Photodynamic action of some sensitizers by photooxidation of luminol

We report the development of a novel simple experimental method which allows the comparison of new photosensitizers based on their production of reactive oxygen species. A high-performance liquid chromatography (HPLC) assay permits the monitoring of several substances (sensitizer, reactant and oxidized end product) simultaneously on a single chromatogram. Photoreactions were monitored throughout their course by the HPLC assay surveying the sensitizers' efficiency of singlet oxygen production by the oxidative decomposition of luminol. Several photosensitizers were tested: Rose Bengal, Methylene Blue, Protoporphyrin IX, Photosan III, Photofrin, Hypericin and Pseudohypericin. Additionally, photoreactions were monitored by a standard pO₂ detection system. The measurements of the two detection methods were strongly correlated. Rose Bengal proved to be the most efficient photosensitizer, clearly decreasing the luminol concentration and causing a corresponding increase in aminophthalic acid. Our experiments show that when factors necessary for photochemical reactions are absent or are blocked (antioxidants), no reaction can be detected.     

Hydrogen infrastructure build-up for automotive applications

Some lessons for the introduction of hydrogen fueled vehicles can be learned from experience gained by the introduction of natural gas fueled vehicles, either in Europe or in Argentina. While the European efforts have failed, at least until today, Argentina has achieved a remarkable market share of about 20% natural gas vehicles since the early 80ies. Beyond a short review on the constituents of a hydrogen refueling infrastructure, the Compressed Natural Gas (CNG)-example is analyzed to formulate some ‘must be’s’ for the successful introduction of hydrogen refueling infrastructure: Clear concerted signals have to be sent by all important players, the politicians as well as the involved industry from car producers to fuel suppliers. Bi-fueled hybrid vehicles are not seen as a proper tool, as they are forcing neither the user to look for hydrogen nor the supplier to provide hydrogen. After general considerations, various strategies and policies of different countries and manufacturers are reviewed. For instance, the electric hybrid cars as already today introduced by some Japanese manufacturers offer the chance of settling a maintenance infrastructure for electric drive systems already today which can be easily extended to cover full fuel cell drive systems, once they are available.     

Enzymatic production of biosilica glass using enzymes from sponges: basic aspects and application in nanobiotechnology (material sciences and medicine)

Biomineralization, biosilicification in particular (i.e. the formation of biogenic silica, SiO₂), has become an exciting source of inspiration for the development of novel bionic approaches following “nature as model”. Siliceous sponges are unique among silica forming organisms in their ability to catalyze silica formation using a specific enzyme termed silicatein. In this study, we review the present state of knowledge on silicatein-mediated “biosilica” formation in marine sponges, the involvement of further molecules in silica metabolism and their potential application in nanobiotechnology and medicine. Werner E. G. Müller dedicated this study to Prof. Vera Gamulin (Rudjer Boskovic Institute, Zagreb, Croatia) in honour of her unique contributions in molecular evolution.     

Non-thermal production of pure hydrogen from biomass: HYVOLUTION

The objectives and methodology of the EU-funded research project HYVOLUTION devoted to hydrogen production from biomass are reviewed.The main scientific objective of this project is the development of a novel two-stage bioprocess employing thermophilic and phototrophic bacteria, for the cost-effective production of pure hydrogen from multiple biomass feedstocks in small-scale, cost-effective industries. Results are summarised of the work on pretreatment technologies for optimal biodegradation of energy crops and bio-residues, conditions for maximum efficiency in conversion of fermentable biomass to hydrogen and CO₂, concepts of dedicated installations for optimal gas cleaning and gas quality protocols, as well as innovative system integration aimed at minimizing energy demand and maximizing product output.The main technological objective is the construction of prototype modules of the plant which, when assembled, form the basis of a blueprint for the whole chain for converting biomass to pure hydrogen. A brief outline is presented of the progress made towards developing reactors for thermophilic hydrogen production, reactors for photoheterotrophic hydrogen production and equipment for optimal gas cleaning procedures.     

Life cycle inventory analysis of biological hydrogen production by thermophilic and photo fermentation of potato steam peels (PSP)

The environmental impact of hydrogen production in a 2-step fermentation process from potato steam peels was identified. Based on the ISO 14040, ISO 14044, ecoinvent data base and SimaPro 7.1 software, a life cycle inventory analysis was performed. Reflecting the current state of process development, the LCA shows an impact of 4.3 points (pts) which is at least 5.7 times higher than the selected reference technologies regarded as state-of-the-art. Over half (53.5%) of the environmental impact is generated by the use of phosphate in the fermentation processes. A sensitivity analysis shows a potential impact reduction of 65.8% due to recirculation of sewage or reduction of buffer concentration. The analysis also demonstrates that the production of the process ingredients cause 98.3% of the environmental impact. The impact of the process itself is 0.07 pts which is up to 10 times lower than the reference technologies.     

Methane and nitrous oxide emissions from a subtropical coastal embayment (Moreton Bay,Australia)

Surface water methane (CH₄) and nitrous oxide (N₂O) concentrations and fluxes were investigated in two subtropical coastal embayments (Bramble Bay and Deception Bay, which are part of the greater Moreton Bay, Australia). Measurements were done at 23 stations in seven campaigns covering different seasons during 2010–2012. Water–air fluxes were estimated using the Thin Boundary Layer approach with a combination of wind and currents-based models for the estimation of the gas transfer velocities. The two bays were strong sources of both CH₄ and N₂O with no significant differences in the degree of saturation of both gases between them during all measurement campaigns. Both CH₄ and N₂O concentrations had strong temporal but minimal spatial variability in both bays. During the seven seasons, CH₄ varied between 500% and 4000% saturation while N₂O varied between 128 and 255% in the two bays. Average seasonal CH₄ fluxes for the two bays varied between 0.5 ± 0.2 and 6.0 ± 1.5 mg CH₄/(m²·day) while N₂O varied between 0.4 ± 0.1 and 1.6 ± 0.6 mg N₂O/(m²·day). Weighted emissions (t CO₂-e) were 63%–90% N₂O dominated implying that a reduction in N₂O inputs and/or nitrogen availability in the bays may significantly reduce the bays' greenhouse gas (GHG) budget. Emissions data for tropical and subtropical systems is still scarce. This work found subtropical bays to be significant aquatic sources of both CH₄ and N₂O and puts the estimated fluxes into the global context with measurements done from other climatic regions.     

Distribution of14C-TNT and derivatives in different biochemical compartments ofPhaseolus vulgaris

¹⁴C-TNT was used to quantify the uptake rate and metabolic turnover of TNT inPhaseolus vulgaris. Seventeen plants were analysed by a special cell fractionation method with polar and nonpolar solvents and enzymes. We obtained three cytoplasmic fractions and five cell wall derived fractions. The recovery rate was 72% as measured by liquid scintillation counting.¹⁴C partitioned almost in equal amounts with approximately 50% in the cytoplasm and in the cell wall. The majority of the TNT-metabolites are present in the cytoplasm as was shown by GC/ ECD and thin layer chromatography. The¹⁴C in the cell wall is bound probably resulting in long-term immobilisation of these metabolites. We conclude that plants may also be a model for nitroaromatic turnover and immobilisation in soil components.