Ferrocene-Conjugated L-Tryptophan Copper(II) Complexes of Phenanthroline Bases Showing DNA Photocleavage Activity and Cytotoxicity

Ferrocene-conjugated L-tryptophan (L-Trp) reduced Schiff base (Fc-TrpH) copper(II) complexes [Cu(Fc-Trp)(L)](ClO(4)) of phenanthroline bases (L), viz. 2,2'-bipyridine (bpy in 1), 1,10-phenanthroline (phen in 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 3), and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 4), were prepared and characterized and their photocytotoxicity studied. Cationic reduced Schiff base (Ph-TrpH) complexes [Cu(Ph-Trp)(L)(H(2)O)] (ClO(4)) (L = phen in 5; dppz in 6) having the ferrocenyl moiety replaced by a phenyl group and the Zn(II) analogue (7) of complex 4 were prepared and used as control species. The crystal structures of 1 and 5 with respective square-planar CuN(3)O and square-pyramidal CuN(3)O(2) coordination geometry show significantly different core structures. Complexes 1-4 exhibit a Cu(II)-Cu(I) redox couple near -0.1 V and the Fc(+)-Fc couple at similar to 0.5 V vs SCE in DMF-0.1 M [Bu(4)(n)N] (ClO(4)) (Fc = ferrocenyl moiety). The complexes display a copper(II)-based d-d band near 600 nm and a Fc-centered band at similar to 450 nm in DMF-Tris-HCl buffer. The complexes are efficient binders to calf thymus DNA. They are synthetic chemical nucleases in the presence of thiol or H(2)O(2), forming hydroxyl radicals. The photoactive complexes are cleavers of pUC19 DNA in visible light, forming hydroxyl radicals. Complexes 2-6 show photocytotoxicity in HeLa cancer cells, giving IC(50) values of 4.7, 10.2, 1.3, 4.8, and 4.3 mu M, respectively, in visible light with the appearance of apoptotic bodies. The complexes also show photocytotoxicity in MCF-7 cancer cells. Nuclear chromatin cleavage has been observed with acridine orange/ethidium bromide (AO/EB) dual staining with complex 4 in visible light. The complexes induce caspase-independent apoptosis in the HeLa cells.

Synthesis, characterization and phosphotriesterase mimetic activity of some Zn(II) and Cu(II) complexes

We report here the synthesis and characterization of a few phenolate-based ligands bearing tert- amino substituent and their Zn(II) and Cu(II) metal complexes. Three mono/binuclear Zn(II) and Cu(II) complexes Zn(L1)(H2O)].CH3OH.H2O (1) (H (2) L1 = 6,6(')-(((2-dimethylamino)ethylazanediyl)bis(methylene))bis(2, 4-dimethylphenol), Zn-2(L2)(2)] (2) (H (2) L2 = 2,2(')-(((2-dimethylamino)ethyl)azanediyl)bis(methylene)bis(4- methylphenol) and Cu-2(L3)(2).CH2 Cl-2] (3) (H (2) L3 = (6,6(')-(((2-(diethylamino)ethyl)azanediyl)bis(methylene)) bis(methylene))bis(2,4-dimethylphenol) were synthesized by using three symmetrical tetradendate ligands containing N2O2 donor sites. These complexes are characterized by a variety of techniques including; elemental analysis, mass spectrometry, H-1, C-13 NMR spectroscopic and single crystal X-ray analysis. The new complexes have been tested for the phosphotriesterase (PTE) activity with the help of P-31 NMR spectroscopy. The P-31 NMR studies show that mononuclear complex Zn(L1)(H2O)].CH3OH.H2O (1) can hydrolyse the phosphotriester i.e., p-nitrophenyl diphenylphosphate (PNPDPP), more efficiently than the binuclear complexes Zn-2(L2)(2)] (2) and Cu-2(L3)(2).CH2Cl2] (3). The mononuclear Zn(II) complex (1) having one coordinated water molecule exhibits significant PTE activity which may be due to the generation of a Zn(II)-bound hydroxide ion during the hydrolysis reactions in CHES buffer at pH 9.0.

Palladium(II) complexes as biologically potent metallo-drugs: Synthesis, spectral characterization, DNA interaction studies and antibacterial activity

Four novel mononuclear Pd(II) complexes have been synthesized with the biologically active Schiff base ligands (L-1-L-4) derived from 3-amino-2-methyl-4(3H)-quinazolinone. The structure of the complexes has been proposed by elemental analysis, molar conductance, IR, H-1 NMR, mass, UV-Vis spectrometric and thermal studies. The investigation of interaction of the complexes with calf thymus DNA (CT-DNA) has been performed with absorption and fluorescence spectroscopic studies. The nuclease activity was done using pUC19 supercoiled DNA by gel-electrophoresis. All the ligands and their Pd(II) complexes have also been screened for their antibacterial activity by discolor diffusion technique. (C) 2013 Elsevier B.V. All rights reserved.

