Oceanographic observations in the Gulf of Guayaquil, 1962-1964. Part II. Biological, chemical and physical.

ENGLISH: During 1961 the government of Ecuador, with the financial assistance of the Special Fund of the United Nations and the technical assistance of FAO experts, initiated an extensive program of fisheries research centered in a fisheries institute established in Guayaquil. In cooperation with this program, and in connection with Ecuador's adherence in 1961 to the Convention for the Establishment of an Inter-American Tropical Tuna Commission, a two-and-a-half year investigation of the ecology of the Gulf of Guayaquil and adjacent waters was started by the Inter-American Tropical Tuna Commission. SPANISH: Durante 1961 el gobierno ecuatoriano con el apoyo financiero del Fondo Especial de las Naciones Unidas y la ayuda técnica de los expertos de la FAO, inició un programa extensivo de investigación pesquera, centralizado en el instituto pesquero establecido en Guayaquil. En cooperación con este programa y en conexión a la afiliaci6n del Ecuador a la Convención, en 1961, para el establecimiento de una Comisión Interamericana del Atún Tropical, Cue iniciada por la Comisión una investigación de dos aftos y medio sobre la ecología del Golfo de Guayaquil y de las aguas adyacentes. (PDF contains 501 pages.)

Dissipative particle dynamics simulation of wettability alternation phenomena in the chemical flooding process

Wettability alternation phenomena is considered one of the most important enhanced oil recovery (EOR) mechanisms in the chemical flooding process and induced by the adsorption of surfactant on the rock surface. These phenomena are studied by a mesoscopic method named as dissipative particle dynamics (DPD). Both the alteration phenomena of water-wet to oil-wet and that of oil-wet to water-wet are simulated based on reasonable definition of interaction parameters between beads. The wetting hysteresis phenomenon and the process of oil-drops detachment from rock surfaces with different wettability are simulated by adding long-range external forces on the fluid particles. The simulation results show that, the oil drop is liable to spread on the oil-wetting surface and move in the form of liquid film flow, whereas it is likely to move as a whole on the water-wetting surface. There are the same phenomena occuring in wettability-alternated cases. The results also show that DPD method provides a feasible approach to the problems of seepage flow with physicochemical phenomena and can be used to study the mechanism of EOR of chemical flooding.

Language distance and non-native syntactic processing: Evidence from event-related potentials

[EN] In this study, we explore native and non-native syntactic processing, paying special attention to the language distance factor. To this end, we compared how native speakers of Basque and highly proficient non-native speakers of Basque who are native speakers of Spanish process certain core aspects of Basque syntax. Our results suggest that differences in native versus non-native language processing strongly correlate with language distance: native/non-native processing differences obtain if a syntactic parameter of the non-native grammar diverges from the native grammar. Otherwise, non-native processing will approximate native processing as levels of proficiency increase. We focus on three syntactic parameters: (i) the head parameter, (ii) argument alignment (ergative/accusative), and (iii) verb agreement. The first two diverge in Basque and Spanish, but the third is the same in both languages. Our results reveal that native and non-native processing differs for the diverging syntactic parameters, but not for the convergent one. These findings indicate that language distance has a significant impact in non-native language processing.

Plasma-Arc Technology For The Thermal Treatment Of Chemical Wastes

Plasma-arc technology was developed to dispose of chemical wastes from a chemical plant by the Institute of Mechanics, Chinese Academy of Sciences (CAS-IMECH). A pilot plant system with this technology was constructed to destroy two types of chemical wastes. The system included shredding, mixing, and feeding subsystems, a plasma-arc reactor of 150 kW, an off-gas burning subsystem, and a scrubbing subsystem. The additives (CaO, SiO2, and Fe) were added into the reactor to form vitrified slag and capture the hazardous elements. The molten slag was quickly quenched to form an amorphous glassy structure. A direct current (DC) experimental facility of 30kW with plasma-arc technology was also set up to study the pyrolysis process in the laboratory, and the experimental results showed the cooling speed is the most important factor for good vitrified structure of the slag. According to previous tests, the destruction and removal efficiency (DRE) for these chemical wastes was more than 99.999%, and the polychlorinated biphenyls (PCBs) concentration in the solid residues was in the range of 1.28 to 12.9mg/kg, which is far below the Chinese national emission limit for the hazardous wastes. A simplified electromagneto model for numerical simulation was developed to predict the temperature and velocity fields. This model can make satisfactory maximum temperature and velocity distributions in the arc region, as well as the results by the magneto hydrodynamic approach.

