Solid-phase synthesis of oxetane modified peptides

Solid-phase peptide synthesis (SPPS) is used to create peptidomimetics in which one of the backbone amide C=O bonds is replaced by a four-membered oxetane ring. The oxetane containing dipeptide building blocks are made in three steps in solution, then integrated into peptide chains by conventional Fmoc SPPS. This methodology is used to make a range of peptides in high purity including backbone modified derivatives of the nonapeptide bradykinin and Met- and Leu-enkephalin

Clarifying the Dominant Sources and Mechanisms of Cirrus Cloud Formation

Formation of cirrus clouds depends on the availability of ice nuclei to begin condensation of atmospheric water vapor. Although it is known that only a small fraction of atmospheric aerosols are efficient ice nuclei, the critical ingredients that make those aerosols so effective have not been established. We have determined in situ the composition of the residual particles within cirrus crystals after the ice was sublimated. Our results demonstrate that mineral dust and metallic particles are the dominant source of residual particles, whereas sulfate and organic particles are underrepresented, and elemental carbon and biological materials are essentially absent. Further, composition analysis combined with relative humidity measurements suggests that heterogeneous freezing was the dominant formation mechanism of these clouds.National Science Foundation (U.S.) (NSF AGS-0840732)National Science Foundation (U.S.) (NSF grant AGS-1036275)United States. National Aeronautics and Space Administration (NASA Earth and Space Science Graduate Fellowship)United States. National Aeronautics and Space Administration (NASA Radiation Sciences Program award number NNX07AL11G)United States. National Aeronautics and Space Administration (NASA Radiation Sciences Program award number NNX08AH57G)United States. National Aeronautics and Space Administration (NASA Earth Science Division Atmospheric Composition program award number NNH11AQ58UI

Impact of the representation of marine stratocumulus clouds on the anthropogenic aerosol effect

Stratocumulus clouds are important for climate as they reflect large amounts of solar radiation back into space. However they are difficult to simulate in global climate models because they form under a sharp inversion and are thin. A comparison of model simulations with the ECHAM6-HAM2 global aerosol climate model to observations, reanalysis and literature data revealed too strong turbulent mixing at the top of stratocumulus clouds and a lack of vertical resolution. Further reasons for cloud biases in stratocumulus regions are the too "active" shallow convection scheme, the cloud cover scheme and possibly too low subsidence rates. To address some of these issues and improve the representation of stratocumulus clouds, we made three distinct changes to ECHAM6-HAM2. With a "sharp" stability function in the turbulent mixing scheme we have observed, similar to previous studies, increases in stratocumulus cloud cover and liquid water path. With an increased vertical resolution in the lower troposphere in ECHAM6-HAM2 the stratocumulus clouds form higher up in the atmosphere and their vertical extent agrees better with reanalysis data. The recently implemented in-cloud aerosol processing in stratiform clouds is used to improve the aerosol representation in the model. Including the improvements also affects the anthropogenic aerosol effect. In-cloud aerosol processing in ECHAM6-HAM2 leads to a decrease in the anthropogenic aerosol effect in the global annual mean from −1.19 Wm−2 in the reference simulation to −1.08 Wm−2, while using a "sharp" stability function leads to an increase to −1.34 Wm−2. The results from the simulations with increased vertical resolution are diverse but increase the anthropogenic aerosol effect to −2.08 Wm−2 at 47 levels and −2.30 Wm−2 at 95 levels

The relevance of nanoscale biological fragments for ice nucleation in clouds

Most studies of the role of biological entities as atmospheric ice-nucleating particles have focused on relatively rare supermicron particles such as bacterial cells, fungal spores and pollen grains. However, it is not clear that there are sufficient numbers of these particles in the atmosphere to strongly influence clouds. Here we show that the ice-nucleating activity of a fungus from the ubiquitous genus Fusarium is related to the presence of nanometre-scale particles which are far more numerous, and therefore potentially far more important for cloud glaciation than whole intact spores or hyphae. In addition, we quantify the ice-nucleating activity of nano-ice nucleating particles (nano-INPs) washed off pollen and also show that nano-INPs are present in a soil sample. Based on these results, we suggest that there is a reservoir of biological nano-INPs present in the environment which may, for example, become aerosolised in association with fertile soil dust particles

