The insertion of the antimicrobial peptide dicynthaurin monomer in model membranes: thermodynamics and structural characterization

This paper is focused on the thermodynamics and the structural investigation of the interaction of the antimicrobial peptide dicynthaurin monomer with model lipid membranes composed of mixtures of 1-palmitoyl-2-oleyl-glycerophosphocholine and -glycerophosphoglycerol. The thermodynamic binding parameters as obtained by isothermal titration calorimetry reveal strong binding toward the lipid model system dominated by large chemical binding constants which exceeds the electrostatic binding effects and thus suggests insertion of the amphipathic alpha-helical peptide into the hydrophobic membrane core. Circular dichroism study shows that the peptide exhibits trans-membrane alpha-helix secondary structure. Neutron diffraction measurements using partially deuterated sequences were successfully applied to determine the orientation of the peptide thus proving insertion into the hydrophobic membrane core. This insertion and the formation of higher order porelike aggregates is assumed to be the most relevant event in microbial membrane perturbation that in vivo finally leads to bacterial cell death on a fast time scale.     

Carbon Recycling for Renewable Materials and Energy Supply

The current flow of carbon for the production, use, and waste management of polymer‐based products is still mostly linear from the lithosphere to the atmosphere with rather low rates of material recycling. In view of a limited future supply of biomass, this article outlines the options to further develop carbon recycling (C‐REC). The focus is on carbon dioxide (CO₂) capture and use for synthesis of platform chemicals to produce polymers. CO₂ may be captured from exhaust gases after combustion or fermentation of waste in order to establish a C‐REC system within the technosphere. As a long‐term option, an external C‐REC system can be developed by capturing atmospheric CO₂. A central role may be expected from renewable methane (or synthetic natural gas), which is increasingly being used for storage and transport of energy, but may also be used for renewable carbon supply for chemistry. The energy input for the C‐REC processes can come from wind and solar systems, in particular, power for the production of hydrogen, which is combined with CO₂ to produce various hydrocarbons. Most of the technological components for the system already exist, and, first modules for renewable fuel and polymer production systems are underway in Germany. This article outlines how the system may further develop over the medium to long term, from a piggy‐back add‐on flow system toward a self‐carrying recycling system, which has the potential to provide the material and energy backbone of future societies. A critical bottleneck seems to be the capacity and costs of renewable energy supply, rather than the costs of carbon capture.     

Methodology and Indicators of Economy‐wide Material Flow Accounting

This contribution presents the state of the art of economy‐wide material flow accounting. Starting from a brief recollection of the intellectual and policy history of this approach, we outline system definition, key methodological assumptions, and derived indicators. The next section makes an effort to establish data reliability and uncertainty for a number of existing multinational (European and global) material flow accounting (MFA) data compilations and discusses sources of inconsistencies and variations for some indicators and trends. The results show that the methodology has reached a certain maturity: Coefficients of variation between databases lie in the range of 10% to 20%, and correlations between databases across countries amount to an average R² of 0.95. After discussing some of the research frontiers for further methodological development, we conclude that the material flow accounting framework and the data generated have reached a maturity that warrants material flow indicators to complement traditional economic and demographic information in providing a sound basis for discussing national and international policies for sustainable resource use.     

More than a monolayer: relating lung surfactant structure and mechanics to composition

Survanta, a clinically used bovine lung surfactant extract, in contact with surfactant in the subphase, shows a coexistence of discrete monolayer islands of solid phase coexisting with continuous multilayer "reservoirs" of fluid phase adjacent to the air-water interface. Exchange between the monolayer, the multilayer reservoir, and the subphase determines surfactant mechanical properties such as the monolayer collapse pressure and surface viscosity by regulating solid-fluid coexistence. Grazing incidence x-ray diffraction shows that the solid phase domains consist of two-dimensional crystals similar to those formed by mixtures of dipalmitoylphosphatidylcholine and palmitic acid. The condensed domains grow as the surface pressure is increased until they coalesce, trapping protrusions of liquid matrix. At approximately 40 mN/m, a plateau exists in the isotherm at which the solid phase fraction increases from approximately 60 to 90%, at which the surface viscosity diverges. The viscosity is driven by the percolation of the solid phase domains, which depends on the solid phase area fraction of the monolayer. The high viscosity may lead to high monolayer collapse pressures, help prevent atelectasis, and minimize the flow of lung surfactant out of the alveoli due to surface tension gradients.     

