Geminate recombination of hydroxyl radicals generated in 200 nm photodissociation of aqueous hydrogen peroxide

The picosecond dynamics of hydroxyl radicals generated in 200 nm photoinduced dissociation of aqueous hydrogen peroxide have been observed through their transient absorbance at 266 nm. It is shown that these kinetics are nearly exponential, with a decay time of ca. 30 ps. The prompt quantum yield for the decomposition of H2O2 is 0.56, and the fraction of hydroxyl radicals escaping from the solvent cage to the water bulk is 64-68%. These recombination kinetics suggest strong caging of the geminate hydroxyl radicals by water. Phenomenologically, these kinetics may be rationalized in terms of the diffusion of hydroxide radicals out of a shallow potential well (a solvent cage) with an Onsager radius of 0.24 nm.Comment: 14 pages, 1 figur

Physical properties of glasses exposed to Earth-facing and trailing-side environments on LDEF

The exposure of 108 glass samples and 12 glass-ceramic samples to Earth-orbit environments permitted measurements which establish the effects of each environment. Examination of five glass types and one glass ceramic located on both the Earth-facing side and the trailing edge revealed no reduction in strength within experimental limits. Strength measurements subjected less than 5 percent of the sample surface area to stresses above 90 percent of the glass's failure strength. Seven micrometeorite or space debris impacts occurred on trailing edge samples. One of those impacts occurred in a location which was subjected to 50 percent of the applied stress at failure. Micrometeorite or space debris impacts were not observed on Earth-facing samples. The physical shape and structure of the impact sites were carefully examined using stereographic scanning electron microscopy. These impacts induce a stress concentration at the damaged region which influences mechanical strength. The flaw size produced by such damage was examined to determine the magnitude of strength degradation in micrometeorite or space-debris impacted glasses. Scanning electron microscopy revealed topographical details of impact sites which included central melt zones and glass fiber production. The overall crater structure is similar to much larger impacts of large meteorite on the Moon in that the melt crater is surrounded by shocked regions of material which fracture zones and spall areas. Residual stresses arising from shock compression and cooling of the fused zone cannot currently be included in fracture mechanics analyses based on simple flaw size examination

Developing Conceptual and Methodological Foundations in Community Engagement

We describe the efforts of two related undergraduate projects to promote lasting social change in marginalized communities in the Dominican Republic and Nicaragua. The projects represent a test of the premise that undergraduate projects can engage academically based strategies and transcend good intentions to achieve effective community partnerships to improve health and health care. The projects proceed from a perspective and theory of marginalization and its consequences. Specifically, marginalization undermines individual and collective capacity to meet basic needs and efforts to thrive. Through strengthening social infrastructure, communities can overcome the effects of marginalization. Project work begins with annual medical clinics and, with the permission of community residents, team members conduct ethnographic descriptions of the communities and their health and health care concerns and resources. We use social network analysis (SNA) and geographic information system (GIS) techniques to describe social infrastructure. Working from those foundations, both projects have enabled increased social infrastructure. To date, we have observed increased communication among community residents, facilitated the development of community-endorsed five-year plans, and established partnerships with regional and international groups

Untethered soft robotic matter with passive control of shape morphing and propulsion

There is growing interest in creating untethered soft robotic matter that can repeatedly shape-morph and self-propel in response to external stimuli. Toward this goal, we printed soft robotic matter composed of liquid crystal elastomer (LCE) bilayers with orthogonal director alignment and different nematic-to-isotropic transition temperatures (T_(NI)) to form active hinges that interconnect polymeric tiles. When heated above their respective actuation temperatures, the printed LCE hinges exhibit a large, reversible bending response. Their actuation response is programmed by varying their chemistry and printed architecture. Through an integrated design and additive manufacturing approach, we created passively controlled, untethered soft robotic matter that adopts task-specific configurations on demand, including a self-twisting origami polyhedron that exhibits three stable configurations and a “rollbot” that assembles into a pentagonal prism and self-rolls in programmed responses to thermal stimuli

Untethered soft robotic matter with passive control of shape morphing and propulsion

