Detailed properties of high redshift galaxies

Galaxies evolve throughout the history of the universe from the first star-forming sources, through gas-rich asymmetric structures with rapid star formation rates, to the massive symmetrical stellar systems observed at the present day. Determining the physical processes which drive galaxy formation and evolution is one of the most important questions in observational astrophysics. This thesis presents four projects aimed at improving our understanding of galaxy evolution from detailed measurements of star forming galaxies at high redshift.

We use resolved spectroscopy of gravitationally lensed z ≃ 2 - 3 star forming galaxies to measure their kinematic and star formation properties. The combination of lensing with adaptive optics yields physical resolution of ≃ 100 pc, sufficient to resolve giant Hii regions. We find that ~ 70 % of galaxies in our sample display ordered rotation with high local velocity dispersion indicating turbulent thick disks. The rotating galaxies are gravitationally unstable and are expected to fragment into giant clumps. The size and dynamical mass of giant Hii regions are in agreement with predictions for such clumps indicating that gravitational instability drives the rapid star formation. The remainder of our sample is comprised of ongoing major mergers. Merging galaxies display similar star formation rate, morphology, and local velocity dispersion as isolated sources, but their velocity fields are more chaotic with no coherent rotation.

We measure resolved metallicity in four lensed galaxies at z = 2.0 − 2.4 from optical emission line diagnostics. Three rotating galaxies display radial gradients with higher metallicity at smaller radii, while the fourth is undergoing a merger and has an inverted gradient with lower metallicity at the center. Strong gradients in the rotating galaxies indicate that they are growing inside-out with star formation fueled by accretion of metal-poor gas at large radii. By comparing measured gradients with an appropriate comparison sample at z = 0, we demonstrate that metallicity gradients in isolated galaxies must flatten at later times. The amount of size growth inferred by the gradients is in rough agreement with direct measurements of massive galaxies. We develop a chemical evolution model to interpret these data and conclude that metallicity gradients are established by a gradient in the outflow mass loading factor, combined with radial inflow of metal-enriched gas.

We present the first rest-frame optical spectroscopic survey of a large sample of low-luminosity galaxies at high redshift (L < L*, 1.5 < z < 3.5). This population dominates the star formation density of the universe at high redshifts, yet such galaxies are normally too faint to be studied spectroscopically. We take advantage of strong gravitational lensing magnification to compile observations for a sample of 29 galaxies using modest integration times with the Keck and Palomar telescopes. Balmer emission lines confirm that the sample has a median SFR ∼ 10 M_sun yr^−1 and extends to lower SFR than has been probed by other surveys at similar redshift. We derive the metallicity, dust extinction, SFR, ionization parameter, and dynamical mass from the spectroscopic data, providing the first accurate characterization of the star-forming environment in low-luminosity galaxies at high redshift. For the first time, we directly test the proposal that the relation between galaxy stellar mass, star formation rate, and gas phase metallicity does not evolve. We find lower gas phase metallicity in the high redshift galaxies than in local sources with equivalent stellar mass and star formation rate, arguing against a time-invariant relation. While our result is preliminary and may be biased by measurement errors, this represents an important first measurement that will be further constrained by ongoing analysis of the full data set and by future observations.

We present a study of composite rest-frame ultraviolet spectra of Lyman break galaxies at z = 4 and discuss implications for the distribution of neutral outflowing gas in the circumgalactic medium. In general we find similar spectroscopic trends to those found at z = 3 by earlier surveys. In particular, absorption lines which trace neutral gas are weaker in less evolved galaxies with lower stellar masses, smaller radii, lower luminosity, less dust, and stronger Lyα emission. Typical galaxies are thus expected to have stronger Lyα emission and weaker low-ionization absorption at earlier times, and we indeed find somewhat weaker low-ionization absorption at higher redshifts. In conjunction with earlier results, we argue that the reduced low-ionization absorption is likely caused by lower covering fraction and/or velocity range of outflowing neutral gas at earlier epochs. This result has important implications for the hypothesis that early galaxies were responsible for cosmic reionization. We additionally show that fine structure emission lines are sensitive to the spatial extent of neutral gas, and demonstrate that neutral gas is concentrated at smaller galactocentric radii in higher redshift galaxies.