Assessing severe Drought and wet events over India in a future climate using a nested bias-correction approach

General circulation models (GCMs) are routinely used to simulate future climatic conditions. However, rainfall outputs from GCMs are highly uncertain in preserving temporal correlations, frequencies, and intensity distributions, which limits their direct application for downscaling and hydrological modeling studies. To address these limitations, raw outputs of GCMs or regional climate models are often bias corrected using past observations. In this paper, a methodology is presented for using a nested bias-correction approach to predict the frequencies and occurrences of severe droughts and wet conditions across India for a 48-year period (2050-2099) centered at 2075. Specifically, monthly time series of rainfall from 17 GCMs are used to draw conclusions for extreme events. An increasing trend in the frequencies of droughts and wet events is observed. The northern part of India and coastal regions show maximum increase in the frequency of wet events. Drought events are expected to increase in the west central, peninsular, and central northeast regions of India. (C) 2013 American Society of Civil Engineers.

Modeling and analysis of MOS capacitor controlled by independent double gates

This paper, for the first time, explores the charcatersictics of MOS capacitor controlled by independent double gates by numerical simulation and analytical modeling for its possible use in RF circuit design as a varactor. By numerical simulation it is shown how the quasi-static and non-quasi-static characteristics of the first gate capacitance could be tuned by the second gate biases. Effect of body doping and energy quantization are also discussed in this regard. A semi-empirical quasi-static model is also developed by using the existing incomplete Poisson solution of independent double gate transistors. Proposed model, which is valid from accumulation to inversion, is shown to have excellent agreement with numerical simulation for practical bias conditions.

Effect of Rock Mass Structure and Block Size on the Slope Stability-Physical Modeling and Discrete Element Simulation

This paper studies the stability of jointed rock slopes by using our improved three-dimensional discrete element methods (DEM) and physical modeling. Results show that the DEM can simulate all failure modes of rock slopes with different joint configurations. The stress in each rock block is not homogeneous and blocks rotate in failure development. Failure modes depend on the configuration of joints. Toppling failure is observed for the slope with straight joints and sliding failure is observed for the slope with staged joints. The DEM results are also compared with those of limit equilibrium method (LEM). Without considering the joints in rock masses, the LEM predicts much higher factor of safety than physical modeling and DEM. The failure mode and factor of safety predicted by the DEM are in good agreement with laboratory tests for any jointed rock slope.

Extreme events and ecological forecasting

Almost all extreme events lasting less than several weeks that significantly impact ecosystems are weather related. This review examines the response of estuarine systems to intense short-term perturbations caused by major weather events such as hurricanes. Current knowledge concerning these effects is limited to relatively few studies where hurricanes and storms impacted estuaries with established environmental monitoring programs. Freshwater inputs associated with these storms were found to initially result in increased primary productivity. When hydrographic conditions are favorable, bacterial consumption of organic matter produced by the phytoplankton blooms and deposited during the initial runoff event can contribute to significant oxygen deficits during subsequent warmer periods. Salinity stress and habitat destruction associated with freshwater inputs, as well as anoxia, adversely affect benthic populations and fish. In contrast, mobile invertebrate species such as shrimp, which have a short life cycle and the ability to migrate during the runoff event, initially benefit from the increased primary productivity and decreased abundance of fish predators. Events studied so far indicate that estuaries rebound in one to three years following major short-term perturbations. However, repeated storm events without sufficient recovery time may cause a fundamental shift in ecosystem structure (Scavia et al. 2002). This is a scenario consistent with the predicted increase in hurricanes for the east coast of the United States. More work on the response of individual species to these stresses is needed so management of commercial resources can be adjusted to allow sufficient recovery time for affected populations.

Phase 1: Florida's ocean and coastal economics report

This report was prepared for and funded by the Florida State Department of Environmental Protection with the encouragement of members from the Florida Ocean Alliance, Florida Oceans and Coastal Resources Council and other groups with deep interests in the future of Florida’s coast. It is a preliminary study of Florida’s Ocean and Coastal Economies based only on information currently found within the datasets of the National Ocean Economics Program. (NOEP). It reflects only a portion of the value of Florida’s coastal related economy and should not be considered comprehensive. A more customized study based on the unique coastal and ocean-dependent economic activities of the State of Florida should be carried out to complete the picture of Florida’s dependence upon its coasts. (PDF has 129 pages.)

