Preliminary studies of the dual role of cotton-seed cake as fish feed and fish pond fertilizer in aquaculture

Many locally available fish feeds have been tried in fish culture. These include guinea corn, soya bean, groundnut cake and rice bran. Cotton seed cake has been successfully used as a fishpond organic fertilizer at Ado-Ekiti Government fish farm. Three fishponds stocked respectively with common carps, Heterotis, Tilapia spp., Clarias lazera and Heterobranchus were fed with cotton seed cake. Carps, Tilapia and Heterotis increased rapidly in weight and length while the catifishes did not grow

Atomistic simulation studies of the cement paste components

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Kinetic studies of gas flows

Our recent studies on kinetic behaviors of gas flows are reviewed in this paper. These flows have a wide range of background, but share a common feature that the flow Knudsen number is larger than 0.01. Thus kinetic approaches such as the direct simulation Monte Carlo method are required for their description. In the past few years, we studied several micro/nano-scale flows by developing novel particle simulation approach, and investigated the flows in low-pressure chambers and at high altitude. In addition, the microscopic behaviors of a couple of classical flow problems were analyzed, which shows the potential for kinetic approaches to reveal the microscopic mechanism of gas flows.

Space experimental studies of microgravity fluid science in China

Microgravity fluid physics is an important part of microgravity sciences, which consists of simple fluids of many new systems, gas-liquid two-phase flow and heat transfer, and complex fluid mechanics. In addition to the importance of itself in sciences and applications, microgravity fluid physics closely relates to microgravity combustion, space biotechnology and space materials science, and promotes the developments of interdisciplinary fields. Many space microgravity experiments have been per- formed on board the recoverable satellites and space ships of China and pushed the rapid development of microgravity sciences in China. In the present paper, space experimental studies and the main re- sults of the microgravity fluid science in China in the last 10 years or so are introduced briefly.

Spawning of yellowfin tuna and skipjack in the Eastern Tropical Pacific, as inferred from studies of gonad development

(PDF contains 70 pages.)

Experimental and finite element studies of a large arch dam

Forced vibration field tests and finite element studies have been conducted on Morrow Point (arch) Dam in order to investigate dynamic dam-water interaction and water compressibility. Design of the data acquisition system incorporates several special features to retrieve both amplitude and phase of the response in a low signal to noise environment. These features contributed to the success of the experimental program which, for the first time, produced field evidence of water compressibility; this effect seems to play a significant role only in the symmetric response of Morrow Point Dam in the frequency range examined. In the accompanying analysis, frequency response curves for measured accelerations and water pressures as well as their resonating shapes are compared to predictions from the current state-of-the-art finite element model for which water compressibility is both included and neglected. Calibration of the numerical model employs the antisymmetric response data since they are only slightly affected by water compressibility, and, after calibration, good agreement to the data is obtained whether or not water compressibility is included. In the effort to reproduce the symmetric response data, on which water compressibility has a significant influence, the calibrated model shows better correlation when water compressibility is included, but the agreement is still inadequate. Similar results occur using data obtained previously by others at a low water level. A successful isolation of the fundamental water resonance from the experimental data shows significantly different features from those of the numerical water model, indicating possible inaccuracy in the assumed geometry and/or boundary conditions for the reservoir. However, the investigation does suggest possible directions in which the numerical model can be improved.

Studies of the equation of state and elasticity of mantle minerals

Because the Earth’s upper mantle is inaccessible to us, in order to understand the chemical and physical processes that occur in the Earth’s interior we must rely on both experimental work and computational modeling. This thesis addresses both of these geochemical methods. In the first chapter, I develop an internally consistent comprehensive molar volume model for spinels in the oxide system FeO-MgO-Fe₂O₃-Cr₂O₃-Al₂O₃-TiO₂. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure. In the second chapter, I calibrate a molar volume model for cubic garnets in the system SiO₂-Al₂O₃-TiO₂-Fe₂O₃-Cr₂O₃-FeO-MnO-MgO-CaO-Na₂O. I use the method of singular value analysis to calibrate excess volume of mixing parameters for the garnet model. The implications the model has for the density of the lithospheric mantle are explored. In the third chapter, I discuss the nuclear inelastic X-ray scattering (NRIXS) method, and present analysis of three orthopyroxene samples with different Fe contents. Longitudinal and shear wave velocities, elastic parameters, and other thermodynamic information are extracted from the raw NRIXS data.

