The impacts of coastal protection structures in California’s Monterey Bay National Marine Sanctuary

This report outlines the potential impacts of coastal protection structures on the resources of the Monterey Bay National Marine Sanctuary. At least 15 miles of the Sanctuary’s 300-mile shoreline are currently armored with seawalls and riprap revetments. Most of these coastal protection structures are placed above the mean high tide line, the official boundary of the Sanctuary, yet some influences of armoring impinge on the marine realm and on recreational use. In addition, continued sea level rise and accompanying coastal retreat will force many of these structures below the high tide line over time. The Monterey Bay National Marine Sanctuary staff has recognized the significance of coastal armoring, identifying it as a critical issue in the Coastal Armoring Action Plan of the draft Joint Management Plan. This summary is intended to provide general background information for Sanctuary policies on coastal armoring. The impacts discussed include: aesthetic depreciation, beach loss due to placement, access restriction, loss of sand supply from eroding cliffs, passive erosion, and active erosion. In addition, the potential biological impacts are explored. Finally, an appraisal of how differing armor types compare in relation to impacts, expense and engineering is presented. While the literature cited in this report focus predominantly on the California coast, the framework for this discussion could have implications for other actively eroding coastlines. (PDF contains 26 pages.)

A review of marine zones in the Monterey Bay National Marine Sanctuary

This report reviews marine zoning in the Monterey Bay National Marine Sanctuary (MBNMS). The 72 zoned areas in the MBNMS are of 13 different zone types. Each marine zone type has associated regulations that restrict or promote specific activities. For example, recreational activities such as boating, fishing, tidepooling, snorkeling, and SCUBA diving are limited in some zones. Scientific research is allowed at all sites, with appropriate permits, and is specifically promoted in a few sites. In addition, motorized personal watercraft use, dredge material disposal, large vessel traffic, jade collection, and aircraft overflight are allowed only in specific zones. The effectiveness of the marine zoning in the MBNMS is difficult to determine for two reasons. Firstly, many of the zones lack a clearly stated purpose or have confusing regulations. Secondly, the majority of the zones have not been evaluated formally by the managing agencies. Of the zones that have been evaluated, such as Dredge Material Disposal zones, Big Creek MRPA Ecological Reserve, and Pt. Lobos State/Ecological Reserve, the majority appear to be achieving their mandated purpose to some extent. Many of the zones in the MBNMS fall under the title "marine reserve." Marine reserves have recently received significant attention internationally, nationally, and in California due to their potential for: improving the status of exploited species; protecting marine habitats and ecosystems from degradation; facilitating scientific research and fisheries management; and increasing ecotourism. However, reserves must be well designed and managed to reach this potential. A well designed and managed reserve will have clearly defined goals, scientifically-based design, proper enforcement of regulations, rigorous evaluation of the reserve's effectiveness, and adaptive management. Based on these criteria, the majority of the marine reserves in California are not well designed or managed. However, the State of California has recognized this problem and is in the process of re-evaluating the California system of marine managed areas. (PDF contains 137 pages.)

Distribution and sighting frequency of reef fishes in the Florida Keys National Marine Sanctuary

This study analyzed species richness, distribution, and sighting frequency of selected reef fishes to describe species assemblage composition, abundance, and spatial distribution patterns among sites and regions (Upper Keys, Middle Keys, Lower Keys, and Dry Tortugas) within the Florida Keys National Marine Sanctuary (FKNMS) barrier reef ecosystem. Data were obtained from the Reef Environmental Education Foundation (REEF) Fish Survey Project, a volunteer fish-monitoring program. A total of 4,324 visual fish surveys conducted at 112 sites throughout the FKNMS were used in these analyses. The data set contained sighting information on 341 fish species comprising 68 families. Species richness was generally highest in the Upper Keys sites (maximum was 220 species at Molasses Reef) and lowest in the Dry Tortugas sites. Encounter rates differed among regions, with the Dry Tortugas having the highest rate, potentially a result of differences in the evenness in fishes and the lower diversity of habitat types in the Dry Tortugas region. Geographic coverage maps were developed for 29 frequently observed species. Fourteen of these species showed significant regional variation in mean sighting frequency (%SF). Six species had significantly lower mean %SF and eight species had significantly higher mean %SF in the Dry Tortugas compared with other regions. Hierarchical clustering based on species composition (presence-absence) and species % SF revealed interesting patterns of similarities among sites that varied across spatial scales. Results presented here indicate that phenomena affecting reef fish composition in the FKNMS operate at multiple spatial scales, including a biogeographic scale that defines the character of the region as a whole, a reef scale (~50-100 km) that include meso-scale physical oceanographic processes and regional variation in reef structure and associated reef habitats, and a local scale that includes level of protection, cross-shelf location and a suite of physical characteristics of a given reef. It is likely that at both regional and local scales, species habitat requirements strongly influence the patterns revealed in this study, and are particularly limiting for species that are less frequently observed in the Dry Tortugas. The results of this report serve as a benchmark for the current status of the reef fishes in the FKNMS. In addition, these data provide the basis for analyses on reserve effects and the biogeographic coupling of benthic habitats and fish assemblages that are currently underway. (PDF contains 61 pages.)