There is growing interest in creating untethered soft robotic matter that can repeatedly shape-morph and self-propel in response to external stimuli. Toward this goal, we printed soft robotic matter composed of liquid crystal elastomer (LCE) bilayers with orthogonal director alignment and different nematic-to-isotropic transition temperatures (T_(NI)) to form active hinges that interconnect polymeric tiles. When heated above their respective actuation temperatures, the printed LCE hinges exhibit a large, reversible bending response. Their actuation response is programmed by varying their chemistry and printed architecture. Through an integrated design and additive manufacturing approach, we created passively controlled, untethered soft robotic matter that adopts task-specific configurations on demand, including a self-twisting origami polyhedron that exhibits three stable configurations and a “rollbot” that assembles into a pentagonal prism and self-rolls in programmed responses to thermal stimuli

Shuttle Ground Support Equipment (GSE) T-0 Umbilical to Space Shuttle Program (SSP) Flight Elements Consultation

The NASA Engineering and Safety Center (NESC) was tasked with assessing the validity of an alternate opinion that surfaced during the investigation of recurrent failures at the Space Shuttle T-0 umbilical interface. The most visible problem occurred during the Space Transportation System (STS)-112 launch when pyrotechnics used to separate Solid Rocket Booster (SRB) Hold-Down Post (HDP) frangible nuts failed to fire. Subsequent investigations recommended several improvements to the Ground Support Equipment (GSE) and processing changes were implemented, including replacement of ground-half cables and connectors between flights, along with wiring modifications to make critical circuits quad-redundant across the interface. The alternate opinions maintained that insufficient data existed to exonerate the design, that additional data needed to be gathered under launch conditions, and that the interface should be further modified to ensure additional margin existed to preclude failure. The results of the assessment are contained in this report

High-Throughput SHAPE Analysis Reveals Structures in HIV-1 Genomic RNA Strongly Conserved across Distinct Biological States

Replication and pathogenesis of the human immunodeficiency virus (HIV) is tightly linked to the structure of its RNA genome, but genome structure in infectious virions is poorly understood. We invent high-throughput SHAPE (selective 2′-hydroxyl acylation analyzed by primer extension) technology, which uses many of the same tools as DNA sequencing, to quantify RNA backbone flexibility at single-nucleotide resolution and from which robust structural information can be immediately derived. We analyze the structure of HIV-1 genomic RNA in four biologically instructive states, including the authentic viral genome inside native particles. Remarkably, given the large number of plausible local structures, the first 10% of the HIV-1 genome exists in a single, predominant conformation in all four states. We also discover that noncoding regions functioning in a regulatory role have significantly lower (p-value < 0.0001) SHAPE reactivities, and hence more structure, than do viral coding regions that function as the template for protein synthesis. By directly monitoring protein binding inside virions, we identify the RNA recognition motif for the viral nucleocapsid protein. Seven structurally homologous binding sites occur in a well-defined domain in the genome, consistent with a role in directing specific packaging of genomic RNA into nascent virions. In addition, we identify two distinct motifs that are targets for the duplex destabilizing activity of this same protein. The nucleocapsid protein destabilizes local HIV-1 RNA structure in ways likely to facilitate initial movement both of the retroviral reverse transcriptase from its tRNA primer and of the ribosome in coding regions. Each of the three nucleocapsid interaction motifs falls in a specific genome domain, indicating that local protein interactions can be organized by the long-range architecture of an RNA. High-throughput SHAPE reveals a comprehensive view of HIV-1 RNA genome structure, and further application of this technology will make possible newly informative analysis of any RNA in a cellular transcriptome

Recombination of Geminate (OH,eaq-) Pairs in Concentrated Alkaline Solutions: Lack of Evidence For Hydroxyl Radical Deprotonation

Picosecond dynamics of hydrated electrons and hydroxyl radicals generated in 200 nm photodissociation of aqueous hydroxide and 400 nm (3-photon) ionization of water in concentrated alkaline solutions were obtained. No deprotonation of hydroxyl radicals was observed on sub-nanosecond time scale, even in 1-10 M KOH solutions. This result is completely at odds with the kinetic data for deprotonation of OH radical in dilute alkaline solutions. We suggest that the deprotonation of hydroxyl radical is slowed down dramatically in concentrated alkaline solutions.Comment: 12 pages; 2 figures; submitted to Chem. Phys. Let