Influence of a Counterion on the Ion Atmosphere of an Anion: A Molecular Dynamics Study of LiX and CsX (X = F-, Cl-, I-) in Methanol

We report molecular dynamics (MD) simulations to explore the influence of a counterion on the structure and dynamics of cationic and anionic solvation shells for various ions in methanol at 298 K. We show that the variation in ionic size of either the cation or the anion in an ion pair influences the solvation structure of the other ion as well as the diffusivity in an electrolyte solution of methanol. The extent of ionic association between the cation and its counteranion of different ionic sizes has been investigated by analyzing the radial distribution functions (RDFs) and the orientation of methanol molecules in the first solvation shell (FSS) of ions. It is shown that the methanol in the FSS of the anion as well the cation exhibit quite different radial and orientational structures as compared to methanol which lie in the FSS of either the anion or the cation but not both. We find that the coordination number (CN) of F-, Cr-, and I- ions decreases with increasing size of the anion which is contrary to the trend reported for the anions in H2O. The mean residence time (MRT) of methanol molecules in the FSS of ions has been calculated using the stable states picture (SSP) approach. It is seen that the ion-counterion interaction has a considerable influence on the MRT of methanol molecules in the FSS of ions. We also discuss the stability order of the ion-counterion using the potentials of mean force (PMFs) for ion pairs with ions of different sizes. The PMF plots reveal that the Li+-F- pair (small-small) is highly stable and the Li+-I- pair is least stable (small-large) in electrolyte solutions.

A Biogeographic Assessment off North/Central California: To Support the Joint Management Plan Review for Cordell Bank, Gulf of the Farallones, and Monterey Bay National Marine Sanctuaries: Phase I - Marine Fishes, Birds and Mammals.

In the spring of 2001, NOAA’s National Marine Sanctuary Program (NMSP) and National Centers for Coastal Ocean Science (NCCOS), in consultation with the National Marine Fisheries Service (NMFS), launched a 24-month effort to define and assess biogeographic patterns of selected marine species found within and adjacent to the boundaries of three west coast National Marine Sanctuaries. These sanctuaries, Monterey Bay, Gulf of the Farallones, and Cordell Bank are conducting a joint review process to update sanctuary management plans. The management plans for these sanctuaries have not been updated for over ten years and the status of the natural resources and their management issues in and around the sanctuaries may have changed. In addition, significant accomplishments in research and resource assessments have been made within the region. Thus, it is important to incorporate new and expanding knowledge into the revised management plans for these Sanctuaries.

A quantitative analysis of the phytoplankton of the Gulf of Panama: I. Results of the regional phytoplankton surveys during July and November 1957 and March 1958