The results of this thesis present a coherent picture of galaxy evolution at high redshifts 2 ≲ z ≲ 4. Roughly 1/3 of massive star forming galaxies at this period are undergoing major mergers, while the rest are growing inside-out with star formation occurring in gravitationally unstable thick disks. Star formation, stellar mass, and metallicity are limited by outflows which create a circumgalactic medium of metal-enriched material. We conclude by describing some remaining open questions and prospects for improving our understanding of galaxy evolution with future observations of gravitationally lensed galaxies.

Measurement of the band bending and surface dipole at chemically functionalized Si(111)/vacuum interfaces

The core-level energy shifts observed using X-ray photoelectron spectroscopy (XPS) have been used to determine the band bending at Si(111) surfaces terminated with Si-Br, Si-H, and Si-CH₃ groups, respectively. The surface termination influenced the band bending, with the Si 2p_3/2 binding energy affected more by the surface chemistry than by the dopant type. The highest binding energies were measured on Si(111)-Br (whose Fermi level was positioned near the conduction band at the surface), followed by Si(111)-H, followed by Si(111)-CH₃ (whose Fermi level was positioned near mid-gap at the surface). Si(111)-CH₃ surfaces exposed to Br₂(g) yielded the lowest binding energies, with the Fermi level positioned between mid-gap and the valence band. The Fermi level position of Br₂(g)-exposed Si(111)-CH₃ was consistent with the presence of negatively charged bromine-containing ions on such surfaces. The binding energies of all of the species detected on the surface (C, O, Br) shifted with the band bending, illustrating the importance of isolating the effects of band bending when measuring chemical shifts on semiconductor surfaces. The influence of band bending was confirmed by surface photovoltage (SPV) measurements, which showed that the core levels shifted toward their flat-band values upon illumination. Where applicable, the contribution from the X-ray source to the SPV was isolated and quantified. Work functions were measured by ultraviolet photoelectron spectroscopy (UPS), allowing for calculation of the sign and magnitude of the surface dipole in such systems. The values of the surface dipoles were in good agreement with previous measurements as well as with electronegativity considerations. The binding energies of the adventitious carbon signals were affected by band bending as well as by the surface dipole. A model of band bending in which charged surface states are located exterior to the surface dipole is consistent with the XPS and UPS behavior of the chemically functionalized Si(111) surfaces investigated herein.

Variable-angle electron spectroscopic studies of various polyatomic molecular systems

The complementary techniques of low-energy, variable-angle electron-impact spectroscopy and ultraviolet variable-angle photoelectron spectroscopy have been used to study the electronic spectroscopy and structure of several series of molecules. Electron-impact studies were performed at incident beam energies between 25 eV and 100 eV and at scattering angles ranging from 0° to 90°. The energy-loss regions from 0 eV to greater than 15 eV were studied. Photoelectron spectroscopic studies were conducted using a HeI radiation source and spectra were measured at scattering angles from 45° to 90°. The molecules studied were chosen because of their spectroscopic, chemical, and structural interest. The operation of a new electron-impact spectrometer with multiple-mode target source capability is described. This spectrometer has been used to investigate the spin-forbidden transitions in a number of molecular systems.

The electron-impact spectroscopy of the six chloro-substituted ethylenes has been studied over the energy-loss region from 0-15 eV. Spin-forbidden excitations corresponding to the π → π*, N → T transition have been observed at excitation energies ranging from 4.13 eV in vinyl chloride to 3.54 eV in tetrachloroethylene. Symmetry-forbidden transitions of the type π → np have been oberved in trans-dichloroethyene and tetrachlor oethylene. In addition, transitions to many states lying above the first ionization potential were observed for the first time. Many of these bands have been assigned to Rydberg series converging to higher ionization potentials. The trends observed in the measured transition energies for the π → π*, N → T, and N → V as well as the π → 3s excitation are discussed and compared to those observed in the methyl- and fluoro- substituted ethylenes.

