Adhesion, stretching, and electrical charge assessment of dermatan sulfate molecules by colloidal probes

Electrical and mechanical properties of dermatan sulfate (DS) molecules are studied in an aqueous environment as a function of pH. DS molecules linked at various points distributed on the surface of mica previously silanizated along with a suitable functionalized microsphere, attached to the cantilever of an atomic force microscope (AFM), provided suitable surfaces for testing interactions through the colloidal probe methodology. The repulsive force between the surfaces indicated that the charge of DS increases with pH as a result of the gradual deprotonation of acidic groups. Pulling experiments revealed increasing adhesion of DS to the monolayer as a function of pH, presumably due both to the electrical nature of the interaction between these molecules and the progressive increase of the charge of DS with pH. Serrations exhibited by the force in pulling experiments indicate that more than a single DS molecule is stretched at the same time. In addition, pulling force remained significant even at extensions that went beyond the average contour length of a single DS molecule, which suggests the existence of a significant link between DS molecules.     

Antimicrobial Hydantoin‐Containing Polyesters

A new N‐hydantoin‐containing biocompatible and enzymatically degradable polyester with antibacterial properties is presented. Different polyesters of dimethyl succinate, 1,4‐butanediol, and 3‐[N,N‐di(β‐hydroxyethyl)aminoethyl]‐5,5‐dimethylhydantoin in varying molar ratios are prepared via two‐step melt polycondensation. The antibacterially active N‐halamine form is obtained by subsequent chlorination of the polyesters with sodium hypochlorite. Chemical structures, thermal properties, and spherulitic morphologies of the copolymers are studied adopting FT‐IR, NMR, TGA, DSC, WAXD, and POM. The polyesters exhibit antibacterial activity against Escherichia coli. The adopted synthetic approach can be transferred to other polyesters in a straightforward manner.

     

Host–Guest Chemistry: Oxoanion Recognition Based on Combined Charge‐Assisted C−H or Halogen‐Bonding Interactions and Anion⋅⋅⋅Anion Interactions Mediated by Hydrogen Bonds

Several bis‐triazolium‐based receptors have been synthesized and their anion‐recognition capabilities have been studied. The central chiral 1,1′‐bi‐2‐naphthol (BINOL) core features either two aryl or ferrocenyl end‐capped side arms with central halogen‐ or hydrogen‐bonding triazolium receptors. NMR spectroscopic data indicate the simultaneous occurrence of several charge‐assisted aliphatic and heteroaromatic C?H noncovalent interactions and combinations of C?H hydrogen and halogen bonding. The receptors are able to selectively interact with HP₂O₇^3?, H₂PO₄^?, and SO₄^2? anions, and the value of the association constant follows the sequence: HP₂O₇^3?>SO₄^2?>H₂PO₄^?. The ferrocenyl end‐capped 7²⁺?2 BF₄ ^? receptor allows recognition and differentiation of H₂PO₄^? and HP₂O₇^3? anions by using different channels: H₂PO₄^? is selectively detected through absorption and emission methods and HP₂O₇^3? by using electrochemical techniques. Significant structural results are the observation of an anion???anion interaction in the solid state (2:2 complex, 6²⁺? [ H₂P₂O₇ ] ^2? ), and a short C?I???O contact is observed in the structure of the complex [ 8 ²⁺][SO₄]_0.5[BF₄].     

Decay heat studies for nuclear energy

The energy associated with the decay of fission products plays an important role in the estimation of the amount of heat released by nuclear fuel in reactors. In this article we present results of the study of the beta decay of some refractory isotopes that were considered important contributors to the decay heat in reactors. The measurements were performed at the IGISOL facility of the University of Jyväskylä, Finland. In these studies we have combined for the first time a Penning trap (JYFLTRAP), which was used as a high resolution isobaric separator, with a total absorption spectrometer. The results of the measurements as well as their consequences for decay heat summation calculations are discussed.     

