Accessing the dynamics of end-grafted flexible polymer chains by atomic force-electrochemical microscopy. Theoretical modeling of the approach curves by the elastic bounded diffusion model and Monte Carlo simulations. Evidence for compression-induced lateral chain escape

The dynamics of a molecular layer of linear poly(ethylene glycol) (PEG) chains of molecular weight 3400, bearing at one end a ferrocene (Fc) label and thiol end-grafted at a low surface coverage onto a gold substrate, is probed using combined atomic force-electrochemical microscopy (AFM-SECM), at the scale of approximately 100 molecules. Force and current approach curves are simultaneously recorded as a force-sensing microelectrode (tip) is inserted within the approximately 10 nm thick, redox labeled, PEG chain layer. Whereas the force approach curve gives access to the structure of the compressed PEG layer, the tip-current, resulting from tip-to-substrate redox cycling of the Fc head of the chain, is controlled by chain dynamics. The elastic bounded diffusion model, which considers the motion of the Fc head as diffusion in a conformational field, complemented by Monte Carlo (MC) simulations, from which the chain conformation can be derived for any degree of confinement, allows the theoretical tip-current approach curve to be calculated. The experimental current approach curve can then be very satisfyingly reproduced by theory, down to a tip-substrate separation of approximately 2 nm, using only one adjustable parameter characterizing the chain dynamics: the effective diffusion coefficient of the chain head. At closer tip-substrate separations, an unpredicted peak is observed in the experimental current approach curve, which is shown to find its origin in a compression-induced escape of the chain from within the narrowing tip-substrate gap. MC simulations provide quantitative support for lateral chain elongation as the escape mechanism.     

Location and base selectivity on fragmentation of brominated oligodeoxynucleotides

Bromine-modified oligodeoxynucleotides (ODNs) were fragmented in the electrospray source to study the influence of brominated bases on fragmentation. Several 13-mer ODNs containing a brominated pyrimidine base, BrdU (5-bromodeoxyuridine) or BrdC (5-bromodeoxycytidine), were analyzed. Low cone voltage fragmentation yields a loss of the brominated base with a preferential loss for the brominated base closer to the 5'-end (2-position > 4-position > 12-position) as well as a preferential loss of BrdU over BrdC. Higher cone voltage produces backbone fragmentation with complementary a(n)-base and w(m) ions close to the brominated base. On the basis of these observations, we located the brominated base in the sequence for all of the ODNs studied.     

Flower patterns in drop impact on thin liquid films

We describe experimentally the formation of a pattern for drop impacts on thin liquid films for a large range of impact parameters. Using the shallow-water approximation, we are able to explain the main mechanisms leading to these patterns: it consists in the linear instability of the self-similar axisymmetric radial solution of the equations. Agreement between the experiments and the theory is remarkably good, leading, in particular, to the prediction that the most unstable fold number scales like (We/h∞)2/7.     

Characterization of hyperbranched glycopolymers produced in vitro using enzymes

Asymmetrical flow field flow fractionation (AF4) has proven to be a very powerful and quantitative method for the determination of the macromolecular structure of high molar mass branched biopolymers, when coupled with multi-angle laser light scattering (MALLS). This work describes a detailed investigation of the macromolecular structure of native glycogens and hyperbranched α-glucans (HBPs), with average molar mass ranging from 2?×?10⁶ to 4.3?×?10⁷ g mol^?1, which are not well fractionated by means of classical size-exclusion chromatography. HBPs were enzymatically produced from sucrose by the tandem action of an amylosucrase and a branching enzyme mimicking in vitro the elongation and branching steps involved in glycogen biosynthesis. Size and molar mass distributions were studied by AF4, coupled with online quasi-elastic light scattering (QELS) and transmission electron microscopy. AF4-MALLS-QELS has shown a remarkable agreement between hydrodynamic radii obtained by online QELS and by AF4 theory in normal mode with constant cross flow. Molar mass, size, and dispersity were shown to significantly increase with initial sucrose concentration, and to decrease when the branching enzyme activity increases. Several populations with different size range were observed: the amount of small size molecules decreasing with increasing sucrose concentration. The spherical and dense global conformation thus highlighted was partly similar to native glycogens. A more detailed study of HBPs synthesized from low and high initial sucrose concentrations was performed using complementary enzymatic hydrolysis of external chains and chromatography. It emphasized a more homogeneous branching pattern than native glycogens with a denser core and shorter external chains.