The electron energy-loss spectra of the group VIb transition metal hexacarbonyls have been studied in the 0 eV to 15 eV region. The differential cross sections were obtained for several features in the 3-7 eV energy-loss region. The symmetry-forbidden nature of the ¹A_1g → ¹A_1g, 2t_2g(π) → 3t_2g(π*) transition in these compounds was confirmed by the high-energy, low-angle behavior of their relative intensities. Several low lying transitions have been assigned to ligand field transitions on the basis of the energy and angular behavior of the differential cross sections for these transitions. No transitions which could clearly be assigned to singlet → triplet excitations involving metal orbitals were located. A number of states lying above the first ionization potential have been observed for the first time. A number of features in the 6-14 eV energy-loss region of the spectra of these compounds correspond quite well to those observed in free CO.

A number of exploratory studies have been performed. The π → π*, N → T, singlet → triplet excitation has been located in vinyl bromide at 4.05 eV. We have also observed this transition at approximately 3.8 eV in a cis-/trans- mixture of the 1,2-dibromoethylenes. The low-angle spectrum of iron pentacarbonyl was measured over the energy-loss region extending from 2-12 eV. A number of transitions of 8 eV or greater excitation energy were observed for the first time. Cyclopropane was also studied at both high and low angles but no clear evidence for any spin- forbidden transitions was found. The electron-impact spectrum of the methyl radical resulting from the pyrolysis of tetramethyl tin was obtained at 100 eV incident energy and at 0° scattering angle. Transitions observed at 5.70 eV and 8.30 eV agree well with the previous optical results. In addition, a number of bands were observed in the 8-14 eV region which are most likely due to Rydberg transitions converging to the higher ionization potentials of this molecule. This is the first reported electron-impact spectrum of a polyatomic free radical.

Variable-angle photoelectron spectroscopic studies were performed on a series of three-membered-ring heterocyclic compounds. These compounds are of great interest due to their highly unusual structure. Photoelectron angular distributions using HeI radiation have been measured for the first time for ethylene oxide and ethyleneimine. The measured anisotropy parameters, β, along with those measured for cyclopropane were used to confirm the orbital correlations and photoelectron band assignments. No high values of β similar to those expected for alkene π orbitals were observed for the Walsh or Forster-Coulson-Moffit type orbitals.

Self-assembly of brush polymers

The unique structure and properties of brush polymers have led to increased interest in them within the scientific community. This thesis describes studies on the self-assembly of these brush polymers.

Chapter 2 describes a study on the rapid self-assembly of brush block copolymers into nanostructures with photonic bandgaps spanning the entire visible spectrum, from ultraviolet to near infrared. Linear relationships are observed between the peak wavelengths of reflection and polymer molecular weights. This work enables "bottom-up" fabrication of photonic crystals with application-tailored bandgaps, through synthetic control of the polymer molecular weight and the method of self-assembly.

Chapter 3 details the analysis of the self-assembly of symmetrical brush block copolymers in bulk and thin films. Highly ordered lamellae with domain spacing ranging from 20 to 240 nm are obtained by varying molecular weight of the backbone. The relationship between degree of polymerization and the domain spacing is reported, and evidence is provided for how rapidly the brush block copolymers self-assemble and achieve thermodynamic equilibrium.

Chapter 4 describes investigations into where morphology transitions take place as the volume fraction of each block is varied in asymmetrical brush block copolymers. Imaging techniques are used to observe a transition from lamellar to a cylindrical morphology as the volume fraction of one of the blocks exceeds 70%. It is also shown that the asymmetric brush block copolymers can be kinetically trapped into undulating lamellar structures by drop casting the samples.

Chapter 5 explores the capability of macromolecules to interdigitate into densely grafted molecular brush copolymers using stereocomplex formation as a driving force. The stereocomplex formation between complementary linear polymers and brush copolymers is demonstrated, while the stereocomplex formation between complementary brush copolymers is shown to be restricted.

Did galaxies reionize the universe?

The epoch of reionization remains one of the last uncharted eras of cosmic history, yet this time is of crucial importance, encompassing the formation of both the first galaxies and the first metals in the universe. In this thesis, I present four related projects that both characterize the abundance and properties of these first galaxies and uses follow-up observations of these galaxies to achieve one of the first observations of the neutral fraction of the intergalactic medium during the heart of the reionization era.

