Change in electron and spin density upon electron transfer to haem

Haems are the cofactors of cytochromes and important catalysts of biological electron transfer. They are composed of a planar porphyrin structure with iron coordinated at the centre. It is known from spectroscopy that ferric low-spin haem has one unpaired electron at the iron, and that this spin is paired as the haem receives an electron upon reduction (I. Bertini, C. Luchinat, NMR of Paramagnetic Molecules in Biological Systems, Benjamin/Cummins Publ. Co., Menlo Park, CA, 1986, pp. 165-170; H.M. Goff, in: A.B.P. Lever, H.B. Gray (Eds.), Iron Porphyrins, Part I, Addison-Wesley Publ. Co., Reading, MA, 1983, pp. 237-281; G. Palmer, in: A.B.P. Lever, H.B. Gray (Eds.), Iron Porphyrins, Part II, Addison-Wesley Publ. Co., Reading, MA, 1983, pp. 43-88). Here we show by quantum chemical calculations on a haem a model that upon reduction the spin pairing at the iron is accompanied by effective delocalisation of electrons from the iron towards the periphery of the porphyrin ring, including its substituents. The change of charge of the iron atom is only approx. 0.1 electrons, despite the unit difference in formal oxidation state. Extensive charge delocalisation on reduction is important in order for the haem to be accommodated in the low dielectric of a protein, and may have impact on the distance dependence of the rates of electron transfer. The lost individuality of the electron added to the haem on reduction is another example of the importance of quantum mechanical effects in biological systems.     

Plant litter feedback and population dynamics in an annual plant,<Emphasis Type="Italic"> Cardamine pensylvanica</Emphasis>

The presence of litter has the potential to alter the population dynamics of plants. In this paper, we explore the effects of litter on population dynamics using a simple experimental laboratory system with populations of the annual crucifer, Cardamine pensylvanica. Using a factorial experiment with four densities and three litter levels, we determined the effect of litter on biomass and plant fecundity, and the life stages responsible for these changes in yield. Although litter had significant effects on seed germination and on seedling survivorship, we show, using a population dynamics model, that these effects were not demographically significant. Rather, the potential effect of litter on population dynamics resulted almost entirely from its effect on biomass. Persistent litter suppressed plant biomass and apparently removed the direct density effect present in the absence of litter. Thus, litter changed the shape of the recruitment curve from slightly humped to asymptotic. In addition to changing the shape of the recruitment curve, litter reduced the carrying capacity of the populations. Thus, the population dynamics model indicated that not all statistically significant responses were dynamically significant. Given the potential complexity of litter effects, simple population models provide a powerful tool for understanding the potential consequences of short-term responses. Received: 8 September 1999 / Accepted: 5 April 2000     

Computational Investigations of the Chalcogen-Substituted Carboxylic Acids RC(=O)XH and RC(=X)OH and their Dimers [RC(=O)XH]2 and [RC(=X)OH]2 (X=S, Se, Te)

Semiempirical and ab initio theoretical methods have been used to investigate molecular structures of the chalcogen-substituted carboxylic acid isomers RC(=O)XH (chalcogenol acid) and RC(=X)OH (chalcogenon acid). A recent experimental report suggests that the chalcogenon isomers, although less stable at room temperature, predominate at low temperature in polar solvents and that there is only a small barrier to isomerization between the isomers. Theoretical calculations have been used to locate minimum energy structures of chalcogen-substituted carboxylic acid isomers and to calculate energy differences between pairs of isomers. Carboxylic acids are well known to dimerize, especially in the gas phase and in non-polar solvents. We have, therefore, also calculated energies of dimerization of the chalcogen-substituted acids by optimizing the geometries of the symmetric dimers. We note that the PM3 level of theory is only qualitatively correct for sulfur- and selenium-containing species but fails even qualitatively for the tellurium-containing compounds. Ab initio results confirm the experimental observations and provide good estimates of both isomerization and dimerization energies. We conclude that for many functional groups with tautomers RC(=X)YH and RC(=Y)XH, the more acidic tautomer is the one with the acid proton on the smaller, more electronegative atom, although in many cases this may not be the more stable tautomer.Electronic Supplementary Material available.     