NOAA Coastal Change Analysis Program (C-CAP): Guidance for Regional Implementation

EXECUTIVE SUMMARY: The Coastal Change Analysis Programl (C-CAP) is developing a nationally standardized database on landcover and habitat change in the coastal regions of the United States. C-CAP is part of the Estuarine Habitat Program (EHP) of NOAA's Coastal Ocean Program (COP). C-CAP inventories coastal submersed habitats, wetland habitats, and adjacent uplands and monitors changes in these habitats on a one- to five-year cycle. This type of information and frequency of detection are required to improve scientific understanding of the linkages of coastal and submersed wetland habitats with adjacent uplands and with the distribution, abundance, and health of living marine resources. The monitoring cycle will vary according to the rate and magnitude of change in each geographic region. Satellite imagery (primarily Landsat Thematic Mapper), aerial photography, and field data are interpreted, classified, analyzed, and integrated with other digital data in a geographic information system (GIS). The resulting landcover change databases are disseminated in digital form for use by anyone wishing to conduct geographic analysis in the completed regions. C-CAP spatial information on coastal change will be input to EHP conceptual and predictive models to support coastal resource policy planning and analysis. CCAP products will include 1) spatially registered digital databases and images, 2) tabular summaries by state, county, and hydrologic unit, and 3) documentation. Aggregations to larger areas (representing habitats, wildlife refuges, or management districts) will be provided on a case-by-case basis. Ongoing C-CAP research will continue to explore techniques for remote determination of biomass, productivity, and functional status of wetlands and will evaluate new technologies (e.g. remote sensor systems, global positioning systems, image processing algorithms) as they become available. Selected hardcopy land-cover change maps will be produced at local (1:24,000) to regional scales (1:500,000) for distribution. Digital land-cover change data will be provided to users for the cost of reproduction. Much of the guidance contained in this document was developed through a series of professional workshops and interagency meetings that focused on a) coastal wetlands and uplands; b) coastal submersed habitat including aquatic beds; c) user needs; d) regional issues; e) classification schemes; f) change detection techniques; and g) data quality. Invited participants included technical and regional experts and representatives of key State and Federal organizations. Coastal habitat managers and researchers were given an opportunity for review and comment. This document summarizes C-CAP protocols and procedures that are to be used by scientists throughout the United States to develop consistent and reliable coastal change information for input to the C-CAP nationwide database. It also provides useful guidelines for contributors working on related projects. It is considered a working document subject to periodic review and revision.(PDF file contains 104 pages.)

Abundance and Distribution of Ichthyoplankton along an Inshore-Offshore Transect in Onslow Bay, North Carolina

The distribution and abundance of ichthyoplankton was investigated from November 1979 to March 1980 along a transect from coastal to continental slope waters in Onslow Bay, North Carolina. Representatives of 66 families were collected; 24 of which were tropical families, a category that also includes families of typically oceanic and deep-sea fishes. Larvae of tropical species were collected in coastal and shelf waters, demonstrating the intrusion of Gulf Stream waters onto the continental shelf. From December through March, frontal waters that separated cold open-shelf surface waters from warm Gulf Stream surface waters were observed. Higher abundances of fish larvae were sometimes, but not consistently, associated with frontal waters. A great diversity of taxa was collected in offshore waters, and densities of larvae were low in coastal waters; low densities were attributed to gear selectivity rather than low larval abundance. Larvae of commercially and recreationally important estuarine-dependent species, especially Leiostomus xanthus and Micropogonias undulatus, were dominant components of the ichthyoplankton. Representatives of the families Bothidae, Clupeidae, Gadidae, Gonostomatidae, Myctophidae, Ophidiidae, and Sparidae were also important components of the ichthyoplankton. Larvae of species representing two strikingly different life history types-mesopelagic and estuarine-dependent frequently cooccurred.(PDF file contains 32 pages.)

Water quality assessment and characterisation of chlorophyll-a variability related to river discharges, within the southeastern Bay of Biscay : evaluation and development of chlorophyll-a algorithms for MODIS and MERIS imagery

222 p. : il.

