Geographical distribution of yellowfin and skipjack tuna catches in the Eastern Pacific Ocean, and fleet and total catch statistics, 1975-1978

ENGLISH: Logbook records of purse seiners and baitboats fishing for yellowfin and skipjack tunas in the eastern Pacific Ocean were used to prepare charts showing the distribution of catches by one-degree area and quarter of the year for each gear and regulation status, for the years 1975-1978. Changes in geographical distribution of the catch over the four-year period are described. Information on annual catch statistics and fleet composition by country is presented. SPANISH: Se emplearon los registros de bitácora de las embarcaciones cerqueras y de carnada que pescan atún aleta amarilla y barrilete en el Océano Pacífico oriental, para preparar los diagramas que indican la distribución de captura por zonas de un grado y trimestres del año de cada arte y condición de las reglamentaciones, en los años de 19'75 a 1978. Se describen los cambios de la distribución geográfica de la captura durante un período de cuatro Se presenta la información, por país, de las estadísticas de captura y de la composición de la flota. (PDF contains 120 pages.)

Experimental Demonstration Of A New Concept Of Drag Reduction And Thermal Protection For Hypersonic Vehicles

A new idea of drag reduction and thermal protection for hypersonic vehicles is proposed based on the combination of a physical spike and lateral jets for shock-reconstruction. The spike recasts the bow shock in front of a blunt body into a conical shock, and the lateral jets work to protect the spike tip from overheating and to push the conical shock away from the blunt body when a pitching angle exists during flight. Experiments are conducted in a hypersonic wind tunnel at a nominal Mach number of 6. It is demonstrated that the shock/shock interaction on the blunt body is avoided due to injection and the peak pressure at the reattachment point is reduced by 70% under a 4A degrees attack angle.

Panama City Fisheries Resources Office: FY 2005 Annual Report

HIGHLIGHTS FOR FY 2005 1. Assisted with a study to assess hurricane impacts to Gulf sturgeon critical foraging habitat. 2. Documented Gulf sturgeon marine movement and habitat use in the Gulf of Mexico. 3. Documented Gulf sturgeon spawning with the collection of fertilized eggs in the Apalachicola River, Florida. 4. Documented Gulf sturgeon spawning with the collection of fertilized eggs in the Yellow River, Florida. 5. Assisted with benthic invertebrate survey at Gulf sturgeon marine foraging grounds. 6. Implemented Gulf Striped Bass Restoration Plan by coordinating the 22nd Annual Morone Workshop, leading the technical committee, transporting broodfish, and coordinating the stocking on the Apalachicola-Chattahoochee-Flint (ACF) river system. 7. Over 87,000 Phase II Gulf striped bass were marked with sequential coded wire tags and stocked in the Apalachicola River. Post-stocking evaluations were conducted at 45 sites in the fall and spring and 8 thermal refuges in the summer. 8. Completed fishery surveys on 4 ponds on Eglin AFB totaling 53 acres, and completed a report with recommendations for future recreational fishery needs. 9. Completed final report for aquatic monitoring at Eglin AFB from 1999 to 2004. 10. Completed a field collection of the endangered Okaloosa darter to be incorporated into a status review to be completed in FY06. 11. Provided technical assistance to the Region 4 National Wildlife Refuge (NWR) program on changes to the fishery conservation targets for the region. Also provided technical assistance to four NWRs (i.e., Okefenokee NWR, Banks Lake NWR, St. Vincent NWR, and St. Marks NWR) relative to hurricanes and recreational fishing. 12. A draft mussel sampling protocol was tested in wadeable streams in Northwest Florida and southwest Georgia, and an associated field guide, poster, and Freshwater Mussel Survey Protocol and Identification workshop were completed in FY05. 13. Implemented recovery plan and candidate conservation actions for 14 listed and candidate freshwater mussels in the Northeast Gulf Watersheds. 14. Initiated or completed multiple stream restoration and watershed management projects. A total of 7.5 stream miles were restored for stream fishes, and 11 miles of coastline were enhanced for sea turtle lighting. A total of 630 acres of wetlands and 2,401 acres of understory habitat were restored. 15. Conducted a watershed assessment to develop a threats analysis for prioritizing restoration, protection, and enhancement to natural resources of Spring Creek, Georgia and Canoe Creek, Florida. 16. Continued the formation of an Unpaved Road Interagency Team of Federal, State, and local agencies in Northwest Florida to promote stream protection and restoration from unpaved road sediment runoff. Began the development of a technical committee agreement. 17. Conducted Alabama Unpaved Road Inventory within the Northeast Gulf Ecosystem. Data collection will be completed during FY06. 18. Finalized the development of two North Florida hydrophysiographic regional curves for use by the Florida Department of Transportation (DOT) and others involved with stream restoration and protection. Initiated the development of the Alabama Coastal Plain Riparian Reference Reach and Regional Curves for use by the Alabama Department of Environmental Management (ADEM). 19. Provided technical assistance in collecting data, analysis, and thesis formulation with Troy University, Alabama, to identify the influence of large woody debris in southeastern coastal plain streams. 20. Completed pre- and post-restoration fish community monitoring at several restoration projects including Big Escambia Creek, Magnolia Creek, and Oyster Lake, Florida. 21. Established a watershed partnership for the Chipola River in Alabama and Florida and expanded development and participation in the Spring Creek Watershed Partnership, Georgia. 22. Continued to identify barriers which inhibit the movement of aquatic species within the Northeast Gulf Ecoregion. 23. Completed a report on road crossing structures in Okaloosa darter streams to guide the closure/repair/maintenance of roads to contribute to recovery of the endangered species. In cooperation with Three Rivers RC&D Council, fish passage sites identified in the report were prioritized for restoration. 24. Monitored Aquatic Nuisance Species in the Apalachicola River and tested the sterility of exotic grass carp. 25. Multiple outreach projects were completed to detail aquatic resources conservation needs and opportunities. Participated in National Fishing Week event, several festivals, and school outreach.