Structure-function studies of serine hydrolases: synthesis of a gene for ∝-lytic protease and the purification and characterization of a mutant β-lactamase

The author has constructed a synthetic gene for ∝-lytic protease. Since the DNA sequence of the protein is not known, the gene was designed by using the reverse translation of ∝-lytic protease's amino acid sequence. Unique restriction sites are carefully sought in the degenerate DNA sequence to aid in future mutagenesis studies. The unique restriction sites are designed approximately 50 base pairs apart and their appropriate codons used in the DNA sequence. The codons used to construct the DNA sequence of ∝-lytic protease are preferred codons in E-coli or used in the production of β-lactamase. Codon usage is also distributed evenly to ensure that one particular codon is not heavily used. The gene is essentially constructed from the outside in. The gene is built in a stepwise fashion using plasmids as the vehicles for the ∝-lytic oligomers. The use of plasmids allows the replication and isolation of large quantities of the intermediates during gene synthesis. The ∝-lytic DNA is a double-stranded oligomer that has sufficient overhang and sticky ends to anneal correctly in the vector. After six steps of incorporating ∝-lytic DNA, the gene is completed and sequenced to ensure that the correct DNA sequence is present and that no mutations occurred in the structural gene.

β-lactamase is the other serine hydrolase studied in this thesis. The author used the class A RTEM-1 β- lactamase encoded on the plasmid pBR322 to investigate the roll of the conserved threonine residue at position 71. Cassette mutagenesis was previously used to generate all possible amino acid substitutions at position 71. The work presented here describes the purification and kinetic characterization of a T71H mutant previously constructed by S. Schultz. The mutated gene was transferred into plasmid pJN for expression and induced with IPTG. The enzyme is purified by column chromatography and FPLC to homogeneity. Kinetic studies reveal that the mutant has lower k_(cat) values on benzylpenicillin, cephalothin and 6-aminopenicillanic acid but no changes in k_m except for cephalothin which is approximately 4 times higher. The mutant did not change siginificantly in its pH profile compared to the wild-type enzyme. Also, the mutant is more sensitive to thermal denaturation as compared to the wild-type enzyme. However, experimental evidence indicates that the probable generation of a positive charge at position 71 thermally stabilized the mutant.

Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

Stormsmart coasts in action: Two case studies of local level climate change adaptation

Coastal communities throughout the United States have dealt with the devastating effects of storms for centuries, however today’s threats are greater due to three factors. First, the population along the coastline has grown, and is projected to increase.i Additionally, past land use management decisions in the coastal zone have rarely led to the greatest protection from threats. Finally, climate change is predicted to affect coastal areas by accelerating current sea level rise rates and possibly increasing storm intensity.ii These factors compounded together mean that coastal communities are facing a very dangerous situation that threatens economies and human life. (PDF contains 4 pages)

Studies of ambient and chamber aerosol composition using the aerosol mass spectrometer

This thesis presents composition measurements for atmospherically relevant inorganic and organic aerosol from laboratory and ambient measurements using the Aerodyne aerosol mass spectrometer. Studies include the oxidation of dodecane in the Caltech environmental chambers, and several aircraft- and ground-based field studies, which include the quantification of wildfire emissions off the coast of California, and Los Angeles urban emissions.

The oxidation of dodecane by OH under low NO conditions and the formation of secondary organic aerosol (SOA) was explored using a gas-phase chemical model, gas-phase CIMS measurements, and high molecular weight ion traces from particle- phase HR-TOF-AMS mass spectra. The combination of these measurements support the hypothesis that particle-phase chemistry leading to peroxyhemiacetal formation is important. Positive matrix factorization (PMF) was applied to the AMS mass spectra which revealed three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition.

Airborne measurements of biomass burning emissions from a chaparral fire on the central Californian coast were carried out in November 2009. Physical and chemical changes were reported for smoke ages 0 – 4 h old. CO₂ normalized ammonium, nitrate, and sulfate increased, whereas the normalized OA decreased sharply in the first 1.5 - 2 h, and then slowly increased for the remaining 2 h (net decrease in normalized OA). Comparison to wildfire samples from the Yucatan revealed that factors such as relative humidity, incident UV radiation, age of smoke, and concentration of emissions are important for wildfire evolution.

Ground-based aerosol composition is reported for Pasadena, CA during the summer of 2009. The OA component, which dominated the submicron aerosol mass, was deconvolved into hydrocarbon-like organic aerosol (HOA), semi-volatile oxidized organic aerosol (SVOOA), and low-volatility oxidized organic aerosol (LVOOA). The HOA/OA was only 0.08–0.23, indicating that most of Pasadena OA in the summer months is dominated by oxidized OA resulting from transported emissions that have undergone photochemistry and/or moisture-influenced processing, as apposed to only primary organic aerosol emissions. Airborne measurements and model predictions of aerosol composition are reported for the 2010 CalNex field campaign.

