Electrodynamic Tethers For Planetary And De-orbiting Missions

Nuevas aplicaciones tecnológicas y científicas mediante amarras electrodinámicas son analizadas para misiones planetarias. i) Primero, se considera un conjunto de amarras cilíndricas en paralelo (veleros electrosolares) para una misión interplanetaria. Los iones provenientes del viento solar son repelidos por el alto potencial de dichas amarras generando empuje sobre el velero. Para conocer el intercambio de momento que provocan los iones sobre las amarras se ha considerado un modelo de potencial estacionario. Se ha analizado la transferencia orbital de la Tierra a Júpiter siguiendo un método de optimización de trayectoria indirecto. ii) Una vez que el velero se encuentra cerca de Júpiter, se ha considerado el despliegue de una amarra para diferentes objetivos científicos. iia) Una amarra podría ser utilizada para diagnóstico de plasmas, al ser una fuente efectiva de ondas, y también como un generador de auroras artificiales. Una amarra conductora que orbite en la magnetosfera jovial es capaz de producir ondas. Se han analizado las diferentes ondas radiadas por un conductor por el que circula una corriente constante que sigue una órbita polar de alta excentricidad y bajo apoápside, como ocurre en la misión Juno de la NASA. iib) Además, se ha estudiado una misión tentativa que sigue una órbita ecuatorial (LJO) por debajo de los intensos cinturones de radiación. Ambas misiones requiren potencia eléctrica para los sistemas de comunicación e instrumentos científicos. Las amarras pueden generar potencia de manera más eficiente que otros sistemas que utlizan paneles solares o sistemas de potencia de radioisótopos (RPS). La impedancia de radiación es necesaria para determinar la corriente que circula por todo el circuito de la amarra. En un modelo de plasma frío, la radiación ocurre principalmente en los modos de Alfven y magnetosónica rápida, mostrando un elevado índice de refracción. Se ha estudiado la impedancia de radiación en amarras con recubrimiento aislante para los dos modos de radiación y cada una de las misiones. A diferencia del caso ionosférico terrestre, la baja densidad y el intenso campo magnético que aparecen en el entorno de Júpiter consiguen que la girofrecuencia de los electrones sea mucho mayor que la frecuencia del plasma; esto hace que el espectro de potencia para cada modo se modifique substancialmente, aumentando la velocidad de Alfven. Se ha estimado también la impedancia de radiación para amarras sin aislante conductor. En la misión LJO, un vehículo espacial bajando lentamente la altitud de su órbita permitiría estudiar la estructura del campo magnético y composición atmosférica para entender la formación, evolución, y estructura de Júpiter. Adicionalmente, si el contactor (cátodo) se apaga, se dice que la amarra flota eléctricamente, permitiendo emisión de haz de electrones que generan auroras. El continuo apagado y encendido produce pulsos de corriente dando lugar a emisiones de señales, que pueden ser utilizadas para diagnóstico del plasma jovial. En Órbita Baja Jovial, los iones que impactan contra una amarra polarizada negativamente producen electrones secundarios, que, viajando helicoidalmente sobre las líneas de campo magnético de Júpiter, son capaces de alcanzar su atmósfera más alta, y, de esta manera, generar auroras. Se han identificado cuáles son las regiones donde la amarra sería más eficiente para producir auroras. iic) Otra aplicación científica sugerida para la misión LJO es la detección de granos cargados que orbitan cerca de Júpiter. Los electrones de alta energía en este ambiente pueden ser modelados por una distribucción no Maxwelliana conocida como distribución kappa. En escenarios con plasmas complejos, donde los campos eléctricos en Júpiter pueden acelerar las cargas hasta velocidades que superen la velocidad térmica, este tipo de distribuciones son muy útiles. En este caso las colas de las distribuciones de electrones siguen una ley de potencias. Se han estudiado las fluctuaciones de granos cargados para funciones de distribución kappa. iii) La tesis concluye con el análisis para deorbitar satélites con amarras electrodinámicas que siguen una Órbita Baja Terrestre (LEO). Una amarra debe presentar una baja probabilidad de corte por pequeño debris y además debe ser suficientemente ligero para que el cociente entre la masa de la amarra y el satélite sea muy pequeño. En este trabajo se estiman las medidas de la longitud, anchura y espesor que debe tener una amarra para minimizar el producto de la probabilidad de corte por el cociente entre las masas de la amarra y el satélite. Se presentan resultados preliminares del diseño de una amarra con forma de cinta para deorbitar satélites