First, we present the results of a spectroscopic survey using the Keck telescopes targeting 6.3 < z < 8.8 star-forming galaxies. We secured observations of 19 candidates, initially selected by applying the Lyman break technique to infrared imaging data from the Wide Field Camera 3 (WFC3) onboard the Hubble Space Telescope (HST). This survey builds upon earlier work from Stark et al. (2010, 2011), which showed that star-forming galaxies at 3 < z < 6, when the universe was highly ionized, displayed a significant increase in strong Lyman alpha emission with redshift. Our work uses the LRIS and NIRSPEC instruments to search for Lyman alpha emission in candidates at a greater redshift in the observed near-infrared, in order to discern if this evolution continues, or is quenched by an increase in the neutral fraction of the intergalactic medium. Our spectroscopic observations typically reach a 5-sigma limiting sensitivity of < 50 AA. Despite expecting to detect Lyman alpha at 5-sigma in 7-8 galaxies based on our Monte Carlo simulations, we only achieve secure detections in two of 19 sources. Combining these results with a similar sample of 7 galaxies from Fontana et al. (2010), we determine that these few detections would only occur in < 1% of simulations if the intrinsic distribution was the same as that at z ~ 6. We consider other explanations for this decline, but find the most convincing explanation to be an increase in the neutral fraction of the intergalactic medium. Using theoretical models, we infer a neutral fraction of X_HI ~ 0.44 at z = 7.

Second, we characterize the abundance of star-forming galaxies at z > 6.5 again using WFC3 onboard the HST. This project conducted a detailed search for candidates both in the Hubble Ultra Deep Field as well as a number of additional wider Hubble Space Telescope surveys to construct luminosity functions at both z ~ 7 and 8, reaching 0.65 and 0.25 mag fainter than any previous surveys, respectively. With this increased depth, we achieve some of the most robust constraints on the Schechter function faint end slopes at these redshifts, finding very steep values of alpha_{z~7} = -1.87 +/- 0.18 and alpha_{z~8} = -1.94 +/- 0.23. We discuss these results in the context of cosmic reionization, and show that given reasonable assumptions about the ionizing spectra and escape fraction of ionizing photons, only half the photons needed to maintain reionization are provided by currently observable galaxies at z ~ 7-8. We show that an extension of the luminosity function down to M_{UV} = -13.0, coupled with a low level of star-formation out to higher redshift, can fit all available constraints on the ionization history of the universe.

Third, we investigate the strength of nebular emission in 3 < z < 5 star-forming galaxies. We begin by using the Infrared Array Camera (IRAC) onboard the Spitzer Space Telescope to investigate the strength of H alpha emission in a sample of 3.8 < z < 5.0 spectroscopically confirmed galaxies. We then conduct near-infrared observations of star-forming galaxies at 3 < z < 3.8 to investigate the strength of the [OIII] 4959/5007 and H beta emission lines from the ground using MOSFIRE. In both cases, we uncover near-ubiquitous strong nebular emission, and find excellent agreement between the fluxes derived using the separate methods. For a subset of 9 objects in our MOSFIRE sample that have secure Spitzer IRAC detections, we compare the emission line flux derived from the excess in the K_s band photometry to that derived from direct spectroscopy and find 7 to agree within a factor of 1.6, with only one catastrophic outlier. Finally, for a different subset for which we also have DEIMOS rest-UV spectroscopy, we compare the relative velocities of Lyman alpha and the rest-optical nebular lines which should trace the cites of star-formation. We find a median velocity offset of only v_{Ly alpha} = 149 km/s, significantly less than the 400 km/s observed for star-forming galaxies with weaker Lyman alpha emission at z = 2-3 (Steidel et al. 2010), and show that this decrease can be explained by a decrease in the neutral hydrogen column density covering the galaxy. We discuss how this will imply a lower neutral fraction for a given observed extinction of Lyman alpha when its visibility is used to probe the ionization state of the intergalactic medium.

