Solvent cage effects: the influence of radical mass and volume on the recombination dynamics of radical cage pairs generated by photolysis of [CpCH2CH2N(CH3)C(O)(CH2)nCH3Mo(CO)3]2 (n = 3, 8, 13, 18) (Cp = eta 5-C5H4) complexes

The photochemistry of the [(CpR)Mo(CO)(3)](2) molecules, where CpR = eta(5)-C(5)H(4)(CH(2))(2)C(O)NCH(3)(CH(2))(n)CH(3) (n = 3, 8, 13, and 18), was examined using femtosecond pump-probe transient absorption spectroscopy. The goal of this study was to investigate the importance of radical size and mass on the dynamics and efficiency of geminate radical-radical recombination. The femtosecond results demonstrated the lack of any size/mass dependence of the recombination efficiency. This finding contrasts with results from a prior study that did find a size/mass dependence using a steady-state photochemical technique. To explain these conflicting results, it is proposed that the femtosecond pump-probe results are a measurement of the efficiency of primary geminate recombination whereas the steady-state method results are a measurement of the sum of primary and secondary geminate recombination efficiencies. The size/mass dependence is evident in the latter because secondary geminate recombination is a slower diffusive recombination process and therefore depends on the steric properties of the radicals. Although the existence of primary and secondary recombination channels is often taken for granted, experimental differentiation of primary and secondary caging has proven to be difficult because it is not possible for a single experimental technique to span the entire timescale for recombination of a radical cage pair and adequately resolve these recombination pathways.     

Influence of the phosphorus and nitrogen source on nisin production in Lactococcus lactis subsp. lactis batch fermentations using a complex medium

The influence of different phosphorus and nitrogen sources on Lactococcus lactis subsp. lactis NIZO 22186 growth and nisin production was studied in batch fermentations using a complex medium. KH₂PO₄ was found to be the best phosphorus source for nisin production. Increasing initial phosphate concentrations from 0 to 5% KH₂PO₄ exerted a double effect, creating favourable pH conditions and particularly stimulating the nisin production levels, which were highest at 5% KH₂PO₄. Up to now, no such high initial phosphate concentrations have been reported for the production of other antibiotics or bacteriocins. Nisin, a lanthionine-containing peptide antibiotic with bacteriocin properties, clearly behaved as a primary metabolite, since its formation was linked with active growth and was not suppressed by phosphate concentrations up to 5%. A complex medium supplemented with cotton seed meal as nitrogen source also gave very high nisin yields. Correspondence to: L. De Vuyst     

l-DOPA Cytotoxicity to PC12 Cells in Culture Is via Its Autoxidation

Abstract: The mechanism of cytotoxicity of l -DOPA was studied in the rat pheochromocytoma PC12 cell line. The cytotoxicity of l -DOPA to PC12 cells was time and concentration dependent. Carbidopa, which inhibited the conversion of l -DOPA to dopamine, did not protect against l -DOPA cytotoxicity in PC12 cells. Furthermore, clorgyline, a selective inhibitor of monoamine oxidase type A, and pargyline, an inhibitor of both monoamine oxidase types A and B, both did not have an effect on l -DOPA toxicity. These findings suggest that cytotoxicity was not due to dopamine formed from l -DOPA. Catalase or superoxide dismutase each partially protected against l -DOPA toxicity in PC12 cells. In combination, the effects were synergistic and provided almost total protection against cytotoxicity. 6-Cyano-7-nitroquinoxaline-2,3-dione, an antagonist of non-NMDA receptors, did not protect against l -DOPA toxicity. These data suggest that toxicity of l -DOPA is most likely due to the action of free radicals formed as a result of its autoxidation. Furthermore, these findings suggest that patients on long-term l -DOPA therapy are potentially at risk from the toxic intermediates formed as a result of its autoxidation.     

Hydrologic,vegetation, and substrate characteristics of floating marshes in sediment-rich wetlands of the Mississippi river delta plain,Louisiana, USA

Floating marshes occur over 70% of the western Terrebonne Basin, Louisiana, USA, freshwater coastal wetlands. They are of several types: A free-floating thick-mat (45–60 cm) marsh dominated by Panicum hemitomon and Sagittaria lancifolia; a thick mat marsh dominated by Panicum hemitomon and Sagittaria lancifolia that floats part of the year, but whose vertical floating range is damped compared to adjacent water; and an irregularly-floating thin mat (< 30 cm) dominated by Eleocharis spp. in the spring and Ludwigia leptocarpa and Bidens laevis in the summer and fall. Floating mats must be almost entirely organic in order to be buoyant enough to float. The western Terrebonne wetlands receive large winter/spring supplies of suspended sediments from the Atchafalaya River. Even though sediment concentrations in the adjacent bayou are as high as 100 mg l^–1, the Panicum hemitomon/Sagittaria lancifolia free-floating marsh probably receives no over-surface sediments since it floats continuously. The bulk density data of the damped-floating marsh, however, suggest some mineral sediment input, probably during winter when this marsh is submerged. These two types of floating marsh could not have developed in the present sediment regime of the Atchafalaya River, but as long as they remain floating can continue to exist. Thin floating mats are found in areas receiving the least sediment (<20 mg 1^–1 suspended sediment concentration in adjacent bayous). This low sediment environment probably made possible their formation within the past 20 years. They may represent a transitional stage in mat succession from (1) existing thick-mat floating marsh to a degrading floating marsh, or (2) a floating marsh developing in shallow open water.Corresponding editor: D. Whigham     