Intercomparison of Large-Eddy Simulations of Arctic Mixed-Phase Clouds: Importance of Ice Size Distribution Assumptions

Large-eddy simulations of mixed-phase Arctic clouds by 11 different models are analyzed with the goal of improving understanding and model representation of processes controlling the evolution of these clouds. In a case based on observations from the Indirect and Semi-Direct Aerosol Campaign (ISDAC), it is found that ice number concentration, Ni, exerts significant influence on the cloud structure. Increasing Ni leads to a substantial reduction in liquid water path (LWP), in agreement with earlier studies. In contrast to previous intercomparison studies, all models here use the same ice particle properties (i.e., mass-size, mass-fall speed, and mass-capacitance relationships) and a common radiation parameterization. The constrained setup exposes the importance of ice particle size distributions (PSDs) in influencing cloud evolution. A clear separation in LWP and IWP predicted by models with bin and bulk microphysical treatments is documented and attributed primarily to the assumed shape of ice PSD used in bulk schemes. Compared to the bin schemes that explicitly predict the PSD, schemes assuming exponential ice PSD underestimate ice growth by vapor deposition and overestimate mass-weighted fall speed leading to an underprediction of IWP by a factor of two in the considered case. Sensitivity tests indicate LWP and IWP are much closer to the bin model simulations when a modified shape factor which is similar to that predicted by bin model simulation is used in bulk scheme. These results demonstrate the importance of representation of ice PSD in determining the partitioning of liquid and ice and the longevity of mixed-phase clouds

Aerosols in the Pre-industrial Atmosphere

Purpose of Review: We assess the current understanding of the state and behaviour of aerosols under pre-industrial conditions and the importance for climate. Recent Findings: Studies show that the magnitude of anthropogenic aerosol radiative forcing over the industrial period calculated by climate models is strongly affected by the abundance and properties of aerosols in the pre-industrial atmosphere. The low concentration of aerosol particles under relatively pristine conditions means that global mean cloud albedo may have been twice as sensitive to changes in natural aerosol emissions under pre-industrial conditions compared to present-day conditions. Consequently, the discovery of new aerosol formation processes and revisions to aerosol emissions have large effects on simulated historical aerosol radiative forcing. Summary: We review what is known about the microphysical, chemical, and radiative properties of aerosols in the pre-industrial atmosphere and the processes that control them. Aerosol properties were controlled by a combination of natural emissions, modification of the natural emissions by human activities such as land-use change, and anthropogenic emissions from biofuel combustion and early industrial processes. Although aerosol concentrations were lower in the pre-industrial atmosphere than today, model simulations show that relatively high aerosol concentrations could have been maintained over continental regions due to biogenically controlled new particle formation and wildfires. Despite the importance of pre-industrial aerosols for historical climate change, the relevant processes and emissions are given relatively little consideration in climate models, and there have been very few attempts to evaluate them. Consequently, we have very low confidence in the ability of models to simulate the aerosol conditions that form the baseline for historical climate simulations. Nevertheless, it is clear that the 1850s should be regarded as an early industrial reference period, and the aerosol forcing calculated from this period is smaller than the forcing since 1750. Improvements in historical reconstructions of natural and early anthropogenic emissions, exploitation of new Earth system models, and a deeper understanding and evaluation of the controlling processes are key aspects to reducing uncertainties in future