Finally, we utilize the recent CANDELS wide-field, infra-red photometry over the GOODS-N and S fields to re-analyze the use of Lyman alpha emission to evaluate the neutrality of the intergalactic medium. With this new data, we derive accurate ultraviolet spectral slopes for a sample of 468 3 < z < 6 star-forming galaxies, already observed in the rest-UV with the Keck spectroscopic survey (Stark et al. 2010). We use a Bayesian fitting method which accurately accounts for contamination and obscuration by skylines to derive a relationship between the UV-slope of a galaxy and its intrinsic Lyman alpha equivalent width probability distribution. We then apply this data to spectroscopic surveys during the reionization era, including our own, to accurately interpret the drop in observed Lyman alpha emission. From our most recent such MOSFIRE survey, we also present evidence for the most distant galaxy confirmed through emission line spectroscopy at z = 7.62, as well as a first detection of the CIII]1907/1909 doublet at z > 7.

We conclude the thesis by exploring future prospects and summarizing the results of Robertson et al. (2013). This work synthesizes many of the measurements in this thesis, along with external constraints, to create a model of reionization that fits nearly all available constraints.

Analyses of planetary atmospheres across the spectrum : from Titan to exoplanets

Planetary atmospheres exist in a seemingly endless variety of physical and chemical environments. There are an equally diverse number of methods by which we can study and characterize atmospheric composition. In order to better understand the fundamental chemistry and physical processes underlying all planetary atmospheres, my research of the past four years has focused on two distinct topics. First, I focused on the data analysis and spectral retrieval of observations obtained by the Ultraviolet Imaging Spectrograph (UVIS) instrument onboard the Cassini spacecraft while in orbit around Saturn. These observations consisted of stellar occultation measurements of Titan's upper atmosphere, probing the chemical composition in the region 300 to 1500 km above Titan's surface. I examined the relative abundances of Titan's two most prevalent chemical species, nitrogen and methane. I also focused on the aerosols that are formed through chemistry involving these two major species, and determined the vertical profiles of aerosol particles as a function of time and latitude. Moving beyond our own solar system, my second topic of investigation involved analysis of infra-red light curves from the Spitzer space telescope, obtained as it measured the light from stars hosting planets of their own. I focused on both transit and eclipse modeling during Spitzer data reduction and analysis. In my initial work, I utilized the data to search for transits of planets a few Earth masses in size. In more recent research, I analyzed secondary eclipses of three exoplanets and constrained the range of possible temperatures and compositions of their atmospheres.

Investigation of competitive antagonist binding to the nicotinic acetylcholine receptor using voltage-jump and light-flash techniques

1. The effect of 2,2’-bis-[α-(trimethylammonium)methyl]azobenzene (2BQ), a photoisomerizable competitive antagonist, was studied at the nicotinic acetycholine receptor of Electrophorus electroplaques using voltage-jump and light-flash techniques.

2. 2BQ, at concentrations below 3 μΜ, reduced the amplitude of voltage-jump relaxations but had little effect on the voltage-jump relaxation time constants under all experimental conditions. At higher concentrations and voltages more negative than -150 mV, 2BQ caused significant open channel blockade.

3. Dose-ratio studies showed that the cis and trans isomers of 2BQ have equilibrium binding constants (K _ᵢ) of .33 and 1.0 μΜ, respectively. The binding constants determined for both isomers are independent of temperature, voltage, agonist concentration, and the nature of the agonist.

4. In a solution of predominantly cis-2BQ, visible-light flashes led to a net cis→trans isomerization and caused an increase in the agonist-induced current. This increase had at least two exponential components; the larger amplitude component had the same time constant as a subsequent voltage-jump relaxation; the smaller amplitude component was investigated using ultraviolet light flashes.

5. In a solution of predominantly trans-2BQ, UV-light flashes led to a net trans→cis isomerization and caused a net decrease in the agonist-induced current. This effect had at least two exponential components. The smaller and faster component was an increase in agonist-induced current and had a similar time constant to the voltage-jump relaxation. The larger component was a slow decrease in the agonist-induced current with rate constant approximately an order of magnitude less than that of the voltage-jump relaxation. This slow component provided a measure of the rate constant for dissociation of cis-2BQ (k_ = 60/s at 20°C). Simple modelling of the slope of the dose-rate curves yields an association rate constant of 1.6 x 10⁸/M/s. This agrees with the association rate constant of 1.8 x 10⁸/M/s estimated from the binding constant (K_i). The Q₁₀ of the dissociation rate constant of cis-2BQ was 3.3 between 6° and 20°C. The rate constants for association and dissociation of cis-28Q at receptors are independent of voltage, agonist concentration, and the nature of the agonist.

