An annotated bibliography on the biology and fishery of the skipjack tuna, Katsuwonis pelamis, of the Pacific Ocean

ENGLISH: The skipjack tuna, Katsuwonus pelamis is an important resource of the tropical and subtropical waters of the world ocean. Fishermen of many countries exploit this resource; at the present time, the annual world catch is approximately 200 thousand metric tons. Many fishery experts believe that the skipjack is not being fully utilized while stocks of other tunas are being fished, in some areas, at levels exceeding their maximum sustainable yields. In addition to the importance of skipjack as a commercial fish and as a source of food, there is a small but expanding recreational fishery in some countries bordering the Pacific. This bibliography provides a list of publications pertaining to the biology and fishery of the Pacific skipjack tuna. Papers concerned with food technology, food chemistry, radio-chemistry, and certain other subjects are excluded. The main sources for our publication have been the existing bibliographies of tunas, which are listed and indexed accordingly. In addition, reports of various marine laboratories and other scientific organizations have been checked; these are too numerous to list. We are fairly confident that all major works pertaining to skipjack tuna in the Pacific, printed prior to the end of 1966, appear in this bibliography. Only reports considered to be in permanent form are included. Annotations are based on actual examination of each of the entries listed here. The annotations do not evaluate a paper but serve rather to give a more precise idea of its contents if not revealed by the title alone. If the title sufficed in this respect, no annotation was prepared. A relatively small number of works believed to contain information pertinent to our bibliography could not be examined, but a list of such papers is provided. SPANISH: El atún barrilete, Katsuwonus pelamis, es un recurso importante de las aguas tropicales y subtropicales del océano mundial. Los pescadores de varios países explotan este recurso; actualmente, la captura mundial anual es aproximadamente de 200,000 toneladas métricas. Muchos expertos en la pesquería creen que el barrilete no es utilizado completamente, mientras los stocks de otros atunes son pescados en algunas áreas a niveles que exceden su rendimiento máximo sostenible. Además de la importancia del barrilete como pez comercial y como fuente de alimento, existe una pesquería pequeña recreativa que se está desarrollando en algunos países colindantes con el Pacífico. Esta bibliografía suministra una lista de publicaciones correspondientes a la biología y pesquería del atún barrilete en el Pacífico. Estudios referentes a la tecnología alimenticia, química alimenticia, radioquímica y ciertos otros sujetos son excluídos. Las fuentes principales correspondientes a nuestra publicación han sido las bibliografías existentes sobre atunes, las cuales están enumeradas y catalogadas de acuerdo. Además, se han examinado los informes de varios laboratorios marítimos y los de otras organizaciones científicas; éstos son demasiado numerosos para enumerar. Estamos bastante seguros de que todos los trabajos principales correspondientes al atún barrilete del Pacífico, editados antes de terminar el año de 1966, aparecen en esta bibliografía. Se incluyen únicamente los informes que se consideran permanentes. Las anotaciones se basan en el examen actual de cada una de las entradas aquí referidas. Las anotaciones no evaluan un estudio, pero sirven más bien para dar una idea más precisa de su contenido si el título por sí mismo no lo explica. No se preparó ninguna anotación si el título a este respecto era suficiente. Un número relativamente pequeño de trabajos que se cree tengan información pertinente a nuestra bibliografía no pudo ser examinado, pero se suministra una lista de tales estudios. (PDF contains 227 pages.)

