Facile transformation of glutamic acid into proline residue inside a tripeptide backbone

In this Letter we present a simple reaction pathway which allows the conversion of the glutamic acid residue of a tripeptide into a proline residue. The reaction was performed by using Boc-Val-Glu-Phe-NH₂ as a starting material and is based on a NaH-induced intraresidue alkylation under reaction conditions analogous to that adopted during the Freidinger lactams formation.     

Synthesis of Ether-Linked Di- and Trisaccharide Derivatives Part I- Synthesis Of Disaccharides from 5,6-Anhydro-D-Glucose Derivatives

Abstract

We have synthesized a series of A-O-B disaccharides of the type A(6→n)B obtained by linking the D-glucose derivative (A) with each of the D-fructose, D-galactose, D-glucose, xylitol and glycerol derivatives (B). The key step in each case is the nucleophilic attack of a monosaccharide alkoxide on the C-6 site of 3-O-alkyl-5,6-anhydro-1,2-O-isopropylidene-α-D-glucofuranose; each reaction was performed in toluene-DMSO and using KOH as the base.     

Tantalum nanoparticles enhance the osteoinductivity of multiscale composites based on poly(lactide-co-glycolide) electrospun fibers embedded in a gelatin hydrogel

Bioresorbable polymeric materials have risen great interest as implants for bone tissue regeneration, since they show substantial advantages with respect to conventional metal devices, including biodegradability, flexibility, and the possibility to be easily modified to introduce specific functionalities. In the present work, an innovative nanocomposite scaffold, properly designed to show biomimetic and osteoinductive properties for potential application in bone tissue engineering, was developed. The scaffold is characterized by a multi-layer structure, completely different with respect to the so far employed polymeric implants, consisting in a poly(d,l-lactide-co-glycolide)/polyethylene glycol electrospun nanofibrous mat sandwiched between two hydrogel gelatin layers enriched with tantalum nanoparticles (NPs). The composition of the electrospun fibers, containing 10 wt% of polyethylene glycol, was selected to ensure a proper integration of the fibers in the gel phase, essential to endow the composite with flexibility and to prevent delamination between the layers. The scaffold maintained its structural integrity after six weeks of soaking in physiological solutions, albeit the gelatin phase was partially released. The combined use of gelatin, bioresorbable electrospun fibers and tantalum NPs endows the final device with biomimetic and osteoinductive properties. Indeed, results of the in vitro tests demonstrate that the obtained scaffolds clearly represent a favorable milieu for normal human bone-marrow derived mesenchymal stem cells viability and osteoblastic differentiation; moreover, inclusion of tantalum NPs in the scaffold improves cell performance with particular regard to early and late markers of osteoblastic differentiation.     

Semiclassical dynamics and coherent soliton condensates in self-focusing nonlinear media with periodic initial conditions

The semiclassical (small dispersion) limit of the focusing nonlinear Schrödinger equation with periodic initial conditions (ICs) is studied analytically and numerically. First, through a comprehensive set of numerical simulations, it is demonstrated that solutions arising from a certain class of ICs, referred to as “periodic single-lobe” potentials, share the same qualitative features, which also coincide with those of solutions arising from localized ICs. The spectrum of the associated scattering problem in each of these cases is then numerically computed, and it is shown that such spectrum is confined to the real and imaginary axes of the spectral variable in the semiclassical limit. This implies that all nonlinear excitations emerging from the input have zero velocity, and form a coherent nonlinear condensate. Finally, by employing a formal Wentzel-Kramers-Brillouin expansion for the scattering eigenfunctions, asymptotic expressions for the number and location of the bands and gaps in the spectrum are obtained, as well as corresponding expressions for the relative band widths and the number of “effective solitons.” These results are shown to be in excellent agreement with those from direct numerical computation of the eigenfunctions. In particular, a scaling law is obtained showing that the number of effective solitons is inversely proportional to the small dispersion parameter.     

A nonlinear partial least squares algorithm using quadratic fuzzy inference system

We introduce a new nonlinear partial least squares algorithm ‘Quadratic Fuzzy PLS (QFPLS)’ that combines the outer linear Partial Least Squares (PLS) framework and the Takagi–Sugeno–Kang (TSK) fuzzy inference system. The inner relation between the input and the output PLS score vectors is modeled by a quadratic TSK fuzzy inference system. The performance of the proposed QFPLS method is tested and compared against four other well‐known partial least squares methods (Linear PLS (LPLS), Quadratic PLS (QPLS), Linear Fuzzy PLS (LFPLS), and Neural Network PLS (NNPLS)) on various different types of randomly generated test data. QFPLS outperformed competitors based on two comparison measures: the output variables cumulative per cent variance captured by the PLS latent variables and the root mean‐square error of prediction (RMSEP). Copyright © 2009 John Wiley & Sons, Ltd.     

Heterochromatin and Complexity: A Theoretical Approach

Heterochromatin represents 30% of eukaryotic genome in Drosophila and 15% in humans. Despite extensive research spanning many decades, its evolutionary significance, as well as the forces that guarantee its maintenance, are still elusive. Many theoretical and experimental approaches have led researchers to propose several conceptual frameworks to elucidate the nature of this huge mysterious genetic material and its spreading in all eukaryotic genomes. Junk DNA as well as selfish genetic material are two examples of such attempts, but several lines of evidence suggest that such explanations are incomplete. In fact, if the selfish DNA hypothesis does not explain the mapping of genetic functions in heterochromatin, then the junk DNA hypothesis is incomplete in describing both emergence of genetic functions and their maintenance in the eukaryotic heterochromatin. Recent developments in the physics of complex systems and mathematical concepts such as fractals provide new conceptual clues to answer several basic questions concerning the emergence of heterochromatin in eukaryotic genomes, its evolutionary significance, the forces that guarantee its maintenance, and its peculiar behavior in the eukaryotic cell. The aim of this paper is to provide a new theoretical framework for the heterochromatin, considering such genetic material in physical terms as a complex adaptive system. We apply some computer calculations to demonstrate the nonlinearity of the flux of genetic information along the phylogenic tree. Fractal dimensions of representative heterochromatic sequences are provided. A theory is proposed in which heterochromatin is considered a system that evolves in a self-organized manner at the edge of cellular and environmental chaos.     

n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type

n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods.     

Exploiting the benefits of miniaturization for the enhancement of DNA microarrays

The present study demonstrates that the best way to enhance DNA microarray assays, both in terms of analysis speed and in final spot intensity, is to dissolve the available molar amount of sample in the smallest possible buffer volume and to subsequently convect this solution continuously across the surface of the array. The presently proposed shear-driven flow system is pre-eminently suited for this task, as it allows to induce strongly enhanced lateral transport rates, independently of the degree of miniaturization of the hybridization chamber. This transport enhancement method, however, only increases the hybridization rate and not the final spot intensity, as neither can any of the other transport enhancement methods already proposed in literature. A series of experiments with synthetic single-stranded (ssDNA) samples and an accompanying mass balance analysis are presented to demonstrate these points.