From bilateral two-way to unilateral one-way flow link-formation

Documento de trabajo

Formation of X-waves at fundamental and harmonics by infrared femtosecond pulse filamentation in air

We experimentally observe the formation of X-waves at fundamental, third harmonic, and fifth harmonic wavelengths by infrared (central wavelength at similar to 1500 nm) femtosecond laser pulse filamentation in air. By fitting the angularly resolved spectra of the fundamental and harmonic waves using X-wave relations, we confirm that all the X-waves have nearly the same group velocity, indicating that they are locked in space and time during their propagation in filament.

Pattern formation during Caenorhabditis Elegans vulval development

Pattern formation during animal development involves at least three processes: establishment of the competence of precursor cells to respond to intercellular signals, formation of a pattern of different cell fates adopted by precursor cells, and execution of the cell fate by generating a pattern of distinct descendants from precursor cells. I have analyzed the fundamental mechanisms of pattern formation by studying the development of Caenorhabditis elegans vulva.

In C. elegans, six multipotential vulval precursor cells (VPCs) are competent to respond to an inductive signal LIN-3 (EGF) mediated by LET- 23 (RTK) and a lateral signal via LIN-12 (Notch) to form a fixed pattern of 3°-3°-2°-1°-2°-3°. Results from expressing LIN-3 as a function of time in animals lacking endogenous LIN-3 indicate that both VPCs and VPC daughters are competent to respond to LIN-3. Although the daughters of VPCs specified to be 2° or 3° can be redirected to adopt the 1°fate, the decision to adopt the 1° fate is irreversible. Coupling of VPC competence to cell cycle progression reveals that VPC competence may be periodic during each cell cycle and involve LIN-39 (HOM-C). These mechanisms are essential to ensure a bias towards the 1° fate, while preventing an excessive response.

After adopting the 1° fate, the VPC executes its fate by dividing three rounds to form a fixed pattern of four inner vulF and four outer vulE descendants. These two types of descendants can be distinguished by a molecular marker zmp-1::GFP. A short-range signal from the anchor cell (AC), along with signaling between the inner and outer 1° VPC descendants and intrinsic polarity of 1° VPC daughters, patterns the 1° lineage. The Ras and the Wnt signaling pathways may be involved in these mechanisms.

The temporal expression pattern of egl-17::GFP, another marker ofthe 1° fate, correlates with three different steps of 1° fate execution: the commitment to the 1° fate, as well as later steps before and after establishment of the uterine-vulval connection. Six transcription factors, including LIN-1(ETS), LIN-39 (HOM-C), LIN-11(LIM), LIN-29 (zinc finger), COG-1 (homeobox) and EGL-38 (PAX2/5/8), are involved in different steps during 1° fate execution.

Formation of nanogratings on the surface of a ZnSe crystal irradiated by femtosecond laser pulses

Two collinear femtosecond laser pulses, one at wavelength of 800 nm and the other at 400 nm (double frequency), simultaneously irradiated the surface of ZnSe crystal, which resulted in regular nanograting with period of 180 nm on the whole ablation area. We attribute the formation of the nanograting to be due to the interference between the surface scattered wave of 800 nm lasers and the 400 nm light. The period of the nanograting Lambda is about lambda/2n, where n is refractive index of the sample, and lambda, the laser wavelength. This mechanism is supported by observation of rotation of the nanograting with the polarization of 400 nm light, and by the dependence of Lambda similar to lambda of the nanoripples on the surface of semiconductors and dielectrics.

Studies of ambient organic and inorganic aerosol in Southern California

The negative impacts of ambient aerosol particles, or particulate matter (PM), on human health and climate are well recognized. However, owing to the complexity of aerosol particle formation and chemical evolution, emissions control strategies remain difficult to develop in a cost effective manner. In this work, three studies are presented to address several key issues currently stymieing California's efforts to continue improving its air quality.