Mechanisms underlying two kinds of surface effects on elastic constants

ABSTRACT Recently, people are confused with two opposite variations of elastic modulus with decreasing size of nano scale sample: elastic modulus either decreases or increases with decreas- ing sample size. In this paper, based on intermolecular potentials and a one dimensional model, we provide a unified understanding of the two opposite size effects. Firstly, we analyzed the mi- crostructural variation near the surface of an fcc nanofilm based on the Lennard-Jones potential. It is found that the atomic lattice near the surface becomes looser in comparison with the bulk, indicating that atoms in the bulk are located at the balance of repulsive forces, resulting in the decrease of the elastic moduli with the decreasing thickness of the film accordingly. In addition, the decrease in moduli should be attributed to both the looser surface layer and smaller coor- dination number of surface atoms. Furthermore, it is found that both looser and tighter lattice near the surface can appear for a general pair potential and the governing mechanism should be attributed to the surplus of the nearest force to all other long range interactions in the pair po- tential. Surprisingly, the surplus can be simply expressed by a sum of the long range interactions and the sum being positive or negative determines the looser or tighter lattice near surface re- spectively. To justify this concept, we examined ZnO in terms of Buckingham potential with long range Coulomb interactions. It is found that compared to its bulk lattice, the ZnO lattice near the surface becomes tighter, indicating the atoms in the bulk located at the balance of attractive forces, owing to the long range Coulomb interaction. Correspondingly, the elastic modulus of one- dimensional ZnO chain increases with decreasing size. Finally, a kind of many-body potential for Cu was examined. In this case, the surface layer becomes tighter than the bulk and the modulus increases with deceasing size, owing to the long range repulsive pair interaction, as well as the cohesive many-body interaction caused by the electron redistribution.

Generating artificial homologous proteins according to the representative family character in molecular mechanics properties - an attempt in validating an underlying rule of protein evolution

The molecular mechanics property is the foundation of many characters of proteins. Based on intramolecular hydrophobic force network, the representative family character underlying a protein’s mechanics property is described by a simple two-letter scheme. The tendency of a sequence to become a member of a protein family is scored according to this mathematical representation. Remote homologs of the WW-domain family could be easily designed using such a mechanistic signature of protein homology. Experimental validation showed that nearly all artificial homologs have the representative folding and bioactivity of their assigned family. Since the molecular mechanics property is the only consideration in this study, the results indicate its possible role in the generation of new members of a protein family during evolution.

Fish and fisheries of Bakolori Reservoir

Details are given of fisheries activities carried out in Bakolori Reservoir within the context of many and varied functions of Sokoto Rima River Basin Development Authority. Experimental fishing was conducted for 55 days in 1979 when the reservoir was only one year old and the exercise continued in 1980 and 1981 also for 85 and 52 days respectively. During the exercise, the catch per unit effort showed an increasing trend with increasing efforts by four times to that of the initial. The fish harvest was 1.205 kg/day when 3.8 nets were operated in 1979, this went up to 3.2 kg when the number of nets were increased to 8.37/day in 1980. This increasing trend continued in 1981 season also when 16.15 nets caught 5.756 kg fish per day. A direct relationship was observed in the fishing efforts and catch. Tilapia, Clarias, Labeo, Schilbe and Synodontis spp, were the most predominant fish species in the catch and contributed more than 97% of the total fish harvest

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.

Analysis of a transcriptional network involving PU.1, Notch, and Gata3 in the lymphomyeloid lineage decision during early T-cell development

Hematopoiesis is a well-established system used to study developmental choices amongst cells with multiple lineage potentials, as well as the transcription factor network interactions that drive these developmental paths. Multipotent progenitors travel from the bone marrow to the thymus where T-cell development is initiated and these early T-cell precursors retain lineage plasticity even after initiating a T-cell program. The development of these early cells is driven by Notch signaling and the combinatorial expression of many transcription factors, several of which are also involved in the development of other cell lineages. The ETS family transcription factor PU.1 is involved in the development of progenitor, myeloid, and lymphoid cells, and can divert progenitor T-cells from the T-lineage to a myeloid lineage. This diversion of early T-cells by PU.1 can be blocked by Notch signaling. The PU.1 and Notch interaction creates a switch wherein PU.1 in the presence of Notch promotes T-cell identity and PU.1 in the absence of Notch signaling promotes a myeloid identity. Here we characterized an early T-cell cell line, Scid.adh.2c2, as a good model system for studying the myeloid vs. lymphoid developmental choice dependent on PU.1 and Notch signaling. We then used the Scid.adh.2c2 system to identify mechanisms mediating PU.1 and Notch signaling interactions during early T-cell development. We show that the mechanism by which Notch signaling is protecting pro-T cells is neither degradation nor modification of the PU.1 protein. Instead we give evidence that Notch signaling is blocking the PU.1-driven inhibition of a key set of T-regulatory genes including Myb, Tcf7, and Gata3. We show that the protection of Gata3 from PU.1-mediated inhibition, by Notch signaling and Myb, is important for retaining a T-lineage identity. We also discuss a PU.1-driven mechanism involving E-protein inhibition that leads to the inhibition of Notch target genes. This is mechanism may be used as a lockdown mechanism in pro-T-cells that have made the decision to divert to the myeloid pathway.

