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At least 595 records · Page 33

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↗

Buckling-induced interaction between circular inclusions in an infinite thin plate

Design of slender artificial materials and morphogenesis of thin biological tissues typically involve stimulation of isolated regions (inclusions) in the growing body. These inclusions apply internal stresses on their surrounding areas that are ultimately relaxed by out-of-plane deformation (buckling). Here, we utilize the Föppl-von Kármán model to analyze the interaction between two circular inclusions in an infinite plate that their centers are separated a distance of 2ℓ. In particular, we investigate a region in phase space where buckling occurs at a narrow transition layer of length ℓ D around the radius of the inclusion, $R (ℓ_D \ll R)$. We show that the latter length scale defines two regions within the system, the close separation region, $ℓ – R \sim ℓ_D$, where the transition layers of the two inclusions approximately coalesce, and the far separation region, $ℓ – R \gg ℓ_D$. While the interaction energy decays exponentially in the latter region, $E_{\text{int}} ∝ e^{– (ℓ – R)/ℓ_D}$, it presents nonmonotonic behavior in the former region. While this exponential decay is predicted by our analytical analysis and agrees with the numerical observations, the close separation region is treated only numerically. In particular, we utilize the numerical investigation to explore two different scenarios within the final configuration: The first where the two inclusions buckle in the same direction (up-up solution) and the second where the two inclusions buckle in opposite directions (up-down solution). We show that the up-down solution is always energetically favorable over the up-up solution. In addition, we point to a curious symmetry breaking within the up-down scenario; we show that this solution becomes asymmetric in the close separation region.

42 ENGINEERING↗

Science Opportunities and Capabilities Enabled by LCLS-II and LCLS-II HE

X-Ray Science with LCLS-II and LCLS-II HE: Chemical dynamics: Reaction dynamics, charge transfer, molecular photocatalysts, natural & artificial photosynthesis; Catalysis: Homogeneous and heterogeneous catalysis, interfacial & geo/environmental chemistry; Materials Physics: Heterogeneity, spontaneous fluctuations, nonequilibrium dynamics, extreme environments; Quantum Materials: Emergent phenomena & collective excitations; Biological Function & Structural Dynamics: Dynamics in physiological environments.

43 PARTICLE ACCELERATORS↗

Gamma Irradiation Facility

Gamma irradiation is a process that uses Cobalt60 radionuclide produced artificially in nuclear reactors to irradiate a variety of items using gamma radiation. A key characteristic of gamma irradiation is its high penetration capability and the fact that it can modify physical, chemical, and biological properties of the irradiated materials.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A Novel Laser 3D Printing Method for the Advanced Manufacturing of Protonic Ceramics

Protonic ceramics (PCs) with high proton conductivity at intermediate temperatures (300–600 °C) have attracted many applications in energy conversion and storage devices such as PC fuel/electrolysis cells, PC membrane reactors, hydrogen pump, hydrogen or water-permeable membranes, and gas sensors. One of the essential steps for fulfilling the practical utilization of these intermediate-temperature PC energy devices is the successful development of advanced manufacturing methods for cost-effectively and rapidly fabricating them with high energy density and efficiency in a customized demand. In this work, we developed a new laser 3D printing (L3DP) technique by integrating digital microextrusion-based 3D printing and precise and rapid laser processing (sintering, drying, cutting, and polishing), which showed the capability of manufacturing PCs with desired complex geometries, crystal structures, and microstructures. The L3DP method allowed the fabrication of PC parts such as pellets, cylinders, cones, films, straight/lobed tubes with sealed endings, microchannel membranes, and half cells for assembling PC energy devices. The preliminary measurement of the L3DP electrolyte film showed a high proton conductivity of ≈7 × 10−3 S/cm. This L3DP technique not only demonstrated the potential to bring the PCs into practical use but also made it possible for the rapid direct digital manufacturing of ceramic-based devices.