Supramolecular Immobilization of Laccase on Carbon Nanotube Electrodes Functionalized with (Methylpyrenylaminomethyl)anthraquinone for Direct Electron Reduction of Oxygen

An efficient way of immobilizing and wiring a large amount of laccase on non‐covalently‐functionalized multi‐walled carbon nanotube (MWCNT) electrodes is reported. 1‐(2‐anthraquinonylaminomethyl)pyrene and 1‐[bis(2‐anthraquinonyl)aminomethyl]pyrene were synthesized and studied for their capability to non‐covalently functionalize MWCNT electrodes and immobilize and orientate laccase on the nanostructured electrodes. This led to high‐performance biocathodes for oxygen reduction by direct electron transfer with maximum current densities of (1±0.2) mA cm^?2. The performance of the resulting bioelectrodes could be doubled simply by using the bis‐anthraquinone compound. The bioelectrodes show excellent stability over weeks and can thus be envisioned in enzymatic biofuel cells.     

Aging of a donor conjugated polymer: Photochemical studies of the degradation of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene]

This article is devoted to the study of the photoaging and thermal aging of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene] (MDMO–PPV; also called OC1C10–PPV) used in organic solar cells. Thin MDMO–PPV films (thickness < 1 μm) were exposed to ultraviolet‐light irradiation (λ > 300 nm) in the presence of air or thermooxidized at 60 °C. The modifications of the chemical structure of the matrix were analyzed with ultraviolet–visible and infrared spectroscopy. The oxidation products that formed were identified by postirradiation treatments, including chemical derivatization reactions. On the basis of the identification of the various products formed, a two‐step radical mechanism is proposed to account for the modification of the chemical structure of the polymeric matrix. It involves first the oxidation of the ether substituent followed by the oxidation of the double bonds. These reactions are responsible for a loss of conjugation of MDMO–PPV, chain scissions, and a decrease in the visible absorbance, which are anticipated to drastically impair the photovoltaic properties of the material. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 317–331, 2007     

Molecular size and mass distributions of native starches using complementary separation methods: Asymmetrical Flow Field Flow Fractionation (A4F) and Hydrodynamic and Size Exclusion Chromatography (HDC-SEC)

Starch consists of a mixture of two α-glucans built mainly upon α-(1,4) linkages: amylose, an essentially linear polymer, and amylopectin, a branched polymer containing 5-6% of α-(1,6) linkages. The aim of the present work was to analyze the structural properties of native starches displaying different amylose-to-amylopectin ratios and arising from different botanical sources, using asymmetrical flow field flow fractionation (A4F) and a combination of hydrodynamic and size-exclusion chromatography (HDC-SEC) coupled with multiangle laser light scattering, online quasi-elastic light scattering, and differential refractive index techniques. The procedure, based upon dimethyl sulfoxide pretreatment and then solubilization in water, generates a representative injected sample without altering the initial degree of polymerization. The amylopectin weight-average molar masses and radii of gyration were around 1.0 × 10(8)-4.8 × 10(8) g mol(-1) and 110-267 nm, respectively. For each starch sample, the hydrodynamic radius (R(H)) distributions and the molar mass distributions obtained from the two fractionation systems coupled with light scattering techniques were analyzed. The size determination scales were extended by means of R(H) calibration curves. HDC-SEC and A4F data could be matched. However, A4F enabled a better separation of amylopectins and therefore an enhanced structural characterization of the starches. The two advantages of this experimental approach are (1) it can directly obtain distributions as a function of both molar mass and size, while taking account of sample heterogeneity, and (2) it is possible to compare the results obtained using the different techniques through the direct application of R(H) distributions.     

Exploiting the speckle noise for compressive imaging

An optical setup is proposed for the implementation of compressive sensing with coherent images. This setup specifically exploits the natural multiplicative action of speckle noise occurring with coherent light, in order to optically realize the essential step in compressive sensing which is the multiplication with known random patterns of the image to be acquired. In the test of the implementation, we specifically examine the impact of several departures, that exist in practice, from the ideal conditions of a pure multiplicative action of the speckle. In such practical realistic conditions, we assess the feasibility, performance and robustness of the optical scheme of compressive sensing.