relativamente ligeros como Cryosat y pesados como Envisat. Las misiones espaciales a planetas exteriores y en el ámbito terrestre plantean importantes retos científico-tecnológicos que deben ser abordados y solucionados. Por ello, desde el inicio de la era espacial se han diseñando novedosos métodos propulsivos, sistemas de guiado, navegación y control más robustos, y nuevos materiales para mejorar el rendimiento de los vehículos espaciales (SC). En un gran número de misiones interplanetarias y en todas las misiones a planetas exteriores se han empleado sistemas de radioisótopos (RPS) para generar potencia eléctrica en los vehículos espaciales y en los rovers de exploración. Estos sistemas emplean como fuente de energía el escaso y costoso plutonio-238. La NASA, por medio de un informe de la National Academy of Science (5 de Mayo del 2009), expresó una profunda preocupación por la baja cantidad de plutonio almacenado, insuficiente para desarrollar todas las misiones de exploración planetaria planeadas en el futuro [81, 91]. Esta circustancia ha llevado a dicha Agencia tomar la decisión de limitar el uso de estos sistemas RPS en algunas misiones de especial interés científico y una recomendación de alta prioridad para que el Congreso de los EEUU apruebe el reestablecimiento de la producción de plutonio-238, -son necesarios cerca de 5 kg de este material radiactivo al año-, para salvaguardar las misiones que requieran dichos sistemas de potencia a partir del año 2018. Por otro lado, la Agencia estadounidense ha estado considerando el uso de fuentes de energía alternativa; como la fisión nuclear a través del ambicioso proyecto Prometheus, para llevar a cabo una misión de exploración en el sistema jovial (JIMO). Finalmente, dicha misión fue desestimada por su elevado coste. Recientemente se han estado desarrollando sistemas que consigan energía a través de los recursos naturales que nos aporta el Sol, mediante paneles solares -poco eficientes para misiones a planetas alejados de la luz solar-. En este contexto, la misión JUNO del programa Nuevas Fronteras de la NASA, cuyo lanzamiento fue realizado con éxito en Agosto de 2011, va a ser la primera misión equipada con paneles solares que sobrevolará Júpiter en el 2015 siguiendo una órbita polar. Anteriormente se habían empleado los antes mencionados RPS para las misiones Pioneer 10,11, Voyager 1,2, Ulysses, Cassini-Huygens y Galileo (todas sobrevuelos excepto Galileo). Dicha misión seguirá una órbita elíptica de alta excentricidad con un periápside muy cercano a Júpiter, y apoápside lejano, evitando que los intensos cinturones de radiación puedan dañar los instrumentos de navegación y científicos. Un tether o amarra electrodinámica es capaz de operar como sistema propulsivo o generador de potencia, pero también puede ser considerado como solución científicotecnológica en misiones espaciales tanto en LEO (Órbita Baja Terrestre) como en planetas exteriores. Siguiendo una perspectiva histórica, durante las misiones terrestres TSS-1 (1992) y TSS-1R (1996) se emplearon amarras estandard con recubrimiento aislante en toda su longitud, aplicando como terminal anódico pasivo un colector esférico para captar electrones. En una geometría alternativa, propuesta por J. R. Sanmartín et al. (1993) [93], se consideró dejar la amarra sin recubrimiento aislante (“bare tether”), y sin colector anódico esférico, de forma que recogiera electrones a lo largo del segmento que resulta polarizado positivo, como si se tratara de una sonda de Langmuir de gran longitud. A diferencia de la amarra estandard, el “bare tether” es capaz de recoger electrones a lo largo de una superficie grande ya que este segmento es de varios kilómetros de longitud. Como el radio de la amarra es del orden de la longitud de Debye y pequeño comparado con el radio de Larmor de los electrones, permite una recolección eficiente de electrones en el régimen OML (Orbital Motion Limited) de sondas de Langmuir. La corriente dada por la teoría OML varía en función del perímetro y la longitud. En el caso de una cinta delgada, el perímetro depende de la anchura, que debe ser suficientemente grande para evitar cortes producidos por debris y micrometeoritos, y suficientemente pequeño para que la amarra funcione en dicho régimen [95]. En el experimento espacial TSS-1R mencionado anteriormente, se identificó una recolección de corriente más elevada que la que predecía el modelo teórico de Parker- Murphy, debido posiblemente a que se utilizaba un colector esférico de radio bastante mayor que la longitud de Debye [79]. En el caso de una amarra “bare”, que recoge electrones a lo largo de gran parte de su longitud, se puede producir un fenómeno conocido como atrapamiento adiabático de electrones (adiabatic