Panama City Fisheries Resources Office: FY 2003 Annual Report

HIGHLIGHTS FOR FY 2003 1. Continued a 3-year threatened Gulf sturgeon population estimate in the Escambia River, Florida and conducted presence-absence surveys in 4 other Florida river systems and 1 bay. 2. Five juvenile Gulf sturgeon collected, near the mouth of the Choctawhatchee River, Florida, were equipped with sonic tags and monitored while over-wintering in Choctawhatchee Bay. 3. Continued to examine Gulf sturgeon marine habitat use. 4. Implemented Gulf Striped Bass Restoration Plan by coordinating the 20th Annual Morone Workshop, leading the technical committee, transporting broodfish, and coordinating the stocking on the Apalachicola-Chattahoochee-Flint (ACF) river system. 5. Over 73,000 Phase II Gulf striped bass were marked with sequential coded wire tags and stocked in the Apalachicola River. Post-stocking evaluations were conducted at 31 sites. 6. Three stream fisheries assessment s were completed to evaluate the fish community at sites slated for habitat restoration by the Partners for Fish and Wildlife Program (PFW). 7. PFW program identified restoration needs and opportunities for 10 areas. 8. Developed an Unpaved Road Evaluation Handbook. 9. Completed restoration of Chipola River Greenway, Seibenhener Streambank Restoration, Blackwater River State Forest, and Anderson Property. 10. Assessments for fluvial geomorphic conditions for design criteria were completed for 3 projects. 11. Geomorphology in Florida streams initiated development of Rosgen regional curves for Northwest Florida for use by the Florida Department of Transportation. 12. Developed a Memorandum of Understanding between partners for enhancing, protecting, and restoring stream, wetland, and upland habitat in northwest Florida 13. Completed aquatic fauna and fish surveys with new emphasis on integration of data from reach level into watershed and landscape scale and keeping database current. 14. Compliance based sampling of impaired waterbodies on Eglin Air Force Base in conjunction with Florida Department of Environmental Protection for Total Maximum Daily Load development support. 15. Surveyed 20 sites for the federally endangered Okaloosa darter, provided habitat descriptions, worked with partners to implement key recovery tasks and set priorities for restoration. 16. Worked with partners to develop a freshwater mussel survey protocol to provide standard operating procedures for establishing the presence/absence of federally listed mussel species within a Federal project area. 17. GIS database was created to identify all known freshwater mussel records from the northeast Gulf ecosystem. 18. Completed recovery plan for seven freshwater mussels and drafted candidate elevation package for seven additional mussels. Developed proposals to implement recovery plan. 19. Worked with Corps of Engineers and State partners to develop improved reservoir operating policies to benefit both riverine and reservoir fisheries for the ACF river system. 20. Multiple outreach projects were completed to detail aquatic resources conservation opportunities. 21. Multiple stream restoration and watershed management projects initiated or completed (see Appendix A).