ENGLISH: 1. Quantitative phytoplankton samples were collected by the Inter-American Tropical Tuna Commission at the surface and ten meters in the Gulf of Panama, as follows: a) 18-21 March, 1958 (31 stations)-during the height of the upwelling season, b) 10-12 July, 1957 (10 stations)-during the transition to the rainy season at a time when mild upwelling winds reappear, c) 7-8 November, 1957 (15 stations)-during the height of the rainy season. 2. Maximum phytoplankton populations occurred during the upwelling season, followed by a considerable decline during July, and a further Subsidence during November. 3. A remarkable regional uniformity in species composition was observed during the surveys despite regional differences in growth conditions. Diatoms overwhelmingly dominated the communities. 4. During all surveys, the innermost regions, generally north of 8°30'N, were the most productive. The least productive areas were in the offing of San Miguel Bay and Parita Bay, suggesting that nutrient accretion via runoff is inadequate to sustain sizeable autotrophic plant populations in those regions. 5. During all surveys, phytoplankton growth appeared to be limited by nutrient availability. 6. During all surveys, phytoplankton growth appeared to be related to depth of the water column. 7. Although below average rainfall contributed to unusually favorable growth conditions (reduced stability, increased transparency and, presumably, nutrient reserves) during the November survey relative to November 1955 and 1956 at 8°45'N, 79°23'W, the anticipated heightened phytoplankton response was not observed. 8. During the November survey, the local diatom responses and their regional fluctuations could be satisfactorily related to the accompanying surface salinity conditions. However, this correspondence is undoubtedly attributable to factors associated with the observed salinity levels, probably nutrients, rather than salinity directly. 9. Unusually warm conditions occurred during the March survey, attributable to considerably weaker upwelling winds than normally occurring then, which contributed to a considerably lower standing crop and a retardation in succession of three to five weeks relative to that observed during 1955-1957 at 8°45'N, 79°23'W in the Gulf of Panama. 10. During the March survey, a well defined inverse relationship existed between mean temperature and mean diatom abundance in the upper ten meters, and between transparency and mean diatom abundance. A direct relationship occurred between surface salinity and mean diatom abundance in the upper ten meters. These relationships are interpreted to indicate that diatom abundance primarily reflected the nutrient concentrations associated with a given upwelling intensity, rather than describing casual relationships. 11. The survey results indicate that the phytoplankton dynamics observed at 8°45'N, 79°23'W from November, 1954 through May, 1957 are generally representative of the Gulf of Panama. 12. The following new forms, to be described in a later publication, were observed during the surveys: Actinoptychus undulatus f. catenata n.f., Asterionella japonica f. tropicum n.f., Leptocylindrus maximus n. sp., Skeletonema costatum f. tropicum n.f. SPANISH: 1. La Comisión Interamericana del Atun Tropical recolectó en el Golfo de Panama muestras cuantitativas de fitoplancton en la superficie y a los diez metros, como sigue: a) Del 18 al 21 de marzo de 1958 (31 estaciones)-durante el maximum de la estación de afloramiento. b) Del 10 al 12 de julio de 1957 (10 estaciones)-durante la epóca de transición a la estación lluviosa cuando reaparecen los vientos ligeros que causan el afloramiento. c) Del 7 al 8 de noviembre de 1957 (15 estaciones)-durante el maximum de la estación lluviosa. 2. Las poblaciones maximas de fitoplancton aparecieron durante la estación de afloramiento, seguido por una considerable disminución durante el mes de julio y una calma durante noviembre. 3. Durante la investigación se observó una remarcable uniformidad regional en la composición de las especies a pesar de las diferencias regionales en las condiciones de crecimiento. Las diatomeas predominaban en gran numero en las comunidades. 4. Durante todas las investigaciones, las regiones mas cerca de la costa, generalmente al norte de los 8°30'N, eran las mas productivas. Las areas menos productivas fueron las mar afuera de las Bahias de San Miguel y Parita, lo que sugiere que el aumento en las sales nutritivas causado por las escorrentias es inadecuado para sostener poblaciones grandes de plantas autotróficas en estas regiones. 5. Durante todas las investigaciones, el crecimiento del fitoplancton parecio estar limitado por la disponibilidad de las. sales nutritivas. 6. Durante todas las investigaciones el crecimiento del fitoplancton parecio estar relacionado con la profundidad de la columna de agua. 7. Aunque las precipitacion por debajo del promedio normal contribuyo a condiciones desusadamente favorables de crecimiento (estabilidad reducida, aumento de la transparencia y, presumiblemente, de la reserva de sales nutritivas) durante la investigación de noviembre en relación a noviembre de 1955 y de 1956 en los 8°45'N, 79°23'W, no se observo-la alta reacción de fitoplancton que se esperaba. 8. Durante la investigación de noviembre, las reacciones locales de las diatomeas y sus fluctuaciones regionales pudieron relacionarse en forma satisfactoria con condiciones asociadas con la salinidad de la superficie. Sin embargo, esta correspondencia puede atribuirse sin duda a factores asociados con los niveles observados de salinidad, probablemente con las sales nutritivas, en lugar de directamente con la salinidad. 9. Condiciones calurosas no comunes ocurrieron durante la investigación de marzo, las que pueden atribuirse a que los vientos que ocasionan el afloramiento fueran mas debiles que los normales, lo que contribuyó a que la cosecha estable fuera considerablemente mas baja y a la demora de tres a cinco semanas en la sucecion relativa a la que se observó durante 1955-1957 en los 8°45'N, 8°23'W, en el Golfo de Panama. 10. Durante la investigación de marzo, existió una relación inversa bien definida entre la temperatura y la abundancia media de las diatomeas en los diez metros superiores, y entre la transparencia y la abundancia media de las diatomeas. Una relación directa ocurrio entre la salinidad de superficie y la abundancia media de las diatomeas en los diez metros superiores. Estas relaciones se interpretan como indicadoras de que la abundancia de diatomeas refleja primeramente las concentraciones de las sales nutritivas asociadas con una intensidad de afloramiento dada, en lugar de describir relaciones causales. 11. Los resultados de la investigacion indican que la dinamica del fitoplancton observada en los 8°45'N, 79°23'W, desde noviembre de 1954 a mayo de 1957, es generalmente representativa del Golfo de Panama. 12. Durante las investigaciones se observaron las siguientes formas nuevas, las que seran descritas en una publicación posterior: Actinoptychus undulatus f. catenata n.f., Asterionella japonica f. tropicum n.f., Leptocylindrus maximus n. sp., Skeletonema costatum f. tropicum n.f.