electron trapping) [25, 40, 60, 73, 74, 97]. En el caso terrestre (LEO) se da la condición mesotérmica en la que la amarra se mueve con una velocidad muy superior a la velocidad térmica de los iones del ambiente y muy inferior a la velocidad térmica de los electrones. J. Laframboise y L. Parker [57] mostraron que, para una función de distribución quasi-isotrópica, la densidad de electrones debe entonces ser necesariamente inferior a la densidad ambiente. Por otra parte, debido a su flujo hipersónico y a la alta polarización positiva de la amarra, la densidad de los iones es mayor que la densidad ambiente en una vasta región de la parte “ram” del flujo, violando la condición de cuasi-neutralidad,-en una región de dimensión mayor que la longitud de Debye-. La solución a esta paradoja podría basarse en el atrapamiento adiabático de electrones ambiente en órbitas acotadas entorno al tether. ABSTRACT New technological and scientific applications by electrodynamic tethers for planetary missions are analyzed: i) A set of cylindrical, parallel tethers (electric solar sail or e-sail) is considered for an interplanetary mission; ions from the solar wind are repelled by the high potential of the tether, providing momentum to the e-sail. An approximated model of a stationary potential for a high solar wind flow is considered. With the force provided by a negative biased tether, an indirect method for the optimization trajectory of an Earth-to-Jupiter orbit transfer is analyzed. ii) The deployment of a tether from the e-sail allows several scientific applications in Jupiter. iia) It might be used as a source of radiative waves for plasma diagnostics and artificial aurora generator. A conductive tether orbiting in the Jovian magnetosphere produces waves. Wave radiation by a conductor carrying a steady current in both a polar, highly eccentric, low perijove orbit, as in NASA’s Juno mission, and an equatorial low Jovian orbit (LJO) mission below the intense radiation belts, is considered. Both missions will need electric power generation for scientific instruments and communication systems. Tethers generate power more efficiently than solar panels or radioisotope power systems (RPS). The radiation impedance is required to determine the current in the overall tether circuit. In a cold plasma model, radiation occurs mainly in the Alfven and fast magnetosonic modes, exhibiting a large refraction index. The radiation impedance of insulated tethers is determined for both modes and either mission. Unlike the Earth ionospheric case, the low-density, highly magnetized Jovian plasma makes the electron gyrofrequency much larger than the plasma frequency; this substantially modifies the power spectrum for either mode by increasing the Alfven velocity. An estimation of the radiation impedance of bare tethers is also considered. iib) In LJO, a spacecraft orbiting in a slow downward spiral under the radiation belts would allow determining magnetic field structure and atmospheric composition for understanding the formation, evolution, and structure of Jupiter. Additionally, if the cathodic contactor is switched off, a tether floats electrically, allowing e-beam emission that generate auroras. On/off switching produces bias/current pulses and signal emission, which might be used for Jovian plasma diagnostics. In LJO, the ions impacting against the negative-biased tether do produce secondary electrons, which racing down Jupiter’s magnetic field lines, reach the upper atmosphere. The energetic electrons there generate auroral effects. Regions where the tether efficiently should produce secondary electrons are analyzed. iic) Other scientific application suggested in LJO is the in-situ detection of charged grains. Charged grains naturally orbit near Jupiter. High-energy electrons in the Jovian ambient may be modeled by the kappa distribution function. In complex plasma scenarios, where the Jovian high electric field may accelerate charges up superthermal velocities, the use of non-Maxwellian distributions should be considered. In these cases, the distribution tails fit well to a power-law dependence for electrons. Fluctuations of the charged grains for non-Mawellian distribution function are here studied. iii) The present thesis is concluded with the analysis for de-orbiting satellites at end of mission by electrodynamic tethers. A de-orbit tether system must present very small tether-to-satellite mass ratio and small probability of a tether cut by small debris too. The present work shows how to select tape dimensions so as to minimize the product of those two magnitudes. Preliminary results of tape-tether design are here discussed to minimize that function. Results for de-orbiting Cryosat and Envisat are also presented.