Stereoselective inverse conjugate addition of nitrogen and carbon nucleophiles to allenyl phosphine oxide. Synthesis of α,β-unsaturated phosphine oxides

Issue in Honor of Prof. Paweł Kafarski

EcoGIS – GIS tools for ecosystem approaches to fisheries management

Executive Summary: The EcoGIS project was launched in September 2004 to investigate how Geographic Information Systems (GIS), marine data, and custom analysis tools can better enable fisheries scientists and managers to adopt Ecosystem Approaches to Fisheries Management (EAFM). EcoGIS is a collaborative effort between NOAA’s National Ocean Service (NOS) and National Marine Fisheries Service (NMFS), and four regional Fishery Management Councils. The project has focused on four priority areas: Fishing Catch and Effort Analysis, Area Characterization, Bycatch Analysis, and Habitat Interactions. Of these four functional areas, the project team first focused on developing a working prototype for catch and effort analysis: the Fishery Mapper Tool. This ArcGIS extension creates time-and-area summarized maps of fishing catch and effort from logbook, observer, or fishery-independent survey data sets. Source data may come from Oracle, Microsoft Access, or other file formats. Feedback from beta-testers of the Fishery Mapper was used to debug the prototype, enhance performance, and add features. This report describes the four priority functional areas, the development of the Fishery Mapper tool, and several themes that emerged through the parallel evolution of the EcoGIS project, the concept and implementation of the broader field of Ecosystem Approaches to Management (EAM), data management practices, and other EAM toolsets. In addition, a set of six succinct recommendations are proposed on page 29. One major conclusion from this work is that there is no single “super-tool” to enable Ecosystem Approaches to Management; as such, tools should be developed for specific purposes with attention given to interoperability and automation. Future work should be coordinated with other GIS development projects in order to provide “value added” and minimize duplication of efforts. In addition to custom tools, the development of cross-cutting Regional Ecosystem Spatial Databases will enable access to quality data to support the analyses required by EAM. GIS tools will be useful in developing Integrated Ecosystem Assessments (IEAs) and providing pre- and post-processing capabilities for spatially-explicit ecosystem models. Continued funding will enable the EcoGIS project to develop GIS tools that are immediately applicable to today’s needs. These tools will enable simplified and efficient data query, the ability to visualize data over time, and ways to synthesize multidimensional data from diverse sources. These capabilities will provide new information for analyzing issues from an ecosystem perspective, which will ultimately result in better understanding of fisheries and better support for decision-making. (PDF file contains 45 pages.)

Hydrazides and hydrazones as versatile Michael-Donors for iminium-catalyzed conjugate addition reactions

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Silver King Creek Paiute cutthroat trout restoration, 1991 through 1993

Silver King Creek, Alpine County, is the native range of the Federally-threatened Paiute cutthroat trout, Oncorhynchus clarki seleniris. Paiute cutthroat currently inhabit Coyote Valley and Corral Valley creeks, which are tributaries to Silver King Creek below Llewellyn Falls, and also Silver King Creek and tributaries aboye Llewellyn Falls. Rainbow trout, O. mykiss, were introduced into the basin during 1949 and became hybridized with Paiute cutthroat. Chemical treatments attempted by the California Department of Fish and Game (CDFG) in 1964 and 1976 failed to eliminate hybrid trout. A chemical treatment project was again conducted by the CDFG from 1991 through 1993 to eliminate hybrid trout from within the range of Paiute cutthroat. This report presents a summary of events for the first two years of the Silver King Paiute Cutthroat Trout Restoration Project; a more thorough analysis is made of the third and final year of the project. (PDF contains 39 pages.)

Chiral gold(I) vs chiral silver complexes as catalysts for the enantioselective synthesis of the second generation GSK-hepatitis C virus inhibitor

The synthesis of a GSK 2(nd) generation inhibitor of the hepatitis C virus, by enantioselective 1,3-dipolar cycloaddition between a leucine derived iminoester and tert-butyl acrylate, was studied. The comparison between silver(I) and gold(I) catalysts in this reaction was established by working with chiral phosphoramidites or with chiral BINAP. The best reaction conditions were used for the total synthesis of the hepatitis C virus inhibitor by a four step procedure affording this product in 99% ee and in 63% overall yield. The origin of the enantioselectivity of the chiral gold(I) catalyst was justified according to DFT calculations, the stabilizing coulombic interaction between the nitrogen atom of the thiazole moiety and one of the gold atoms being crucial.

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.

Femtosecond filamentation and supercontinuum generation in silver-nanoparticle-doped water

The authors report the investigation of filament and supercontinuum generation by focusing a femtosecond laser beam into water doped with silver nanoparticles. The silver nanoparticles enhance the nonlinear optical response of water, leading to broadening of supercontinuum spectra in self-focused femtosecond filaments. During the propagation of the supercontinuum light in the filament, the silver nanoparticles preferentially scatter the short-wavelength light near the plasmon resonant wavelength peak, followed by the scattering of the long-wavelength light. Thus, a side view of the filament shows a full-color spectrum in the visible range, which is herein called "rainbow filament." (c) 2007 American Institute of Physics.

Studies of the representation of interatomic distances in molecules and crystal as sum of atomic radii

The electron diffraction investigation of the following compounds has been carried out: sulfur, sulfur nitride, realgar, arsenic trisulfide, spiropentane, dimethyltrisulfide, cis and trans lewisite, methylal, and ethylene glycol.

The crystal structures of the following salts have been determined by x-ray diffraction: silver molybdateand hydrazinium dichloride.

Suggested revisions of the covalent radii for B, Si, P, Ge, As, Sn, Sb, and Pb have been made, and values for the covalent radii of Al, Ga, In, Ti, and Bi have been proposed.

The Schomaker-Stevenson revision of the additivity rule for single covalent bond distances has been used in conjunction with the revised radii. Agreement with experiment is in general better with the revised radii than with the former radii and additivity.

The principle of ionic bond character in addition to that present in a normal covalent bond has been applied to the observed structures of numerous molecules. It leads to a method of interpretation which is at least as consistent as the theory of multiple bond formation.

The revision of the additivity rule has been extended to double bonds. An encouraging beginning along these lines has been made, but additional experimental data are needed for clarification.