Reversible conformational transitions of a polymer brush containing boronic acid and its interaction with mucin glycoprotein

Reversible changes of the height of a polymer brush containing phenylboronic acid were studied. The polymer brush thickness underwent reversible changes of 0.5–1 nm, in response to the changes in composition of the contacting aqueous phase from deionized water to bicarbonate buffer and vice versa, apparently due to the conformational transition of the weak polyelectrolyte to the more extended electrically charged state. Adsorption of mucin glycoprotein to the polymer brush took place due to boronate/sugar interactions between the glycoprotein and the graft copolymer and resulted in further increase of the brush height by ca. 1.5 nm, as observed by means of spectral correlation spectroscopy and ellipsometry.

     

Sequence-specific predictive chromatography to assist mass spectrometric analysis of asparagine deamidation and aspartate isomerization in peptides

Deamidation of asparagine and spontaneous isomerization of aspartic acid in proteins and peptides occur frequently. These modifications result in a mixture of peptide variants containing all three residues in the sequences. Identification and isomer quantification for these systems are challenging tasks for tandem mass spectrometry commonly utilized in protein analysis. Chromatographic data provide a set of sequence-specific information complementary to mass spectrometry. In order to compare measured retention times (RTs) with those calculated from the sequences derived from protein databases, it is necessary to develop chromatographic models and tools allowing the prediction of RT and elution order for peptides with modified residues. In this work we extended recently introduced critical liquid chromatography of biomacromolecule model for prediction of RTs for peptides containing asparagines, aspartic acid, and isoaspartic acid residues.     

Bivariate rational approximations of the general temperature integral

Journal of Mathematical Chemistry - The non-isothermal analysis of materials with the application of the Arrhenius equation involves temperature integration. If the frequency factor in the...     

Finite Alternation Theorems and a Constructive Approach to Piecewise Polynomial Approximation in Chebyshev Norm

Set-Valued and Variational Analysis - One of the purposes in this paper is to provide a better understanding of the alternance property which occurs in Chebyshev polynomial approximation and...     

The surface limit of Brownian motion in tubular neighborhoods of an embedded Riemannian manifold

We construct the surface measure on the space C([0,1],M) of paths in a compact Riemannian manifold M without boundary embedded into which is induced by the usual flat Wiener measure on conditioned to the event that the Brownian particle does not leave the tubular ε-neighborhood of M up to time 1. We prove that the limit as ε→0 exists, the limit measure is equivalent to the Wiener measure on C([0,1],M), and we compute the corresponding density explicitly in terms of scalar and mean curvature.     

Thermal degradation of natural and treated hemp hurds under air and nitrogen atmosphere

Sustainability goals are essential driving principles for the development of innovative materials in the construction industry. Natural fibers represent an attractive alternative as reinforcing material due to good mechanical properties and sustainability prerequisites. The study has been focused on the comparative investigation of chemical and physical treatments of hemp hurds and their influence on the thermal behavior of main hemp constituents in air and nitrogen atmosphere. Thermal decomposition of hemp hurds involves several parallel reactions related to heat and mass transfer processes. A comparison of DSC and TG/DTG results of hemp hurds samples before and after treatments demonstrates a better thermal stability for treated samples. It is caused by changes in chemical composition due to a partial removal of non-cellulosic components from hemp hurds structure, an increase in cellulose content and decrease in its degree of polymerization. The results show different thermal behavior of the hurds samples heated under nitrogen and air atmosphere. Based on DTG records, several-stage process of mass loss has been found for the samples under air, whereas only two-stage process under nitrogen.

     

Intramolecular cyclization assistance for fast degradation of ornithine‐based poly(ester amide)s

Inspired by the spontaneous cyclization of ornithine in peptides, polyesters containing protected ornithine (Orn) side chains along the backbone were synthesized and shown to degrade rapidly upon deprotection through intramolecular cyclization. A new ornithine‐based poly(ester amide) PEA 1 and a lysine‐based control PEA 2, both bearing the light‐sensitive protecting group o‐nitrobenzyl alcohol (ONB), were synthesized. Tert‐butyl carbamate (Boc)‐protected versions 1‐Boc and 2‐Boc were also synthesized for proof of concept. GPC confirmed that 1‐Boc degrades over 40 times faster than 2‐Boc following deprotection into the designed intramolecular cyclization products. Finally, TEM visualization of particles made from 1 encapsulating iron oxide nanoparticles reveals complete disruption of nanoparticles and release of payload within a day upon UV irradiation. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3783–3790     

Pyridinyl hydrazone derivatives of thiacalix[4]arene as selective extractants of transition metal ions

The recognition ability of pyridinyl hydrazone derivatives of cone- and 1,3-alternate tetrathiacalix[4]arenes towards transition and alkali metals has been investigated by picrate extraction method. The stoichiometry of complexes and the extraction constants have been determined. It has been found that hydrazones do not extract alkali metal ions but show an excellent affinity towards transition and heavy metal cations. The removal of tert-butyl groups from calix[4]arene platform in the case of cone and 1,3-alternate isomers leads to an increase of d-ion extraction selectivity or efficiency.