Solid‐State Chemistry on the Nanoscale: Ion Transport through Interstitial Sites or Vacancies?

How can ion‐exchange process occur in nanocrystals without the size and shape changing and why is the ion transport much faster than in classical interdiffusion processes in macrocrystalline solids? We have investigated these processes at the molecular level by means of high‐resolution and analytical electron microscopy in temperature‐dependent kinetic experiments for several model reactions. The results clearly show a diffusion process that proceeds exclusively through the interstitial lattice positions with a subsequent “kick out” to remove individual ions from lattice sites without the formation of vacancies. This mechanism has not been observed in nanocrystalline systems before.     

An abstract setting for hamiltonian actions

In this paper we develop an abstract setup for hamiltonian group actions as follows: Starting with a continuous 2-cochain ω on a Lie algebra \mathfrak h{\mathfrak h} with values in an \mathfrak h{\mathfrak h}-module V, we associate subalgebras \mathfrak sp(\mathfrak h,w) ê \mathfrak ham(\mathfrak h,w){\mathfrak {sp}(\mathfrak h,\omega) \supseteq \mathfrak {ham}(\mathfrak h,\omega)} of symplectic, resp., hamiltonian elements. Then \mathfrak ham(\mathfrak h,w){\mathfrak {ham}(\mathfrak h,\omega)} has a natural central extension which in turn is contained in a larger abelian extension of \mathfrak sp(\mathfrak h,w){\mathfrak {sp}(\mathfrak h,\omega)}. In this setting, we study linear actions of a Lie group G on V which are compatible with a homomorphism \mathfrak g ? \mathfrak ham(\mathfrak h,w){\mathfrak g \to \mathfrak {ham}(\mathfrak h,\omega)}, i.e., abstract hamiltonian actions, corresponding central and abelian extensions of G and momentum maps J : \mathfrak g ? V{J : \mathfrak g \to V}.     

Reactions on polymers with amine groups. III. Description of the addition reaction of pyridine and imidazole compounds with α,β-unsaturated monocarboxylic acids

A detailed study of the synthesis of betaine products that result from addition reactions of poly (4-vinylpyridine) and poly (N-vinylimidazole) as well as of their model compounds, with α,β-unsaturated monocarboxylic acids is presented. A reaction mechanism based on experimental observations and proved by kinetic analysis is proposed. It consists of two reactions: the addition, which involves two molecules of acid and leads to X⁺B⁻-like structures, where the cation X⁺ results from the addition of the amino nitrogen to the double bond of acid and B⁻ is the carboxyl anion, and an equilibrium reaction between X⁺B⁻ and the betaine structure X^±. The latter occurs only in protic solvents and is coupled with the addition reaction. The process was especially investigated in methanol, because this solvent allows determination of the kinetic parameters. Some values of the addition rate constants are given. The study is based on ¹H-NMR measurements and observations. © 1996 John Wiley & Sons, Inc.     

13C NMR Study of the grafting of 13C labeled maleic anhydride onto PE,PP and EPM

The chemical structure of polyolefins grafted with maleic anhydride (MA) has been the subject of much speculation, but thorough experimental studies are rare. MA with 99% ¹³C in the double bond was synthesized and grafted onto PE, EPM and PP in the melt and solution. 1D INADEQUATE ¹³C NMR spectroscopy was used to characterize the products. Saturated, monomeric MA graft structures are formed. Only for grafted PE short MA oligomers are demonstrated. Grafting occurs on secondary and tertiary carbons depending on the composition of the polyolefin. For PP a new, unsaturated MA graft structure on the polymer chain terminus is identified. All graft structures are rationalized using a simple grafting mechanism.     

Transients and cooperative action of β-carotene, vitamin E and C in biological systems in vitro under irradiation

Using N^•₃ species as specific electron acceptor a defined ascorbate radical: AH^•↔A^•−+H⁺ (λ_max=360 nm, =3400 dm³ mol⁻¹ cm⁻¹) is observed. The attack of DMSO^•+ on vit.E results in a vit.E^• radical (k=1×10⁹ dm³ mol⁻¹ s⁻¹; λ_max=425 nm, =2400 dm³ mol⁻¹ cm⁻¹; 2k=4.7×10⁸ dm³ mol⁻¹ s⁻¹). Vit.E-acetate leads to the formation of a radical cation (vit.E-ac^•+). β-carotene reacts also with DMSO^•+ forming a radical cation, β-car^•+ (k=1.75×10⁸ dm³ mol⁻¹ s⁻¹; λ_max=942 nm, =14 600 dm³ mol⁻¹ cm⁻¹), which probably leads to the formation of a dimer radical cation, (β-car)^•+₂ (k=2.5×10⁷ dm³ mol⁻¹ s⁻¹).

Using E.coli bacteria (AB1157) as a model system in vitro it was found that all three vitamins are rather efficient radiation protecting agents. They can also increase the activity of cytostatica, e.g., mitomycin C (MMC), by electron transfer process. The mixture of vit.E-ac and β-car acts contradictory, but adding vit.C to it a strong cooperative enhancement of the MMC activity is observed once again. A relationship between the pulse radiolysis and the radiation biological data is found and discussed. A possible explanation of the previously reported trials concerning the role of vit.E and β-car on the increased occurence of lung and other types of cancer in smokers and drinkers is presented.