Rhizobium leguminosarum HupE is a highly-specific diffusion facilitator for nickel uptake

Bacteria require nickel transporters for the synthesis of Ni-containing metalloenzymes in natural, low nickel habitats. In this work we carry out functional and topological characterization of Rhizobium leguminosarum HupE, a nickel permease required for the provision of this element for [NiFe] hydrogenase synthesis. Expression studies in the Escherichia coli nikABCDE mutant strain HYD723 revealed that HupE is a medium-affinity permease (apparent Km 227 ! 21 nM; Vmax 49 ! 21 pmol Ni2+ min"1 mg"1 bacterial dry weight) that functions as an energy-independent diffusion facilitator for the uptake of Ni(II) ions. This Ni2+ transport is not inhibited by similar cations such as Mn2+, Zn2+, or Co2+, but is blocked by Cu2+. Analysis of site-directed HupE mutants allowed the identification of several residues (H36, D42, H43, F69, E90, H130, and E133) that are essential for HupE-mediated Ni uptake in E. coli cells. By using translational fusions to reporter genes we demonstrated the presence of five transmembrane domains with a periplasmic N-terminal domain and a C-terminal domain buried in the lipid bilayer. The periplasmic N-terminal domain contributes to stability and functionality of the protein

Physical reasons for the unusual α-helix stabilization afforded by charged or neutral polar residues in alanine-rich peptides

We have carried out conformational energy calculations on alanine-based copolymers with the sequence Ac-AAAAAXAAAA-NH2 in water, where X stands for lysine or glutamine, to identify the underlying source of stability of alanine-based polypeptides containing charged or highly soluble polar residues in the absence of charge–charge interactions. The results indicate that ionizable or neutral polar residues introduced into the sequence to make them soluble sequester the water away from the CO and NH groups of the backbone, thereby enabling them to form internal hydrogen bonds. This solvation effect dictates the conformational preference and, hence, modifies the conformational propensity of alanine residues. Even though we carried out simulations for specific amino acid sequences, our results provide an understanding of some of the basic principles that govern the process of folding of these short sequences independently of the kind of residues introduced to make them soluble. In addition, we have investigated through simulations the effect of the bulk dielectric constant on the conformational preferences of these peptides. Extensive conformational Monte Carlo searches on terminally blocked 10-mer and 16-mer homopolymers of alanine in the absence of salt were carried out assuming values for the dielectric constant of the solvent ɛ of 80, 40, and 2. Our simulations show a clear tendency of these oligopeptides to augment the α-helix content as the bulk dielectric constant of the solvent is lowered. This behavior is due mainly to a loss of exposure of the CO and NH groups to the aqueous solvent. Experimental evidence indicates that the helical propensity of the amino acids in water shows a dramatic increase on addition of certain alcohols, such us trifluoroethanol. Our results provide a possible explanation of the mechanism by which alcohol/water mixtures affect the free energy of helical alanine oligopeptides relative to nonhelical ones.

