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DOE OSTI2018

Solvent-dependent transition from concerted electron–proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites

The bimolecular rate coefficients ($k_q^{obs}$) for quenching the metal-to-ligand charge transfer excited states of two Ru polypyridine complexes containing H-bond accepting sites by six p-substituted phenols exhibit abrupt deviations from the expected linear correlations of log$k_q^{obs}$ with phenol’s Hammett σ p constant. This pattern is attributed to a transition of the quenching mechanism from a concerted electron-proton transfer (EPT) to a proton transfer (PT); the latter becomes predominant for the most acidic phenols in MeCN, but not in CH 2 Cl 2 . This assertion is supported by a detailed thermochemical analysis, which also excludes the quenching pathways involving electron transfer from phenols with or without deprotonation of phenols to the solvent, either concerted or sequential. The transition from EPT to PT upon the σ p increase is consistent/supported by the magnitudes of the measured and computed PhOH/OD kinetic isotope effects and by the observed reduction of the EPT product yields upon replacing the low σ p methoxyphenol by the high σ p nitrophenol. In addition to modulating the relative contribution of the EPT and PT quenching pathways, the solvent strongly affects the bimolecular rate coefficients for the EPT quenching proper. Unlike with H-atom transfer reactions, this kinetic solvent effect could not be quantitatively accounted for by the phenol-solvent H-bonding alone, which suggests a solvent effect on the H-bonding constants in the phenol-Ru complex precursor exciplexes and/or on the unimolecular EPT rate coefficients within these exciplexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Shock wave formation in radiative plasmas

The temporal evolution of weak shocks in radiative media is theoretically investigated in this work. The structure of radiative shocks has traditionally been studied in a stationary framework. Their systematic classification is complex because layers of optically thick and thin regions alternate to form a radiatively-driven precursor and a temperature-relaxation layer, between which the hydrodynamic shock is embedded. In this work, we analyze the formation of weak shocks when two radiative plasmas with different pressures are put in contact. Applying a reductive perturbative method yields a Burgers-type equation that governs the temporal evolution of the perturbed variables including the radiation field. The conditions upon which optically thick and thin solutions exist have been derived and expressed as a function of the shock strength and Boltzmann number. Below a certain Boltzmann number threshold, weak shocks always become optically thick asymptotically in time, while thin solutions appear as transitory structures. The existence of an optically thin regime is related to the presence of an overdense layer in the compressed material. Scaling laws for the characteristic formation time and shock width are provided for each regime. The theoretical analysis is supported by FLASH simulations, and a comprehensive testcase has been designed to benchmark radiative hydrodynamic codes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2017

Synthesis and Crystal Structures of Volatile Neptunium(IV) β- Diketonates

Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl 4 ) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np 4+ . Products of this reaction were characterized via X-ray diffraction and infrared spectroscopy, and were found to be neutral 8-coordinate complexes that adopt square antiprismatic crystal geometry. Synthesis of Np β-diketonates by this approach circumvents the necessity of using NpCl 4 in tetravalent Np coordination compound synthesis. The volatility of the complexes was assessed using thermogravimetric analysis, where the temperature of sublimation was determined to be in the range of 180° to 205° C. The extent of fluorination did not appreciably alter the sublimation temperature of the complex. Thermal decomposition of these compounds was not observed during sublimation. High volatility and thermal stability of Np β-diketonates make them an ideal candidate for gaseous introduction into isotopic separation instruments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1997

Identification of the prooxidant site of human ceruloplasmin: a model for oxidative damage by copper bound to protein surfaces

Free transition metal ions oxidize lipids and lipoproteins in vitro; however, recent evidence suggests that free metal ion-independent mechanisms are more likely in vivo. We have shown previously that human ceruloplasmin (Cp), a serum protein containing seven Cu atoms, induces low density lipoprotein oxidation in vitro and that the activity depends on the presence of a single, chelatable Cu atom. We here use biochemical and molecular approaches to determine the site responsible for Cp prooxidant activity. Experiments with the His-specific reagent diethylpyrocarbonate (DEPC) showed that one or more His residues was specifically required. Quantitative [14C]DEPC binding studies indicated the importance of a single His residue because only one was exposed upon removal of the prooxidant Cu. Plasmin digestion of [14C]DEPC-treated Cp (and N-terminal sequence analysis of the fragments) showed that the critical His was in a 17-kDa region containing four His residues in the second major sequence homology domain of Cp. A full length human Cp cDNA was modified by site-directed mutagenesis to give His-to-Ala substitutions at each of the four positions and was transfected into COS-7 cells, and low density lipoprotein oxidation was measured. The prooxidant site was localized to a region containing His426 because CpH426A almost completely lacked prooxidant activity whereas the other mutants expressed normal activity. These observations support the hypothesis that Cu bound at specific sites on protein surfaces can cause oxidative damage to macromolecules in their environment. Cp may serve as a model protein for understanding mechanisms of oxidant damage by copper-containing (or -binding) proteins such as Cu, Zn superoxide dismutase, and amyloid precursor protein.