Predicting the effects of climate change on sea turtle nesting habitat in Florida

Rising global temperatures threaten the survival of many plant and animal species. Having already risen at an unprecedented rate in the past century, temperatures are predicted to rise between 0.3 and 7.5C in North America over the next 100 years (Hawkes et al. 2007). Studies have documented the effects of climate warming on phenology (timing of seasonal activities), with observations of early arrival at breeding grounds, earlier ends to the reproductive season, and delayed autumnal migrations (Pike et al. 2006). In addition, for species not suited to the physiological demands of cold winter temperatures, increasing temperatures could shift tolerable habitats to higher latitudes (Hawkes et al. 2007). More directly, climate warming will impact thermally sensitive species like sea turtles, who exhibit temperature-dependent sexual determination. Temperatures in the middle third of the incubation period determine the sex of sea turtle offspring, with higher temperatures resulting in a greater abundance of female offspring. Consequently, increasing temperatures from climate warming would drastically change the offspring sex ratio (Hawkes et al. 2007). Of the seven extant species of sea turtles, three (leatherback, Kemp’s ridley, and hawksbill) are critically endangered, two (olive ridley and green) are endangered, and one (loggerhead) is threatened. Considering the predicted scenarios of climate warming and the already tenuous status of sea turtle populations, it is essential that efforts are made to understand how increasing temperatures may affect sea turtle populations and how these species might adapt in the face of such changes. In this analysis, I seek to identify the impact of changing climate conditions over the next 50 years on the availability of sea turtle nesting habitat in Florida given predicted changes in temperature and precipitation. I predict that future conditions in Florida will be less suitable for sea turtle nesting during the historic nesting season. This may imply that sea turtles will nest at a different time of year, in more northern latitudes, to a lesser extent, or possibly not at all. It seems likely that changes in temperature and precipitation patterns will alter the distribution of sea turtle nesting locations worldwide, provided that beaches where the conditions are suitable for nesting still exist. Hijmans and Graham (2006) evaluate a range of climate envelope models in terms of their ability to predict species distributions under climate change scenarios. Their results suggested that the choice of species distribution model is dependent on the specifics of each individual study. Fuller et al. (2008) used a maximum entropy approach to model the potential distribution of 11 species in the Arctic Coastal Plain of Alaska under a series of projected climate scenarios. Recently, Pike (in press) developed Maxent models to investigate the impacts of climate change on green sea turtle nest distribution and timing. In each of these studies, a set of environmental predictor variables (including climate variables), for which ‘current’ conditions are available and ‘future’ conditions have been projected, is used in conjunction with species occurrence data to map potential species distribution under the projected conditions. In this study, I will take a similar approach in mapping the potential sea turtle nesting habitat in Florida by developing a Maxent model based on environmental and climate data and projecting the model for future climate data. (PDF contains 5 pages)

Engineering nucleic acid mechanisms for regulation and readout of gene expression : conditional Dicer substrate formation and sensitive multiplexed northern blots

Nucleic acids are most commonly associated with the genetic code, transcription and gene expression. Recently, interest has grown in engineering nucleic acids for biological applications such as controlling or detecting gene expression. The natural presence and functionality of nucleic acids within living organisms coupled with their thermodynamic properties of base-pairing make them ideal for interfacing (and possibly altering) biological systems. We use engineered small conditional RNA or DNA (scRNA, scDNA, respectively) molecules to control and detect gene expression. Three novel systems are presented: two for conditional down-regulation of gene expression via RNA interference (RNAi) and a third system for simultaneous sensitive detection of multiple RNAs using labeled scRNAs.