Interaction between like-charged colloidal spheres in electrolyte solutions

How colloidal particles interact with each other is one of the key issues that determines our ability to interpret experimental results for phase transitions in colloidal dispersions and our ability to apply colloid science to various industrial processes. The long-accepted theories for answering this question have been challenged by results from recent experiments. Herein we show from Monte-Carlo simulations that there is a short-range attractive force between identical macroions in electrolyte solutions containing divalent counterions. Complementing some recent and related results by others, we present strong evidence of attraction between a pair of spherical macroions in the presence of added salt ions for the conditions where the interacting macroion pair is not affected by any other macroions that may be in the solution. This attractive force follows from the internal-energy contribution of counterion mediation. Contrary to conventional expectations, for charged macroions in an electrolyte solution, the entropic force is repulsive at most solution conditions because of localization of small ions in the vicinity of macroions. Both Derjaguin–Landau–Verwey–Overbeek theory and Sogami–Ise theory fail to describe the attractive interactions found in our simulations; the former predicts only repulsive interaction and the latter predicts a long-range attraction that is too weak and occurs at macroion separations that are too large. Our simulations provide fundamental “data” toward an improved theory for the potential of mean force as required for optimum design of new materials including those containing nanoparticles.

Computation of Surface Electrical Potentials of Plant Cell Membranes : Correspondence to Published Zeta Potentials from Diverse Plant Sources

A Gouy-Chapman-Stern model has been developed for the computation of surface electrical potential (ψ0) of plant cell membranes in response to ionic solutes. The present model is a modification of an earlier version developed to compute the sorption of ions by wheat (Triticum aestivum L. cv Scout 66) root plasma membranes. A single set of model parameters generates values for ψ0 that correlate highly with published ζ potentials of protoplasts and plasma membrane vesicles from diverse plant sources. The model assumes ion binding to a negatively charged site (R− = 0.3074 μmol m−2) and to a neutral site (P0 = 2.4 μmol m−2) according to the reactions R− + IΖ ⇌ RIΖ−1 and P0 + IΖ ⇌ PIΖ, where IΖ represents an ion of charge Ζ. Binding constants for the negative site are 21,500 m−1 for H+, 20,000 m−1 for Al3+, 2,200 m−1 for La3+, 30 m−1 for Ca2+ and Mg2+, and 1 m−1 for Na+ and K+. Binding constants for the neutral site are 1/180 the value for binding to the negative site. Ion activities at the membrane surface, computed on the basis of ψ0, appear to determine many aspects of plant-mineral interactions, including mineral nutrition and the induction and alleviation of mineral toxicities, according to previous and ongoing studies. A computer program with instructions for the computation of ψ0, ion binding, ion concentrations, and ion activities at membrane surfaces may be requested from the authors.

Clusters of charged residues in protein three-dimensional structures.

Statistically significant charge clusters (basic, acidic, or of mixed charge) in tertiary protein structures are identified by new methods from a large representative collection of protein structures. About 10% of protein structures show at least one charge cluster, mostly of mixed type involving about equally anionic and cationic residues. Positive charge clusters are very rare. Negative (or histidine-acidic) charge clusters often coordinate calcium, or magnesium or zinc ions [e.g., thermolysin (PDB code: 3tln), mannose-binding protein (2msb), aminopeptidase (1amp)]. Mixed-charge clusters are prominent at interchain contacts where they stabilize quaternary protein formation [e.g., glutathione S-transferase (2gst), catalase (8act), and fructose-1,6-bisphosphate aldolase (1fba)]. They are also involved in protein-protein interaction and in substrate binding. For example, the mixed-charge cluster of aspartate carbamoyl-transferase (8atc) envelops the aspartate carbonyl substrate in a flexible manner (alternating tense and relaxed states) where charge associations can vary from weak to strong. Other proteins with charge clusters include the P450 cytochrome family (BM-3, Terp, Cam), several flavocytochromes, neuraminidase, hemagglutinin, the photosynthetic reaction center, and annexin. In each case in Table 2 we discuss the possible role of the charge clusters with respect to protein structure and function.

Mutation of conserved negatively charged residues in the S2 and S3 transmembrane segments of a mammalian K+ channel selectively modulates channel gating.