NASA Discipline Regulatory Physiology↗

DOE OSTI2025

Nonenzymatic RNA copying with a potentially primordial genetic alphabet

Nonenzymatic RNA copying is thought to have been responsible for the replication of genetic information during the origin of life. However, chemical copying with the canonical nucleotides (A, U, G, and C) strongly favors the incorporation of G and C and disfavors the incorporation of A and especially U because of the stronger G:C vs. A:U base pair and the weaker stacking interactions of U. Recent advances in prebiotic chemistry suggest that the 2-thiopyrimidines were precursors to the canonical pyrimidines, raising the possibility that they may have played an important early role in RNA copying chemistry. Furthermore, 2-thiouridine (s 2 U) and inosine (I) form by deamination of 2-thiocytidine (s 2 C) and A, respectively. We used thermodynamic and crystallographic analyses to compare the I:s 2 C and A:s 2 U base pairs. We find that the I:s 2 C base pair is isomorphic and isoenergetic with the A:s 2 U base pair. The I:s 2 C base pair is weaker than a canonical G:C base pair, while the A:s 2 U base pair is stronger than the canonical A:U base pair, so that a genetic alphabet consisting of s 2 U, s 2 C, I, and A generates RNA duplexes with uniform base pairing energies. Consistent with these results, kinetic analysis of nonenzymatic template-directed primer extension reactions reveals that s 2 C and s 2 U substrates bind similarly to I and A in the template, and vice versa. Our work supports the plausibility of a potentially primordial genetic alphabet consisting of s 2 U, s 2 C, I, and A and offers a potential solution to the long-standing problem of biased nucleotide incorporation during nonenzymatic template copying.

Science & Technology - Other Topics↗

NASA NTRS1997

Organometallic Polymeric Conductors

For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

Youngs, Wiley J.↗

NASA NTRS2016

Tropospheric Ozone Change from 1980 to 2010 Dominated by Equatorward Redistribution of Emissions

Ozone is an important air pollutant at the surface, and the third most important anthropogenic greenhouse gas in the troposphere. Since 1980, anthropogenic emissions of ozone precursors methane, non-methane volatile organic compounds, carbon monoxide and nitrogen oxides (NOx) have shifted from developed to developing regions. Emissions have thereby been redistributed equatorwards, where they are expected to have a stronger effect on the tropospheric ozone burden due to greater convection, reaction rates and NOx sensitivity. Here we use a global chemical transport model to simulate changes in tropospheric ozone concentrations from 1980 to 2010, and to separate the influences of changes in the spatial distribution of global anthropogenic emissions of short-lived pollutants, the magnitude of these emissions, and the global atmospheric methane concentration. We estimate that the increase in ozone burden due to the spatial distribution change slightly exceeds the combined influences of the increased emission magnitude and global methane. Emission increases in Southeast, East and South Asia may be most important for the ozone change, supported by an analysis of statistically significant increases in observed ozone above these regions. The spatial distribution of emissions dominates global tropospheric ozone, suggesting that the future ozone burden will be determined mainly by emissions from low latitudes.