RNAi is a powerful tool to study genetic circuits by knocking down a gene of interest. RNAi executes the logic: If gene Y is detected, silence gene Y. The fact that detection and silencing are restricted to the same gene means that RNAi is constitutively on. This poses a significant limitation when spatiotemporal control is needed. In this work, we engineered small nucleic acid molecules that execute the logic: If mRNA X is detected, form a Dicer substrate that targets independent mRNA Y for silencing. This is a step towards implementing the logic of conditional RNAi: If gene X is detected, silence gene Y. We use scRNAs and scDNAs to engineer signal transduction cascades that produce an RNAi effector molecule in response to hybridization to a nucleic acid target X. The first mechanism is solely based on hybridization cascades and uses scRNAs to produce a double-stranded RNA (dsRNA) Dicer substrate against target gene Y. The second mechanism is based on hybridization of scDNAs to detect a nucleic acid target and produce a template for transcription of a short hairpin RNA (shRNA) Dicer substrate against target gene Y. Test-tube studies for both mechanisms demonstrate that the output Dicer substrate is produced predominantly in the presence of a correct input target and is cleaved by Dicer to produce a small interfering RNA (siRNA). Both output products can lead to gene knockdown in tissue culture. To date, signal transduction is not observed in cells; possible reasons are explored.

Signal transduction cascades are composed of multiple scRNAs (or scDNAs). The need to study multiple molecules simultaneously has motivated the development of a highly sensitive method for multiplexed northern blots. The core technology of our system is the utilization of a hybridization chain reaction (HCR) of scRNAs as the detection signal for a northern blot. To achieve multiplexing (simultaneous detection of multiple genes), we use fluorescently tagged scRNAs. Moreover, by using radioactive labeling of scRNAs, the system exhibits a five-fold increase, compared to the literature, in detection sensitivity. Sensitive multiplexed northern blot detection provides an avenue for exploring the fate of scRNAs and scDNAs in tissue culture.

Assessment of inland waters fisheries in Nigeria with implications for improved freshwater fish production, poverty alleviation and food security

Rapid Appraisals of the current fisheries situations of some selected inland water bodies in Nigeria were carried out within the framework of Aquaculture and Inland Fisheries Project (AIFP) Annex II of the National Special Programme for Food Security (NSPFS). This paper presents the results of the fishery assessment of one of the selected inland water bodies (Sabke Lake) in Nigeria with a view to optimizing the fish yield through the adoption of improved culture based fishery techniques and community-based fisheries management. The lake is unmanaged and the fishing pressure was found to be very high. Also a number of fishermen were found using small mesh size nets to crop the juveniles of highly valued fish species for an optimum catch. About 14 fishermen ought to have been engaged in full time fishing activities if the fisheries of this lake is to be managed on a sustainable basis. However, a surplus of over 100 fishermen was recorded actively fishing during the period of the study. The results further revealed that Fisheries Rules and Regulations were not established for the national exploitation and proper management of the fisheries of many inland water bodies including Sabke Lake. All these have a depilatory effect on the abundance and sizes of fish harvested from the nigerian inland water bodies especially Sabke Lake. A community based management system that establishes a participatory involvement of fishermen in the conservation and national exploitation of fisheries resources for their own well being is recommended for Sabke Lake and other inland water bodies in Nigeria

Utilization of some aquatic macrophytes in Nigeria in-land water bodies: a review

