Synthesis,characterization and computational evaluation of bicyclooctadienes towards molecular solar thermal energy storage

Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy. In this context, bicyclooctadienes (BODs) undergo a photoinduced transformation to the corresponding higher energy tetracyclooctanes (TCOs), but the photoswitch system has not until now been evaluated for MOST application, due to the short half-life of the TCO form and limited available synthetic methods. The BOD system degrades at higher temperature via a retro-Diels–Alder reaction, which complicates the synthesis of the compounds. We here report a cross-coupling reaction strategy that enables an efficient synthesis of a series of 4 new BOD compounds. We show that the BODs were able to switch to the corresponding tetracyclooctanes (TCOs) in a reversible way and can be cycled 645 times with only 0.01% degradation. Half-lives of the TCOs were measured, and we illustrate how the half-life could be engineered from seconds to minutes by molecular structure design. A density functional theory (DFT) based modelling framework was developed to access absorption spectra, thermal half-lives, and storage energies which were calculated to be 143–153 kJ mol⁻¹ (0.47–0.51 MJ kg⁻¹), up to 76% higher than for the corresponding norbornadiene. The combined computational and experimental findings provide a reliable way of designing future BOD/TCO systems with tailored properties.

Molecular solar-thermal energy storage (MOST) systems are based on photoswitches that reversibly convert solar energy into chemical energy.     

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.     

Phase stratification in the Nd1 − x BaxCoO3 − δ (0.3 ≤ x ≤ 0.54) system

Slowly cooled Nd_{1 ? x} Ba_xCoO_{3 ? δ} samples were two-phase in the concentration interval 0.3 ≤ x ≤ 0.46. One of the phases had O-orthorhombic lattice distortions (Pbnm) characteristic of ferromagnetic samples with x ≤ 0.3, and the other phase had tetragonal distortions (P4/mmm) characteristic of samples with x ≥ 0.46. Tetragonal distortions were caused by ordering of Nd³⁺ and Ba²⁺ ions. Samples with ordered neodymium and barium ions (Nd_{1 ? y} Ba_{1 + y} Co₂O_{6 ? γ} at ?0.08 ≤ y ≤ 0.08) experienced metal-dielectric and orientation magnetic phase transitions.     

Inorganic constituents in aerosols, cloud water and precipitation collected at the high alpine measurement station Sonnblick: Sampling, analysis and exemplary results

Background measurements at the high alpine station of the Sonnblick (altitude 3106 m) are reported. For a period of 13 months samples have been collected during 4 campaigns of 1–2 weeks duration each and analysed for their ionic and elemental composition, pH and conductivity. These samples were aerosols collected with filters, cloud water and precipitation. The samples were mainly analysed with ion chromatography (IC) and atomic absorption spectrometry (AAS). Analysis proved to be difficult due to the low amounts of aerosols collected and the low concentrations of components in cloud water and wet precipitation. Also major problems arose in sampling due to the extreme climatic conditions. The analytical techniques, particularly those for sampling the materials, are critically evaluated and results on pollutant levels, their variation with time and the distribution of the components between the gaseous and liquid phases are presented.Abbreviations ET-AAS Electrothermal Atomic Absorption Spectrometry - F-AAS Flame Atomic Absorption Spectrometry - FIA Flow Injection Analysis - IC Ion Chromatography Dedicated to Prof. Dr. Dieter Klockow on the occasion of his 60th birthday     

Remarks on the Idea of Spontaneous Break-Down of Symmetry,Cosmic Variability of Eddington's Number,Mach's Idea Concering the Origin of Inertia,and Field Equations Describing Global and Local Gravitational Fields