Zhang, Yuqiang↗

DOE OSTI2018

A novel 1-acyl-sn-glycerol-3-phosphate O-acyltransferase homolog for the synthesis of membrane phospholipids with a branched-chain fatty acyl group in Shewanella livingstonensis Ac10

Highlights: • A new 1-acyl-sn-glycerol-3-phosphate O-acyltransferase (PlsC) was discovered. • The enzyme introduces a branched-chain fatty acyl group into membrane phospholipids. • The substrate specificity of the enzyme is unprecedented in the PlsC family enzymes. • Multiple PlsC homologs contribute to generation of membrane phospholipid diversity. 1-Acyl-sn-glycerol-3-phosphate O-acyltransferase (PlsC) plays an essential role in the formation of phosphatidic acid, a precursor of various membrane phospholipids (PLs), in bacteria by catalyzing the introduction of an acyl group into the sn-2 position of lysophosphatidic acid. Various bacteria produce more than one PlsC. However, the physiological significance of the occurrence of multiple PlsCs is poorly understood. A psychrotrophic bacterium, Shewanella livingstonensis Ac10, which produces eicosapentaenoic acid at low temperatures, has five putative PlsCs (PlsC1-5). We previously showed that PlsC1 is responsible for the production of PLs containing an eicosapentaenoyl group. Here, we characterized another putative PlsC of this bacterium named PlsC4. We generated a plsC4-disrupted mutant and found that PLs containing 13:0 found in the parental strain were almost completely absent in the mutant. The loss of these PLs was suppressed by introduction of a plsC4-expression plasmid. PLs containing 15:0 were also drastically decreased by plsC4 disruption. Gas chromatography-mass spectrometry analysis of fatty acyl methyl esters derived from PLs of the parental strain showed that the 13:0 and 15:0 groups were an 11-methyllauroyl group and a 13-methylmyristoyl group, respectively. Phospholipase A2 treatment revealed that these fatty acyl groups were linked to the sn-2 position of PLs. Thus, PlsC4 is a new type of PlsC homolog that is responsible for the synthesis of PLs containing a branched-chain fatty acyl group at the sn-2 position and plays a clearly different role from that of PlsC1 in vivo.

60 APPLIED LIFE SCIENCES↗

NASA NTRS2003

On the Eastward Travelling Wavenumber Two in the Northern Stratosphere

Disturbances in the middle atmosphere are often interpreted in the framework of waves superimposed on a zonal-mean flow. This paper presents an analysis of travelling waves in the northern hemisphere stratosphere, concentrating on planetary wavenumber two (W2). Space-time spectral analysis reveals the existence of a substantial eastward-travelling planetary W2 at high latitudes in winter. While a similar feature is well documented in the southern hemisphere stratosphere, where it is observed in most winters, this northern hemisphere counterpart is less common and has not been examined in detail. A climatology of occurrence of the wave is given for the northern stratospheric winter. It is denoted as the quasi-16-day eastward travelling W2, because of its dominant periodicity, which ranges from about one to three weeks. Although the wave has some similarities with the southern hemispheric wave, there is much larger interannual and intraseasonal variability in the northern hemisphere. will emphasize the variations in the spatial and temporal structure of this wave, as isolated in meteorological analyses of radiosonde and satellite data. The possible role of these travelling waves in preconditioning the stratosphere as a precursor to sudden stratospheric warmings in both hemispheres will be discussed.

Pawson, Steven↗

DOE OSTI2017

Effect of Autohydrolysis Pretreatment Conditions on Sugarcane Bagasse Structures and Product Distribution Resulting from Pyrolysis

Pyrolysis has been increasingly perceived as a promising technology to produce biofuel precursors (bio-oil) from agricultural residuals; however, there is a significant quality gap between a bio-oil and the fuels used for transportation. In this paper, we autohydrolyzed pretreated sugarcane bagasse at three different conditions (180 °C–10 min, 180 °C–40 min, 200 °C–40 min), then we investigated the effect of this pretreatment on a subsequent pyrolysis stage. High-pressure ion-exchange chromatography (HPIC) and the 13 C cross-polarization/magic angle spinning (CP/MAS) solid-state nuclear magnetic resonance (NMR) revealed that the autohydrolysis pretreatment significantly disrupted the hemicellulose fractions in the sugarcane bagasse and caused the breakage of lignin ether linkages in the sugarcane bagasse feedstocks. As the 31 P NMR results indicated, the autohydrolysis pretreatment removed carboxylic acid groups up to 66.7 %, which could significantly address the corrosion problem of bio-oils. Heteronuclear single quantum correlation (HSQC) analysis suggested that the autohydrolysis pretreatment effectively lowered the presence of the oxygenated aromatic compounds in the bio-oils. Finally, gel permeation chromatography (GPC) analysis of the bio-oils indicated that the oils from severely pretreated sugarcane bagasse pyrolyzed at a low temperature (i.e., 400 °C) contained lower-molecular-weight components similar to those present gasoline products.