The assessment of physico-chemical parameters of Shiroro Lake and its major tributaries

The physico-chemical parameters of the surface water of Shiroro Lake and its major tributaries at their entry point to the reservoir were assessed over a period of eighteen months. As in other African inland water bodies there were seasonal variations in the parameters measured. The hydrological regime of the lake, precipitation chemistry, bedrock chemistry and hydro-electric power generation influence and determine the inputs of dissolved organic carbon, nutrient levels and water quality of the lake. The added nutrients to the lake by means of the major tributary rivers and inundation of surrounding areas also influence the water quality of the lake. The wet season mean values for water and air temperature were significantly (P <0.05) higher than dry season mean values in all stations. However, for pH, Dissolved oxygen and Phosphate-phosphorus the dry season mean values were higher than wet season mean values

Chemical and mineralogical characterization of micro-inclusions in diamonds

Secondary-ion mass spectrometry (SIMS), electron probe analysis (EPMA), analytical scanning electron microscopy (SEM) and infrared (IR) spectroscopy were used to determine the chemical composition and the mineralogy of sub-micrometer inclusions in cubic diamonds and in overgrowths (coats) on octahedral diamonds from Zaire, Botswana, and some unknown localities.

The inclusions are sub-micrometer in size. The typical diameter encountered during transmission electron microscope (TEM) examination was 0.1-0.5 µm. The micro-inclusions are sub-rounded and their shape is crystallographically controlled by the diamond. Normally they are not associated with cracks or dislocations and appear to be well isolated within the diamond matrix. The number density of inclusions is highly variable on any scale and may reach 10^(11) inclusions/cm^3 in the most densely populated zones. The total concentration of metal oxides in the diamonds varies between 20 and 1270 ppm (by weight).

SIMS analysis yields the average composition of about 100 inclusions contained in the sputtered volume. Comparison of analyses of different volumes of an individual diamond show roughly uniform composition (typically ±10% relative). The variation among the average compositions of different diamonds is somewhat greater (typically ±30%). Nevertheless, all diamonds exhibit similar characteristics, being rich in water, carbonate, SiO_2, and K_2O, and depleted in MgO. The composition of micro-inclusions in most diamonds vary within the following ranges: SiO_2, 30-53%; K_2O, 12-30%; CaO, 8-19%; FeO, 6-11%; Al_2O_3, 3-6%; MgO, 2-6%; TiO_2, 2-4%; Na_2O, 1-5%; P_2O_5, 1-4%; and Cl, 1-3%. In addition, BaO, 1-4%; SrO, 0.7-1.5%; La_2O_3, 0.1-0.3%; Ce_2O_3, 0.3-0.5%; smaller amounts of other rare-earth elements (REE), as well as Mn, Th, and U were also detected by instrumental neutron activation analysis (INAA). Mg/(Fe+Mg), 0.40-0.62 is low compared with other mantle derived phases; K/ AI ratios of 2-7 are very high, and the chondrite-normalized Ce/Eu ratios of 10-21 are also high, indicating extremely fractionated REE patterns.

SEM analyses indicate that individual inclusions within a single diamond are roughly of similar composition. The average composition of individual inclusions as measured with the SEM is similar to that measured by SIMS. Compositional variations revealed by the SEM are larger than those detected by SIMS and indicate a small variability in the composition of individual inclusions. No compositions of individual inclusions were determined that might correspond to mono-mineralic inclusions.

