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At least 955 records · Page 53

Strapped calix[4]pyrroles: from syntheses to applications

Supramolecular chemistry is a central topic in modern chemistry. It touches on many traditional disciplines, such as organic chemistry, inorganic chemistry, physical chemistry, materials chemistry, environmental chemistry, and biological chemistry. Supramolecular hosts, inter alia macrocyclic hosts, play critical roles in supramolecular chemistry. Calix[4]pyrroles, non-aromatic tetrapyrrolic macrocycles defined by sp 3 hybridized meso bridges, have proved to be versatile receptors for neutral species, anions, and cations, as well as ion pairs. Compared to the parent system, octamethylcalix[4]pyrrole and its derivatives bearing simple appended functionalities, strapped calix[4]pyrroles typically display enhanced binding affinities and selectivities. In this review, we summarize advances in the design and synthesis of strapped calix[4]pyrroles, as well as their broad utility in molecular recognition, supramolecular extraction, separation technology, ion transport, and as agents capable of inhibiting cancer cell proliferation. Future challenges within this sub-field are also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

BioSentinel: Mission Development of a Radiation Biosensor to Gauge DNA Damage and Repair Beyond Low Earth Orbit on a 6U Nanosatellite

We are designing and developing a 6U (10 x 22 x 34 cm; 14 kg) nanosatellite as a secondary payload to fly aboard NASAs Space Launch System (SLS) Exploration Mission (EM) 1, scheduled for launch in late 2017. For the first time in over forty years, direct experimental data from biological studies beyond low Earth orbit (LEO) will be obtained during BioSentinels 12- to 18-month mission. BioSentinel will measure the damage and repair of DNA in a biological organism and allow us to compare that to information from onboard physical radiation sensors. In order to understand the relative contributions of the space environments two dominant biological perturbations, reduced gravity and ionizing radiation, results from deep space will be directly compared to data obtained in LEO (on ISS) and on Earth. These data points will be available for validation of existing biological radiation damage and repair models, and for extrapolation to humans, to assist in mitigating risks during future long-term exploration missions beyond LEO. The BioSentinel Payload occupies 4U of the spacecraft and will utilize the monocellular eukaryotic organism Saccharomyces cerevisiae (yeast) to report DNA double-strand-break (DSB) events that result from ambient space radiation. DSB repair exhibits striking conservation of repair proteins from yeast to humans. Yeast was selected because of 1) its similarity to cells in higher organisms, 2) the well-established history of strains engineered to measure DSB repair, 3) its spaceflight heritage, and 4) the wealth of available ground and flight reference data. The S. cerevisiae flight strain will include engineered genetic defects to prevent growth and division until a radiation-induced DSB activates the yeasts DNA repair mechanisms. The triggered culture growth and metabolic activity directly indicate a DSB and its successful repair. The yeast will be carried in the dry state within the 1-atm PL container in 18 separate fluidics cards with each card having 16 independent culture microwells, with integral microchannels and filters to supply nutrients and reagents, confine the yeast to the wells, and enable optical measurement. The measurement subsystem will monitor each subgroup of culture wells continuously for several weeks, optically tracking DSB-triggered cell growth and metabolism. BioSentinel will also include physical radiation sensors based on the TimePix sensor, as implemented by JSCs RadWorks group, which record individual radiation events including estimates of their linear-energy-transfer (LET) values. Radiation-dose and LET data will be compared directly to the rate of DSB-and-repair events measured by the S. cerevisiae biosentinels.

Radiation Biosensor↗

A state-of-the-art review of experimental and computational studies of granular materials: Properties, advances, challenges, and future directions

Modeling of heterogeneous materials and media is a problem of fundamental importance to a wide class of phenomena and systems, ranging from condensed matter physics, soft materials, and composite media to porous media, biological systems, geosystems, ceramic engineering, pharmaceutical science and even in space discoveries. Among the most important materials are granular systems, which have received intense interest from the engineering, physics, and mathematics communities. In this review paper, the recent developments and new advances in experimental, and computational methods on a variety of scales and physics that extend understanding to a wide range of materials and phenomena are reviewed. Experimental advances include computed neutron and nanometer-scale tomography, magnetic resonance imaging, refractive index matching, digital image correlation, acoustic emission analysis, and the most recent 4D techniques. Furthermore, a tremendous shift has occurred from the continuum scale to micro-scale and developing multiscale approaches. As such, various computational methods, including, constitutive modeling, discrete modeling, and multiscale approaches, have been developed. In conclusion, aside from all these evolutions, more complicated modeling called coupled, or multiphysics, systems representing a simultaneous presence of heat, fluid, chemical variation, and mechanical effect are also explored.