Aquatic vegetation is an essential component of the aquatic ecosystem with both positive and negative implications on the water body. Efforts are always made to curtail the excessive growth of aquatic plants in order to prevent them from becoming a nuisance in the ecosystem. One of the ways of solving such problem is the positive economic use of such plants. Utilization as a method of weed control within the aquatic ecosystem is considered to be one of the safest methods of weed control as this provides the riparian communities double advantages in terms of save environment and personal benefits of the plant. The flora diversity of freshwater and brackish environments posses a great potential to both man and higher animals alike. Due to this fact, this paper attempt to review the exploited and unexploited aquatic plants resources of many of our water bodies in Nigeria both economica/ly and socially, to the populace. Recommendations are also advanced for further studies that will enhance sound management of the resources for maximum benefits and sustainability

Investigation of hypervelocity impact phenomena using real-time concurrent diagnostics

Hypervelocity impact of meteoroids and orbital debris poses a serious and growing threat to spacecraft. To study hypervelocity impact phenomena, a comprehensive ensemble of real-time concurrently operated diagnostics has been developed and implemented in the Small Particle Hypervelocity Impact Range (SPHIR) facility. This suite of simultaneously operated instrumentation provides multiple complementary measurements that facilitate the characterization of many impact phenomena in a single experiment. The investigation of hypervelocity impact phenomena described in this work focuses on normal impacts of 1.8 mm nylon 6/6 cylinder projectiles and variable thickness aluminum targets. The SPHIR facility two-stage light-gas gun is capable of routinely launching 5.5 mg nylon impactors to speeds of 5 to 7 km/s. Refinement of legacy SPHIR operation procedures and the investigation of first-stage pressure have improved the velocity performance of the facility, resulting in an increase in average impact velocity of at least 0.57 km/s. Results for the perforation area indicate the considered range of target thicknesses represent multiple regimes describing the non-monotonic scaling of target perforation with decreasing target thickness. The laser side-lighting (LSL) system has been developed to provide ultra-high-speed shadowgraph images of the impact event. This novel optical technique is demonstrated to characterize the propagation velocity and two-dimensional optical density of impact-generated debris clouds. Additionally, a debris capture system is located behind the target during every experiment to provide complementary information regarding the trajectory distribution and penetration depth of individual debris particles. The utilization of a coherent, collimated illumination source in the LSL system facilitates the simultaneous measurement of impact phenomena with near-IR and UV-vis spectrograph systems. Comparison of LSL images to concurrent IR results indicates two distinctly different phenomena. A high-speed, pressure-dependent IR-emitting cloud is observed in experiments to expand at velocities much higher than the debris and ejecta phenomena observed using the LSL system. In double-plate target configurations, this phenomena is observed to interact with the rear-wall several micro-seconds before the subsequent arrival of the debris cloud. Additionally, dimensional analysis presented by Whitham for blast waves is shown to describe the pressure-dependent radial expansion of the observed IR-emitting phenomena. Although this work focuses on a single hypervelocity impact configuration, the diagnostic capabilities and techniques described can be used with a wide variety of impactors, materials, and geometries to investigate any number of engineering and scientific problems.

Synthetic, kinetic and mechanistic studies in early transition metal systems. I. α- and β-hydrogen elimination reactions in derivatives of permethyltitanocene, -zirconocene, and -hafnocene. II. The reactions of aluminum alkyls with derivatives of permethylniobocene

The thermal decomposition of Cp*Ti(CH_3)_2 (Cp*≡ ƞ^5-C_5Me_5) toluene solution follows cleanly first-order kinetics and produces a single titanium product Cp*(C_5Me_4CH_2)Ti(CH_3) concurrent with the evolution of one equivalent of methane. Labeling studies using Cp*_2Ti- (CD_3)_2 and (Cp*-d_(15))_2Ti(CH_3)_2 show the decomposition to be intramolecular and the methane to be produced by the coupling of a methyl group with a hydrogen from the other TiCH_3 group. Activation parameters, ΔH^‡ and ΔS^‡, and kinetic deuterium isotope effects have been measured. The alternative decomposition pathways of α-hydrogen abstraction and a-hydrogen elimination, both leading to a titanium-methylidene intermediate, are discussed.

