Relevance of the programmes of the federal fisheries schools to Nigeria's fishing industry

Nigeria's three federal fisheries schools are administered by three autonomous research institutes located in Lagos, New Bussa, and Maiduguri. The schools were established at different periods to train the required manpower for Nigeria's fishing industry which has remained predominantly artisanal since its inception in 1942 as a Second World War exigency. Despite the establishment of the schools, the industry's manpower is still being dominated by non-nationals especially in the capture fisheries sub-sector. The common features of the schools include the apparent insensitivity of their programmes to the industry's dynamic manpower needs; the absence of coordination of their programmes by a national body which would have ensured that the schools are able to communicate with one another and are willing to act and share a purpose. The need and the methodology for a change of emphasis from the on-going training of extension agents and officers to that of fishing operatives and technicians to enable Nigeria effectively harness her local fish resources towards self-sufficiency is highlighted.

High-Strength Composite Fibers: Realizing True Potential of Carbon Nanotubes in Polymer Matrix through Continuous Reticulate Architecture and Molecular Level Couplings

Carbon nanotubes have unprecedented mechanical properties as defect-free nanoscale building blocks, but their potential has not been fully realized in composite materials due to weakness at the interfaces. Here we demonstrate that through load-transfer-favored three-dimensional architecture and molecular level couplings with polymer chains, true potential of CNTs can be realized in composites as Initially envisioned. Composite fibers with reticulate nanotube architectures show order of magnitude improvement in strength compared to randomly dispersed short CNT reinforced composites reported before. The molecular level couplings between nanotubes and polymer chains results in drastic differences in the properties of thermoset and thermoplastic composite fibers, which indicate that conventional macroscopic composite theory falls to explain the overall hybrid behavior at nanoscale.

Trace metals -- a potential threat to our fishing industry

Trace metals constitute a major form of water pollutant that can adversely affect fish production. The potentially toxic metals have been identified as lead, zinc, copper, arsenic, antimony, mercury beryllium, barium, cadmium, chromium, nickel, selenium among others. Preliminary laboratory studies have been directed to the determination of traces of lead in the aquatic biota and its toxicity. There are indications that the levels reported in effluents from some of the industries may be above the tolerant limits of local fish species and organisms that make up their food. Metal pollution could become a serious problem to freshwater fisheries in the future as a result of increasing urbanization and industrialization, unless efforts are made to prevent it

Artisanal canoe fishing industry of the Rivers State: its economic viability and investment potentials

Consequent upon the present national call in Nigeria for all to go back to agriculture including fishing, most retrenched workers and unemployed youths from the riverine areas are taking up fishing as a legitimate and gainful livelihood. To sustain this tempo and attract more investment, the economic viability of such projects must be known. This study is an attempt to document the profitability and investment potential of artisanal canoe fishing. Socio-economic information including catches, operational cost and returns were obtained through a personal interview questionnaire survey of 240 randomly selected artisanal canoe fishermen from Bonny, Brass and Degema Local Government Areas (LGA) of the State and analyzed. With an investment cost of about 8,135, 8,490 and 6,571 and operation cost of 750, 776 and 627, the analysis showed an average monthly gross income of 1,869, 3,221 and 1,775 for the three local government areas respectively. A benefit-cost-ratio of 1:8, net present value of 400, 603 and internal rate of return greater than 50% were obtained. Since capital invested in fisheries is not tied up for long before benefits start flowing, coupled with the high IRR, it is concluded that artisanal canoe fishing would be an economically viable venture if well managed

An economic overview of the fish and shrimp production of the Nigeria fish trawling industry under the structural adjustment programme

Over the years, Nigeria have witnessed different government with different policy measures. Against the negative consequences of the past policies, the structural adjustment was initiated in 1986. Its aims is to effectively altar and restructure the consumption patterns of the economy as well as to eliminate price distortions and heavy dependence on the oil and the imports of consumer goods and services. Within the period of implementation, there has been a decreasing trend in yearly fish catch landings and sizes but the reverse in shrimping. There is also a gradual shift from fishing to shrimping, from the vessels purchased with 83.3% increase of shrimpers from 1985 to 1989. Decreasing fish catch sizes and quantity aggravated by the present high cost of fishing coupled with the favourable export market for Nigeria shrimp tend to influence the sift. This economic situation is the result of the supply measures of SAP through the devaluation of the Naira. There is also overconcentration of vessels on the inshore waters as majority of the vessels are old and low powers hence incapable of fishing on the deep sea. Rotterdam price being paid for automotive gas oil (AGO) by fishing industries is observed to be discriminating and unhealthy to the growth of the industry as it is exceedingly high and unstable thus affecting planning for fishing operation. Fuel alone takes 43% of the total cost of operation. The overall consequences is that fishing days are loss and therefore higher overhead cost. It was concluded that for a healthy growth and sustainable resources of our marine fishery under the structural adjustment programme licensing of new fishing vessels should be stopped immediately and the demand side of SAP should be employed by subsidizing high powered fishing vessels which can operate effectively on the deep sea

