mandelshtam, Phys. Rev. B 82, 094305 (2010)]. As in the centroid molecular dynamics (CMD), in TGMD the N-body quantum system is mapped to an N-body classical system. The associated both effective Hamiltonian and effective force are computed within the variational Gaussian wave-packet approximation. The TGMD is exact for the high-temperature limit, accurate for short times, and preserves the quantum canonical distribution. For a harmonic potential and any form of operator A?, it provides exact time correlation functions C(AB)(t) at least for the case of B, a linear combination of the position, x, and momentum, p, operators. While conceptually similar to CMD and other quantum molecular dynamics approaches, the great advantage of TGMD is its computational efficiency. We introduce the many-body implementation and demonstrate it on the benchmark problem of calculating the velocity time auto-correlation function for liquid para-hydrogen, using a system of up to N = 2592 particles.     

Surface light-scattering at the air-liquid interface: from newtonian to viscoelastic polymer solutions

The dynamics of the liquid-air interface of aqueous solutions of a tensioactive triblock copolymer (Pluronic F-68) has been studied using surface quasielastic light scattering over a broad range of concentrations and temperatures. Ancillary surface tension and bulk rheometry data have been obtained for the same system. The results show that the classical theoretical spectrum for monolayers on a Newtonian fluid can be applied only for concentrations below 4.10(-2) mM. For concentrations above c = 14 mM a clear peak centered at zero frequency appears in the spectrum. This feature is incompatible with the classical theoretical spectrum. The SQELS spectra have been described in terms of the theory of Wang and Huang [Wang, C. H.; Huang, Q. R. J. Chem. Phys. 1997, 107, 5898] considering that the loss modulus of the concentrated solutions shows the existence of two relaxation modes even at low frequencies. The theory is able to explain the existence of a peak centered at zero frequency in the spectra, and the theoretical spectra point out the existence of an elastic peak together with the capillary one. There is a reasonable agreement between the relaxation times and the product Gtau obtained from the fits of the SQELS spectra to the theory of Wang and Huang and those obtained from bulk rheology.     

Pharmacophore modeling as an efficient tool in the discovery of novel noncompetitive AMPA receptor antagonists

A three-dimensional pharmacophore model for the binding of noncompetitive AMPA receptor antagonists was developed in order to map common structural features of highly active compounds. This hypothesis, which consists of two hydrophobic regions, one hydrogen bond acceptor and one aromatic region, was successfully used as framework for the design of a new class of allosteric modulators containing a tetrahydroisoquinoline skeleton and for in silico screening. The promising biological results suggested that the identified molecules might be useful "lead compounds" for future drug development.     

Colloids for Catalysts: A Concept for the Preparation of Superior Catalysts of Industrial Relevance

Compared to conventional preparation methods for supported heterogeneous catalysts, the use of colloidal nanoparticles (NPs) allows for a precise control over size, size distribution, and distribution/location of the NPs on the support. However, common colloidal syntheses have restrictions that limit their applicability for industrial catalyst preparation. We present a simple, surfactant‐free, and scalable preparation method for colloidal NPs to overcome these restrictions. We demonstrate how precious‐metal NPs are prepared in alkaline methanol, how the particle size can be tuned, and how supported catalysts are obtained. The potential of these colloids in the preparation of improved catalysts is demonstrated by two examples from heterogeneous catalysis and electrocatalysis.