The possible role of local air pollution in climate change in West Africa

The climate of West Africa is characterized by a sensitive monsoon system that is associated with marked natural precipitation variability. This region has been and is projected to be subject to substantial global and regional-scale changes including greenhouse-gas-induced warming and sea-level rise, land-use and land-cover change, and substantial biomass burning. We argue that more attention should be paid to rapidly increasing air pollution over the explosively growing cities of West Africa, as experiences from other regions suggest that this can alter regional climate through the influences of aerosols on clouds and radiation, and will also affect human health and food security. We need better observations and models to quantify the magnitude and characteristics of these impacts

The study of atmospheric ice-nucleating particles via microfluidically generated droplets

Ice-nucleating particles (INPs) play a significant role in the climate and hydrological cycle by triggering ice formation in supercooled clouds, thereby causing precipitation and affecting cloud lifetimes and their radiative properties. However, despite their importance, INP often comprise only 1 in 10³–10⁶ ambient particles, making it difficult to ascertain and predict their type, source, and concentration. The typical techniques for quantifying INP concentrations tend to be highly labour-intensive, suffer from poor time resolution, or are limited in sensitivity to low concentrations. Here, we present the application of microfluidic devices to the study of atmospheric INPs via the simple and rapid production of monodisperse droplets and their subsequent freezing on a cold stage. This device offers the potential for the testing of INP concentrations in aqueous samples with high sensitivity and high counting statistics. Various INPs were tested for validation of the platform, including mineral dust and biological species, with results compared to literature values. We also describe a methodology for sampling atmospheric aerosol in a manner that minimises sampling biases and which is compatible with the microfluidic device. We present results for INP concentrations in air sampled during two field campaigns: (1) from a rural location in the UK and (2) during the UK’s annual Bonfire Night festival. These initial results will provide a route for deployment of the microfluidic platform for the study and quantification of INPs in upcoming field campaigns around the globe, while providing a benchmark for future lab-on-a-chip-based INP studies

CubeSat Reusable Interface Software Platform (CRISP): A Lightweight Message-Bus-Based Flight Software Architecture for Rapid Payload Integration

The Agile Space portfolio of projects at Los Alamos National Laboratory (LANL) develops low-cost, rapidly-deployable space payloads and systems. To increase the agility of future missions, we are developing CRISP: the CubeSat Reusable Interface Software Platform. CRISP provides a lightweight and reusable flight software framework for rapid integration of custom payloads with commercial microsatellite platforms. CRISP cuts development time and costs by reducing non-recurring engineering (NRE); thereby accelerating mission agility. To achieve these goals, CRISP provides a core set of payload/data management functions and abstracts the interface between the bus avionics and the payload(s). CRISP currently consists of the following core software modules: a lightweight and scalable publish-subscribe message bus, a space vehicle interface, volatile and nonvolatile memory management, time and ephemeris distribution, debug printing and logging, and watchdogs. We have also developed a modular ground support utility to ease integration and testing, as well as a template flight software application that can be quickly adapted to new missions. Two upcoming CubeSat missions at LANL have already adopted CRISP: the Experiment for Space Radiation Analysis (ESRA) and the Mini Astrophysical MeV Background Observatory (MAMBO)

A marine biogenic source of atmospheric ice nucleating particles

The amount of ice present in clouds can affect cloud lifetime, precipitation and radiative properties1,2. The formation of ice in clouds is facilitated by the presence of airborne ice nucleating particles1,2. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice3-11. Sea spray aerosol contains large amounts of organic material that is ejected into the atmosphere during bubble bursting at the organically enriched sea-air interface or sea surface microlayer12-19. Here we show that organic material in the sea surface microlayer nucleates ice under conditions relevant for mixed-phase cloud and high-altitude ice cloud formation. The ice nucleating material is likely biogenic and less than ~0.2 μm in size. We find that exudates separated from cells of the marine diatom T. Pseudonana nucleate ice and propose that organic material associated with phytoplankton cell exudates is a likely candidate for the observed ice nucleating ability of the microlayer samples. Global model simulations of marine organic aerosol in combination with our measurements suggest that marine organic material may be an important source of ice nucleating particles in remote marine environments such as the Southern Ocean, North Pacific and North Atlantic