A novel route towards the synthesis of well‐defined linear–dendronized diblock copolymers is reported. Precursor alkyne containing diblock copolymers were modified in a highly efficient cycloaddition reaction with dendritic azides of different generation. The dendronization has been shown to be selective and could be driven to completion under ambient conditions. The phase separation of such dendronized diblock copolymers was investigated in dependence of the generation size being attached. Compared to a linear–linear diblock copolymer as starting material the dendronization yielded in a pronounced phase separation. The nanoscaled features observed in thin films strongly depended on the dendron size and a variety of morphologies could be identified. Hence, the unique combination of controlled radical polymerization and click chemistry allows for the triggering of structured surfaces in the nanometer‐regime.
ζ-potential measurements on LUVs allow to evidence the influence of pH, ionic salt concentration, and polyelectrolyte charge on the interaction between polyelectrolyte (chitosan and hyaluronan) and zwitterionic lipid membrane. First, chitosan adsorption is studied: adsorption is independent on the chitosan molecular weight and corresponds to a maximum degree of decoration of 40% in surface coverage. From the dependence with pH and independence with MW, it is concluded that electrostatic interactions are responsible of chitosan adsorption which occurs flat on the external surface of the liposomes. The vesicles become positively charged in the presence of around two repeat units of chitosan added per lipid accessible polar head in acid medium down to pH = 7.2. Direct optical microscopy observations of GUVs shows a stabilization of the composite liposomes under different external stresses (pH and salt shocks) which confirms the strong electrostatic interaction between the chitosan and the lipid membrane. It is also demonstrated that the liposomes are stabilized by chitosan adsorption in a very wide range of pH (2.0 < pH < 12.0). Then, hyaluronan (HA), a negatively charged polyelectrolyte, is added to vesicles; the vesicles turn rapidly negatively charged in presence of adsorbed HA Finally, we demonstrated that hyaluronan adsorbs on positively charged chitosan-decorated liposomes at pH < 7.0 leading to charge inversion in the liposome decorated by the chitosan-hyaluronan bilayer. Our results demonstrate the adsorption of positive and/or negative polyelectrolyte at the surface of lipidic vesicles as well as their role on vesicle stabilization and charge control. 相似文献
Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)), similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol?1 for methanol and scissions, respectively). Furthermore, a comparison of the rate constants $ \left( {k_{{{\text{CH}}_{ 3} {\text{OH}}}} /k_{\text{scissions}} } \right) Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has
been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited
naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil
weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly
increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)),
similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression
of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good
agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol−1 for methanol and scissions, respectively). Furthermore, a comparison of the rate constants shows approximately constant values indicating an apparent yield for the methanol of about one-third molecule per every scission
for the tests under air (0.27 ± 0.04 for Clupak HD75 and 0.37 ± 0.14 for Munksj? TH70) and even lower for the ones under N2 (0.12 ± 0.03 for Munksj? E.G.). As expected from a pseudo-zero order model, these values were shown to be consistent with
a similar comparison of the amount of CH3OH and chain-end groups produced under specific time–temperature ageing conditions (168 h at 120 °C). Finally, an additional
test carried out with unaged cellulose in contact with a fresh solution of methanol in oil (cellulose/oil weight–volume ratio
of 1:18) shows that at equilibrium, over 58% of the species is lost from the solution due to penetration into the fibres.
Such results reveal the importance of the species partitioning in establishing the true correspondence between the molecules
of CH3OH produced and the scissions. 相似文献
Summary: Polyisobutylene is an industrially important polymer which is conventionally prepared by polymerization at temperatures below 0 °C. The application of solvent ligated metal complexes associated with weakly coordinating counteranions (WCAs), however, allows the room temperature (30 °C) polymerization of isobutylene resulting in highly reactive polyisobutylene (HR-PIB) containing a high content of terminal double bonds. Recently described complexes include manganese (II), copper(II), molybdenum(III) and zink(II) complexes which were coordinated octahedrally with the boron and alumina based WCAs, each with its own advantages and traits. 相似文献
Blocking is an important step before an enzyme-linked immunosorbent assay (ELISA) can be performed. It reduces non-specific
binding to the microtiter plate to a minimum. For detecting food allergens by means of ELISA, the problem with protein blocking
solutions is obvious. The blocker might interfere with the antibodies of the assay and leads to false positive results. Therefore,
other blocking solutions are greatly needed. There are some alternatives like synthetic blockers or carbohydrates. Comparisons
of these different blocking agents, namely proteins, carbohydrates, and synthetic blockers, were made at different reaction
conditions. The incubation periods and temperatures were varied, as well as the pH. The best combinations were evaluated and
compared, in respect of their blocking efficiency. The two best non-proteinaceous blockers, i.e. polyvinylalcohol and Ficoll,
were subsequently applied to ELISA tests for the determination of α-casein and peanut. The study showed that Ficoll and PVA
did as well as BSA in buffer solution. Therefore, they can be considered as alternative blocking reagents for ELISA, especially
for the detection of food allergens. 相似文献
The nature of vibronic coupling in fused polycyclic benzene-thiophene structures has been studied using an approach that combines high-resolution gas-phase photoelectron spectroscopy measurements with first-principles quantum-mechanical calculations. The results indicate that in general the electron-vibrational coupling is stronger than the hole-vibrational coupling. In acenedithiophenes, the main contributions to the hole-vibrational coupling arise from medium- and high-frequency vibrations. In thienobisbenzothiophenes, however, the interaction of holes with low-frequency vibrations becomes significant and is larger than the corresponding electron-vibrational interaction. This finding is in striking contrast with the characteristic pattern in oligoacenes and acenedithiophenes in which the low-frequency vibrations contribute substantially only to the electron-vibrational coupling. The impact of isomerism has been studied as well. 相似文献