09 BIOMASS FUELS↗

DOE OSTI2025

Roles of surface Mn(III) and MgOH + /CaOH + complexation in photochemically assisted Mn 2+ oxidation and Todorokite formation

Todorokite, a Mn oxide phase commonly found in seafloor Mn nodules, is one of the most abundant Mn oxides in nature and has wide applications in environmental engineering, including heavy metal remediation, contaminant adsorption for water purification, and catalysis for organic pollutant degradation. However, traditional abiotic formation of todorokite reported to date typically requires high temperature, pressure, and pH outside circumneutral conditions, or involves several days of phase transformations from precursor phases. In this study, we demonstrate rapid todorokite formation within 6 h via photochemically assisted oxidation of Mn 2+ (aq) in the presence of Mg 2+ or Ca 2+ , notably at ambient temperature and pressure. The concentrations of aqueous MgOH + and CaOH + , as well as the pH (initial 9 or 6), had significant collective influences on the crystalline phases of the formed Mn oxide solids. The proportions of the Mn oxidation states (IV, III, and II) and the extent of Mn(III) surface complexation with MgOH + or CaOH + controlled the crystalline phases (todorokite, feitknechtite, and birnessite) and the extent of cation incorporation into the resulting Mn oxide solids. Specifically, the oxidation state of Mn influenced the crystallization of different Mn oxide phases, and the formed Mn(III) complexed with MgOH + or CaOH + facilitated the formation of todorokite, along with cation incorporation. X-ray pair distribution function analysis revealed that incorporated Mg species were located at the inside corner sites of the 5 × 3 MnO 6 octahedral tunnel structure of todorokite, suggesting complexation between MgOH + and Mn(III) at the corners of the tunnel. Furthermore, this study provides novel insights into the elusive formation of todorokite and its potential for applications in advanced water treatment and environmental remediation.

Abiotic Mn2+ oxidation↗

DOE OSTI2019

Bimodal Nickel-Binding Site on Escherichia coli [NiFe]-Hydrogenase Metallochaperone HypA

[NiFe]-hydrogenase enzymes catalyze the reversible oxidation of hydrogen at a bimetallic active site and they are used by bacteria and archaea for anaerobic growth and pathogenesis. Maturation of the [NiFe]-hydrogenase requires several accessory proteins to assemble and insert the components of the active site. The penultimate maturation step is the delivery of nickel to a primed hydrogenase enzyme precursor protein, a process that is accomplished by two nickel metallochaperones, the accessory protein HypA and the GTPase HypB. Recent work demonstrated that nickel is rapidly transferred to HypA from GDP-loaded HypB within the context of a protein complex in a nickel selective and unidirectional process. To investigate the mechanism of metal transfer, we examined the allosteric effect of nucleotide cofactors and partner-proteins on the nickel environments of HypA and HypB by using a combination of biochemical, microbiological, computational, and spectroscopic techniques. We observed that loading HypB with either GDP or a non-hydrolyzable GTP analogue resulted in a similar nickel environment. In addition, interaction with a mutant version of HypA with disrupted nickel binding, H2Q-HypA, does not induce substantial changes to the HypB G-domain nickel site. Instead, the results demonstrate that HypB modifies the acceptor site of HypA. Analysis of a peptide maquette derived from the N-terminus of HypA revealed that nickel is predominately coordinated by atoms from the N-terminal Met-His- motif. Furthermore, HypA is capable of two nickel-binding modes at the N-terminus, a HypB-induced mode and a binding mode that mirrors the peptide maquette. Collectively, these results reveal that HypB brings about changes in the nickel coordination of HypA, providing a mechanism for the HypB-dependent control of the acquisition and release of nickel by HypA.