36 MATERIALS SCIENCE↗

Hydropower Biological Evaluation Toolset Best Practice Guide

Field studies using live fish are necessary for the evaluation of turbine biological performance, but they cannot determine the specific hydraulic conditions or physical stresses experienced by the fish, the locations where deleterious conditions occur, or the specific causes of the biological response. Using the Sensor Fish (SF) sensing technology, this deficiency can be overcome because the SF can be released independently or concurrently with live fish directly into operating infrastructure, and it takes high-frequency measurements of hydraulic conditions such as pressure, acceleration, and rotation acting on a body in situ during downstream passage. The Hydropower Biological Evaluation Tools (HBET; Hou et al. 2018) software package, developed by Pacific Northwest National Laboratory (PNNL), is designed to assemble, organize, and process data collected by the PNNL-developed SF and by live fish. HBET was developed specifically to design SF field studies, process the raw data, and analyze the processed data efficiently and scientifically. Its objectives are to facilitate SF studies focused on characterizing hydraulic conditions and to apply SF data for evaluating the impacts on fish from passage through hydro-structures. HBET allows users to design new studies, analyze data, perform statistical analyses, and evaluate predicted biological responses. It can be used by researchers, turbine designers, hydropower operators, and regulators to evaluate hydro-structures to enhance environmental sustainability in a cost-effective manner.

13 HYDRO ENERGY↗

Plastic and low-cost axial zero thermal expansion alloy by a natural dual-phase composite

Zero thermal expansion (ZTE) alloys possess unique dimensional stability, high thermal and electrical conductivities. Their practical application under heat and stress is however limited by their inherent brittleness because ZTE and plasticity are generally exclusive in a single-phase material. Besides, the performance of ZTE alloys is highly sensitive to change of compositions, so conventional synthesis methods such as alloying or the design of multiphase to improve its thermal and mechanical properties are usually inapplicable. In this study, by adopting a one-step eutectic reaction method, we overcome this challenge. A natural dual-phase composite with ZTE and plasticity was synthesized by melting 4 atom% holmium with pure iron. The dual-phase alloy shows moderate plasticity and strength, axial zero thermal expansion, and stable thermal cycling performance as well as low cost. By using synchrotron X-ray diffraction, in-situ neutron diffraction and microscopy, the critical mechanism of dual-phase synergy on both thermal expansion regulation and mechanical property enhancement is revealed. These results demonstrate that eutectic reaction is likely to be a universal and effective method for the design of high-performance intermetallic-compound-based ZTE alloys.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A quantitative model for a nanoscale switch accurately predicts thermal actuation behavior

Manipulation of temperature can be used to actuate DNA origami nano-hinges containing gold nanoparticles. We develop a physical model of this system that uses partition function analysis of the interaction between the nano-hinge and nanoparticle to predict the probability that the nano-hinge is open at a given temperature. The model agrees well with experimental data and predicts experimental conditions that allow the actuation temperature of the nano-hinge to be tuned over a range of temperatures from 30 °C to 45 °C. Additionally, the model identifies microscopic interactions that are important to the macroscopic behavior of the system, revealing surprising features of the system. This combination of physical insight and predictive potential is likely to inform future designs that integrate nanoparticles into dynamic DNA origami structures or use strand binding interactions to control dynamic DNA origami behavior. Furthermore, our modeling approach could be expanded to consider the incorporation, stability, and actuation of other types of functional elements or actuation mechanisms integrated into nucleic acid devices.

36 MATERIALS SCIENCE↗

Observation of conformational dynamics in single light-harvesting proteins from cryptophyte algae

Photosynthetic organisms use pigment–protein complexes to capture the sunlight that powers most life on earth. Within these complexes, the position of the embedded pigments is all optimized for light harvesting. At the same time, the protein scaffold undergoes thermal fluctuations that vary the structure, and, thus, photophysics, of the complexes. While these variations are averaged out in ensemble measurements, single-molecule spectroscopy provides the ability to probe these conformational changes. We used single-molecule fluorescence spectroscopy to identify the photophysical substates reflective of distinct conformations and the associated conformational dynamics in phycoerythrin 545 (PE545), a pigment–protein complex from cryptophyte algae. Rapid switching between photophysical states was observed, indicating that ensemble measurements average over a conformational equilibrium. A highly quenched conformation was also identified, and its population increased under high light. This discovery establishes that PE545 has the characteristics to serve as a photoprotective site. Finally, unlike homologous proteins from the evolutionarily related cyanobacteria and red algae, quenching was not observed upon photobleaching, which may allow for robust photophysics without the need for rapid repair or replacement machinery. Collectively, these observations establish the presence of a rich and robust set of conformational states of PE545. Cryptophytes exhibit particularly diverse energetics owing to the variety of microenvironments in which they survive, and the conformational states and dynamics reported here may provide photophysical flexibility that contributes to their remarkable ability to flourish under diverse conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A chemical dynamics study on the gas-phase formation of triplet and singlet C 5 H 2 carbenes