Platinum Group Metal Flows of Europe, Part II

A model of the use of the platinum group metals (PGMs) platinum, palladium, and rhodium in Europe has been developed and combined with a model of the environmental pressures related to PGM production. Compared to the base case presented in Part I of this pair of articles, potential changes in PGM production and use are quantified with regard to cumulative and yearly environmental impacts and PGM resource use, for the period 2005–2020. Reducing sulfur dioxide (SO₂) emissions of PGM producer Norilsk Nickel could cut the cumulative SO₂ emissions associated with the use of PGMs in Europe by 35%. Cleaner electricity generation in South Africa could reduce cumulative SO₂ emissions by another 9%. Increasing the recycling rate of end-of-life catalytic converters to 70% in 2020 could save 15% of the cumulative primary PGM input into car catalysts and 10% of the SO₂ emissions associated with PGM production. In 2020, PGM requirements and SO₂ emissions would be, respectively, 40% and 22% lower than the base case.
Substituting palladium for part of the platinum in diesel catalysts, coupled with a probable palladium price increase, could imply 15% more cumulative SO₂ emissions if recycling rates do not increase.
A future large-scale introduction of fuel cell vehicles would require technological improvements to significantly reduce the PGM content of the fuel cell stack. The basic design of such vehicles greatly influences the vehicle power, a key parameter in determining the total PGM requirement.     

Environmental Implications and Costs of Municipal Solid Waste‐Derived Ethylene

Carbon recycling, in which organic waste is recycled into chemical feedstock for material production, may provide benefits in resource efficiency and a more cyclical economy—but may also create “trade‐offs” in increased impacts elsewhere. We investigate the system‐wide environmental burdens and cost associated with carbon recycling routes capable of converting municipal solid waste (MSW) by gasification and Fischer‐Tropsch synthesis into ethylene. Results are compared to business‐as‐usual (BAU) cases in which ethylene is derived from fossil resources and waste is either landfilled with methane and energy recovery (BAU#1) or incinerated (BAU#2) with energy recovery. Monte Carlo and sensitivity analysis is used to assess uncertainties of the results. Results indicate that carbon recycling may lead to a reduction in cumulative energy demand (CED), total material requirement (TMR), and acidification, when compared to BAU#1. Global warming potential is found to be similar or slightly lower than BAU#1 and BAU#2. In comparison to BAU#2, carbon recycling results in higher CED, TMR, acidification, and smog potential, mainly as a result of larger (fossil‐based) energy offsets from energy recovery. However, if a renewable power mix (envisioned for the future) is assumed to be offset, BAU#2 impacts may be similar or higher than carbon recycling routes. Production cost per kilogram (kg) MSW‐derived ethylene range between US$1.85 and US$2.06 (Jan 2011 US$). This compares to US$1.17 per kg for fossil‐based ethylene. Waste‐derived ethylene breaks even with its fossil‐based counterpart at a tipping fee of roughly US$42 per metric ton of waste feedstock.     

Mechanism of the lamellar/inverse hexagonal phase transition examined by high resolution x-ray diffraction

For the first time the electron density of the lamellar liquid crystalline as well as of the inverted hexagonal phase could be retrieved at the transition temperature. A reliable decomposition of the d-spacings into hydrophobic and hydrophilic structure elements could be performed owing to the presence of a sufficient number of reflections. While the hydrocarbon chain length, d(C), in the lamellar phase with a value of 14.5 A lies within the extreme limits of the estimated chain length of the inverse hexagonal phase 10 A < d(C) < 16 A, the changes in the hydrophilic region vary strongly. During the lamellar-to-inverse hexagonal phase transition the area per lipid molecule reduces by approximately 25%, and the number of water molecules per lipid increases from 14 to 18. On the basis of the analysis of the structural components of each phase, the interface between the coexisting mesophases between 66 and 84 degrees C has been examined in detail, and a model for the formation of the first rods in the matrix of the lamellar phospholipid stack is discussed. Judging from the structural relations between the inverse hexagonal and the lamellar phase, we suggest a cooperative chain reaction of rod formation at the transition midpoint, which is mainly driven by minimizing the interstitial region.     