Gas-phase organic mass (GPOM) and CO emission factors are used in conjunction with measured enhancements in oxygenated organic aerosol (OOA) relative to CO to quantify the significant lack of closure between expected and observed organic aerosol concentrations attributable to fossil-fuel emissions. Two possible conclusions emerge from the analysis to yield consistency with the ambient organic data: (1) vehicular emissions are not a dominant source of anthropogenic fossil SOA in the Los Angeles Basin, or (2) the ambient SOA mass yields used to determine the SOA formation potential of vehicular emissions are substantially higher than those derived from laboratory chamber studies. Additional laboratory chamber studies confirm that, owing to vapor-phase wall loss, the SOA mass yields currently used in virtually all 3D chemical transport models are biased low by as much as a factor of 4. Furthermore, predictions from the Statistical Oxidation Model suggest that this bias could be as high as a factor of 8 if the influence of the chamber walls could be removed entirely.

Once vapor-phase wall loss has been accounted for in a new suite of laboratory chamber experiments, the SOA parameterizations within atmospheric chemical transport models should also be updated. To address the numerical challenges of implementing the next generation of SOA models in atmospheric chemical transport models, a novel mathematical framework, termed the Moment Method, is designed and presented. Assessment of the Moment Method strengths and weaknesses provide valuable insight that can guide future development of SOA modules for atmospheric CTMs.

Finally, regional inorganic aerosol formation and evolution is investigated via detailed comparison of predictions from the Community Multiscale Air Quality (CMAQ version 4.7.1) model against a suite of airborne and ground-based meteorological measurements, gas- and aerosol-phase inorganic measurements, and black carbon (BC) measurements over Southern California during the CalNex field campaign in May/June 2010. Results suggests that continuing to target sulfur emissions with the hopes of reducing ambient PM concentrations may not the most effective strategy for Southern California. Instead, targeting dairy emissions is likely to be an effective strategy for substantially reducing ammonium nitrate concentrations in the eastern part of the Los Angeles Basin.

Nematic ordering pattern formation in the process of self-organization of microtubules in a gravitational field

Papaseit et al. (Proc. Nati. Acad. Sci. U.S.A. 97, 8364, 2000) showed the decisive role of gravity in the formation of patterns by assemblies of microtubules in vitro. By virtue of a functional scaling, the free energy for MT systems in a gravitational field was constructed. The influence of the gravitational field on MT's self-organization process, that can lead to the isotropic to nematic phase transition, is the focus of this paper. A coupling of a concentration gradient with orientational order characteristic of nernatic ordering pattern formation is the new feature emerging in the presence of gravity. The concentration range corresponding to a phase coexistence region increases with increasing g or NIT concentration. Gravity facilitates the isotropic to nernatic phase transition leading to a significantly broader transition region. The phase transition represents the interplay between the growth in the isotropic phase and the precipitation into the nematic phase. We also present and discuss the numerical results obtained for local NIT concentration change with the height of the vessel, order parameter and phase transition properties.

Formation mechanisms of uniform arrays of periodic nanoparticles and nanoripples on 6H-SiC crystal surface induced by femtosecond laser ablation

Uniform arrays of periodic nanoparticles with 80-nm period are formed on 6H-SiC crystal irradiated by circularly polarized 400-nm femtosecond laser pulses. In order to understand the formation mechanism, the morphology evolvement as a function of laser pulse energy and number is studied. Periodic nanoripples are also formed on the sample surface irradiated by linearly polarized 400-, 510- and 800-nm femtosecond laser pulses. All these results support well the mechanism that second-harmonic generation plays an important role in the formation of periodic nanostructures.

Standing electron plasma wave mechanism of void array formation inside glass by femtosecond laser irradiation

We investigate the mechanism of formation of periodic void arrays inside fused silica and BK7 glass irradiated by a tightly focused femtosecond (fs) laser beam. Our results show that the period of each void array is not uniform along the laser propagation direction, and the average period of the void array decreases with increasing pulse number and pulse energy. We propose a mechanism in which a standing electron plasma wave created by the interference of a fs-laser-driven electron wave and its reflected wave is responsible for the formation of the periodic void arrays.