Significance Carbenes represent key reactive intermediates in molecular mass growth processes leading to carbonaceous nanostructures in the interstellar medium and in combustion systems. However, due to their short lifetimes and tendency for dimerization, carbenes represent one of the foremost obscured classes of reactive intermediates, with the preparation of carbenes in the gas phase remaining largely elusive. By merging molecular beams with electronic structure and quasi-classical trajectory calculations and exploiting triplet pentadiynylidene (HCCCCCH) and singlet ethynylcyclopropenylidene (c-C 5 H 2 ) carbene as benchmarks, we present a versatile protocol to unravel the dynamics leading to exotic carbenes under single-collision conditions. These elementary mechanisms are of significance to our understanding of the fundamental processes leading to unsaturated organic transients in extreme, hydrocarbon-rich environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The origin of life in a cosmic context

It is shown that there is at present no aspect of contemporary biology where the contingent can be distinguished from the necessary, or the evolutionary accident from the biological sine qua non; and no amount of terrestrial experimentation alone is likely to make such distinctions possible. Hence, biology suffers from a deadening parochialism, much like the physics of falling bodies before Newton showed that the same laws applied to the motion of apples in England and to the planets about the sun. The deparochialization of biology can only come in the same way and must therefore await the search for extraterrestrial life. It is in this sense that the significance of explorations of the planets and their satellites, asteroids, comets, and the interplanetary medium for the origin of life is assessed.

Sagan, C.↗

What Threats to Human Health Does Space Radiation Pose in Orbit

The Space Shuttle program spanned more than the entire length of a solar cycle. Investigations aimed towards understanding the health risks of the astronauts from exposures to space radiation involved mostly physical measurements of the dose and the linear energy transfer (LET) spectrum. Measurement of the dose rate on the Shuttle provided invariable new data for different periods of the solar cycle, whereas measurement of the LET spectrum using the tissue equivalent proportional counter (TEPC) produced the most complete mapping of the radiation environment of the low Earth orbits (LEO). Exposures to the Shuttle astronauts were measured by the personal dosimeter worn by the crewmembers. Analysis of over 300 personal dosimeter readings indicated a dependence on the mission duration, the altitude and inclination of the orbit, and the solar cycle, with the crewmembers on the launch and repair of the Hubble telescope receiving the highest doses due to the altitude of the mission. Secondary neutrons inside the Shuttle were determined by recoil protons or with Bonner spheres, and may contribute significantly to the risks of the crewmembers. In addition, the skin dose and the doses received at different organs were compared using a human phantom onboard a Shuttle mission. A number of radiobiology investigations wer e also performed. The biological doses were determined on six astronauts/cosmonauts on long-duration Shuttle/Mir missions and on two crewmembers on a Hubble repair mission by analyzing the damages in the chromosomes of the crewmembers? white blood cells. Several experiments were also conducted to address the question of possible synergistic effects of spaceflight, microgravity in particular, on the repair of radiation-induced DNA damages. The experimental design included exposure of cells before launch, during flight, or after landing. These physical and biological studies were invaluable in predicting the health risks for astronauts on ISS and future exploration missions. Educational Objectives: A group of high school students flew color negative films on tw o Shuttle missions to detect the radiation environment in orbit. This and other experiments onboard of the Shuttle were aimed at educating the general public of the space program.

Wu, Honglu↗

Controlled molecule injector for cold, dense, and pure molecular beams at the European x-ray free-electron laser

A permanently available molecular-beam injection setup for controlled molecules (COMO) was installed and commissioned at the small quantum systems (SQS) instrument at the European x-ray free-electron laser (EuXFEL). A b-type electrostatic deflector allows for pure state-, size-, and isomer-selected samples of polar molecules and clusters. The source provides a rotationally cold (T ≈ 1 K) and dense (ρ ≈ 10 8 cm −3 ) molecular beam with pulse durations up to 100 µs generated by a new version of the Even-Lavie valve. Here, a performance overview of the COMO setup is presented along with characterization experiments performed both with an optical laser at the Center for Free-Electron-Laser Science and with x rays at EuXFEL under burst-mode operation. COMO was designed to be attached to different instruments at the EuXFEL, in particular, the SQS and single particles, clusters, and biomolecules (SPB) instruments. This advanced controlled-molecules injection setup enables x-ray free-electron laser studies using highly defined samples with soft and hard x-ray FEL radiation for applications ranging from atomic, molecular, and cluster physics to elementary processes in chemistry and biology.