Studies of Organic Molecule Recognition by Synthetic Cyclophane Receptors in Aqueous Media

The behaviors of six new cyclophane receptors for organic guest molecules in aqueous media are reported. These new hosts are modifications of more basic parent structures, and the main goal of their examination has been to determine how the modifications affect host selectivity for cationic guests. In particular, we have been interested in determining how additional non-covalent binding interactions can complement the cation-π interactions active in the parent systems. Three types of modifications were made to these systems. Firstly, neutral methoxy and bromine substituents were added to produce four of the six new macrocycles. Secondly, two additional aromatic rings (relative to the parent host) capable of making cation-π interactions with charged guest species were appended. Thirdly, a negatively charged carboxyl group was attached to produce a cavity in which electrostatic interactions should enhance cationic guest binding. ^1H-NMR and circular dichroic techniques were employed to determine the binding affinities of a wide variety of organic guests for the parent and modified structures in aqueous media.

Bromination of the parent host greatly enhances its binding in a general fashion, primarily as the result of hydrophobic interactions. The addition of methoxy groups does not enhance binding, apparently as a result of a collapse of the hosts into a conformation that is not suitable for binding. The appendage of extra aromatic rings enhances the binding of positively charged guests, most likely in response to more complete encapsulation of guest species. The addition of a negatively charged carboxylate enhances the binding to only selective groups of cationic guests. AM1 calculations of the electrostatic potentials of several guests molecules suggests that the enhancements seen with the modified receptor compared to the parent are most likely the result of close contact between regions of highest potential on the guest and the appended carboxylate.

Mechanistic and kinetic studies of the surface chemistry of iridium and ruthenium

Quantitative investigations of the mechanisms and the kinetics of the surface-catalyzed activation of C-H, N-H, C-C, and C-N bonds on the close-packed surfaces of Ir(111) and Ru(001) have been performed. The interaction of CH_3NH_2 with Ru(001) was investigated in ultrahigh vacuum with the techniques of high-resolution electron energy loss spectroscopy and thermal desorption mass spectrometry. Activation of the central C-N bond is observed, but it is less favored than the competing channel of complete dehydrogenation, by a ratio between 2:1 to 3:1. The decomposition mechanism has been characterized with several surface intermediates and gas-phase products identified. A pronounced preference for the activation of C-H over N-H and C-N bonds has been established. Additionally, the kinetics of the initial dissociation of short chain alkanes on Ir(111) has been examined, and the rate parameters of the activation of C-C bonds and primary, secondary, and tertiary C-H bonds have been determined. The formation of primary alkyl products is favored, over most of the experimental temperature range, despite the thermodynamic preference for the activation of individual secondary and tertiary C-H bonds in comparison to individual primary C-H bonds. At higher surface temperatures, the activation of C-C bonds occurs at competitive rates to the C-H reaction channel. The measured deuterium kinetic isotope effect implicates substantial deformation of the terminal methyl group in the transition state of C-C bond cleavage. Finally, the surface structure sensitivity of C-H bond cleavage has been quantified for smooth (111) and corrugated (110) surfaces of iridium and platinum, as well as for step edge defect sites on Ir(111).

Application of the Schwinger multichannel method to multichannel studies of electronically inelastic electron-molecule collisions

We have applied the Schwinger Multichannel Method(SMC) to the study of electronically inelastic, low energy electron-molecule collisions. The focus of these studies has been the assessment of the importance of multichannel coupling to the dynamics of these excitation processes. It has transpired that the promising quality of results realized in early SMC work on such inelastic scattering processes has been far more difficult to obtain in these more sophisticated studies.

We have attempted to understand the sources of instability of the SMC method which are evident in these multichannel studies. Particular instances of such instability have been considered in detail, which indicate that linear dependence, failure of the separable potential approximation, and difficulties in converging matrix elements involving recorrelation or Q-space terms all conspire to complicate application of the SMC method to these studies. A method involving singular value decomposition(SVD) has been developed to, if not resolve these problems, at least mitigate their deleterious effects on the computation of electronically inelastic cross sections.

In conjunction with this SVD procedure, the SMC method has been applied to the study of the H_2 , H_2O, and N_2 molecules. Rydberg excitations of the first two molecules were found to be most sensitive to multichannel coupling near threshold. The (3σ_g → 1π_g ) and (1π_u → 1π_g) valence excitations of the N_2 molecule were found to be strongly influenced by the choice of channel coupling scheme at all collision energies considered in these studies.