A small arc-heated plasma testing facility for thermal protection materials

Experimental research on a 150 kW arc-heated plasma testing facility was conducted. Stable plasma jets with different gas compositions, temperatures and velocities were obtained at chamber pressure between 400 Pa – 100 kPa. Stagnation ablation experiments were conducted on samples of typical super alloys used for thermal protection systems. The microstructure and hardness of alloys before and after ablation were compared.

Developing effective restoration plans to tackle the widespread impairment of coastal swimming and shellfishing waters

Congress established a legal imperative to restore the quality of our surface waters when it enacted the Clean Water Act in 1972. The act requires that existing uses of coastal waters such as swimming and shellfishing be protected and restored. Enforcement of this mandate is frequently measured in terms of the ability to swim and harvest shellfish in tidal creeks, rivers, sounds, bays, and ocean beaches. Public-health agencies carry out comprehensive water-quality sampling programs to check for bacteria contamination in coastal areas where swimming and shellfishing occur. Advisories that restrict swimming and shellfishing are issued when sampling indicates that bacteria concentrations exceed federal health standards. These actions place these coastal waters on the U.S. Environmental Protection Agencies’ (EPA) list of impaired waters, an action that triggers a federal mandate to prepare a Total Maximum Daily Load (TMDL) analysis that should result in management plans that will restore degraded waters to their designated uses. When coastal waters become polluted, most people think that improper sewage treatment is to blame. Water-quality studies conducted over the past several decades have shown that improper sewage treatment is a relatively minor source of this impairment. In states like North Carolina, it is estimated that about 80 percent of the pollution flowing into coastal waters is carried there by contaminated surface runoff. Studies show this runoff is the result of significant hydrologic modifications of the natural coastal landscape. There was virtually no surface runoff occurring when the coastal landscape was natural in places such as North Carolina. Most rainfall soaked into the ground, evaporated, or was used by vegetation. Surface runoff is largely an artificial condition that is created when land uses harden and drain the landscape surfaces. Roofs, parking lots, roads, fields, and even yards all result in dramatic changes in the natural hydrology of these coastal lands, and generate huge amounts of runoff that flow over the land’s surface into nearby waterways. (PDF contains 3 pages)

The island of Kauai, Hawaii's progressive shoreline setback and coastal protection ordinance

Approximately two-thirds of coastal and Great Lakes states have some type of shoreline construction setback or construction control line requiring development to be a certain distance from the shoreline or other coastal feature (OCRM, 2008). Nineteen of 30 coastal states currently use erosion rates for new construction close to the shoreline. Seven states established setback distances based on expected years from the shoreline: the remainder specify a fixed setback distance (Heinz Report, 2000). Following public hearings by the County of Kauai Planning Commission and Kauai County Council, the ‘Shoreline Setback and Coastal Protection Ordinance’ was signed by the Mayor of Kauai on January 25, 2008. After a year of experience implementing this progressive, balanced shoreline setback ordinance several amendments were recently incorporated into the Ordinance (#887; Bill #2319 Draft 3). The Kauai Planning Department is presently drafting several more amendments to improve the effectiveness of the Ordinance. The intent of shoreline setbacks is to establish a buffer zone to protect shorefront development from loss due to coastal erosion - for a period of time; to provide protection from storm waves; to allow the natural dynamic cycles of erosion and accretion of beaches and dunes to occur; to maintain beach and dune habitat; and, to maintain lateral beach access and open space for the enjoyment of the natural shoreline environment. In addition, a primary goal of the Kauai setback ordinance is to avoid armoring or hardening of the shore which along eroding coasts has been documented to ultimately eliminate the fronting beach. (PDF contains 4 pages)

The intramolecular Buchner reaction of α-diazo-β-ketonitriles : development and application to the total synthesis of (+)-Salvileucalin B

Since its discovery in 1896, the Buchner reaction has fascinated chemists for more than a century. The highly reactive nature of the carbene intermediates allows for facile dearomatization of stable aromatic rings, and provides access to a diverse array of cyclopropane and seven-membered ring architectures. The power inherent in this transformation has been exploited in the context of a natural product total synthesis and methodology studies.