Voltage-gated channel proteins sense a change in the transmembrane electric field and respond with a conformational change that allows ions to diffuse across the pore-forming structure. Site-specific mutagenesis combined with electrophysiological analysis of expressed mutants in amphibian oocytes has previously established the S4 transmembrane segment as an element of the voltage sensor. Here, we show that mutations of conserved negatively charged residues in S2 and S3 of a brain K+ channel, thought of as countercharges for the positively charged residues in S4, selectively modulate channel gating without modifying the permeation properties. Mutations of Glu235 in S2 that neutralize or reverse charge increase the probability of channel opening and the apparent gating valence. In contrast, replacements of Glu272 by Arg or Thr268 by Asp in S3 decrease the open probability and the apparent gating valence. Residue Glu225 in S2 tolerated replacement only by acidic residues, whereas Asp258 in S3 was intolerant to any attempted change. These results imply that S2 and S3 are unlikely to be involved in channel lining, yet, together with S4, may be additional components of the voltage-sensing structure.

Search for ultrahigh energy neutrinos in highly inclined events at the Pierre Auger Observatory

The Surface Detector of the Pierre Auger Observatory is sensitive to neutrinos of all flavors above 0.1 EeV. These interact through charged and neutral currents in the atmosphere giving rise to extensive air showers. When interacting deeply in the atmosphere at nearly horizontal incidence, neutrinos can be distinguished from regular hadronic cosmic rays by the broad time structure of their shower signals in the water-Cherenkov detectors. In this paper we present for the first time an analysis based on down-going neutrinos. We describe the search procedure, the possible sources of background, the method to compute the exposure and the associated systematic uncertainties. No candidate neutrinos have been found in data collected from 1 January 2004 to 31 May 2010. Assuming an E-2 differential energy spectrum the limit on the single-flavor neutrino is E(2)dN/dE < 1.74 x 10(-7)GeVcm(-2)s(-1)sr(-1) at 90% C.L. in the energy range 1 x 10(17) eV < E < 1 x 10(20)eV.

Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array.

Spectroscopy and metastability of CO 2 2+ molecular ions

The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO ₂ ²⁺ dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340±0.010 eV. The fragmentation of energy selected CO ₂ ²⁺ ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from ∼38.7 to ∼41 eV above the ground state of neutral CO ₂ has been observed in the experimental time window of ∼0.1-2.3 μs with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO ⁺+O ⁺ formation in indirect dissociative double photoionization below the threshold for formation of CO ₂ ²⁺. The threshold for CO ⁺+O ⁺ formation is found to be 35.56±0.10 eV or lower, which is more than 2 eV lower than previous measurements.

Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Tissue Proteomes: Quantitative Mass Spectrometry of Murine Liver and Ovarian Endometrioma

A human genome contains more than 20 000 protein-encoding genes. A human proteome, instead, has been estimated to be much more complex and dynamic. The most powerful tool to study proteins today is mass spectrometry (MS). MS based proteomics is based on the measurement of the masses of charged peptide ions in a gas-phase. The peptide amino acid sequence can be deduced, and matching proteins can be found, using software to correlate MS-data with sequence database information. Quantitative proteomics allow the estimation of the absolute or relative abundance of a certain protein in a sample. The label-free quantification methods use the intrinsic MS-peptide signals in the calculation of the quantitative values enabling the comparison of peptide signals from numerous patient samples. In this work, a quantitative MS methodology was established to study aromatase overexpressing (AROM+) male mouse liver and ovarian endometriosis tissue samples. The workflow of label-free quantitative proteomics was optimized in terms of sensitivity and robustness, allowing the quantification of 1500 proteins with a low coefficient of variance in both sample types. Additionally, five statistical methods were evaluated for the use with label-free quantitative proteomics data. The proteome data was integrated with other omics datasets, such as mRNA microarray and metabolite data sets. As a result, an altered lipid metabolism in liver was discovered in male AROM+ mice. The results suggest a reduced beta oxidation of long chain phospholipids in the liver and increased levels of pro-inflammatory fatty acids in the circulation in these mice. Conversely, in the endometriosis tissues, a set of proteins highly specific for ovarian endometrioma were discovered, many of which were under the regulation of the growth factor TGF-β1. This finding supports subsequent biomarker verification in a larger number of endometriosis patient samples.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.