San Francisco Bay regional sediment management strategy development

The San Francisco Bay Conservation and Development Commission (BCDC), in continued partnership with the San Francisco Bay Long Term Management Strategies (LTMS) Agencies, is undertaking the development of a Regional Sediment Management Plan for the San Francisco Bay estuary and its watershed (estuary). Regional sediment management (RSM) is the integrated management of littoral, estuarine, and riverine sediments to achieve balanced and sustainable solutions to sediment related needs. Regional sediment management recognizes sediment as a resource. Sediment processes are important components of coastal and riverine systems that are integral to environmental and economic vitality. It relies on the context of the sediment system and forecasting the long-range effects of management actions when making local project decisions. In the San Francisco Bay estuary, the sediment system includes the Sacramento and San Joaquin delta, the bay, its local tributaries and the near shore coastal littoral cell. Sediment flows from the top of the watershed, much like water, to the coast, passing through rivers, marshes, and embayments on its way to the ocean. Like water, sediment is vital to these habitats and their inhabitants, providing nutrients and the building material for the habitat itself. When sediment erodes excessively or is impounded behind structures, the sediment system becomes imbalanced, and rivers become clogged or conversely, shorelines, wetlands and subtidal habitats erode. The sediment system continues to change in response both to natural processes and human activities such as climate change and shoreline development. Human activities that influence the sediment system include flood protection programs, watershed management, navigational dredging, aggregate mining, shoreline development, terrestrial, riverine, wetland, and subtidal habitat restoration, and beach nourishment. As observed by recent scientific analysis, the San Francisco Bay estuary system is changing from one that was sediment rich to one that is erosional. Such changes, in conjunction with increasing sea level rise due to climate change, require that the estuary sediment and sediment transport system be managed as a single unit. To better manage the system, its components, and human uses of the system, additional research and knowledge of the system is needed. Fortunately, new sediment science and modeling tools provide opportunities for a vastly improved understanding of the sediment system, predictive capabilities and analysis of potential individual and cumulative impacts of projects. As science informs management decisions, human activities and management strategies may need to be modified to protect and provide for existing and future infrastructure and ecosystem needs. (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)

Effects of suspended sediments on the development of eggs and larvae of striped bass and white perch

The possible ecological effects of suspended sediments are manifold. Briefly, suspended sediments may cause an increased surface for microorganism growth, fewer temperature fluctuations, chemical adsorption or absorption, blanketing, mechanical-abrasive actions, and light penetration reduction (Cairns, 1968). Sherk and Cronin (1970) have pointed out that the above effects have been little studied in the estuarine environment. The ecological effects of suspended sediments on fish eggs and larvae may be of prime importance t o the C and D Canal area, an important spawning and primary nursery area for a variety of estuary: e species (Johnson,1972). This section discusses the effects of suspended sediment on the eggs and larvae of striped bass and white perch.

I. The structure and properties of closed circular duplex DNA. II. Chemically interacting systems at equilibrium in a buoyant density gradient

I. The binding of the intercalating dye ethidium bromide to closed circular SV 40 DNA causes an unwinding of the duplex structure and a simultaneous and quantitatively equivalent unwinding of the superhelices. The buoyant densities and sedimentation velocities of both intact (I) and singly nicked (II) SV 40 DNAs were measured as a function of free dye concentration. The buoyant density data were used to determine the binding isotherms over a dye concentration range extending from 0 to 600 µg/m1 in 5.8 M CsCl. At high dye concentrations all of the binding sites in II, but not in I, are saturated. At free dye concentrations less than 5.4 µg/ml, I has a greater affinity for dye than II. At a critical amount of dye bound I and II have equal affinities, and at higher dye concentration I has a lower affinity than II. The number of superhelical turns, τ, present in I is calculated at each dye concentration using Fuller and Waring's (1964) estimate of the angle of duplex unwinding per intercalation. The results reveal that SV 40 DNA I contains about -13 superhelical turns in concentrated salt solutions.

The free energy of superhelix formation is calculated as a function of τ from a consideration of the effect of the superhelical turns upon the binding isotherm of ethidium bromide to SV 40 DNA I. The value of the free energy is about 100 kcal/mole DNA in the native molecule. The free energy estimates are used to calculate the pitch and radius of the superhelix as a function of the number of superhelical turns. The pitch and radius of the native I superhelix are 430 Å and 135 Å, respectively.

A buoyant density method for the isolation and detection of closed circular DNA is described. The method is based upon the reduced binding of the intercalating dye, ethidium bromide, by closed circular DNA. In an application of this method it is found that HeLa cells contain in addition to closed circular mitochondrial DNA of mean length 4.81 microns, a heterogeneous group of smaller DNA molecules which vary in size from 0.2 to 3.5 microns and a paucidisperse group of multiples of the mitochondrial length.

II. The general theory is presented for the sedimentation equilibrium of a macromolecule in a concentrated binary solvent in the presence of an additional reacting small molecule. Equations are derived for the calculation of the buoyant density of the complex and for the determination of the binding isotherm of the reagent to the macrospecies. The standard buoyant density, a thermodynamic function, is defined and the density gradients which characterize the four component system are derived. The theory is applied to the specific cases of the binding of ethidium bromide to SV 40 DNA and of the binding of mercury and silver to DNA.