The total synthesis work details efforts employed in the enantioselective total synthesis of (+)-salvileucalin B. The fully-substituted cyclopropane within the core of the molecule arises from an unprecedented intramolecular Buchner reaction involving a highly functionalized arene and an α-diazo-β-ketonitrile. An unusual retro-Claisen rearrangement of a complex late-stage intermediate was discovered on route to the natural product.

The unique reactivity of α-diazo-β-ketonitriles toward arene cyclopropanation was then investigated in a broader methodological study. This specific di-substituted diazo moiety possesses hitherto unreported selectivity in intramolecular Buchner reactions. This technology was enables the preparation of highly functionalized norcaradienes and cyclopropanes, which themselves undergo various ring opening transformations to afford complex polycyclic structures.

Finally, an enantioselective variant of the intramolecular Buchner reaction is described. Various chiral copper and dirhodium catalysts afforded moderate stereoinduction in the cyclization event.

Palladium-catalyzed asymmetric allylic alkylation: insights, application toward cyclopentanoid and cycloheptanoid molecules, and the total synthesis of several daucane sesquiterpenes

The asymmetric construction of quaternary stereocenters is a topic of great interest in the organic chemistry community given their prevalence in natural products and biologically active molecules. Over the last decade, the Stoltz group has pursued the synthesis of this challenging motif via a palladium-catalyzed allylic alkylation using chiral phosphinooxazoline (PHOX) ligands. Recent results indicate that the alkylation of lactams and imides consistently proceeds with enantioselectivities substantially higher than any other substrate class previously examined in this system. This observation prompted exploration of the characteristics that distinguish these molecules as superior alkylation substrates, resulting in newfound insights and marked improvements in the allylic alkylation of carbocyclic compounds.

General routes to cyclopentanoid and cycloheptanoid core structures have been developed that incorporate the palladium-catalyzed allylic alkylation as a key transformation. The unique reactivity of α-quaternary vinylogous esters upon addition of hydride or organometallic reagents enables divergent access to γ-quaternary acylcyclopentenes or cycloheptenones through respective ring contraction or carbonyl transposition pathways. Derivatization of the resulting molecules provides a series of mono-, bi-, and tricyclic systems that can serve as valuable intermediates for the total synthesis of complex natural products.

The allylic alkylation and ring contraction methodology has been employed to prepare variably functionalized bicyclo[5.3.0]decane molecules and enables the enantioselective total syntheses of daucene, daucenal, epoxydaucenal B, and 14-p-anisoyloxydauc-4,8-diene. This route overcomes the challenge of accessing β-substituted acylcyclopentenes by employing a siloxyenone to effect the Grignard addition and ring opening in a single step. Subsequent ring-closing metathesis and aldol reactions form the hydroazulene core of these targets. Derivatization of a key enone intermediate allows access to either the daucane sesquiterpene or sphenobolane diterpene carbon skeletons, as well as other oxygenated scaffolds.

Progress towards the total synthesis of a spermine-conjugated dynemicin analog

Progress towards the synthesis of the spermine-conjugated Dynemicin analog 4 is described. The synthetic route starts with the Michael addition of menthyl acetoacetate to trans-ethyl crotonate followed by a Dieckman condensation to form the cyclohexanedione 14 which, through a series of chemical reactions, is transformed into the quinone imine 6. Key features in the route include the Suzuki coupling reaction of the aryl boronic acid 11 and the enol triflate 12, thermal deprotection/internal amidation of the biaryl 19, cis addition of the (Z)-enediyne 33 to the quinoline 25, intramolecular acetylide addition to a carbonyl within the ketone 29, and an addition/elimination of the cyanophthalide to the quinone imine 6 to form the anthraquinone 36 utilizing the Kraus and Sugimoto methodology.

New strategies for the total synthesis of aza-propellane natural products

The propellane alkaloids comprise a large class of natural products that possess varying degrees of structural complexity and biological activity. The earliest of these to be isolated was acutumine, a chlorinated alkaloid that has been shown to exhibit selective T-cell cytotoxicity and antiamnesic properties. Alternatively, the hasubanan family of natural products has garnered considerable attention from the synthetic community in part due to its structural similarities to morphine. While these alkaloids have been the subject of numerous synthetic studies over the last forty years, very few enantioselective total syntheses have been reported to date.