Functionalization of Si(111) surfaces and the formation of mixed monolayers for the covalent attachment of molecular catalysts in photoelectrochemical devices

The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH₃CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)₂vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir L_III edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.

Nonlinear X-wave formation and conical emission at different powers of a femtosecond laser pulse in water

Nonlinear X-wave formation at different pulse powers in water is simulated using the standard model of nonlinear Schrodinger equation (NLSE). It is shown that in near field X-shape originally emerges from the interplay between radial diffraction and optical Kerr effect. At relatively low power group-velocity dispersion (GVD) arrests the collapse and leads to pulse splitting on axis. With high enough power, multi-photon ionization (NIPI) and multi-photon absorption (MPA) play great importance in arresting the collapse. The tailing part of pulse is first defocused by MPI and then refocuses. Pulse splitting on axis is a manifestation of this process. Double X-wave forms when the split sub-pulses are self-focusing. In the far field, the character of the central X structure of conical emission (CE) is directly related to the single or double X-shape in the near field. (c) 2007 Elsevier B.V. All rights reserved.

New insights into the formation and modification of carbonate-bearing minerals and methane gas in geological systems using multiply substituted isotopologues

This thesis describes the use of multiply-substituted stable isotopologues of carbonate minerals and methane gas to better understand how these environmentally significant minerals and gases form and are modified throughout their geological histories. Stable isotopes have a long tradition in earth science as a tool for providing quantitative constraints on how molecules, in or on the earth, formed in both the present and past. Nearly all studies, until recently, have only measured the bulk concentrations of stable isotopes in a phase or species. However, the abundance of various isotopologues within a phase, for example the concentration of isotopologues with multiple rare isotopes (multiply substituted or 'clumped' isotopologues) also carries potentially useful information. Specifically, the abundances of clumped isotopologues in an equilibrated system are a function of temperature and thus knowledge of their abundances can be used to calculate a sample’s formation temperature. In this thesis, measurements of clumped isotopologues are made on both carbonate-bearing minerals and methane gas in order to better constrain the environmental and geological histories of various samples.

Clumped-isotope-based measurements of ancient carbonate-bearing minerals, including apatites, have opened up paleotemperature reconstructions to a variety of systems and time periods. However, a critical issue when using clumped-isotope based measurements to reconstruct ancient mineral formation temperatures is whether the samples being measured have faithfully recorded their original internal isotopic distributions. These original distributions can be altered, for example, by diffusion of atoms in the mineral lattice or through diagenetic reactions. Understanding these processes quantitatively is critical for the use of clumped isotopes to reconstruct past temperatures, quantify diagenesis, and calculate time-temperature burial histories of carbonate minerals. In order to help orient this part of the thesis, Chapter 2 provides a broad overview and history of clumped-isotope based measurements in carbonate minerals.

In Chapter 3, the effects of elevated temperatures on a sample’s clumped-isotope composition are probed in both natural and experimental apatites (which contain structural carbonate groups) and calcites. A quantitative model is created that is calibrated by the experiments and consistent with the natural samples. The model allows for calculations of the change in a sample’s clumped isotope abundances as a function of any time-temperature history.

In Chapter 4, the effects of diagenesis on the stable isotopic compositions of apatites are explored on samples from a variety of sedimentary phosphorite deposits. Clumped isotope temperatures and bulk isotopic measurements from carbonate and phosphate groups are compared for all samples. These results demonstrate that samples have experienced isotopic exchange of oxygen atoms in both the carbonate and phosphate groups. A kinetic model is developed that allows for the calculation of the amount of diagenesis each sample has experienced and yields insight into the physical and chemical processes of diagenesis.