Physical investigations of small particles : (I) aerosol particle charging and flux enhancement and (II) whispering gallery mode sensing

Part I

Particles are a key feature of planetary atmospheres. On Earth they represent the greatest source of uncertainty in the global energy budget. This uncertainty can be addressed by making more measurement, by improving the theoretical analysis of measurements, and by better modeling basic particle nucleation and initial particle growth within an atmosphere. This work will focus on the latter two methods of improvement.

Uncertainty in measurements is largely due to particle charging. Accurate descriptions of particle charging are challenging because one deals with particles in a gas as opposed to a vacuum, so different length scales come into play. Previous studies have considered the effects of transition between the continuum and kinetic regime and the effects of two and three body interactions within the kinetic regime. These studies, however, use questionable assumptions about the charging process which resulted in skewed observations, and bias in the proposed dynamics of aerosol particles. These assumptions affect both the ions and particles in the system. Ions are assumed to be point monopoles that have a single characteristic speed rather than follow a distribution. Particles are assumed to be perfect conductors that have up to five elementary charges on them. The effects of three body interaction, ion-molecule-particle, are also overestimated. By revising this theory so that the basic physical attributes of both ions and particles and their interactions are better represented, we are able to make more accurate predictions of particle charging in both the kinetic and continuum regimes.

The same revised theory that was used above to model ion charging can also be applied to the flux of neutral vapor phase molecules to a particle or initial cluster. Using these results we can model the vapor flux to a neutral or charged particle due to diffusion and electromagnetic interactions. In many classical theories currently applied to these models, the finite size of the molecule and the electromagnetic interaction between the molecule and particle, especially for the neutral particle case, are completely ignored, or, as is often the case for a permanent dipole vapor species, strongly underestimated. Comparing our model to these classical models we determine an “enhancement factor” to characterize how important the addition of these physical parameters and processes is to the understanding of particle nucleation and growth.

Part II

Whispering gallery mode (WGM) optical biosensors are capable of extraordinarily sensitive specific and non-specific detection of species suspended in a gas or fluid. Recent experimental results suggest that these devices may attain single-molecule sensitivity to protein solutions in the form of stepwise shifts in their resonance wavelength, \lambda_{R}, but present sensor models predict much smaller steps than were reported. This study examines the physical interaction between a WGM sensor and a molecule adsorbed to its surface, exploring assumptions made in previous efforts to model WGM sensor behavior, and describing computational schemes that model the experiments for which single protein sensitivity was reported. The resulting model is used to simulate sensor performance, within constraints imposed by the limited material property data. On this basis, we conclude that nonlinear optical effects would be needed to attain the reported sensitivity, and that, in the experiments for which extreme sensitivity was reported, a bound protein experiences optical energy fluxes too high for such effects to be ignored.

Part I. Influence of membrane morphology on ion-exchange and charge propagation in composite polyelectrolyte electrode coatings. Part II. Dynamic surface tension measurements of polarization relaxation at mercury pool electrodes by the method of Wilhelmy.

Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

I. Efforts toward the synthesis of aliphatic iodonium salts. II. Flourine-19 nuclear magnetic resonance spectroscopy of cyclic and bicyclic systems

The synthesis of iodonium salts of the general formula [C₆H₅IR]⁺X^-, where R is an alkyl group and x- is a stabilizing anion, was attempted. For the choice of R three groups were selected, whose derivatives are known to be sluggish in S_N1 and S_N2 substitutions: cyclopropyl, 7, 7 -dimethyl-1-norbornyl, and 9 -triptycyl. The synthetic routes followed along classical lines which have been exploited in recent years by Beringer and students. Ultimately, the object of the present study was to study the reactions of the above salts with nucleophiles. In none of the three cases, however, was it possible to isolate a stable salt. A thermodynamic argument suggests that this must be due to kinetic instability rather than thermodynamic instability. Only iodocyclopropane and 1-iodoapocamphane formed isolable iododichlorides.