As part of a research program directed towards the synthesis of various alkaloid natural products, we have developed a unified strategy for the preparation of the hasubanan and acutumine alkaloids. Specifically, a highly diastereoselective 1,2-addition of organometallic reagents to benzoquinone-derived tert-butanesulfinimines was established, which provides access to enantioenriched 4-aminocyclohexadienone products. This methodology enabled the enantioselective construction of functionalized dihydroindolones, which were found to undergo intramolecular Friedel-Crafts conjugate additions to furnish the propellane cores of several hasubanan alkaloids. As a result of these studies, the first enantioselective total syntheses of 8-demethoxyrunanine and cepharatines A, C, and D were accomplished in 9-11 steps from commercially available starting materials.

More recent efforts have focused on applying the sulfinimine methodology to the synthesis of a more structurally complex propellane alkaloid, acutumine. Extensive studies have determined that a properly functionalized dihydroindolone undergoes a photochemical [2+2] cycloaddition followed by a lactone fragmentation/Dieckmann cyclization to establish the carbocyclic framework of the natural product. The preparation of more appropriately oxidized propellane intermediates is currently under investigation, and is anticipated to facilitate our synthetic endeavors toward acutumine.

Linking Reduced Deforestation and a Global Carbon Market: Impacts on Costs, Financial Flows, and Technological Innovation

25 p.

A unified strategy to ent-kauranoid natural products : total syntheses of (–)-maoecrystal Z, (–)-trichorabdal A, and (–)-longikaurin E

The diterpenoid constituents of the Isodon plants have attracted reasearchers interested in both their chemical structures and biological properties for more than a half-century. In recent years, the isolations of new members displaying previously unprecedented ring systems and highly selective biological properties have piqued interest from the synthetic community in this class of natural products.

Reported herein is the first total synthesis of such a recently isolated diterpenoid, (–)-maoecrystal Z. The principal transformations implemented in this synthesis include two highly diastereoselective radical cyclization reactions: a Sm^(II)-mediated reductive cascade cyclization, which forms two rings and establishes four new stereocenters in a single step, and a Ti^(III)-mediated reductive epoxide-acrylate coupling that yields a functionalized spirolactone product, which forms a core bicycle of maoecrystal Z.

The preparation of two additional ent-kauranoid natural products, (–)-trichorabdal A and (–)-longikaurin E, is also described from a derivative of this key spirolactone. These syntheses are additionally enabled by the palladium-mediated oxidative cyclization reaction of a silyl ketene acetal precursor that is used to install the bridgehead all-carbon quaternary stereocenter and bicyclo[3.2.1]octane present in each natural product. These studies have established a synthetic relationship among three architecturally distinct ent-kaurane diterpenoids and have forged a path for the preparation of interesting unnatural ent-kauranoid structural analogs for more thorough biological study.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

Studies toward the total synthesis of ritterazine B : the investigation of alkynylation reactions for use in the synthesis of the western fragment

The ritterazine and cephalostatin natural products have biological activities and structures that are interesting to synthetic organic chemists. These products have been found to exhibit significant cytotoxicity against P388 murine leukemia cells, and therefore have the potential to be used as anticancer drugs. The ritterazines and cephalostatins are steroidal dimers joined by a central pyrazine ring. Given that the steroid halves are unsymmetrical and highly oxygenated, there are several challenges in synthesizing these compounds in an organic laboratory.

Ritterazine B is the most potent derivative in the ritterazine family. Its biological activity is comparable to drugs that are being used to treat cancer today. For this reason, and the fact that there are no reported syntheses of ritterazine B to date, our lab set out to synthesize this natural product.

Herein, efforts toward the synthesis of the western fragment of ritterazine B are described. Two different routes are explored to access a common intermediate. An alkyne conjugate addition reaction was initially investigated due to the success of this key reaction in the synthesis of the eastern fragment. However, it has been found that a propargylation reaction has greater reactivity and yields, and has the potential to reduce the step count of the synthesis of the western fragment of ritterazine B.