The insertion of unactivated acetylenes into the metal-hydride bonds of Cp*_2MH_2 (M = Zr, Hf) proceeds rapidly at low temperature to form monoand/ or bisinsertion products, dependent upon the steric bulk of the acetylene substituents. Cp*_2M(H)(C(Me)=CHMe), Cp*_2M(H)(CH=CHCMe_3), Cp*_2M(H)-(CH=CHPh), Cp*_2M(CH=CHPh)_2, Cp*_2M(CH=CHCH_3)_2 and Cp*_2Zr- (CH=CHCH_2CH_3)_2 have been isolated and characterized. To extend the study of unsaturated-carbon ligands, Cp*_2M(C≡CCH_3)_2 have been prepared by treating Cp*_2MCl_2 with LiC≡CCH_3. The reactivity of many of these complexes with carbon monoxide and dihydrogen is surveyed. The mono(2- butenyl) complexes Cp*_2M(H)(C(Me)=CHMe) rearrange at room temperature, forming the crotyl-hydride species Cp*_2M(H)(ƞ^3-C_4H_7). The bis(propenyl) and bis(l-butenyl) zirconium complexes Cp*_2Zr(CH=CHR)_2 (R = CH_3, CH_2CH_3) also rearrange, forming zirconacyclopentenes. Labeling studies, reaction chemistry, and kinetic measurements, including deuterium isotope effects, demonstrate that the unusual 6-hydrogen elimination from an sp^2-hybridized carbon is the first step in these latter rearrangements but is not observed in the former. Details of these mechanisms and the differences in reactivity of the zirconium and hafnium complexes are discussed.

The reactions of hydride- and alkyl-carbonyl derivatives of permethylniobocene with equimolar amounts of trialkylaluminum reagents occur rapidly producing the carbonyl adducts Cp*_2Nb(R)(COAlR'_3) (R = H, CH_3, CH_2CH_3, CH_2CH_2Ph, C(Me)=CHMe; R' = Me, Et). The hydride adduct Cp*_2NbH_3•AlEt_3 has also been formed. In solution, each of these compounds exists in equilibrium with the uncomplexed species. The formation constants for Cp*_2Nb(H)(COA1R'_R) have been measured. They indicate the steric bulk of the Cp* ligands plays a deciding factor in the isolation of the first example of an aluminum Lewis acid bound to a carbonyl-oxygen in preference to a metalhydride. Reactions of Cp*_2Nb(H)CO with other Lewis acids and of the one:one adducts with H_2, CO and C_2H_4 are also discussed.

Cp*_2Nb(H)(C_2H_4) also reacts with equimolar amounts of trialkylaluminum reagents, forming a one:one complex that ^1H NMR spectroscopy indicates contains a Nb-CH_2CH_2-Al bridge. This adduct also exists in equilibrium with the uncomplexed species in solution. The formation constant for Cp*_2N+/b(H)(CH_2CH_2ĀlEt_3) has been measured. Reactions of Cp*_2Nb(H)(C_2H_4) with other Lewis acids and the reactions of Cp*_2N+b(H)- (CH_2CH_2ĀlEt_3) with CO and C_2H_4 are described, as are the reactions of Cp_*2Nb(H)(CH_2=CHR) (R = Me, Ph), Cp*_2Nb(H)(CH_3C≡CCH_3) and Cp*_2Ti-(C_2H_4) with AlEt_3.

Transition metal clusters supported by multinucleating ligand frameworks as models of biological active sites

This dissertation describes efforts to model biological active sites with small molecule clusters. The approach used took advantage of a multinucleating ligand to control the structure and nuclearity of the product complexes, allowing the study of many different homo- and heterometallic clusters. Chapter 2 describes the synthesis of the multinucleating hexapyridyl trialkoxy ligand used throughout this thesis and the synthesis of trinuclear first row transition metal complexes supported by this framework, with an emphasis on tricopper systems as models of biological multicopper oxidases. The magnetic susceptibility of these complexes were studied, and a linear relation was found between the Cu-O(alkoxide)-Cu angles and the antiferromagnetic coupling between copper centers. The triiron(II) and trizinc(II) complexes of the ligand were also isolated and structurally characterized.