08 HYDROGEN↗

DOE OSTI2016

Conformational landscape of an amyloid intra-cellular domain and Landau-Ginzburg-Wilson paradigm in protein dynamics

The Landau-Ginzburg-Wilson paradigm is proposed as a framework, to investigate the conformational landscape of intrinsically unstructured proteins. A universal Cα-trace Landau free energy is deduced from general symmetry considerations, with the ensuing all-atom structure modeled using publicly available reconstruction programs Pulchra and Scwrl. As an example, the conformational stability of an amyloid precursor protein intra-cellular domain (AICD) is inspected; the reference conformation is the crystallographic structure with code 3DXC in Protein Data Bank (PDB) that describes a heterodimer of AICD and a nuclear multi-domain adaptor protein Fe65. Those conformations of AICD that correspond to local or near-local minima of the Landau free energy are identified. For this, the response of the original 3DXC conformation to variations in the ambient temperature is investigated, using the Glauber algorithm. The conclusion is that in isolation the AICD conformation in 3DXC must be unstable. A family of degenerate conformations that minimise the Landau free energy is identified, and it is proposed that the native state of an isolated AICD is a superposition of these conformations. The results are fully in line with the presumed intrinsically unstructured character of isolated AICD and should provide a basis for a systematic analysis of AICD structure in future NMR experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Structure–Composition Relationship of Platelike Ferrospheres in Calcium-Rich Power Plant Ash

The structure–composition relationship for polished sections of individual platelike ferrospheres in the–0.04 + 0.032 mm size fraction isolated from fly ash from the combustion of brown coal has been studied systematically by scanning electron microscopy and energy dispersive X-ray spectroscopy. We have identified groups of globules whose overall composition, as well as the composition of local areas on their polished sections, can be represented by general equations for component concentrations: CaO = f(FeO) and SiO{sub 2} = f(FeO). Analysis of the structure–composition relationship for the globules leads us to conclude that their structure is determined by transformations that occur in the CaO–Fe{sub x}O{sub y} system in response to an increase in its oxidation potential. It has been shown that the platelike globules containing 68–73 wt % FeO are made up of Ca{sub 2}Fe{sub 2}O{sub 5} and CaFe{sub 2}O{sub 4} crystallites resulting from the oxidative transformation of Fe, Ca, and Mg complex humates in the parent brown coal. The ferrospheres containing 79–90 wt % FeO have a fragmentary core–shell structure, where the platelike shell consists of Ca{sub 2}Fe{sub 2}O{sub 5} and CaFe{sub 2}O{sub 4} crystallites, and the core consists of Fe{sub 2}O{sub 3} and a Ca-, Mg-, and Al-promoted magnetite. Precursors for the formation of this type of globule are pyrite associates with complex humates. It has also been demonstrated that the low concentration of aluminum and silicon oxides in the composition of the globules and the viscosity of their melt have no effect on the structure of the platelike ferrospheres.

36 MATERIALS SCIENCE↗

NASA NTRS2002

Role of Rotation in Massive Stars in the SMC

We report on an analysis of FUSE+STIS+optical spectra of 17 O-type stars in the SMC. We found an enormous range in N abundances. Three stars in the sample have the same (low) CN abundances as the nebular material out of which they formed, namely C=0.08 C(sub circle dot) and N=0.03 N(sub circle dot). However, more than half shows N~O, an enrichment factor of 30X! Such a high level of N enrichment cannot be reproduced by current evolutionary models accounting for rotationally induced mixing. It suggests that the sum of CNO nuclei may not be conserved, i.e. massive stars might be producing primary nitrogen. It raises questions concerning the sources of nitrogen in the early universe, presently thought to be almost exclusively intermediate-mass stars. It also raises basic questions about the evolution of massive stars in low-metallicity environments, including the precursors to supernovae.

Heap, Sara R.↗

DOE OSTI2019

Sustainable Use of Chloroprene Rubber Waste as Blend Component with Natural Rubber, Epoxidized Natural Rubber and Styrene Butadiene Rubber