08 HYDROGEN↗

Toxicology of the air in closed spaces

Sources and identification of contaminants in artificial gas atmospheres are discussed. They include biological sources (microflora and man), materials, processes, aerosols, and malfunctions. Acute or chronic toxicity may result from spacecraft air contamination. Air quality standards are presented in tabular form.

Ralph C. Wands↗

Smoke toxicity methodology

The toxicity of pyrolysis products for aircraft interior materials must be within some reasonable limit. The toxicity of pyrolysis products from five candidate aircraft materials is evaluated. The most important part of this study was to demonstrate that pyrolysis of materials could be controlled and biological endpoints are reproducible.

Dilley, J. V.↗

Summary results of the Industry Conference on the Commercial Use of Space

The future intentions of the Federal Republic of Germany in the area of the commercialization of space are presented. It is shown that significant advances in microgravity research, particulary in the areas of materials science, composite materials, physical chemistry, crystal growth, biology, and process engineering will have an effect on future plans for establishing sponsoring organizations to guide commercial interests in German space research. An organizational and functional outline of a proposed sponsoring organization to promote space commercialization under German supervision, including the objectives, the target group to be served, and the administrative structure, is presented. The role of the DFVLR (German Aerospace Research Establishment) and the BMFT (German Ministry for Research and Technology) as sponsoring organizations representing the interests of the German government is shown.

REUSE↗

Light-Hydrocarbon Bearing Solids on Planetesimal 5145 Pholus

Object 5145 Pholus (=1992 AD) is a planetesimal in an orbit that crosses those of Saturn, Uranus, and Neptune (period 92.7 years). It is particularly notable because of its extreme red color, corroborated by several observing teams. A spectrum of Pholus obtained in 1992 shows a strong absorption band with a characteristic shape at 2.27 micrometers, plus a weaker band at 1.7 micrometers. A better spectrum of the 2.0-2.5 micrometer region in 1993 confirms the position and shape of the 2.27-micrometer band. The color and spectral bands are identified with the aliphatic-rich and high H/C organic solid called asphaltite, which in a terrestrial setting originates from thermal processing of products of biological activity. In Pholus, this material is attributed to formation from radiation processing of ices on grains in the interstellar medium. Laboratory spectra of asphaltite and related materials have been published by Moroz et al., while Cloutis showed similar bands in comparable materials and identified them as the overtone and combination bands of C-H stretching and bending modes in CH2 and CH3 groups. Asphaltites, kerites, and anthraxolites are solid non-graphite members of a sequence ranging from oil to graphite; diffuse reflectance spectra of suites of these intermediate materials show color characteristics similar to those of the low-albedo asteroids (C,P,D), although specific identifications have not been made because of the lack of distinct absorption bands in the spectra of most low-albedo solar system bodies. In the case of Pholus, however, the primary band is strong; its wavelength and its shape, plus the match of the extremely red color, leads us to the identification of aliphatic-rich, asphaltite-like organic solid. The C, P, and D-type asteroids vary in degree of "redness", but are all less red than Pholus. Pholus and the Ctype asteroids are the end members of a sequence that represents the radiation processing of hydrocarbons, with Pholus being the least processed. Solar irradiation processes and heating reduce the H/C and aliphatic content of hydrocarbons preserved from the interstellar medium, and in the end produce opaque solids of neutral reflectance, including the kerogens (similar to anthraxolites) found in profusion in the carbonaceous meteorites.