6. We have measured the molecular rate constants of a competitive antagonist which has roughly the same K _ᵢ as d-tubocurarine but interacts more slowly with the receptor. This leads to the conclusion that curare itself has an association rate constant of 4 x 10⁹/M/s or roughly as fast as possible for an encounter-limited reaction.

Solar System Small-Body Demographics with the Palomar Transient Factory Survey

Observational studies of our solar system's small-body populations (asteroids and comets) offer insight into the history of our planetary system, as these minor planets represent the left-over building blocks from its formation. The Palomar Transient Factory (PTF) survey began in 2009 as the latest wide-field sky-survey program to be conducted on the 1.2-meter Samuel Oschin telescope at Palomar Observatory. Though its main science program has been the discovery of high-energy extragalactic sources (such as supernovae), during its first five years PTF has collected nearly five million observations of over half a million unique solar system small bodies. This thesis begins to analyze this vast data set to address key population-level science topics, including: the detection rates of rare main-belt comets and small near-Earth asteroids, the spin and shape properties of asteroids as inferred from their lightcurves, the applicability of this visible light data to the interpretation of ultraviolet asteroid observations, and a comparison of the physical properties of main-belt and Jovian Trojan asteroids. Future sky-surveys would benefit from application of the analytical techniques presented herein, which include novel modeling methods and unique applications of machine-learning classification. The PTF asteroid small-body data produced in the course of this thesis work should remain a fertile source of solar system science and discovery for years to come.

I. Electronic states of heavily-doped molecular crystals--naphthalene. I. Theoretical. II. Experimental. II. Lowest singlet and triplet excited states of pyrazine

PART I

The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.

PART II

The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h₈ and d₈, (2) naphthalene--h₈ and αd₄, and (3) naphthalene--h₈ and βd₁, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.

PART III

The phosphorescence, fluorescence and absorption spectra of pyrazine-h₄ and d₄ have been obtained at 4˚K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h₄ in d₄ were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.

The analysis of the weak fluorescence spectrum resolves the long-disputed question of whether one or two transitions are involved in the near-ultraviolet absorption of pyrazine. The “mirror-image relationship” between absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as ¹B_3u ← ¹A_1g. The forbidden component ¹B_2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.

The phosphorescence spectrum when compared with the excitation phosphorescence spectra, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and a “mirror-image relationship” between absorption and emission. In accordance with previous work, the triplet state is designated as ³B_3u.

The vibronic structure of the phosphorescence spectrum is very complicated. Previous work on the analysis of this spectrum all concluded that a long progression of v_6a exists. Under the high resolution attainable in our work, the supposed v_6a progression proves to have a composite triplet structure, starting from the second member of the progression. Not only is the v_9a hydrogen-bending mode present as shown by the appearance of the C-D bending mode in the d₄ spectrum, but a band of 1207 cm^-1 in the pyrazine in benzene system and 1231 cm^-1 in the mixed crystal system is also observed. This band is assigned as 2v_6b and of a_1g symmetry. Its anonymously strong intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with the 2v_6a and v_9a band.

To help resolve the present controversy over the crystal phosphorescence spectrum of pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.

Radiobiological and biochemical investigations of polyoma virus-cell interactions

The cytolytic interaction of Polyoma virus with mouse embryo cells has been studied by radiobiological methods known to distinguish temperate from virulent bacteriophage. No evidence for "temperate" properties of Polyoma was found. During the course of these studies, it was observed that the curve of inactivation of Polyoma virus by ultraviolet light had two components - a more sensitive one at low doses, and a less sensitive one at higher doses. Virus which survives a low dose has an eclipse period similar to that of unirradiated virus, while virus surviving higher doses shows a significantly longer eclipse period. If Puromycin is present during the early part of the eclipse period, the survival curve becomes a single exponential with the sensitivity of the less sensitive component. These results suggest a repair mechanism in mouse cells which operates more effectively if virus development is delayed.

