Computer und chemische Synthese

Numerous computer programs have gained entry into drug research; some of them are already used as a matter of routine, whereas others are still being tested. The special advantages of the use of computer programs are shown for the two fields “computer-assisted synthesis planning” and “quantitative structure-activity relationships”. Several aspects of cooperation between man and computer are briefly discussed.     

Sequential supercritical fluid extraction (SSFE) for estimating the availability of high molecular weight polycyclic aromatic hydrocarbons in historically polluted soils

Sequential supercritical fluid (CO2) extraction (SSFE) was applied to eight historically contaminated soils from diverse sources with the aim to elucidate the sorption-desorption behavior of high molecular weight polycyclic aromatic hydrocarbons (PAHs). The method involved five extraction phases applying successively harsher conditions by increasing fluid temperature and density mobilizing target compounds from different soil particle sites. Two groups of soils were identified based on readily desorbing (available) PAH fractions obtained under mildest extraction conditions (e.g., readily desorbing fractions of fluoranthene and pyrene significantly varied between the soils ranging from <10 to >90%). Moreover, extraction behavior strongly correlated with molecular weight revealing decreasing available PAH fractions with increasing weight. Physicochemical soil parameters such as particle size distribution and organic dry mass were found to have no distinct effect on the sorption-desorption behavior of PAHs in the different soils. However, PAH profiles significantly correlated with readily available pollutant fractions; soils with relatively less mobile PAHs had higher proportions of five- and six-ring PAHs and vice versa. Eventually, biodegradability corresponded well with PAH recoveries under the two mildest extraction phases. However, a quantitative relationship was only established for soils with biodegradable PAHs. Out of eight soils, five showed no biodegradation including the four soils with the lowest fraction of readily desorbing PAHs. Only one soil (which was found to be highly toxic to Vibrio fischeri) did not match the overall pattern showing no PAH biodegradability but large fractions of highly mobile PAHs, concluding that mass transfer limitations may only be one of many factors governing biodegradability of PAHs.     

A new type of insect infrared organ of low thermal mass

The Australian beetle Acanthocnemus nigricans is attracted by forest fires and has a pair of complex infrared (IR) receptor organs on the first thoracic segment. Each organ consists of a tiny sensory disc (diameter 120-130 µm) which serves as an absorbing structure for IR radiation. The disc is arranged above an air-filled cavity which is located just anteriorly to the coxae of the prothoracic legs. Inside the disc, about 30 multipolar thermoreceptors (warmth receptors) are tightly attached to the cuticle which is directed to the outside. The many dendrites of each multipolar neuron are tightly wrapped around the soma and contain a large number of mitochondria. Absorption of IR radiation by the disc causes an increase in temperature which is measured by the warmth receptors. Therefore, the IR receptors of A. nigricans can be classified as microbolometers with reduced thermal mass and in principle can be compared to the IR organs of pit vipers.     

A multivariate analysis of beta diversity across organisms and environments

We examined variability in hierarchical beta diversity across ecosystems, geographical gradients, and organism groups using multivariate spatial mixed modeling analysis of two independent data sets. The larger data set comprised reported ratios of regional species richness (RSR) to local species richness (LSR) and the second data set consisted of RSR:LSR ratios derived from nested species-area relationships. There was a negative, albeit relatively weak, relationship between beta diversity and latitude. We found only relatively subtle differences in beta diversity among the realms, yet beta diversity was lower in marine systems than in terrestrial or freshwater realms. Beta diversity varied significantly among organisms' major characteristics such as body mass, trophic position, and dispersal type in the larger data set. Organisms that disperse via seeds had highest beta diversity, and passively dispersed organisms showed the lowest beta diversity. Furthermore, autotrophs had lower beta diversity than organisms higher up the food web; omnivores and carnivores had consistently higher beta diversity. This is evidence that beta diversity is simultaneously controlled by extrinsic factors related to geography and environment, and by intrinsic factors related to organism characteristics.     

An optimised sequential extraction scheme for the evaluation of vanadium mobility in soils

Reviewing the current state of knowledge about sequential extraction applied for soil vanadium(V) fractionation, we identified an urgent requirement of an sequential extraction(SE) specified for V. Namely, almost all previous SE extracted only 8.4%–48% of total V in soils(excluding residue). Thus, we proposed an eight-step SE for V fractionation in soils according to the knowledge gained from literature and our own dissolution experiments with model minerals. After extracting the mobilisable and adsorbed V with de-ionised water and 5 mmol/L phosphate, 1 mol/L pyrophosphate was applied to gather organic matter bound V which minimised the artefact dissolving Al and Fe(hydr)oxides occurred when using HNO_3–H_2O_2for extraction. Extraction with 0.4 mol/L NH_2OH·HCl was highly selective toward manganese oxides. Fractionation of different crystalline Al and Fe(hydr)oxides associated V with 1 mol/L HCl, 0.2 mol/L oxalate buffer and 4 mol/L HCl at 95°C especially improved the extractability of V incorporated with crystalline phase associated V. The suitability of our new SE scheme was confirmed by its higher selectivity against the target phases and higher extraction efficiencies(55%–77% of total V) with model minerals and 6 soils of different properties than previous SE.