Relationships of reproductive performance indicators in black rhinoceros (Diceros bicornis michaeli) with plant available moisture,plant available nutrients and woody cover

Plant available moisture and plant available nutrients in soils influence forage quality and availability and subsequently affect reproductive performance in herbivores. However, the relationship of soil moisture, soil nutrients and woody forage with reproductive performance indicators is not well understood in mega‐browsers yet these three are important in selecting suitable areas for conservation of mega‐browsers. Here, the eastern black rhinoceros (Diceros bicornis michaeli), a mega‐browser, was studied in seven geographically distinct populations in Kenya to understand the relationships between its reproductive performance indicators and plant available moisture, plant available nutrients and woody cover. Reproductive parameters showed a complex relationship with plant available moisture and plant available nutrients. We found an increase in the predicted yearly percentage of females calving as plant available nutrients decreased in areas of high levels of plant available moisture but no relationship with plant available nutrients in areas of low plant available moisture. Age at first calving was earlier, inter‐calving interval was longer and yearly percentage of females calving was higher at higher woody cover. Woody plant cover contributes positively to black rhino reproduction performance indicators, whereas plant available moisture and plant available nutrients add to the selection of conservation areas, in more subtle ways.     

Acute Hypoxemia Does Not Increase the Oxidative Stress in Resting and Contracting Muscle in Humans

In healthy humans sustaining static handgrip at 60% of maximal voluntary contraction (MVC) until exhaustion, we measured the venous blood concentration of reduced ascorbic acid (RAA) and thiobarbituric acid reactive substances (TBARS), respectively, used as markers of the post-exercise oxidative stress and lipid peroxidation. Measurements were conducted in normoxemia, then during a 30-min period of hypoxemia (PaO 2 =56 mmHg) produced by inhalation of an hypoxic gas mixture. Compared to normoxemia, hypoxemia did not significantly modify the resting concentrations of TBARS and RAA, and did not affect the consumption of ascorbic acid after 60% MVC but suppressed the post-exercise TBARS increase. We conclude that acute hypoxemia does not modify the production of oxygen free radicals after strenuous static efforts and even seems to attenuate the lipid peroxidation.     

A study of the anti‐plasmodium activity of angiotensin II analogs

Controlling the dissemination of malaria requires the development of new drugs against its etiological agent, a protozoan of the Plasmodium genus. Angiotensin II and its analog peptides exhibit activity against the development of immature and mature sporozoites of Plasmodium gallinaceum. In this study, we report the synthesis and characterization of angiotensin II linear and cyclic analogs with anti‐plasmodium activity. The peptides were synthesized by a conventional solid‐phase method on Merrifield's resin using the t‐Boc strategy, purified by RP‐HPLC and characterized by liquid chromatography/ESI (+) MS (LC‐ESI(+)/MS), amino acid analysis, and capillary electrophoresis. Anti‐plasmodium activity was measured in vitro by fluorescence microscopy using propidium iodine uptake as an indicator of cellular damage. The activities of the linear and cyclic peptides are not significantly different (p < 0.05). Kinetics studies indicate that the effects of these peptides on plasmodium viability overtime exhibit a sigmoidal profile and that the system stabilizes after a period of 1 h for all peptides examined. The results were rationalized by partial least‐square analysis, assessing the position‐wise contribution of each amino acid. The highest contribution of polar amino acids and a Lys residue proximal to the C‐terminus, as well as that of hydrophobic amino acids in the N‐terminus, suggests that the mechanism underlying the anti‐malarial activity of these peptides is attributed to its amphiphilic character. Copyright © 2013 European Peptide Society and John Wiley & Sons, Ltd.     

Cthulhu Macrofasciculumque n. g., n. sp. and Cthylla Microfasciculumque n. g., n. sp., a Newly Identified Lineage of Parabasalian Termite Symbionts

The parabasalian symbionts of lower termite hindgut communities are well-known for their large size and structural complexity. The most complex forms evolved multiple times independently from smaller and simpler flagellates, but we know little of the diversity of these small flagellates or their phylogenetic relationships to more complex lineages. To understand the true diversity of Parabasalia and how their unique cellular complexity arose, more data from smaller and simpler flagellates are needed. Here, we describe two new genera of small-to-intermediate size and complexity, represented by the type species Cthulhu macrofasciculumque and Cthylla microfasciculumque from Prorhinotermes simplex and Reticulitermes virginicus, respectively (both hosts confirmed by DNA barcoding). Both genera have a single anterior nucleus embeded in a robust protruding axostyle, and an anterior bundle flagella (and likely a single posterior flagellum) that emerge slightly subanteriorly and have a distinctive beat pattern. Cthulhu is relatively large and has a distinctive bundle of over 20 flagella whereas Cthylla is smaller, has only 5 anterior flagella and closely resembles several other parababsalian genera. Molecular phylogenies based on small subunit ribosomal RNA (SSU rRNA) show both genera are related to previously unidentified environmental sequences from other termites (possibly from members of the Tricercomitidae), which all branch as sisters to the Hexamastigitae. Altogether, Cthulhu likely represents another independent origin of relatively high cellular complexity within parabasalia, and points to the need for molecular characterization of other key taxa, such as Tricercomitus.