Life Cycle Assessment of Carbon Dioxide–Based Production of Methane and Methanol and Derived Polymers

Previous studies showed that using carbon dioxide (CO₂) as a raw material for chemical syntheses may provide an opportunity for achieving greenhouse gas (GHG) savings and a low‐carbon economy. Nevertheless, it is not clear whether carbon capture and utilization benefits the environment in terms of resource efficiency. We analyzed the production of methane, methanol, and synthesis gas as basic chemicals and derived polyoxymethylene, polyethylene, and polypropylene as polymers by calculating the output‐oriented indicator global warming impact (GWI) and the resource‐based indicators raw material input (RMI) and total material requirement (TMR) on a cradle‐to‐gate basis. As carbon source, we analyzed the capturing of CO₂ from air, raw biogas, cement plants, lignite‐fired power, and municipal waste incineration plants. Wind power serves as an energy source for hydrogen production. Our data were derived from both industrial processes and process simulations. The results demonstrate that the analyzed CO₂‐based process chains reduce the amount of GHG emissions in comparison to the conventional ones. At the same time, the CO₂‐based process chains require an increased amount of (abiotic) resources. This trade‐off between decreased GHG emissions and increased resource use is assessed. The decision about whether or not to recycle CO₂ into hydrocarbons depends largely on the source and amount of energy used to produce hydrogen.     

Membrane binding of a lipidated N-Ras protein studied in lipid monolayers

The adsorption of doubly lipidated full-length N-Ras protein on 1,2-dipalmitoyl-sn-phosphatidylcholine (DPPC) monolayers was studied by lateral pressure analysis, grazing incidence X-ray diffraction (GIXD), and specular reflectivity (XR). N-Ras protein adsorbs to the DPPC monolayer (lateral pressure of 20 mN/m) from the subphase thereby increasing the lateral pressure in the monolayer by 4 mN/m. The protein insertion does not alter the tilt angle and structure of the lipid molecules at the air/water interface but influences the electron density profile of the monolayer. Further, electron density differences into the subphase were observed. The Fresnel normalized reflectivity could be reconstructed in the analysis using box models yielding electron density profiles of the DPPC monolayer in the absence and in the presence of N-Ras protein. The electron density profiles of the DPPC monolayer in the presence of Ras showed clear intensity variations in the headgroup/glycerol/upper chain region, the so-called interface region where previous bilayer studies had confirmed Ras binding. Dedicated to Prof. K. Arnold on the occasion of his 65th birthday.     

Rationale for and Interpretation of Economy-Wide Materials Flow Analysis and Derived Indicators

Economy-wide material flow analysis (MFA) and derived indicators have been developed to monitor and assess the metabolic performance of economies, that is, with respect to the internal economic flows and the exchange of materials with the environment and with other economies. Indicators such as direct material input (DMI) and direct material consumption (DMC) measure material use related to either production or consumption. Domestic hidden flows (HF) account for unused domestic extraction, and foreign HF represent the upstream primary resource requirements of the imports. DMI and domestic and foreign HF account for the total material requirement (TMR) of an economy. Subtracting the exports and their HF provides the total material consumption (TMC).
DMI and TMR are used to measure the (de-) coupling of resource use and economic growth, providing the basis for resource efficiency indicators. Accounting for TMR allows detection of shifts from domestic to foreign resource requirements. Net addition to stock (NAS) measures the physical growth of an economy. It indicates the distance from flow equilibrium of inputs and outputs that may be regarded as a necessary condition of a sustainable mature metabolism.
We discuss the extent to which MFA-based indicators can also be used to assess the environmental performance. For that purpose we consider different impacts of material flows, and different scales and perspectives of the analysis, and distinguish between turnover-based indicators of generic environmental pressure and impact-based indicators of specific environmental pressure. Indicators such as TMR and TMC are regarded as generic pressure indicators that may not be used to indicate specific environmental impacts. The TMR of industrial countries is discussed with respect to the question of whether volume and composition may be regarded as unsustainable.