Aspects of the fishing industry and an overview of artificial reefs and fish aggregating devices for increasing fisheries output and viability in Nigeria

Aspects of the Nigerian fishing industry are outlined to explain the concept of fishing systems viability which is often influenced by a combination of factors including biological productivity, as well as technical, economic and social factors. The productivity of the aquatic environments can be increased by the construction and installation of artificial reefs and fish aggregating devices. These man-made structures provide shelters, food and breeding grounds for fin fish and shell fish. The habitat enhancement techniques are appropriate, efficient, cheap and simple strategic options for increase in fish production. Recommendations for effective utilization and long term management are outlined.

Sequence specific recognition and cleavage of DNA by synthetic molecules

DNA recognition is an essential biological process responsible for the regulation of cellular functions including protein synthesis and cell division and is implicated in the mechanism of action of some anticancer drugs. Studies directed towards defining the elements responsible for sequence specific DNA recognition through the study of the interactions of synthetic organic ligands with DNA are described.

DNA recognition by poly-N-methylpyrrolecarboxamides was studied by the synthesis and characterization of a series of molecules where the number of contiguous N-methylpyrrolecarboxamide units was increased from 2 to 9. The effect of this incremental change in structure on DNA recognition has been investigated at base pair resolution using affinity cleaving and MPE•Fe(II) footprinting techniques. These studies led to a quantitative relationship between the number of amides in the molecule and the DNA binding site size. This relationship is called the n + 1 rule and it states that a poly-N methylpyrrolecarboxamide molecule with n amides will bind n + 1 base pairs of DNA. This rule is consistent with a model where the carboxamides of these compounds form three center bridging hydrogen bonds between adjacent base pairs on opposite strands of the helix. The poly-N methylpyrrolecarboxamide recognition element was found to preferentially bind poly dA•poly dT stretches; however, both binding site selection and orientation were found to be affected by flanking sequences. Cleavage of large DNA is also described.

One approach towards the design of molecules that bind large sequences of double helical DNA sequence specifically is to couple DNA binding subunits of similar or diverse base pair specificity. Bis-EDTA-distamycin-fumaramide (BEDF) is an octaamide dimer of two tri-N methylpyrrolecarboxamide subunits linked by fumaramide. DNA recognition by BEDF was compared to P7E, an octaamide molecule containing seven consecutive pyrroles. These two compounds were found to recognize the same sites on pBR322 with approximately the same affinities demonstrating that fumaramide is an effective linking element for Nmethylpyrrolecarboxamide recognition subunits. Further studies involved the synthesis and characterization of a trimer of tetra-N-methylpyrrolecarboxamide subunits linked by β-alanine ((P4)_(3)E). This trimerization produced a molecule which is capable of recognizing 16 base pairs of A•T DNA, more than a turn and a half of the DNA helix.

DNA footprinting is a powerful direct method for determining the binding sites of proteins and small molecules on heterogeneous DNA. It was found that attachment of EDTA•Fe(II) to spermine creates a molecule, SE•Fe(II), which binds and cleaves DNA sequence neutrally. This lack of specificity provides evidence that at the nucleotide level polyamines recognize heterogeneous DNA independent of sequence and allows SE•Fe(II) to be used as a footprinting reagent. SE•Fe(II) was compared with two other small molecule footprinting reagents, EDTA•Fe(II) and MPE•Fe(II).

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.

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.

A Convergent Synthetic Route to the Tunicamycin Antiobiotics. Synthesis of (+)-Tunicamycin V

A concise synthetic route to the tunicamycin antibiotics is described, illustrated by the preparation of (+)-tunicamycin-V (1-V). Key features of the synthesis include: (1) the development and application of a silicon-mediated reductive coupling of aldehydes and allylic alcohols to construct the undecose core of the natural product; and (2) the development of an efficient procedure for the synthesis of the trehalose glycosidic bond within the antibiotic. These innovations allow for the coupling of a uridine-derived aldehyde fragment with a preformed trehalose-linked disaccharide allylic alcohol to form the carbohydrate core (1) of the natural product in a highly convergent manner. The resultant amino polyol is a versatile intermediate for the synthesis of any of the homologous tunicamycin antibiotics.