Cruikshank, Dale P.↗

Light-Hydrocarbon Bearing Solids on Planetesimal 5145 Pholus

Object 5145 Pholus (=1992 AD) is a planetesimal in an orbit that crosses those of Saturn, Uranus, and Neptune (period 92.7 years). It is particularly notable because of its extreme red color, corroborated by several observing teams. A spectrum of Pholus obtained in 1992 shows a strong absorption band with a characteristic shape at 2.27 micron, plus a weaker band at 1.7 microns. A better spectrum of the 2.0-2.5 micron region in 1993 confirms the position and shape of the 2.27 micron band. The color and spectral bands are identified with the aliphatic-rich and high H/C organic solid called asphaltite, which in a terrestrial setting originates from thermal processing of products of biological activity. In Pholus, this material is attributed to formation from radiation processing of ices on grains in the interstellar medium. Laboratory spectra of asphaltite and related materials have been published by Moroz et al., while Cloutis showed similar bands in comparable materials and identified them as the overtone and combination bands of C-H stretching and bending modes in CH2 and CH3 groups. Asphaltites, kerites, and anthraxolites are solid non-graphite members of a sequence ranging from oil to graphite; diffuse reflectance spectra of suites of these intermediate materials show color characteristics similar to those of the low-albedo asteroids (C,P,D), although specific identifications have not been made because of the lack of distinct absorption bands in the spectra of most low-albedo solar system bodies. In the case of Pholus, however, the primary band is strong; its wavelength and its shape, plus the match of the extremely red color, leads us to the identification of aliphatic-rich, asphaltite-like organic solid. The C, P, and D-type asteroids vary in degree of 'redness', but are all less red than Pholus. Pholus and the C-type asteroids are the end members of a sequence that represents the radiation processing of hydrocarbons, with Pholus being the least processed. Solar irradiation processes and heating reduce the H/C and aliphatic content of hydrocarbons preserved from the interstellar medium, and in the end produce opaque solids of neutral reflectance, including the kerogens (similar to anthraxolites) found in profusion in the carbonaceous meteorites.

Cruikshank, Dale P.↗

A Draft Protocol for Detecting Possible Biohazards in Martian Samples Returned to Earth

In preparation for missions to Mars that will involve the return of samples, it is necessary to prepare for the safe receiving, handling, testing, distributing, and archiving of martian materials here on Earth. Previous groups and committees have studied selected aspects of sample return activities, but a specific protocol for handling and testing of returned -=1 samples from Mars remained to be developed. To refine the requirements for Mars sample hazard testing and to develop criteria for the subsequent release of sample materials from precautionary containment, NASA Planetary Protection Officer, working in collaboration with CNES, convened a series of workshops to produce a Protocol by which returned martian sample materials could be assessed for biological hazards and examined for evidence of life (extant or extinct), while safeguarding the samples from possible terrestrial contamination. The Draft Protocol was then reviewed by an Oversight and Review Committee formed specifically for that purpose and composed of senior scientists. In order to preserve the scientific value of returned martian samples under safe conditions, while avoiding false indications of life within the samples, the Sample Receiving Facility (SRF) is required to allow handling and processing of the Mars samples to prevent their terrestrial contamination while maintaining strict biological containment. It is anticipated that samples will be able to be shipped among appropriate containment facilities wherever necessary, under procedures developed in cooperation with international appropriate institutions. The SRF will need to provide different types of laboratory environments for carrying out, beyond sample description and curation, the various aspects of the protocol: Physical/Chemical analysis, Life Detection testing, and Biohazard testing. The main principle of these tests will be described and the criteria for release will be discussed, as well as the requirements for the SRF and its personnel.

Viso, M.↗

Near-infrared detection of potential evidence for microscopic organisms on Europa

The possibility of an ocean within the icy shell of Jupiter's moon Europa has established that world as a primary candidate in the search for extraterrestrial life within our Solar System. This paper evaluates the potential to detect evidence for microbial life by comparing laboratory studies of terrestrial microorganisms with measurements from the Galileo Near Infrared Imaging Spectrometer (NIMS). If the interior of Europa at one time harbored life, some evidence may remain in the surface materials. Examination of laboratory spectra of terrestrial extremophiles measured at cryogenic temperatures reveals distorted, asymmetric nearinfrared absorption features due to water of hydration. The band centers, widths, and shapes of these features closely match those observed in the Europa spectra. These features are strongest in reddish-brown, disrupted terrains such as linea and chaos regions. Narrow spectral features due to amide bonds in the microbe proteins provide a means of constraining the abundances of such materials using the NIMS data. The NIMS data of disrupted terrains exhibit distorted, asymmetric near-infrared absorption features consistent with the presence of water ice, sulfuric acid octahydrate, hydrated salts, and possibly as much as 0.2 mg cm(-3) of carbonaceous material that could be of biological origin. However, inherent noise in the observations and limitations of spectral sampling must be taken into account when discussing these findings.