Chapter 3 describes the synthesis of a series of heterometallic tetranuclear manganese dioxido complexes with various incorporated apical redox-inactive metal cations (M = Na⁺, Ca²⁺, Sr²⁺, Zn²⁺, Y³⁺). Chapter 4 presents the synthesis of heterometallic trimanganese(IV) tetraoxido complexes structurally related to the CaMn₃ subsite of the oxygen-evolving complex (OEC) of Photosystem II. The reduction potentials of these complexes were studied, and it was found that each isostructural series displays a linear correlation between the reduction potentials and the Lewis acidities of the incorporated redox-inactive metals. The slopes of the plotted lines for both the dioxido and tetraoxido clusters are the same, suggesting a more general relationship between the electrochemical potentials of heterometallic manganese oxido clusters and their “spectator” cations. Additionally, these studies suggest that Ca²⁺ plays a role in modulating the redox potential of the OEC for water oxidation.

Chapter 5 presents studies of the effects of the redox-inactive metals on the reactivities of the heterometallic manganese complexes discussed in Chapters 3 and 4. Oxygen atom transfer from the clusters to phosphines is studied; although the reactivity is kinetically controlled in the tetraoxido clusters, the dioxido clusters with more Lewis acidic metal ions (Y³⁺ vs. Ca²⁺) appear to be more reactive. Investigations of hydrogen atom transfer and electron transfer rates are also discussed.

Appendix A describes the synthesis, and metallation reactions of a new dinucleating bis(N-heterocyclic carbene)ligand framework. Dicopper(I) and dicobalt(II) complexes of this ligand were prepared and structurally characterized. A dinickel(I) dichloride complex was synthesized, reduced, and found to activate carbon dioxide. Appendix B describes preliminary efforts to desymmetrize the manganese oxido clusters via functionalization of the basal multinucleating ligand used in the preceding sections of this dissertation. Finally, Appendix C presents some partially characterized side products and unexpected structures that were isolated throughout the course of these studies.

Studies of phonon anharmonicity in solids

Today our understanding of the vibrational thermodynamics of materials at low temperatures is emerging nicely, based on the harmonic model in which phonons are independent. At high temperatures, however, this understanding must accommodate how phonons interact with other phonons or with other excitations. We shall see that the phonon-phonon interactions give rise to interesting coupling problems, and essentially modify the equilibrium and non-equilibrium properties of materials, e.g., thermodynamic stability, heat capacity, optical properties and thermal transport of materials. Despite its great importance, to date the anharmonic lattice dynamics is poorly understood and most studies on lattice dynamics still rely on the harmonic or quasiharmonic models. There have been very few studies on the pure phonon anharmonicity and phonon-phonon interactions. The work presented in this thesis is devoted to the development of experimental and computational methods on this subject.

Modern inelastic scattering techniques with neutrons or photons are ideal for sorting out the anharmonic contribution. Analysis of the experimental data can generate vibrational spectra of the materials, i.e., their phonon densities of states or phonon dispersion relations. We obtained high quality data from laser Raman spectrometer, Fourier transform infrared spectrometer and inelastic neutron spectrometer. With accurate phonon spectra data, we obtained the energy shifts and lifetime broadenings of the interacting phonons, and the vibrational entropies of different materials. The understanding of them then relies on the development of the fundamental theories and the computational methods.

We developed an efficient post-processor for analyzing the anharmonic vibrations from the molecular dynamics (MD) calculations. Currently, most first principles methods are not capable of dealing with strong anharmonicity, because the interactions of phonons are ignored at finite temperatures. Our method adopts the Fourier transformed velocity autocorrelation method to handle the big data of time-dependent atomic velocities from MD calculations, and efficiently reconstructs the phonon DOS and phonon dispersion relations. Our calculations can reproduce the phonon frequency shifts and lifetime broadenings very well at various temperatures.