Recycling of rubber waste and finding the effective methods to extend its use are one of major challenges nowadays. The potential approach to reduce rubber waste is to blend it with virgin rubber, perhaps with synergistic advantages. In this study, chloroprene rubber waste (CRw) is used as blend component in binary blends with natural rubber (NR), epoxidized natural rubber with 50 mol% epoxidation level (ENR50), and styrene butadiene rubber (SBR). The effects of blend ratio [95/5, 85/15, 75/25, 65/35 and 50/50 (phr/phr)] on the properties were studied. The results indicate that CRw prolongs scorch and curing times, due to the differences in unsaturation contents and cure incompatibility. The maximum torque (M{sub H}), minimum torque (M{sub L}), and torque difference (M{sub H}–M{sub L}) in all cases increased with CRw content in the blend. Because CRw has a crosslink precursor, crosslink density also increased with CRw content. This is clearly confirmed by the combination of swelling resistance, crosslink density and dynamic mechanical properties observed. SEM micrographs showed mostly rough surface and tearing areas for low CRw contents in the blends. The blends also showed less crack paths with increasing CRw content over 50 phr. Further increase in CRw content obviously enhanced the thermal stability of the blends, with elevated decomposition temperatures in TGA results.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Rapid Polyolefin Plastic Hydrogenolysis Mediated by Single-Site Heterogeneous Electrophilic/Cationic Organo-group IV Catalysts

A homologous series of cationic electrophilic group IV metal hydrides (M = Ti, Zr, Hf) created by chemisorption of the corresponding MNp 4 precursors on highly Brønsted acidic sulfated alumina (AlS) to yield loosely coordinated surface AlS/MNp 2 (Np = neopentyl) species are systematically characterized by ICP, EXAFS/XANES, DRIFTS, and solid-state high-resolution multidimensional NMR spectroscopy (SSNMR), as well as by energy span DFT computation. With effective stirring, these complexes readily undergo reaction with H 2 to yield AlS/M(alkyl)H species, which are highly active for the hydrogenolysis of diverse commercial polyethylenes, α-olefin-ethylene copolymers, isotactic polypropylene, and postconsumer polyolefins including high-density polyethylenes, yielding medium and small linear and branched hydrocarbons at turnover frequencies as high as 36,300 h –1 at 200 °C/17 atm H 2 for M = Zr. For given polyolefin and reaction conditions, turnover frequencies scale approximately as M = Zr > Hf > Ti, whereas catalyst thermal stability scales approximately as M = Hf ≈ Zr > Ti, and these trends are qualitatively understandable from the DFT analysis. These catalytic results reveal that the AlS/Hf(R)H-mediated hydrogenolysis favors wax-like and liquid products, whereas the AlS/Zr(R)H-mediated hydrogenolysis can be tuned between gases and liquids. Finally, DFT analysis identifies β-alkyl elimination as the turnover-limiting C–C scission process, which is particularly facile in these cationic d 0 complexes but not so in the neutrally charged analogues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2010

A Dual Launch Robotic and Human Lunar Mission Architecture

This paper describes a comprehensive lunar exploration architecture developed by Marshall Space Flight Center's Advanced Concepts Office that features a science-based surface exploration strategy and a transportation architecture that uses two launches of a heavy lift launch vehicle to deliver human and robotic mission systems to the moon. The principal advantage of the dual launch lunar mission strategy is the reduced cost and risk resulting from the development of just one launch vehicle system. The dual launch lunar mission architecture may also enhance opportunities for commercial and international partnerships by using expendable launch vehicle services for robotic missions or development of surface exploration elements. Furthermore, this architecture is particularly suited to the integration of robotic and human exploration to maximize science return. For surface operations, an innovative dual-mode rover is presented that is capable of performing robotic science exploration as well as transporting human crew conducting surface exploration. The dual-mode rover can be deployed to the lunar surface to perform precursor science activities, collect samples, scout potential crew landing sites, and meet the crew at a designated landing site. With this approach, the crew is able to evaluate the robotically collected samples to select the best samples for return to Earth to maximize the scientific value. The rovers can continue robotic exploration after the crew leaves the lunar surface. The transportation system for the dual launch mission architecture uses a lunar-orbit-rendezvous strategy. Two heavy lift launch vehicles depart from Earth within a six hour period to transport the lunar lander and crew elements separately to lunar orbit. In lunar orbit, the crew transfer vehicle docks with the lander and the crew boards the lander for descent to the surface. After the surface mission, the crew returns to the orbiting transfer vehicle for the return to the Earth. This paper describes a complete transportation architecture including the analysis of transportation element options and sensitivities including: transportation element mass to surface landed mass; lander propellant options; and mission crew size. Based on this analysis, initial design concepts for the launch vehicle, crew module and lunar lander are presented. The paper also describes how the dual launch lunar mission architecture would fit into a more general overarching human space exploration philosophy that would allow expanded application of mission transportation elements for missions beyond the Earth-moon realm.

Jones, David L.↗