Extraterrestrial Environment↗

Mars Sample Handling Protocol Workshop Series: Workshop 4

In preparation for missions to Mars that will involve the return of samples to Earth, it will be necessary to prepare for the receiving, handling, testing, distributing, and archiving of martian materials here on Earth. Previous groups and committees have studied selected aspects of sample return activities, but specific detailed protocols for the handling and testing of returned samples must still be developed. To further refine the requirements for sample hazard testing and to develop the criteria for subsequent release of sample materials from quarantine, the NASA Planetary Protection Officer convened a series of workshops in 2000-2001. The overall objective of the Workshop Series was to produce a Draft Protocol by which returned martian sample materials can be assessed for biological hazards and examined for evidence of life (extant or extinct) while safeguarding the purity of the samples from possible terrestrial contamination. This report also provides a record of the proceedings of Workshop 4, the final Workshop of the Series, which was held in Arlington, Virginia, June 5-7, 2001. During Workshop 4, the sub-groups were provided with a draft of the protocol compiled in May 2001 from the work done at prior Workshops in the Series. Then eight sub-groups were formed to discuss the following assigned topics: Review and Assess the Draft Protocol for Physical/Chemical Testing Review and Assess the Draft Protocol for Life Detection Testing Review and Assess the Draft Protocol for Biohazard Testing Environmental and Health/Monitoring and Safety Issues Requirements of the Draft Protocol for Facilities and Equipment Contingency Planning for Different Outcomes of the Draft Protocol Personnel Management Considerations in Implementation of the Draft Protocol Draft Protocol Implementation Process and Update Concepts This report provides the first complete presentation of the Draft Protocol for Mars Sample Handling to meet planetary protection needs. This Draft Protocol, which was compiled from deliberations and recommendations from earlier Workshops in the Series, represents a consensus that emerged from the discussions of all the sub-groups assembled over the course of the five Workshops of the Series. These discussions converged on a conceptual approach to sample handling, as well as on specific analytical requirements. Discussions also identified important issues requiring attention, as well as research and development needed for protocol implementation.

Race Margaret S.↗

Planetary Protection Technology for Mars Sample Return

The NASA Mars Exploration Program has recently adopted a plan that includes a first Mars sample return (MSR) mission proposed for launch in 2013. Such a mission would deal with two new categories of planetary protection requirements: (1) assuring a very low probability of inadvertent release of the sample in order to provide extra protection against the extremely unlikely possibility of biological hazards in the returned material and (2) keeping the samples free of round-trip Earth organisms to facilitate confirmation of safety after return to Earth. This paper describes the planetary-protection-related technical challenges awaiting any MSR mission and describes work in progress on technology needed to meet these challenges. New technology is needed for several functions. Containment assurance requires breaking the chain of contact with Mars: the exterior of the sample container must not be contaminated with Mars material either during the loading process or during launch from the Mars surface.

planetary protection↗

Organic Entrainment and Preservation in Volcanic Glasses

Unaltered pyroclastic deposits have previously been deemed to have "low" potential for the formation, concentration and preservation of organic material on the Martian surface. Yet volcanic glasses that have solidified very quickly after an eruption may be good candidates for containment and preservation of refractory organic material that existed in a biologic system pre-eruption due to their impermeability and ability to attenuate UV radiation. Analysis using NanoSIMS of volcanic glass could then be performed to both deduce carbon isotope ratios that indicate biologic origin and confirm entrainment during eruption. Terrestrial contamination is one of the biggest barriers to definitive Martian organic identification in soil and rock samples. While there is a greater potential to concentrate organics in sedimentary strata, volcanic glasses may better encapsulate and preserve organics over long time scales, and are widespread on Mars. If volcanic glass from many sites on Earth could be shown to contain biologically derived organics from the original environment, there could be significant implications for the search for biomarkers in ancient Martian environments.

