EPR characterization of oxide supported transition metal ions: Relevance to catalysis

EPR spectroscopy is a powerful tool to identify at a molecular level, the different steps of catalyst preparation, and of catalytic reactions:

1. Deposition of paramagnetic transition metal ions onto a support is monitored, and the coordination sphere of the metallic center is characterized by EPR.
2. The catalyst is also characterized after activation (thermal oxidation or reduction):

- the distribution among the different sites in zeolites can be determined;

- the dispersion of the active phase may be appreciated;

- the unsaturation degree of the active site may be evaluated using probe molecules such as water or¹³C enriched carbon monoxide.

1. The catalytic mechanisms can be investigated by studying the elementary steps of the catalytic reaction, as illustrated for methanol oxidation over Mo/SiO₂ catalysts whose EPR results have extended the reaction mechanism proposed on the basis of kinetic data. In addition, reaction intermediates may be isolated inquasi-in situ conditions as in the case of olefin oligomerization catalyzed by Ni/SiO₂ systems.

     

Fruiting of ectomycorrhizal basidiomycetes on unburned and prescribed burned hard-pine/hardwood plots after drought-breaking rainfalls on the Allegheny Mountains of southwestern Virginia

A headfire upward along the crest to the peak of a foothill during February 1988 had been prescribed to lower the possibility of a wildfire during the dry season on the Jefferson National Forest. Some surface litter plus annual and perennial stems on one-half of a stand of Pinus pungens/P. rigida had been destroyed. Subsequent development of ectomycorrhizal sporophores of basidiomycetes was recorded regularly within equal areas of burned and unburned portions and within a nearby unburned stand of P. virginiana. Each plot had a few ectomycorrhizal hardwoods, mainly Quercus spp. First fruiting was noted under burned P. pungens 3 weeks after a general rain in mid-July and after 4 weeks under both. By the end of November, when fruiting ceased, 138 separable taxa had been collected of which 95 had been identified. A list of the fungi and data on current and previously reported host associations, occurrence on each of the substrates, times and frequencies of fruiting, periodicity of genera, and variations in weather conditions are presented.     

TGGE and HIEF: a comparison of two methods in the detection of carriers of the Z mutation of the alpha-1-antitrypsin gene

Alpha-1-antitrypsin (-1-AT) deficiency can lead to juvenile liver cirrhosis and lung emphysema in adulthood. The deficiency Z allele is caused by a base transition. Temperature gradient gel electrophoresis (TGGE) and hybrid isoelectric focusing (HIEF) were used to detect carriers of the Z mutation of the -1-AT gene. The resulting data were compared. To verify carriers at the sequence level, a manual nonradioactive sequencing strategy was established. Among our sample of carriers of the Z mutation, two were not detected by HIEF that could be identified by TGGE. DNA of all TGGE identified individuals harboring the Z mutation of the -1-AT gene were sequenced nonradioactively. All carriers harbored a G to A transition at position 11.940. This mutation is described to cause the altered protein.     

Size structure of the metazoan community in a Piedmont stream

We characterized the size structure of virtually the entire metazoan community in a fourth order, sandybottomed Piedmont stream during late summer. Our study, the first to sample across all habitat types and sizes of metazoans in an aquatic ecosystem, indicates that at the community level, stream size spectra may be bimodal for the benthos or trimodal when fish are included. Animals spanning 10 orders of magnitude in dry mass (from gastrotrichs to fish) were quantitatively collected from nine habitat types. The bimodal benthic size spectrum was characterized by a meiofaunal component (mostly oligochaetes and micro-crustacea) and a macrobenthic component (mostly the introduced asiatic clam, Corbicula fluminea). Insects contributed little to overall standing crop. Size-specific contribution to whole-community metabolism was assessed using allometric equations for respiration, and we found a distinctly bimodal distribution across the entire metazoan size range, with peaks in the meiofaunal and benthic macrofaunal size ranges. Our bimodal benthic size spectrum is similar to that observed for marine benthos but not to other freshwater benthic systems, possibly because the entire range of habitat types and/or animal sizes were not sampled in the latter. Numerous factors may influence size spectra in stream ecosystems, including local geomorphic (habitat) conditions, water level fluctuations, species introductions, and predation processes.     

Regulation of scytophycin accumulation in cultures of Scytonema ocellatum. I. Physical factors

Scytonema ocellatum (Cyanobacteria or Cyanophyta) produces macrolide antibiotics of the scytophycin family that are antifungal, cytostatic agents and act by disrupting actin microfilaments. Scytophycin accumulation paralleled vegetative growth. Tolytoxin continued to accumulate throughout the growth cycle, whereas 6-hydroxy-7-O-methylscytophycin E (HMSE) and 19-O-demethylscytophycin C (DMSC) reached plateau levels prior to cessation of growth, suggesting a logical biosynthetic pathway of DMSC → ? → HMSE → tolytoxin. A rapid decrease in scytophycin content observed in newly inoculated cultures suggests that the scytophycins are continuously metabolized. The optimal temperature for production was 25°C. Continuous illumination at an intensity of at least 25 μml photons m^?2 s^?1 was required for maximum yield. Growth and metabolite production were optimal in the pH range of 8.0 to 8.5.     

The Value of a hoard: not just energy

We present a stochastic dynamic programming model of the contributionof stored food to winter survival. Using the acorn woodpecker(Melanerpes formtcivorus) as a model organism, we demonstratethat a hoard of small energetic value can impart considerableimprovement in the probability of surviving the winter and soimprove fitness. With this model we hope to resolve Koenig andMumme's paradox, that acorn woodpeckers expend much time andeffort to create and maintain hoards of acorns which provideno more that 16% of their energetic needs over the period inwhich they are used. We further demonstrate that the contributionof hoarded acorns to survival depends on the variability inforaging outcome, independently of the energetic value of thehoard in absolute terms. We point out that the results applyin principle to all hoarding animals and suggest a number offurther elaborations of the model.     

ANTIVIRAL ACTIVITY OF CULTURED BLUE-GREEN ALGAE (CYANOPHYTA)1

Lipophilic and hydrophilic extracts from approximately 600 strains of cultured cyanophytes, representing some 300 species, were examined for antiviral activity against three pathogenic viruses. Approximately 10% of the cultures produced substances that caused significant reduction in cytopathic effect normally associated with viral infection. The screening program identified the order Chroococcales as commonly producing antiviral agents.