IR spectra of inclusion- bearing zones exhibit characteristic absorption due to: (1) pure diamonds, (2) nitrogen and hydrogen in the diamond matrix; and (3) mineral phases in the micro-inclusions. Nitrogen concentrations of 500-1100 ppm, typical of the micro-inclusion-bearing zones, are higher than the average nitrogen content of diamonds. Only type IaA centers were detected by IR. A yellow coloration may indicate small concentration of type IB centers.

The absorption due to the micro-inclusions in all diamonds produces similar spectra and indicates the presence of hydrated sheet silicates (most likely, Fe-rich clay minerals), carbonates (most likely calcite), and apatite. Small quantities of molecular CO_2 are also present in most diamonds. Water is probably associated with the silicates but the possibility of its presence as a fluid phase cannot be excluded. Characteristic lines of olivine, pyroxene and garnet were not detected and these phases cannot be significant components of the inclusions. Preliminary quantification of the IR data suggests that water and carbonate account for, on average, 20-40 wt% of the micro-inclusions.

The composition and mineralogy of the micro-inclusions are completely different from those of the more common, larger inclusions of the peridotitic or eclogitic assemblages. Their bulk composition resembles that of potassic magmas, such as kimberlites and lamproites, but is enriched in H_2O, CO_3, K_2O, and incompatible elements, and depleted in MgO.

It is suggested that the composition of the micro-inclusions represents a volatile-rich fluid or a melt trapped by the diamond during its growth. The high content of K, Na, P, and incompatible elements suggests that the trapped material found in the micro-inclusions may represent an effective metasomatizing agent. It may also be possible that fluids of similar composition are responsible for the extreme enrichment of incompatible elements documented in garnet and pyroxene inclusions in diamonds.

The origin of the fluid trapped in the micro-inclusions is still uncertain. It may have been formed by incipient melting of a highly metasomatized mantle rocks. More likely, it is the result of fractional crystallization of a potassic parental magma at depth. In either case, the micro-inclusions document the presence of highly potassic fluids or melts at depths corresponding to the diamond stability field in the upper mantle. The phases presently identified in the inclusions are believed to be the result of closed system reactions at lower pressures.

Chemical-scale studies of G protein-coupled receptors and ligand-gated ion channels

This dissertation describes studies of G protein-coupled receptors (GPCRs) and ligand-gated ion channels (LGICs) using unnatural amino acid mutagenesis to gain high precision insights into the function of these important membrane proteins.

Chapter 2 considers the functional role of highly conserved proline residues within the transmembrane helices of the D2 dopamine GPCR. Through mutagenesis employing unnatural α-hydroxy acids, proline analogs, and N-methyl amino acids, we find that lack of backbone hydrogen bond donor ability is important to proline function. At one proline site we additionally find that a substituent on the proline backbone N is important to receptor function.

In Chapter 3, side chain conformation is probed by mutagenesis of GPCRs and the muscle-type nAChR. Specific side chain rearrangements of highly conserved residues have been proposed to accompany activation of these receptors. These rearrangements were probed using conformationally-biased β-substituted analogs of Trp and Phe and unnatural stereoisomers of Thr and Ile. We also modeled the conformational bias of the unnatural Trp and Phe analogs employed.

Chapters 4 and 5 examine details of ligand binding to nAChRs. Chapter 4 describes a study investigating the importance of hydrogen bonds between ligands and the complementary face of muscle-type and α4β4 nAChRs. A hydrogen bond involving the agonist appears to be important for ligand binding in the muscle-type receptor but not the α4β4 receptor.

Chapter 5 describes a study characterizing the binding of varenicline, an actively prescribed smoking cessation therapeutic, to the α7 nAChR. Additionally, binding interactions to the complementary face of the α7 binding site were examined for a small panel of agonists. We identified side chains important for binding large agonists such as varenicline, but dispensable for binding the small agonist ACh.

Chapter 6 describes efforts to image nAChRs site-specifically modified with a fluorophore by unnatural amino acid mutagenesis. While progress was hampered by high levels of fluorescent background, improvements to sample preparation and alternative strategies for fluorophore incorporation are described.