The thesis then switches gear and turns its attention to clumped isotope measurements of methane. Methane is critical greenhouse gas, energy resource, and microbial metabolic product and substrate. Despite its importance both environmentally and economically, much about methane’s formational mechanisms and the relative sources of methane to various environments remains poorly constrained. In order to add new constraints to our understanding of the formation of methane in nature, I describe the development and application of methane clumped isotope measurements to environmental deposits of methane. To help orient the reader, a brief overview of the formation of methane in both high and low temperature settings is given in Chapter 5.

In Chapter 6, a method for the measurement of methane clumped isotopologues via mass spectrometry is described. This chapter demonstrates that the measurement is precise and accurate. Additionally, the measurement is calibrated experimentally such that measurements of methane clumped isotope abundances can be converted into equivalent formational temperatures. This study represents the first time that methane clumped isotope abundances have been measured at useful precisions.

In Chapter 7, the methane clumped isotope method is applied to natural samples from a variety of settings. These settings include thermogenic gases formed and reservoired in shales, migrated thermogenic gases, biogenic gases, mixed biogenic and thermogenic gas deposits, and experimentally generated gases. In all cases, calculated clumped isotope temperatures make geological sense as formation temperatures or mixtures of high and low temperature gases. Based on these observations, we propose that the clumped isotope temperature of an unmixed gas represents its formation temperature — this was neither an obvious nor expected result and has important implications for how methane forms in nature. Additionally, these results demonstrate that methane-clumped isotope compositions provided valuable additional constraints to studying natural methane deposits.

Understanding planet formation through high precision photometry and spectroscopy

From studies of protoplanetary disks to extrasolar planets and planetary debris, we aim to understand the full evolution of a planetary system. Observational constraints from ground- and space-based instrumentation allows us to measure the properties of objects near and far and are central to developing this understanding. We present here three observational campaigns that, when combined with theoretical models, reveal characteristics of different stages and remnants of planet formation. The Kuiper Belt provides evidence of chemical and dynamical activity that reveals clues to its primordial environment and subsequent evolution. Large samples of this population can only be assembled at optical wavelengths, with thermal measurements at infrared and sub-mm wavelengths currently available for only the largest and closest bodies. We measure the size and shape of one particular object precisely here, in hopes of better understanding its unique dynamical history and layered composition.

Molecular organic chemistry is one of the most fundamental and widespread facets of the universe, and plays a key role in planet formation. A host of carbon-containing molecules vibrationally emit in the near-infrared when excited by warm gas, T~1000 K. The NIRSPEC instrument at the W.M. Keck Observatory is uniquely configured to study large ranges of this wavelength region at high spectral resolution. Using this facility we present studies of warm CO gas in protoplanetary disks, with a new code for precise excitation modeling. A parameterized suite of models demonstrates the abilities of the code and matches observational constraints such as line strength and shape. We use the models to probe various disk parameters as well, which are easily extensible to others with known disk emission spectra such as water, carbon dioxide, acetylene, and hydrogen cyanide.

Lastly, the existence of molecules in extrasolar planets can also be studied with NIRSPEC and reveals a great deal about the evolution of the protoplanetary gas. The species we observe in protoplanetary disks are also often present in exoplanet atmospheres, and are abundant in Earth's atmosphere as well. Thus, a sophisticated telluric removal code is necessary to analyze these high dynamic range, high-resolution spectra. We present observations of a hot Jupiter, revealing water in its atmosphere and demonstrating a new technique for exoplanet mass determination and atmospheric characterization. We will also be applying this atmospheric removal code to the aforementioned disk observations, to improve our data analysis and probe less abundant species. Guiding models using observations is the only way to develop an accurate understanding of the timescales and processes involved. The futures of the modeling and of the observations are bright, and the end goal of realizing a unified model of planet formation will require both theory and data, from a diverse collection of sources.