Several methylated 2, 2-difluoronorbornanes were prepared with the intent of correlating fluorine -19 chemical shifts with geometric features in a rigid system. The effect of a methyl group on the shielding of a β -fluorine is dependent upon the dihedral angle; the maximum effect (an upfield shift of the resonance) occurs at 0° and 180°, whereas almost no effect is felt at a dihedral angle of 120°. The effect of a methyl group on a γ -fluorine is to strongly shift the resonance downfield when fluorine and methyl group are in a 1, 3 - diaxial-like relationship. Molecular orbital calculations of fluorine shielding in a variety of molecules were carried out using the formalism developed by Pople; the results are, at best, in modest agreement with experiment.

I. Proton magnetic resonance of polynucleotides and transfer RNA. II. Electron spin relaxation studies of manganese (II) complexes in acetonitrile

Part I. Proton Magnetic Resonance of Polynucleotides and Transfer RNA.

Proton magnetic resonance was used to follow the temperature dependent intramolecular stacking of the bases in the polynucleotides of adenine and cytosine. Analysis of the results on the basis of a two state stacked-unstacked model yielded values of -4.5 kcal/mole and -9.5 kcal/mole for the enthalpies of stacking in polyadenylic and polycytidylic acid, respectively.

The interaction of purine with these molecules was also studied by pmr. Analysis of these results and the comparison of the thermal unstacking of polynucleotides and short chain nucleotides indicates that the bases contained in stacks within the long chain poly nucleotides are, on the average, closer together than the bases contained in stacks in the short chain nucleotides.

Temperature and purine studies were also carried out with an aqueous solution of formylmethionine transfer ribonucleic acid. Comparison of these results with the results of similar experiments with the homopolynucleotides of adenine, cytosine and uracil indicate that the purine is probably intercalating into loop regions of the molecule.

The solvent denaturation of phenylalanine transfer ribonucleic acid was followed by pmr. In a solvent mixture containing 83 volume per cent dimethylsulf oxide and 17 per cent deuterium oxide, the tRNA molecule is rendered quite flexible. It is possible to resolve resonances of protons on the common bases and on certain modified bases.

Part II. Electron Spin Relaxation Studies of Manganese (II) Complexes in Acetonitrile.

The electron paramagnetic resonance spectra of three Mn⁺² complexes, [Mn(CH₃CN)₆]⁺², [MnCl₄]^-2, and [MnBr₄]^-2, in acetonitrile were studied in detail. The objective of this study was to relate changes in the effective spin Hamiltonian parameters and the resonance line widths to the structure of these molecular complexes as well as to dynamical processes in solution.

Of the three systems studied, the results obtained from the [Mn(CH₃CN)₆]⁺² system were the most straight-forward to interpret. Resonance broadening attributable to manganese spin-spin dipolar interactions was observed as the manganese concentration was increased.

In the [MnCl₄]^-2 system, solvent fluctuations and dynamical ion-pairing appear to be significant in determining electron spin relaxation.

In the [MnBr₄]^-2 system, solvent fluctuations, ion-pairing, and Br- ligand exchange provide the principal means of electron spin relaxation. It was also found that the spin relaxation in this system is dependent upon the field strength and is directly related to the manganese concentration. A relaxation theory based on a two state collisional model was developed to account for the observed behavior.

Part I. Regulation of development in the cellular slime mold Dictyostelium discoideum. Part II. Polysomes and RNA synthesis during early development of the surf clam Spisula solidissima

Part I. The cellular slime mold Dictyostelium discoideum is a simple eukaryote which undergoes a multi-cellular developmental process. Single cell myxamoebae divide vegetatively in the presence of a food source. When the food is depleted or removed, the cells aggregate, forming a migrating pseudoplasmodium which differentiates into a fruiting body containing stalk and spore cells. I have shown that during the developmental cycle glycogen phosphorylase, aminopeptidase, and alanine transaminase are developmentally regulated, that is their specific activities increased at a specific time in the developmental cycle. Phosphorylase activity is undetectable in developing cells until mid-aggregation whereupon it increases and reaches a maximum at mid-culmination. Thereafter the enzyme disappears. Actinomycin D and cycloheximide studies as well as studies with morphologically aberrant and temporally deranged mutants indicate that prior RNA and concomitant protein synthesis are necessary for the rise and decrease in activity and support the view that the appearance of the enzyme is regulated at the transcriptional level. Aminopeptidase and alanine transaminase increase 3 fold starting at starvation and reach maximum activity at 18 and 5 hours respectively.

