Synthesis and reactivity of [2]disilaniobocenophanes

The paramagnetic ansa-niobocene [(Me₂Si)₂(η⁵-C₅H₄)₂NbCl₂] (1) was obtained from the reaction of Li₂[(Me₂Si)₂(C₅H₄)₂] with [NbCl₄(thf)₂]. Further treatment with Li[AlH₄] yielded [(Me₂Si)₂(η⁵-C₅H₄)₂NbH₃] (3), which is prone to decomposition within a few days at room temperature both in solution and in the solid-state, thus affording primarily an insoluble black material. However, after heating or irradiation of a solution of 3 small quantities of the dimeric niobium hydride species, [(Me₂Si)₂{μ-(η¹:η⁵-C₅H₃)}(η⁵-C₅H₄)NbH]₂ (4), were isolated and characterized by X-ray diffraction.     

A simple chemical model for clathrate hydrate inhibition by polyvinylcaprolactam

A dimeric model compound gives structural insight into the mode of interaction of low dosage hydrate inhibitors with water.     

Biosynthesis of the Spermine Alkaloid Aphelandrine

Aphelandrine ( 1 ) is shown to be biosynthesized in the root cells of Aphelandra tetragona (VAHL ) NEES from labelled putrescine ( 4 ), spermidine ( 5 ), and cinnamic acid ( 3 ). Whether spermine ( 6 ) and the (p-hydroxycinnamoyl)spermidine 8 are precursors of 1 is uncertain, since the latter is hydrolysed to a large extent before incorporation, and the former is metabolized to 4 and 5 . Methionine ( 7 ) is the source of the 3-aminopropyl unit of 5 and 6 .     

Hereditarily Optimal Realizations of Consistent Metrics

One of the main problems in phylogenetics is to find good approximations of metrics by weighted trees. As an aid to solving this problem, it could be tempting to consider optimal realizations of metrics—the guiding principle being that, the (necessarily unique) optimal realization of a tree metric is the weighted tree that realizes this metric. And, although optimal realizations of arbitrary metrics are, in general, not trees, but rather weighted networks, one could still hope to obtain a phylogenetically informative representation of a given metric, maybe even more informative than the best approximating tree. However, optimal realizations are not only difficult to compute, they may also be non-unique. Here we focus on one possible way out of this dilemma: hereditarily optimal realizations. These are essentially unique, and can be described in a rather explicit way. In this paper, we recall what a hereditarily optimal realization of a metric is and how it is related to the 1-skeleton of the tight span of that metric, and we investigate under what conditions it coincides with this 1-skeleton. As a consequence, we will show that hereditarily optimal realizations for consistent metrics, a large class of phylogentically relevant metrics, can be computed in a straight-forward fashion. Received August 26, 2004     

Concomitant crystallization of two polymorphs-a ring and a helix: concentration effect on supramolecular isomerism

For the first time in Ag coordination chemistry, two supramolecular isomers, a ring and a helix, are isolated from the same mother liquor as a result of concentration effects.     

Identification of novel biomarker candidates by differential peptidomics analysis of cerebrospinal fluid in Alzheimer's disease

The objective of this work was the application of peptidomics technologies for the detection and identification of reliable and robust biomarkers for Alzheimer's disease (AD) contributing to facilitate and further improve the diagnosis of AD. Using a new method for the comprehensive and comparative profiling of peptides, the differential peptide display (DPD), 312 cerebrospinal fluid (CSF) samples from AD patients, cognitively unimpaired subjects and from patients suffering from other primary dementia disorders were analysed as four independent analytical sets. By combination with a cross validation procedure, candidates were selected from a total of more than 6,000 different peptide signals based on their discriminating power. Twelve candidates were identified using mass-spectrometric techniques as fragments of the possibly neuroprotective neuroendocrine protein VGF and another one as the complement factor C3 descendent C3f. The combination of peptide profiling and cross validation resulted in the detection of novel potential biomarkers with remarkable robustness and a close relation to AD pathophysiology.