Synthetic molecular machines for active self-assembly : prototype algorithms, designs, and experimental study

Computer science and electrical engineering have been the great success story of the twentieth century. The neat modularity and mapping of a language onto circuits has led to robots on Mars, desktop computers and smartphones. But these devices are not yet able to do some of the things that life takes for granted: repair a scratch, reproduce, regenerate, or grow exponentially fast–all while remaining functional.

This thesis explores and develops algorithms, molecular implementations, and theoretical proofs in the context of “active self-assembly” of molecular systems. The long-term vision of active self-assembly is the theoretical and physical implementation of materials that are composed of reconfigurable units with the programmability and adaptability of biology’s numerous molecular machines. En route to this goal, we must first find a way to overcome the memory limitations of molecular systems, and to discover the limits of complexity that can be achieved with individual molecules.

One of the main thrusts in molecular programming is to use computer science as a tool for figuring out what can be achieved. While molecular systems that are Turing-complete have been demonstrated [Winfree, 1996], these systems still cannot achieve some of the feats biology has achieved.

One might think that because a system is Turing-complete, capable of computing “anything,” that it can do any arbitrary task. But while it can simulate any digital computational problem, there are many behaviors that are not “computations” in a classical sense, and cannot be directly implemented. Examples include exponential growth and molecular motion relative to a surface.

Passive self-assembly systems cannot implement these behaviors because (a) molecular motion relative to a surface requires a source of fuel that is external to the system, and (b) passive systems are too slow to assemble exponentially-fast-growing structures. We call these behaviors “energetically incomplete” programmable behaviors. This class of behaviors includes any behavior where a passive physical system simply does not have enough physical energy to perform the specified tasks in the requisite amount of time.

As we will demonstrate and prove, a sufficiently expressive implementation of an “active” molecular self-assembly approach can achieve these behaviors. Using an external source of fuel solves part of the the problem, so the system is not “energetically incomplete.” But the programmable system also needs to have sufficient expressive power to achieve the specified behaviors. Perhaps surprisingly, some of these systems do not even require Turing completeness to be sufficiently expressive.

Building on a large variety of work by other scientists in the fields of DNA nanotechnology, chemistry and reconfigurable robotics, this thesis introduces several research contributions in the context of active self-assembly.

We show that simple primitives such as insertion and deletion are able to generate complex and interesting results such as the growth of a linear polymer in logarithmic time and the ability of a linear polymer to treadmill. To this end we developed a formal model for active-self assembly that is directly implementable with DNA molecules. We show that this model is computationally equivalent to a machine capable of producing strings that are stronger than regular languages and, at most, as strong as context-free grammars. This is a great advance in the theory of active self- assembly as prior models were either entirely theoretical or only implementable in the context of macro-scale robotics.

We developed a chain reaction method for the autonomous exponential growth of a linear DNA polymer. Our method is based on the insertion of molecules into the assembly, which generates two new insertion sites for every initial one employed. The building of a line in logarithmic time is a first step toward building a shape in logarithmic time. We demonstrate the first construction of a synthetic linear polymer that grows exponentially fast via insertion. We show that monomer molecules are converted into the polymer in logarithmic time via spectrofluorimetry and gel electrophoresis experiments. We also demonstrate the division of these polymers via the addition of a single DNA complex that competes with the insertion mechanism. This shows the growth of a population of polymers in logarithmic time. We characterize the DNA insertion mechanism that we utilize in Chapter 4. We experimentally demonstrate that we can control the kinetics of this re- action over at least seven orders of magnitude, by programming the sequences of DNA that initiate the reaction.

In addition, we review co-authored work on programming molecular robots using prescriptive landscapes of DNA origami; this was the first microscopic demonstration of programming a molec- ular robot to walk on a 2-dimensional surface. We developed a snapshot method for imaging these random walking molecular robots and a CAPTCHA-like analysis method for difficult-to-interpret imaging data.

Nonlinear copropagation of two optical pulses of different frequencies in photonic crystal fibers

A theoretical investigation of the nonlinear copropagation of two optical pulses of different frequencies in a photonic crystal fiber is presented. Different phenomena are observed depending on whether the wavelength of the signal pulse is located in the normal or the anomalous dispersion region. In particular, it is found that the phenomenon of pulse trapping occurs when the signal wavelength is located in the normal dispersion region while the pump wavelength is located in the anomalous dispersion region. The signal pulse suffers cross-phase modulation by the Raman shifted soliton pulse and it is trapped and copropagates with the Raman soliton pulse along the fiber. As the input peak power of the pump pulse is increased, the red-shift of the Raman soliton is considerably enhanced with the simultaneous further blue-shift of the trapped pulse to satisfy the condition of group velocity matching.