Trovacenchemie. 13 [1] Weg und Irrweg zu Di([5]trovacenyl)keton

Trovacene Chemistry. 13 [1] On Being Lead and Mislead in the Synthesis of Di([5]trovacenyl)ketone Di([5]trovacenyl)ketone ( 3¨ ) has been prepared from lithio‐[5]trovacene and dimethylcarbamoyl chloride and studied by X‐ray diffraction, cyclic voltammetry, magnetic susceptometry and EPR spectroscopy. Slight variation of the synthetic protocol affords an unusual trinuclear complex 5 ? that is also fully characterized. Spin‐spin exchange interaction is smaller in 3¨ than in 1,1‐di([5]trovacenylethene ( 2¨ ), which differs from 3¨ by a replacement of O for CH₂. The novel trinuclear complex 5 ? , however, displays exchange coupling very similar to that observed in 1‐methoxy‐2,5,6‐tri([5]trovacenyl)benzene ( 7 ? ). In both cases, an unsymmetrical triangular arrangement of S = 1/2 centers is encountered. These findings are discussed in terms of the nature of the respective spacers.     

Space-Time Topology (II)—Causality, the Fourth Stiefel–Whitney Class and Space-Time as a Boundary

We show that stable causality is related to the vanishing of the top Stiefel–Whitney class of a space-time manifold M, and that if M is a stably causal space-time manifold, then it is the boundary of a five-dimensional space-time. We then propose a scheme for making it both a necessary and sufficient condition.     

The Heck reaction under ball-milling conditions

The synthesis of unsaturated unnatural amino acids according to the Heck-Jeffery protocol using a ball-milling procedure is presented. NOE data recorded on the products confirm that the Z-isomer is formed. This type of mechano-chemistry provides an efficient, “solvent free” and reliable method for the synthesis of substituted dehydroalanines. These conditions provide patterns of reactivity complementary to conventional procedures.     

On polynomial symbols for subdivision schemes

Given a dilation matrix A :ℤ^d→ℤ^d, and G a complete set of coset representatives of 2π(A ^−Tℤ^d/ℤ^d), we consider polynomial solutions M to the equation ∑ _g∈G M(ξ+g)=1 with the constraints that M≥0 and M(0)=1. We prove that the full class of such functions can be generated using polynomial convolution kernels. Trigonometric polynomials of this type play an important role as symbols for interpolatory subdivision schemes. For isotropic dilation matrices, we use the method introduced to construct symbols for interpolatory subdivision schemes satisfying Strang–Fix conditions of arbitrary order. Research partially supported by the Danish Technical Science Foundation, Grant No. 9701481, and by the Danish SNF-PDE network.     

Count(q) versus the pigeon-hole principle

For each there exists a model of which satisfies the Count() principle. Furthermore, if contains all prime factors of there exist and a bijective map mapping onto . A corollary is a complete classification of the Count() versus Count() problem. Another corollary shows that the pigeon-hole principle for injective maps does not follow from any of the Count() principles. This solves an open question [Ajtai 94]. Received August 16, 1994 / Revised version received April 29, 1996     

High temperature stability of maghemite in partially oxidized basalt lava

Mössbauer spectroscopy of basalt lava samples, exhibiting reversible thermal magnetization (J_S-T) curves with Curie temperatures of about 580°C, has revealed considerable amounts of maghemite (γ-Fe₂O₃) in many samples. In view of the expected instability, of maghemite at temperatures above 350°C, this reversibility is rather surprising. Here we report Mössbauer studies on heated lava samples, showing high content of maghemite. The samples were kept at 600°C in oxidizing, reducing, and inactive atmospheres, respectively, for different lengths of time, and then analyzed with Mössbauer spectroscopy at room temperature. The Mössbauer spectra showed that maghemite is stable in the oxidizing atmosphere for at least several hours. In the inactive atmosphere a considerable amount of maghemite still exists after two hours heating. In the reducing atmosphere maghemite had transformed to magnetite after only 30 minutes.     

Application of tris-allyl-DOTA in the preparation of DOTA-peptide conjugates

The synthesis of tris-allyl-DOTA starting from cyclen and its application in the preparation of DOTA-peptide conjugates is reported. Clinically important conjugates such as DOTA-Tyr³-octreotide (DOTA-TOC), DOTA-Tyr³-octreotate (DOTA-TATE) as well as a DOTA-RGD peptide were synthesized in high yields with Fmoc solid phase peptide synthesis. The final, extremely reliable de-allylation was achieved on solid phase by different methods identifying morpholine/Pd(0) as the most suitable one obtaining all DOTA peptide conjugates in high yields. All DOTA-peptides were purified by reversed phase HPLC and structural identity was proved using MALDI-TOF mass spectrometry.