To understand non-harmonic interactions in a microscopic way, we have developed a numerical fitting method to analyze the decay channels of phonon-phonon interactions. Based on the quantum perturbation theory of many-body interactions, this method is used to calculate the three-phonon and four-phonon kinematics subject to the conservation of energy and momentum, taking into account the weight of phonon couplings. We can assess the strengths of phonon-phonon interactions of different channels and anharmonic orders with the calculated two-phonon DOS. This method, with high computational efficiency, is a promising direction to advance our understandings of non-harmonic lattice dynamics and thermal transport properties.

These experimental techniques and theoretical methods have been successfully performed in the study of anharmonic behaviors of metal oxides, including rutile and cuprite stuctures, and will be discussed in detail in Chapters 4 to 6. For example, for rutile titanium dioxide (TiO₂), we found that the anomalous anharmonic behavior of the B_1g mode can be explained by the volume effects on quasiharmonic force constants, and by the explicit cubic and quartic anharmonicity. For rutile tin dioxide (SnO₂), the broadening of the B_2g mode with temperature showed an unusual concave downwards curvature. This curvature was caused by a change with temperature in the number of down-conversion decay channels, originating with the wide band gap in the phonon dispersions. For silver oxide (Ag₂O), strong anharmonic effects were found for both phonons and for the negative thermal expansion.

Luminescence properties of electron-hole-droplets in pure and doped germanium

This work contains 4 topics dealing with the properties of the luminescence from Ge.

The temperature, pump-power and time dependences of the photoluminescence spectra of Li-, As-, Ga-, and Sb-doped Ge crystals were studied. For impurity concentrations less than about 10¹⁵cm^-3, emissions due to electron-hole droplets can clearly be identified. For impurity concentrations on the order of 10¹⁶cm^-3, the broad lines in the spectra, which have previously been attributed to the emission from the electron-hole-droplet, were found to possess pump-power and time dependent line shape. These properties show that these broad lines cannot be due to emission of electron-hole-droplets alone. We interpret these lines to be due to a combination of emissions from (1) electron-hole- droplets, (2) broadened multiexciton complexes, (3) broadened bound-exciton, and (4) plasma of electrons and holes. The properties of the electron-hole-droplet in As-doped Ge were shown to agree with theoretical predictions.

The time dependences of the luminescence intensities of the electron-hole-droplet in pure and doped Ge were investigated at 2 and 4.2°K. The decay of the electron-hole-droplet in pure Ge at 4.2°K was found to be pump-power dependent and too slow to be explained by the widely accepted model due to Pokrovskii and Hensel et al. Detailed study of the decay of the electron-hole-droplets in doped Ge were carried out for the first time, and we find no evidence of evaporation of excitons by electron-hole-droplets at 4.2°K. This doped Ge result is unexplained by the model of Pokrovskii and Hensel et al. It is shown that a model based on a cloud of electron-hole-droplets generated in the crystal and incorporating (1) exciton flow among electron-hole-droplets in the cloud and (2) exciton diffusion away from the cloud is capable of explaining the observed results.

It is shown that impurities, introduced during device fabrication, can lead to the previously reported differences of the spectra of laser-excited high-purity Ge and electrically excited Ge double injection devices. By properly choosing the device geometry so as to minimize this Li contamination, it is shown that the Li concentration in double injection devices may be reduced to less than about 10¹⁵cm^-3 and electrically excited luminescence spectra similar to the photoluminescence spectra of pure Ge may be produced. This proves conclusively that electron-hole-droplets may be created in double injection devices by electrical excitation.

The ratio of the LA- to TO-phonon-assisted luminescence intensities of the electron-hole-droplet is demonstrated to be equal to the high temperature limit of the same ratio of the exciton for Ge. This result gives one confidence to determine similar ratios for the electron-hole-droplet from the corresponding exciton ratio in semiconductors in which the ratio for the electron-hole-droplet cannot be determined (e.g., Si and GaP). Knowing the value of this ratio for the electron-hole-droplet, one can obtain accurate values of many parameters of the electron-hole-droplet in these semiconductors spectroscopically.