A comparison of the rates of inactivation of the cytolytic and transforming abilities of Polyoma by ultraviolet light, X-rays, nitrous acid treatment, or the decay of incorporated P³², showed that the transforming ability has a target size roughly 60% of that of the plaque-forming ability. It is thus concluded that only a fraction of the viral genes are necessary for causing transformation.

The appearance of virus-specific RNA in productively infected mouse kidney cells has been followed by means of hybridization between pulse-labelled RNA from the infected cells and the purified virus DNA. The results show a sharp increase in the amount of virus-specific RNA around the time of virus DNA synthesis. The presence of a small amount of virus-specific RNA in virus-free transformed cells has also been shown. This result offers strong evidence for the persistence of at least part of the viral genome in transformed cells.

The interactions of basic proteins and DNA

I. ELECTROPHORESIS OF THE NUCLEIC ACIDS

A zone electrophoresis apparatus using ultraviolet optics has been constructed to study nucleic acids at concentrations less than 0.004%. Native DNA has a mobility about 15% higher than denatured DNA over a range of conditions. Otherwise, the electrophoretic mobility is independent of molecular weight, base composition or source. DNA mobilities change in the expected way with pH but the fractional change in mobility is less than the calculated change in charge. A small decrease in mobility accompanies an increase in ionic strength. RNA’s from various sources have mobilities slightly lower than denatured DNA except for s-RNA which travels slightly faster. The important considerations governing the mobility of nucleic acids appear to be the nature of the hydrodynamic segment, and the binding of counterions. The differences between electrophoresis and sedimentation stem from the fact that all random coil polyelectrolytes are fundamentally free draining in electrophoresis.

II. THE CYTOCHROME C/DNA COMPLEX

The basic protein, cytochrome c, has been complexed to DNA. Up to a cytochrome:DNA mass ratio of 2, a single type of complex is formed. Dissociation of this complex occurs between 0.05F and 0.1F NaCl. The complexing of cytochrome to DNA causes a slight increase in the melting temperature of the DNA, and a reduction of the electrophoretic mobility proportional to the decrease in net charge. Above a cytochrome:DNA mass ratio of 2.5, a different type of complex is formed. The results suggest that complexes such as are formed in the Kleinschmidt technique of electron microscopy would not exist in bulk solution and are exclusively film phenomena.

III. STUDIES OF THE ELECTROPHORESIS AND MELTING BEHAVIOUR OF NUCLEOHISTONES

Electrophoresis studies on reconstituted nucleohistones indicate that the electrophoretic mobility for these complexes is a function of the net charge of the complex. The mobility is therefore dependent on the charge density of the histone complexing the DNA, as well as on the histone/DNA ratio. It is found that the different histones affect the transition from native to denatured DNA in different ways. It appears that histone I is exchanging quite rapidly between DNA molecules in 0.01 F salt, while histone II is irreversibly bound. Histone III-IV enhances the capacity of non-strand separated denatured DNA to reanneal. Studies on native nucleoproteins indicate that there are no gene-sized uncomplexed DNA regions in any preparations studied.

IV. THE DISSOCIATION OF HISTONE FROM CALF THYMUS CROMATIN

Calf thymus nucleoprotein was treated with varying concentrations of NaCl. The identity of the histones associated and dissociated from the DNA at each salt concentration was determined by gel electrophoresis. It was found that there is no appreciable histone dissociation below 0.4 F NaCl. The lysine rich histones dissociate between 0.4 and 0.5 F NaCl. Their dissociation is accompanies by a marked increase in the solubility of the chromatin. The moderately lysine rich histones dissociate mainly between 0.8 and 1.1 F NaCl. There are two arginine rich histone components: the first dissociates between 0.8 F and 1.1 F NaCl, but the second class is the very last to be dissociated from the DNA (dissociation beginning at 1.0 F NaCl). By 2.0 F NaCl, essentially all the histones are dissociated.

The properties of the extracted nucleoprotein were studied. The electrophoretic mobility increases and the melting temperature decreases as more histones are dissociated from the DNA. A comparison with the dissociation of histones from DNA in NaClO₄ shows that to dissociate the same class of histones, the concentration of NaCl required is twice that of NaClO₄.