Chapter 7 describes efforts toward a fluorescence assay for G protein association with a GPCR, with the ultimate goal of probing key protein-protein interactions along the G protein/receptor interface. A wide range of fluorescent protein fusions were generated, expressed in Xenopus oocytes, and evaluated for their ability to associate with each other.

Experimental chemical physics of droplets and clusters

Time-of-flight measurements of energetic He atoms, field ionization of cryogenic liquid helium clusters, and time-of-flight and REMPI spectroscopy of radical salt clusters were investigated experimentally. The excited He atoms were generated in a corona discharge. Two strong neutral peaks were observed, accompanied by a prompt photon peak and a charged peak. All peaks were correlated with the pulsing of the discharge. The neutral hyperthermal and metastable atoms were formed by different mechanisms at different stages of the corona discharge. Positively charged helium droplets were produced by ionization of liquid helium in an electrostatic spraying experiment. The fluid emerging from a thin glass capillary was ionized by a high voltage applied to a needle inside the capillary. Fine droplets (less than 10 µm in diameter) were produced in showers with currents as high as 0.4 µA at 2-4 kV. The high currents resulting from field ionization in helium and the low surface tension of He I, led to charge densities that greatly exceeded the Rayleigh limit, thus resulting in coulombic explosion of the liquid. In contrast, liquid nitrogen formed a well-defined Taylor cone with droplets having diameters comparable to the jet (≈100 µm) at lower currents (10 nA) and higher voltages (8 kV). The metal-halide clusters of calcium and chlorine were generated by laser ablation of calcium metal in a Ar/CCl₄ expansion. A visible spectrum of the Ca₂Cl₃ cluster was observed from 651 to 630 nm by 1 +1' REMPI. The spectra were composed of a strong origin band at 15 350.8 cm^-1 and several weak vibronic bands. Density functional calculations predicted three minimum energy isomers. The spectrum was assigned to the ²B₂ ← X ²A₁ transition of a planar C_2V structure having a ring of two Cl and two Ca atoms and a terminal Cl atom. The ring isomer of Ca₂Cl₃ has the unpaired electron localized on one Ca²⁺ ion to form a Ca⁺ chromophore. A second electronic band of Ca₂Cl₃ was observed at 720 nm. The band is sharply different from the 650 nm band and likely due to a different isomer.

Studies of the serotonin type 3A receptor and the chemical preparation of tRNA

This thesis describes studies surrounding a ligand-gated ion channel (LGIC): the serotonin type 3A receptor (5-HT₃AR). Structure-function experiments using unnatural amino acid mutagenesis are described, as well as experiments on the methodology of unnatural amino acid mutagenesis. Chapter 1 introduces LGICs, experimental methods, and an overview of the unnatural amino acid mutagenesis.

In Chapter 2, the binding orientation of the clinically available drugs ondansetron and granisetron within 5-HT₃A is determined through a combination of unnatural amino acid mutagenesis and an inhibition based assay. A cation-π interaction is found for both ondansetron and granisetron with a specific tryptophan residue (Trp183, TrpB) of the mouse 5-HT₃AR, which establishes a binding orientation for these drugs.

In Chapter 3, further studies were performed with ondansetron and granisetron with 5-HT₃A. The primary determinant of binding for these drugs was determined to not include interactions with a specific tyrosine residue (Tyr234, TyrC2). In completing these studies, evidence supporting a cation-π interaction of a synthetic agonist, meta-chlorophenylbiguanide, was found with TyrC2.

In Chapter 4, a direct chemical acylation strategy was implemented to prepare full-length suppressor tRNA mediated by lanthanum(III) and amino acid phosphate esters. The derived aminoacyl-tRNA is shown to be translationally competent in Xenopus oocytes.

Appendix A.1 gives details of a pharmacological method for determining the equilibrium dissociation constant, K_B, of a competitive antagonist with a receptor, known as Schild analysis. Appendix A.2 describes an examination of the inhibitory activity of new chemical analogs of the 5-HT₃A antagonist ondansetron. Appendix A.3 reports an organic synthesis of an intermediate for a new unnatural amino acid. Appendix A.4 covers an additional methodological examination for the preparation of amino-acyl tRNA.