Synthetic and pharmacophoric studies of quinocarcin

1990 Fall.Includes bibliographical references.A new synthetic approach to the stereoselective total synthesis of the structurally unique antitumor antibiotic quinocarcin (1) is described. The utilization of model studies in this approach has led to novel methodologies concerning the construction of 1-(hydroxymethyl)-8-methoxy-1,2,3,4-tetrahydroisoquinolin-4-one (195) and several variably substituted pyrrolidines (180, 181, 182 and 183). These methodologies are discussed in terms of their synthetic utility as well as their mechanistic aspects. The synthetic approach to quinocarcin described herein allowed for the construction of several oxazolidine containing alkaloids which incorporate various aspects of the 8-11- iminoazepinotetrahydroiso-quinoline skeleton of quinocarcin. To this end the synthesis of a new tetracyclic oxazolidine moiety (240), which mimics quinocarcin's DNA nicking capabilities and represents the isolation of the pharmacophore of this novel antibiotic was achieved. The significance of the chemical stability and biological activity of 240 relative to quinocarcin is discussed

Thermisches Verhalten von Alkalihexachlorotitanaten (IV)

[No abstract available

The MAHB, the Culture Gap, and Some Really Inconvenient Truths

Humanity's failure to take adequate actions to stem a likely environmental collapse calls for extraordinary measures to understand and alter human behavior, argues Paul Ehrlich. His Millennium Assessment of Human Behavior (MAHB) aims to chart the path to a sustainable future

Habitat conversion and global avian biodiversity loss

The magnitude of the impacts of human activities on global biodiversity has been documented at several organizational levels. However, although there have been numerous studies of the effects of local-scale changes in land use (e.g. logging) on the abundance of groups of organisms, broader continental or global-scale analyses addressing the same basic issues remain largely wanting. None the less, changing patterns of land use, associated with the appropriation of increasing proportions of net primary productivity by the human population, seem likely not simply to have reduced the diversity of life, but also to have reduced the carrying capacity of the environment in terms of the numbers of other organisms that it can sustain. Here, we estimate the size of the existing global breeding bird population, and then make a first approximation as to how much this has been modified as a consequence of land-use changes wrought by human activities. Summing numbers across different land-use classes gives a best current estimate of a global population of less than 100 billion breeding bird individuals. Applying the same methodology to estimates of original land-use distributions suggests that conservatively this may represent a loss of between a fifth and a quarter of pre-agricultural bird numbers. This loss is shared across a range of temperate and tropical land-use types

Rate theory for correlated processes: Double-jumps in adatom diffusion

We study the rate of activated motion over multiple barriers, in particular the correlated double-jump of an adatom diffusing on a missing-row reconstructed Platinum (110) surface. We develop a Transition Path Theory, showing that the activation energy is given by the minimum-energy trajectory which succeeds in the double-jump. We explicitly calculate this trajectory within an effective-medium molecular dynamics simulation. A cusp in the acceptance region leads to a sqrt{T} prefactor for the activated rate of double-jumps. Theory and numerical results agree

Nanostructural organization of naturally occurring composites - part II: silica-chitin-based biocomposites

Investigations of the micro- and nanostructures and chemical composition of the sponge skeletons as examples for natural structural biocomposites are of fundamental scientific relevance. Recently, we show that some demosponges (Verongula gigantea, Aplysina sp.) and glass sponges (Farrea occa, Euplectella aspergillum) possess chitin as a component of their skeletons. The main practical approach we used for chitin isolation was based on alkali treatment of corresponding external layers of spicules sponge material with the aim of obtaining alkali-resistant compounds for detailed analysis. Here, we present a detailed study of the structural and physicochemical properties of spicules of the glass sponge Rossella fibulata. The structural similarity of chitin derived from this sponge to invertebrate alpha chitin has been confirmed by us unambiguously using physicochemical and biochemical methods. This is the first report of a silica-chitin composite biomaterial found in Rossella species. Finally, the present work includes a discussion related to strategies for the practical application of silica-chitin-based composites as biomaterials