The cellular DNA s of D. discoideum were characterized by CsC1 buoyant density gradient centrifugation and by renaturation kinetics. Whole cell DNA exhibits three bands in CsCl: ρ = 1.676 g/cc (nuclear main band), 1.687 (nuclear satellite), and 1.682 (mitochondrial). Reassociation kinetics at a criterion of Tm -23°C indicates that the nuclear reiterated sequences make up 30% of the genome (Cot_1/2 (pure) 0.28) and the single-copy DNA 70% (Cot_1/2(pure) 70). The complexity of the nuclear genome is 30 x 10⁹ daltons and that of the mitochondrial DNA is 35-40 x 10⁶ daltons (Cot_1/2 0.15). rRNA cistrons constitute 2.2% of nuclear DNA and have a ρ = 1.682.

RNA extracted from 4 stages during developmental cycle of Dictyostelium was hybridized with purified single-copy nuclear DNA. The hybrids had properties indicative of single-copy DNA-RNA hybrids. These studies indicate that there are, during development, qualitative and quantitative changes in the portion of the single-copy of the genome transcribed. Overall, 56% of the genome is represented by transcripts between the amoeba and mid-culmination stages. Some 19% are sequences which are represented at all stages while 37% of the genome consists of stage specific sequences.

Part II. RNA and protein synthesis and polysome formation were studied during early development of the surf clam Spisula solidissima embryos. The oocyte has a small number of polysomes and a low but measurable rate of protein synthesis (leucine-³H incorporation). After fertilization, there is a continual increase in the percentage of ribosomes sedimenting in the polysome region. Newly synthesized RNA (uridine-5-³H incorporation) was found in polysomes as early as the 2-cell stage. During cleavage, the newly formed RNA is associated mainly with the light polysomes.

RNA extracted from polysomes labeled at the 4-cell stage is polydisperse, nonribosomal, and non-4 S. Actinomycin D causes a reduction of about 30% of the polysomes formed between fertilization and the 16-cell stage.

In the early cleavage stages the light polysomes are mostly affected by actinomycin.

Proton magnetic resonance studies of ribonucleic acid complexes. I. Complexes of biological bases and oligonucleotides with RNA. II. Template recognition and the degeneracy of the genetic code

Part I. Complexes of Biological Bases and Oligonucleotides with RNA

The physical nature of complexes of several biological bases and oligonucleotides with single-stranded ribonucleic acids have been studied by high resolution proton magnetic resonance spectroscopy. The importance of various forces in the stabilization of these complexes is also discussed.

Previous work has shown that purine forms an intercalated complex with single-stranded nucleic acids. This complex formation led to severe and stereospecific broadening of the purine resonances. From the field dependence of the linewidths, T₁ measurements of the purine protons and nuclear Overhauser enhancement experiments, the mechanism for the line broadening was ascertained to be dipole-dipole interactions between the purine protons and the ribose protons of the nucleic acid.

The interactions of ethidium bromide (EB) with several RNA residues have been studied. EB forms vertically stacked aggregates with itself as well as with uridine, 3'-uridine monophosphate and 5'-uridine monophosphate and forms an intercalated complex with uridylyl (3' → 5') uridine and polyuridylic acid (poly U). The geometry of EB in the intercalated complex has also been determined.

The effect of chain length of oligo-A-nucleotides on their mode of interaction with poly U in D₂0 at neutral pD have also been studied. Below room temperatures, ApA and ApApA form a rigid triple-stranded complex involving a stoichiometry of one adenine to two uracil bases, presumably via specific adenine-uracil base pairing and cooperative base stacking of the adenine bases. While no evidence was obtained for the interaction of ApA with poly U above room temperature, ApApA exhibited complex formation of a 1:1 nature with poly U by forming Watson-Crick base pairs. The thermodynamics of these systems are discussed.

Part II. Template Recognition and the Degeneracy of the Genetic Code

The interaction of ApApG and poly U was studied as a model system for the codon-anticodon interaction of tRNA and mRNA in vivo. ApApG was shown to interact with poly U below ~20°C. The interaction was of a 1:1 nature which exhibited the Hoogsteen bonding scheme. The three bases of ApApG are in an anti conformation and the guanosine base appears to be in the lactim tautomeric form in the complex.

Due to the inadequacies of previous models for the degeneracy of the genetic code in explaining the observed interactions of ApApG with poly U, the "tautomeric doublet" model is proposed as a possible explanation of the degenerate interactions of tRNA with mRNA during protein synthesis in vivo.