Nanoparticle directed domain orientation in thin films of asymmetric block copolymers

We investigated the thin film morphology of two different asymmetric block copolymers (BCP), polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and poly(n-pentyl methacrylate)-block-poly(methyl methacrylate) (PPMA-b-PMMA), loaded with pre-synthesized iron oxide nanoparticles (NP). The chemical composition of the BCP constituents determines the strength of the interaction between polymer chains and nanoparticles. In the case of NP/PS-b-P4VP system, the nanoparticles interact preferentially with the P4VP block and hence localize selectively in the P4VP cylindrical microdomains. However, for the NP/PPMA-b-PMMA system, the nanoparticles have no significant preference for the copolymer blocks and segregate at the polymer/substrate interface. Interestingly, this changes the effective substrate surface energy and hence leads to a remarkable change in domain orientation from parallel to perpendicular with respect to the substrate. These results clearly demonstrate the importance of both enthalpic and entropic factors which determine spatial distribution of NP in BCP films and influence domain orientation.     

The sequential analysis of long range fallout debris

A method for the determination of the principal radionuelides of Sr, Ba, Ce, Cs, Y, Zr, Nb, and W in single fallout samples containing bulk Si, Fe, and Ca is presented. The sample and added carriers are dissolved by fusion with sodium carbonate. The melt is leached first with hot water and then with hydrochloric acid. W and Cs are recovered from the water leach. Sr, Ba, Y, and the heavier rare earths appear in the hydrochloric acid leach. Ce is found in the leach residue and Nb in both the residue and the hydrochloric acid leach. The Zr and Nb in the residue are separated from Ce by absorption on an anion-exchanger from hydrochloric acid. The Zr and Nb in the hydrochloric acid leach are separated from Sr and Ba by precipitation of Sr and Ba as nitrates and then separated from Y and the heavier rare earths by absorption on the anion-exchanger. The combined Zr fractions are eluted with dilute hydrochloric acid and Nb with a hydrochloric-hydrofluoric acid mixture.     

Modelling of the Phase Separation Behaviour of Semiflexible Diblock Copolymers

Silver salts are dissolved in poly(butyl methacrylate) to derive polymer electrolytes via coordinative interaction between the silver ion and the carbonyl oxygen atom. The dissolved silver ions react subsequently with propylene to form reversible silver/olefin complexes that can be utilized as olefin carriers for facilitated olefin transport. The complexation behavior and its effects on propylene transport were investigated by means of Raman and FT‐IR spectroscopy, as well as dielectric thermal analysis.     

Eine spektrophotometrische Bestimmung von kleinen Mengen 1-Monoglyceriden in Fetten

Ohne Zusammenfassung     

Tuning the mechanical properties of silica microcapsules

Heat treatment is a standard method to increase the hardness of silica in various applications. Here, we tested the effect of high temperature annealing on the mechanical properties of silica microcapsules by force spectroscopy under point loads applied to the particle shell. The Young's modulus of the shells moderately increases after annealing at temperatures above 500 °C. Temperatures over 850 °C result in a much stronger increase and the Young's modulus is close to that of fused silica after annealing at 1100 °C. NMR analysis revealed that in untreated microcapsules synthesized by seeded growth using the St?ber method only 55% of the silicon atoms form siloxane bonds with four neighbors, whereas the remaining ones only form three or less siloxane bonds each and, thus, a large number of ethoxy and silanol groups still exist. During annealing at 500 °C, these are successively transformed into siloxane bonds through condensation reactions. This process correlates with only a moderate increase in Young's modulus. The strong increase at temperatures above 850 °C was associated with a densification which was associated by a decrease in capsule size and shell thickness while the shells remained homogenous and of spherical shape. The main strengthening of the shells is thus mainly due to compaction by sintering at length scales significantly larger than that of local siloxane bonds.     

High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents

Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.     

Vinylcarbonates and vinylcarbamates: Biocompatible monomers for radical photopolymerization

The last decade has seen a remarkable interest in the use of biocompatible and biodegradable polymers as scaffolds for tissue engineering. The fabrication of 3D scaffolds by lithography‐based additive manufacturing technology (AMT) represents an appealing approach. As poly(lactic acid), the state of the art biocompatible and biodegradable material, cannot be processed by these photopolymerization‐based techniques, it has so far been necessary to use selected (meth)acrylates. By developing new photopolymers based on vinyl carbonates and vinyl carbamates as a reactive group we have been able to avoid most of the disadvantages of classical (meth)acrylate‐based photopolymers. The new generation of biocompatible monomers show low cytotoxicity, have good storage stability, and are sufficiently photoreactive to be structured by lithography based AMT. The mechanical properties and rates of degradation of the polymers can be easily tuned over a broad range. Degradation results in the formation of nonacidic and nontoxic degradation products of low molecular weight that can be easily transported within the human body. Initial in vivo tests showed significant osseointegration of the 3D cellular scaffolds and no signs of implant rejection. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of some furochromonesulfonamide derivatives with potential pharmacological activity

A number of visnagin-9-sulfonamides 1-3 have been prepared. In two instances side-products have been isolated in which the γ-pyrone ring is opened. All compounds were characterized by high-field ¹H and ¹³C nmr and mass spectra.