The role of the spray pyrolysed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> barrier layer in achieving high efficiency solar cells on flexible steel substrates

Thin film chalcopyrite solar cells grown on light-weight, flexible steel substrates are poised to enter the photovoltaic market. To guarantee good solar cell performance, the diffusion of iron from the steel into the CIGSe absorber material must be hindered during layer deposition. A barrier layer is thus required to isolate the solar module from the metal substrate, both electronically and chemically. Ideally the barrier layer would be deposited by a cheap roll-to-roll process suitable to coat flexible steel substrates. Aluminium oxide deposited by spray pyrolysis matches the criteria. The coating is homogeneous over rough substrates allowing comparatively thin barrier layers to be utilized. In this article, solar cell results are presented contrasting the device performance made with a barrier layer to that without a barrier layer. Secondary Ion Mass spectrometry (SIMS) measurements show that the spray pyrolysed barrier layer diminishes iron diffusion to the chalcopyrite absorber layer. The role of sodium, imperative for the growth of high efficiency chalcopyrite solar cells, and how it interacts with Al₂O₃ is discussed.     

Hydrothermal carbon from biomass: structural differences between hydrothermal and pyrolyzed carbons via 13C solid state NMR

The objective of this paper is to better describe the structure of the hydrothermal carbon (HTC) process and put it in relationship with the more classical pyrolytic carbons. Indeed, despite the low energetic impact and the number of applications described so far for HTC, very little is known about the structure, reaction mechanism, and the way these materials relate to coals. Are HTC and calcination processes equivalent? Are the structures of the processed materials related to each other in any way? Which is the extent of polyaromatic hydrocarbons (PAH) inside HTC? In this work, the effect of hydrothermal treatment and pyrolysis are compared on glucose, a good model carbohydrate; a detailed single-quantum double-quantum (SQ-DQ) solid state (13)C NMR study of the HTC and calcined HTC is used to interpret the spectral region corresponding to the signal of furanic and arene groups. These data are compared to the spectroscopic signatures of calcined glucose, starch, and xylose. A semiquantitative analysis of the (13)C NMR spectra provides an estimation of the furanic-to-arene ratio which varies from 1:1 to 4:1 according to the processing conditions and carbohydrate employed. In addition, we formulate some hypothesis, validated by DFT (density functional theory) modeling associated with (13)C NMR chemical shifts calculations, about the possible furan-rich structural intermediates that occur in the coalification process leading to condensed polyaromatic structures. In combination with a broad parallel study on the HTC processing conditions effect on glucose, cellulose, and raw biomass (Falco, C.; Baccile, N.; Titirici, M.-M. Green Chem., 2011, DOI: 10.1039/C1GC15742F), we propose a broad reaction scheme and in which we show that, through HTC, it is possible to tune the furan-to-arene ratio composing the aromatic core of the produced HTC carbons, which is not possible if calcination is used alone, in the temperature range below 350 °C.     

Diels-Alder reactivity of 4-aryl-1-phthalimido-2-siloxy-1,3-butadienes

The reaction of (1Z,3E) and (1E,3E) 4-aryl-1-phthalimido-2-trialkylsiloxy-1,3-butadienes with maleimides and quinones has been studied. The observed exo-stereospecifity can be attributed to the simultaneous presence of the phthalimido and aryl groups, which produce strong hindrance during the endo approach.     

An innovation approach to the smoothing problem from uncertain observations with correlated signal and noise

This paper treats the least mean‐squared error linear fixed‐point and fixed‐lag smoothing problems from uncertain observations, when the variables describing the uncertainty are independent, and the signal and observation white noise are correlated. Using an innovation approach, recursive algorithms are derived for both estimators without requiring the whole knowledge of the state‐space model generating the signal, but only covariance information of the signal and the observation noise, as well as the probability that the signal exists in the observed values. Copyright © 2005 John Wiley & Sons, Ltd.