Habitat characteristics contributing to local occupancy and habitat use in rock pool <Emphasis Type="Italic">Daphnia</Emphasis> metapopulations

The effects of invasive macrophytes, water level fluctuations and predation on freshwater unionids Pyganodon grandis and Utterbackia imbecillis were studied in three small impoundments in Northeastern Texas in 2003–2005. Mussel density was sampled with quadrats. Mortality, associated with the water level fluctuations and predation, was estimated by collecting dead shells on the shore at about two month intervals. In two ponds, horizontal distribution of unionids was limited by dense beds of invasive and noxious macrophytes (mainly Eurasian watermilfoil Myriophyllum spicatum and American lotus Nelumbo lutea): mussel densities were significantly lower in these macrophyte beds (P < 0.001). In the third pond with the lowest density of macrophytes (stonewort Chara sp.), unionids were distributed more evenly, and the average unionid biomass was the highest among all ponds studied. Vertical distribution of unionids in all ponds was likely limited by low oxygen at depth >2 m. The total amount of shells found on the shore per year varied from 0.1% to 28% of the total population in the pond and was negatively correlated with water level (r = −0.72 to −0.81, P < 0.005). Mammalian predators consumed up to 19% of the total unionid population and predation was facilitated by water level fluctuations. Handling editor: K. Martens     

Testing for density dependence

Summary The robustness and sensitivity of a test for density dependence in an animal population against departures from the assumed null and alternative model is assessed via simulation. The test is shown to be nonrobust and insensitive to departures from the assumed models.     

Measuring dominance and diversity in ecological communities: choosing the right variables

Abstract. Although there are many studies in searching for the most useful community diversity index, the importance of choosing an appropriate parameter has been neglected. Here, we examined dominance and diversity in early post-fire chaparral communities using different variables, i.e. plant density, cover and biomass. Significant different results were produced by applying different parameters and the difference may be caused by the inconsistency in density, cover, and biomass allocated in each life form. Among the three parameters, biomass was most successful in detecting differences among communities because the apportionment of biomass among species was more variable than that of density. Although the three species variables represent different aspects of community properties and their relative performance may vary among communities, we recommend the use of biomass or productivity data as the most appropriate variable because it can best represent per capita resource use and resource partitioning among organisms in competitive situations.     

Early Siberians from Lake Baikal and Alaskan population affinities

Among the materials excavated by the 1975 joint USSR–USA team in Siberia are two burials from Shaman's Cape, Olkhon Island, Lake Baikal. One is a middle-aged male of the Serovo culture, 6,000 B.C. , and the other is a young male of the Glaskovo culture of 2,000 B.C. This later burial displays an unusual pathology affecting the nose and post-cranial regions of the pelvic girdle and lower limbs. Osteon analysis confirms the determination of age at death and illustrates the difference between normal and pathological bone. Numerous cultural materials were associated with these burials, including harpoon heads, knives, a compound fishhook and a pestle with the Serovo man, and nephrite ornaments with the Glaskovo man. The skulls, though far apart in time, are pronouncedly Mongoloid and alike in their low cranial vaults. A low, broad and inclined ascending ramus resembles Chukchi, Eskimos and Aleuts. These two specimens document the Mongoloid character of the early inhabitants of Lake Baikal.     

Seed mass,genotype, and density effects on growth and yield of Oenothera biennis L.

Summary Seed mass and genotypic effects on the growth and reproduction of Oenothera biennis L. over a gradient of intraspecific density were examined in a greenhouse experiment. By using genetically identical seeds from five parental genotypes we were able to examine independently the effects of seed mass and genotype on seedling and adult performance. Seedling size was significantly correlated with seed mass for the first five weeks but had no effect on adult size or reproductive output. In contrast, genotype differences became increasingly apparent with time. In particular, there were striking differences in reproductive output among genotypes. Plants grown from two of the genotypes consistently produced more, but lighter, seeds and a greater proportion flowered at high density than the other three genotypes. In all five genotypes, seed number was much more variable than seed mass across the density gradient. Initial seed mass accounted for a significant proportion of the variation in progeny seed mass, and mean seed mass produced in the greenhouse was positively correlated with mean seed mass of the parent (in the field). This result, together with the observed constancy of seed mass within a genotype across the density gradient, indicates the differences in reproductive output among these genotypes are genetically determined.     

On the stabilization of animal numbers. Problems of testing

Summary When testing for regulation of population numbers, rather than using Bulmer's second test in cases where population numbers are estimated instead of measured, we prefer to correct Bulmer's first test for estimation error. A correction method is expounded, discussed, and applied to two series of census data: the pine looper of Klomp and the garden chafer of Milne. In neither case the tentative conclusion from using the uncorrected test was changed after correction. Therefore, in practice Bulmer's first test without correction can be used well as a first orientation. Twelve long series (more than 10 years) of census data of both univoltine and semelparous (a necessary condition) insects were tested for significant density dependence in the fluctuations of numbers with the randomization test of Pollard et al. None of the series, all we could find to meet the necessary condition as well as being longer than 10 years, showed significant density dependence at the 0.05 level, though the pine looper of Klomp did so at the 0.1 level. Next, the same series were tested for regulation in the sense of keeping density within limits with both the first test of Bulmer and the permutation test of Reddingius and Den Boer. Onky Klomp's pine looper population at Hoge Veluwe scored significantly. In a following paper this population will be considered more closely, in order to enable understanding of this test result.Communication No. 362 of the Biological Station, Wijster