glass from lava domes↗

Overview of the Microgravity Science Glovebox (MSG) Facility and the Research Performed in the MSG

The Microgravity Science Glovebox (MSG) is a rack facility aboard the International Space Station (ISS) designed for investigation handling. The MSG was built by the European Space Agency (ESA) which also provides sustaining engineering support for the facility. The MSG has been operating on the ISS since July 2002 and is currently located in the US Laboratory Module. The unique design of the facility allows it to accommodate science and technology investigations in a "workbench" type environment. The facility has an enclosed working volume that is held at a negative pressure with respect to the crew living area. This allows the facility to provide two levels of containment for small parts, particulates, fluids, and gases. This containment approach protects the crew from possible hazardous operations that take place inside the MSG work volume. Research investigations operating inside the MSG are provided a large 255 liter enclosed work space, 1000 watts of direct current power via a versatile supply interface (120, 28, plus or minus 12, and 5 volts direct current), 1000 watts of cooling capability, video and data recording and real time downlink, ground commanding capabilities, access to ISS Vacuum Exhaust and Vacuum Resource Systems, and gaseous nitrogen supply. These capabilities make the MSG one of the most utilized facilities on ISS. The MSG has been used for over 27,000 hours of scientific payload operations. MSG investigations involve research in cryogenic fluid management, fluid physics, spacecraft fire safety, materials science, combustion, plant growth, biological studies and life support technology. The MSG facility is operated by the Payloads Operations Integration Center at Marshall Space Flight Center. Payloads may also operate remotely from different telescience centers located in the United States and Europe. The Investigative Payload Integration Manager (IPIM) is the focal to assist organizations that have payloads operating in the MSG facility. NASA provides an MSG engineering unit for payload developers to verify that their hardware is operating properly before actual operation on the ISS. This poster will provide an overview of the MSG facility, a synopsis of the research that has already been accomplished in the MSG, and an overview of video and biological upgrades. The author would like to acknowledge Teledyne Brown Engineering and the entire MSG Team for their inputs into this poster.

Jordan, Lee↗

Process for enhanced production of desired hydrocarbons from biologically-derived compounds and bio-oils containing cyclic compounds by opening of aromatics and naphthenic ring-containing compounds

A system and process for processing biologically-derived compounds or a complex bio-oil by converting cyclic compounds in a complex bio-oil or biologically-derived compounds to desired materials such as high molecular weight paraffins with minimal carbon loss by using a ring-contraction catalyst to selectively produce C5 ring containing compounds; and then reacting the C5 ring containing compounds with a C5 ring opening catalyst in a second reactor to minimize carbon loss via cracking reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Powerful Toolkit for Synthetic Biology: Over 3.8 Billion Years of Evolution

The combination of evolutionary with engineering principles will enhance synthetic biology. Conversely, synthetic biology has the potential to enrich evolutionary biology by explaining why some adaptive space is empty, on Earth or elsewhere. Synthetic biology, the design and construction of artificial biological systems, substitutes bio-engineering for evolution, which is seen as an obstacle. But because evolution has produced the complexity and diversity of life, it provides a proven toolkit of genetic materials and principles available to synthetic biology. Evolution operates on the population level, with the populations composed of unique individuals that are historical entities. The source of genetic novelty includes mutation, gene regulation, sex, symbiosis, and interspecies gene transfer. At a phenotypic level, variation derives from regulatory control, replication and diversification of components, compartmentalization, sexual selection and speciation, among others. Variation is limited by physical constraints such as diffusion, and chemical constraints such as reaction rates and membrane fluidity. While some of these tools of evolution are currently in use in synthetic biology, all ought to be examined for utility. A hybrid approach of synthetic biology coupled with fine-tuning through evolution is suggested

Rothschild, Lynn J.↗