Pneumocandin Biosynthesis: Involvement of a trans‐Selective Proline Hydroxylase

Echinocandins are cyclic nonribosomal hexapeptides based mostly on nonproteinogenic amino acids and displaying strong antifungal activity. Despite previous studies on their biosynthesis by fungi, the origin of three amino acids, trans‐4‐ and trans‐3‐hydroxyproline, as well as trans‐3‐hydroxy‐4‐methylproline, is still unknown. Here we describe the identification, overexpression, and characterization of GloF, the first eukaryotic α‐ketoglutarate/Fe^II‐dependent proline hydroxylase from the pneumocandin biosynthesis cluster of the fungus Glarea lozoyensis ATCC 74030. In in vitro transformations with L ‐proline, GloF generates trans‐4‐ and trans‐3‐hydroxyproline simultaneously in a ratio of 8:1; the latter reaction was previously unknown for proline hydroxylase catalysis. trans‐4‐Methyl‐L ‐proline is converted into the corresponding trans‐3‐hydroxyproline. All three hydroxyprolines required for the biosynthesis of the echinocandins pneumocandins A₀ and B₀ in G. lozoyensis are thus provided by GloF. Sequence analyses revealed that GloF is not related to bacterial proline hydroxylases, and none of the putative proteins with high sequence similarity in the databases has been characterized so far.     

Durability and surface chemistry of horizontally aligned CNT films as electrodes upon electrolysis of acidic aqueous solution

We devised a simple and effective method of electrochemical functionalization of horizontally aligned CNT films in diluted HCl and H₂SO₄ solutions upon their electrolysis under a constant current mode. We were able to cause notable generation of carbon–oxygen and carbon–chlorine functional groups on the CNT film anodes as proven by EDX, XPS, and Raman spectroscopy. As a consequence, we observed significant changes of the morphology of the material under electron microscopy, what translated into improved compatibility of CNTs with hydrophilic media. In turn, application of CNT films as cathodes was found as a powerful tool for a thorough cleaning of the nanotubes. Finally, we demonstrated that by the selection of appropriate conditions, CNT films can act as easy-to-make and flexible electrodes with a high stability and performance superior to graphite for generation of non-oxidizing gases such as hydrogen from solution. CNT film electrodes are two orders of magnitude lighter and require much lower overpotential for faradaic splitting of water.     

The Role of Higher Lying Electronic States in Charge Photogeneration in Organic Solar Cells

The role of excess photon energy on charge generation efficiency in bulk heterojunction solar cells is still an open issue for the organic photovoltaic community. Here, the spectral dependence of the internal quantum efficiency (IQE) for a poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b]­dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)]:6,6‐phenyl‐C₆₁‐butyric acid methyl ester (PCPDTBT:PC60BM)‐based solar cell is derived combining accurate optoelectronic characterization and comprehensive optical modeling. This joint approach is shown to be essential to get reliable values of the IQE. Photons with energy higher than the bandgap of the donor material can effectively contribute to enhance the IQE of the solar cell. This holds true independently of the device architecture, reflecting an intrinsic property of the active material. Moreover, the nanomorphology of the bulk heterojunction plays a crucial role in determining the IQE spectral dependence: the coarser and more crystalline, the lesser the gain in IQE upon high energy excitation.     

Prospective environmental life cycle assessment of nanosilver T-shirts

A cradle-to-grave life cycle assessment (LCA) is performed to compare nanosilver T-shirts with conventional T-shirts with and without biocidal treatment. For nanosilver production and textile incorporation, we investigate two processes: flame spray pyrolysis (FSP) and plasma polymerization with silver co-sputtering (PlaSpu). Prospective environmental impacts due to increased nanosilver T-shirt commercialization are estimated with six scenarios. Results show significant differences in environmental burdens between nanoparticle production technologies: The "cradle-to-gate" climate footprint of the production of a nanosilver T-shirt is 2.70 kg of CO(2)-equiv (FSP) and 7.67-166 kg of CO(2)-equiv (PlaSpu, varying maturity stages). Production of conventional T-shirts with and without the biocide triclosan has emissions of 2.55 kg of CO(2)-equiv (contribution from triclosan insignificant). Consumer behavior considerably affects the environmental impacts during the use phase. Lower washing frequencies can compensate for the increased climate footprint of FSP nanosilver T-shirt production. The toxic releases from washing and disposal in the life cycle of T-shirts appear to be of minor relevance. By contrast, the production phase may be rather significant due to toxic silver emissions at the mining site if high silver quantities are required.     

Towards a better understanding of the pectin structure-function relationship in broccoli during processing: Part I—macroscopic and molecular analyses

To investigate the structure-function relationship of pectin during (pre)processing, broccoli samples (Brassica oleracea L. cultivar italica) were subjected to one of the following pretreatments: (i) low-temperature blanching (LTB), (ii) LTB in combination with Ca²⁺ infusion, (iii) high-pressure pretreatment (HP), (iv) HP in combination with Ca²⁺ infusion, or (v) no pretreatment (control sample), whether or not in combination with a thermal treatment of 15 min at 90 °C. The macroscopic attributes of broccoli were linked to the chemical structure of broccoli pectin. By enhancing the cross-linking of pectic polymers, both LTB and HP reduced the texture loss that occurred during thermal processing of broccoli. During these pretreatments, homogalacturonan was de-esterified by pectin methylesterase, which led to changes in pectin solubility. When LTB or HP was combined with Ca²⁺ infusion, changes in the structure of pectin occurred, however not always reflected at the macroscopic level. The degree of esterification of pectin in Ca²⁺-soaked broccoli samples was lower compared to non-Ca²⁺-soaked samples and, in addition, a higher amount of ionically cross-linked pectin was retrieved.     

Rare-earth diiodides and derivatives

The rare-earth diiodides, MI₂, may be synthesized from the corresponding triiodides, MI₃, by reduction with their metals at elevated temperatures or, alternatively, through so-called metallothermic reduction reactions with alkaline or alkaline-earth metals. In these cases, ternary iodides may be obtained that may be derived from the binary diiodides by either formal addition or substitution. Prominent formula types that are thus obtained are A^IMI₃, or the mixed-valent A^I₅M^II₂M^IIII₁₂ and A^IIMI₄ with A^I and A^II representing alkaline or alkaline-earth elements (and their analogues), respectively. Further iodides that are relevant in these systems are, for example, Pr₂I₅, Ba₆Pr₃I₁₉ and interstitially stabilized phases such as {Er₁₄(N₂)(C₂)₂}I₂₄, La₉O₄I₁₆ and Ba{Ce₄N₂}I₈.     

Differential responses to male and female depressive reactions.

Suggests that the commonly reported preponderance of female over male depression in incidence and prevalence studies requires further analysis. One explanation is that the social consequences of expression of depressive symptomatology are different for males and females. A comparison of 157 male and 189 female undergraduates' reactions to male and female case histories of common reactions to stress confirmed the hypothesis. Depression elicited more rejection of males than of females, and the sex difference in rejection of depression was more pronounced than for anxiety or flat affect-detached responses. A discriminant analysis suggested that depressed males are especially likely to be perceived as impaired in role functioning as compared with depressed females. Results suggest that depressed males are not rejected for expression of emotionality as such. Speculations about the causes and consequences of differential rejection of depression are noted. (PsycINFO Database Record (c) 2010 APA, all rights reserved)