Subject is considered on the level of classical field theory. We start from some aspects of the theory of ferromagnets. Their counterpart in classical field theory is pointed out using the over simplified model of a selfinteracting scalar field. The ground state (“vacuum expection value”) of the scalar field is interpreted as cosmic background field, which can be considered as constant for local physical phenomena. In practice, however, it is a function of the age of universe. Which kind of function it could be is suggested by a discussion of the cosmic variability of Eddington's number γ = 10⁴⁰, which refers to Dirac's consideration of this problem. But contrary to Dirac's assumption that atomic quantities are constant, we suppose that the inertial mass of elementary particles is a function of the age of universe. The cosmic gravitational field is described by other equations than the gravitational field created by local matter distributions. The field equations for the local gravitational field we start from reduce to Einstein's equations, if we neglect the possible influence of the universe on local phenomena. In case that the cosmic matter is homogeneously and isotropically distributed, the field equations for the cosmic gravitational field permit only such a time dependent solution the three-spaces of which are linearly expanding and spherically closed. The different field equations for cosmic and local gravitational fields are considered approximations of more fundamental field equations which approximately split into two sets of equations, if it is possible to contrast local physical systems with the universe. The described cosmological model taken as a basis, the inertial mass of elementary particles becomes a function of the matter density creating the cosmic gravitational field. This could be considered as, at least, partly realisation of Mach's idea concerning the origin of inertia. Starting from the interpretation of the ground state (vacuum expection value) as a function of a certain cosmic background field, more realistic gage field models could give the following picture of cosmic development: In the far past there was a state of the universe characterized by enormous contraction of matter. In this stage of development, it was impossible to contrast particles with the universe. Matter expands and it becomes possible to contrast certain physical systems with the universe. But the ground state is such a symmetric one that only fields with vanishing rest mass can be contrasted with the universe (ferromagnet above Curie temperature). With further expansion of the universe the ground state will lose certain symmetry properties. By this it becomes possible that you get the impression there are particles with nonvanishing rest mass (ferromagnet below Curie temperature). Finally, the influence of the universe on local physical systems goes to zero with further expansion. Especially, this means the inertial mass of elementary particles goes to zero, too (Curie temperature of ferromagnetic material goes to zero with cosmic expansion).     

Photoinduced Pyridine Cleavage-Closure in Viscous Polymer Solutions

We have found that photoinduced pyridine ring cleavage-closure occurs in polymeric viscous solution, because in certain polymer solutions, pyridine can serve as a photo-modulated crosslinker. We suggest this reaction as a way to control a polymer's optical properties. Irradiation of the system: poly(4-vinyl pyridine)/pyridine/water with 250-nm wavelength range leads to the appearance of a new absorption band centered at 360 nm, new red-shifted emission, and HOMO-LUMO band gap changes. The subsequent irradiation with 360 nm (the new absorption band maximum) leads to reversion almost to the initial stage. A main active product of the photoreaction is aldehyde enamine, which has two active groups: primary amine and aldehyde, which can associate with the polymer molecules to form a physical crosslinked supramolecular structure. We evaluated the activation energy of the pyridine ring cleavage and back reaction depending on the polymer/pyridine/water ratio and by changing the polymer structure. The activation energy of pyridine's ring cleavage in viscous polymeric solutions is in the range of 0.6–3.2 Kcal/mol. The activation energy of the back reaction is significantly lower and is in the range of 0.05–0.15Kcal/mole.     

Investigation of the aromatization of C6+ hydrocarbons on chromia/lanthana-zirconia catalyst: Part I. Catalytic experiments

The aromatization pathway on a chromia/lanthana-zirconia catalyst has been investigated by the conversion of 13 linear and branched hydrocarbons. The product distribution is determined by the educt structure and points to a mechanism without side reactions like isomerization or cracking. The differences in aromatization reactivities could be explained by a mechanism via a stepwise dehydrogenation to a conjugated triene structure. First calculations show that methyl or methylene groups close to terminal double bonds can stabilize these trienes. Such substrates show higher aromatic yields than those without stabilizing groups.     

A finite loop space not rationally equivalent to a compact Lie group

We construct a connected finite loop space of rank 66 and dimension 1254 whose rational cohomology is not isomorphic as a graded vector space to the rational cohomology of any compact Lie group, hence providing a counterexample to a classical conjecture. Aided by machine calculation we verify that our counterexample is minimal, i.e., that any finite loop space of rank less than 66 is in fact rationally equivalent to a compact Lie group, extending the classical known bound of 5. Mathematics Subject Classification (2000) Primary: 55P35; Secondary: 55P15, 55R35     

Cosmology and Description of Local Space-Time Properties by Einstein's Equations

We consider a theory in which the global and local space-time properties are described by different laws. One consequence of such a theory is that the only time-dependent cosmological models are such that their homogeneous and isotropic three-spaces are closed. In the framework of this theory the local space-time properties are approximately described bei Einstein's equations, but with Einstein's gravitational coupling number now being a function of the matter density filling the universe.