He, Lanhai↗

femto-PIXAR: a self-supervised neural network method for reconstructing femtosecond X-ray free electron laser pulses

X-ray Free Electron Lasers (X-FELs) operate in a wide range of lasing configurations for a broad variety of scientific applications at ultrafast time-scales such as structural biology, materials science, and atomic and molecular physics. Shot-by-shot characterization of the X-FEL pulses is crucial for analysis of many experiments as well as tuning the X-FEL performance. However, for the weak pulses found in advanced configurations, e.g. those needed for coherent, two-pulse studies of quantum materials, there is no current method for reliably resolving pulse profiles. Here we show that a physics-based U-net model can reconstruct the individual pulse power profiles for sub-picosecond pulse separation without the need for simulations. Using experimental data from weak X-FEL pulse pairs, we demonstrate we can learn the pulse characteristics on a shot-by-shot basis when conventional methods fail.

43 PARTICLE ACCELERATORS↗

Near-complete extraction of maximum stored energy from large-core fibers using coherent pulse stacking amplification of femtosecond pulses

High field science relies on ultrashort pulse lasers with multi-joule pulse energies for studying light–matter interactions under extreme conditions and for driving particle accelerators and secondary radiation sources of x rays, gamma rays, neutrons, positrons, muons, and protons. Next-generation laser drivers will require a 10 3 -10 4 times increase in pulse repetition rates, producing multi-joule energies at multi-kilowatt average powers to enable practical applications in nuclear engineering, advanced materials, medicine, biology, homeland security, and high-energy physics. Spatially coherently combined femtosecond fiber lasers are recognized as a pathway to these next-generation drivers, with significant practical advantages including high efficiency and the possibility of compact integration. However, chirped pulse amplification in fibers is capable of extracting only a small fraction (usually ~1%) of the maximum stored energy. Here we demonstrate near-complete maximum stored energy extraction with low accumulated nonlinearity from a large-core fiber amplifier using coherent pulse stacking amplification. We have amplified a 81-pulse stacking burst in a 85 µm core chirally coupled core Yb-doped fiber, extracting up to 9.5 mJ (~90% of stored energy) with < 4.5 radians of accumulated nonlinear phase, temporally combined this burst into a single pulse, and achieved 4.2 mJ pulses of 313 fs bandwidth-limited duration after compression. This represents, to our knowledge, the highest energy extracted and compressed into a femtosecond pulse from a single fiber amplifier, enabling approximately two orders of magnitude size reduction of future high-energy coherently spatially combined fiber laser arrays.

47 OTHER INSTRUMENTATION↗

Simulation modeling of estuarine ecosystems

A simulation model has been developed of Galveston Bay, Texas ecosystem. Secondary productivity measured by harvestable species (such as shrimp and fish) is evaluated in terms of man-related and controllable factors, such as quantity and quality of inlet fresh-water and pollutants. This simulation model used information from an existing physical parameters model as well as pertinent biological measurements obtained by conventional sampling techniques. Predicted results from the model compared favorably with those from comparable investigations. In addition, this paper will discuss remotely sensed and conventional measurements in the framework of prospective models that may be used to study estuarine processes and ecosystem productivity.

Johnson, R. W.↗

The evolution of complex life

The emergence of complex living organisms in the context of evolutionary biology, planetary environments, and space events is investigated. The application of data on biological evolution, climatology, and the chemical and physical environments of the earth's surface, to explain the development of extraterrestrial life is described and an example is provided. The possibility of extraplanetary disturbances such as, meteorite and comet bombardments, and supernova explosions, causing the elimination of preexisting life and allowing advanced life development is analyzed. The possible existence of different life cycles (genetic and reproductive strategies) on other planets is studied. The GAIA hypothesis (Lovelock, 1979) which states living things modify the global environment to their own advantage is examined. The improved identification of habitable planetary environments and the possible existence of a form of extraterrestrial intelligent life is discussed.

Billingham, J.↗

Microbial trace fossils in Antarctica and the search for evidence of early life on Mars

It is possible to hypothesize that, if microbial life evolved on early Mars, fossil remnants of these organisms may be preserved on the surface. However, the cooling and drying of Mars probably resembled a cold desert and such an environment is not suitable for the process of fossilization. The frigid Ross Desert of Antarctica is probably the closest terrestrial analog to conditions that may have prevailed on the surface of the cooling and drying Mars. In this desert, cryptoendolithic microbial communities live in the airspaces of porous rocks, the last habitable niche in a hostile outside environment. The organisms produce characteristic chemical and physical changes in the rock substrate. Environmental changes (deterioration of conditions) may result in the death of the community. Although no cellular structures are fossilized, the conspicuous changes in the rock substrate are preserved as trace fossils. Likewise, microbial trace fossils (without cellular structures) may also be preserved on Mars: Discontinuities in structure or chemistry of the rock that are independent of physical or chemical gradients may be of biological origin. Ross Desert trace fossils can be used as a model for planning search strategies and for instrument design to find evidence of past Martian life.

Friedmann, E. Imre↗