Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

Design and Synthesis of a Functional Derivative of the Triazinium Cation and Its Rhodium Complex that Shows Photoinduced DNA Cleavage Activity and Photocytotoxicity

The design and synthesis of an intensely blue rhodium(III) complex 3]+ of a new N,N-donor ligand, 8-(quinolin-8-ylamino)pyrido2,1-c]1,2,4]benzotriazin-11-ium, 2]+, which contains a planar pendant triazinium arm, is described. Structural characterization for 3]+ was carried out by using various spectroscopic techniques and single-crystal X-ray crystallography. The organometallic rhodium(III) compound shows a ligand-based reversible reduction at 0.65 V. The electrochemically reduced compound displays a single-line EPR spectrum that signifies the formation of ligand-based free radicals. Compound 3]+ shows a binding propensity to calf thymus DNA to give a Kapp value of 6.05X105 M1. The parent triazinium salt, pyrido2,1-c]1,2,4]benzotriazin-11-ium 1]+ and the ligand salt 2]+ exhibit photoinduced cleavage of DNA in UV-A light, whereas the reference Rh complex 3]+ photocleaves DNA with red light (647.1 nm). The compounds show photonuclease activities under both aerobic and anaerobic conditions. Mechanistic investigations under aerobic conditions with several inhibitors indicate the formation of hydroxyl radicals by means of a photoredox pathway. Under anaerobic conditions, it is believed that a photoinduced oxidation of DNA mechanism is operative. Compound 3]+ exhibits photocytotoxicity in HeLa cervical cancer cells to give IC50 values of (12+/-0.9) mu M in UV-A light at 365 nm and (31.4+/-1.1) mu M in the dark.

Amperometric acetylcholinesterase biosensor for pesticides monitoring utilising iron oxide nanoparticles and poly(indole-5-carboxylic acid)

A new electrochemical sensing device was constructed for determination of pesticides. In this report, acetylcholinesterase was bioconjugated onto hybrid nanocomposite, i.e. iron oxide nanoparticles and poly(indole-5-carboxylic acid) (Fe(3)O(4)NPs/Pin5COOH) was deposited electrochemically on glassy carbon electrode. Fe(3)O(4)NPs was showed as an amplified sensing interface at lower voltage which makes the sensor more sensitive and specific. The enzyme inhibition by pesticides was detected within concentrations ranges between 0.1-60 and 1.5-70 nM for malathion and chlorpyrifos, respectively, under optimal experimental conditions (sodium phosphate buffer, pH 7.0 and 25 degrees C). Biosensor determined the pesticides level in water samples (spiked) with satisfactory accuracy (96%-100%). Sensor showed good storage stability and retained 50% of its initial activity within 70 days at 4 degrees C.

Carmel River Lagoon Enhancement Project: Water Quality and Aquatic Wildlife Monitoring, 2005-6

In summer and fall 2004, the California Department of Parks and Recreation (DPR) initiated the Carmel River Lagoon Enhancement Project. The project involved excavation of a dry remnant Arm of the lagoon and adjacent disused farmland to form a significant new lagoon volume. The intention was to provide habitat, in particular, for two Federally threatened species: the California Red-Legged Frog, and the Steelhead Trout (South Central-Coastal California Evolutionary Significant Unit). DPR contracted with the Foundation of California State University Monterey Bay (Central Coast Watershed Studies Team, Watershed Institute) to monitor water quality and aquatic invertebrates in association with the enhancement, and to attempt to monitor steelhead using novel video techniques. The monitoring objective was to assess whether the enhancement was successful in providing habitat with good water quality, adequate invertebrate food for steelhead, and ultimately the presence of steelhead. (Document contains 102 pages)

Supporting the planning of a community fisheries monitoring and evaluation database: a collaborative project undertaken by CFDO, FLD, STREAM, VSO and AYAD

Cambodia is one of the poorest countries in the world; much of its population live in rural areas and many live below the local poverty line. The management of common property aquatic resources is of over-riding importance to food security and sustainable rural development in Cambodia. Aquatic resources are utilized principally by subsistence fishers and the landless, for whom aquatic resource use is an important livelihood activity. Subsistence fishers access mainly the rivers, lakes and inundated forests in Tonle Sap provinces, the lower Mekong and Bassac regions and the upper part of the Mekong. Freshwater capture fisheries probably contribute more to national food security and the national economy in Cambodia than in any other country in the world. (PDF contains 52 pages)

Assessment and monitoring of marine debris in Gray's Reef National Marine Sanctuary

Gray’s Reef National Marine Sanctuary (GRNMS) is located 32.4 km offshore of Sapelo Island, Georgia. The ecological importance of this area is related to the transition between tropical and temperate waters, and the existence of a topographically complex system of ledges. Due to its central location, GRNMS can be used as a focal site to study the accumulation and impacts of marine debris on the Atlantic continental shelf offshore of the Southeast United States. Previously, researchers characterized marine debris in GRNMS and reported that incidence of the debris at the limited densely colonized ledge sites was significantly greater than at sand or sparsely colonized live bottom, and is further influenced by the level of boating activity and physiographic characteristics (e.g., ledge height). Information gleaned from the initial marine debris characterization was used to devise a strategy for prioritizing cleanup and monitoring efforts. However, a significant gap in knowledge was the rate of debris accumulation. The primary objective of this study was to select, mark, and perform initial marine debris surveys at permanent monitoring sites within GRNMS to quantify long-term trends in types, abundance, impacts, and accumulation rates of debris. Ledge sites were selected to compare types, abundance, and accumulation rates of marine debris between a) areas of high and low use and b) short and tall ledges. Nine permanent monitoring sites were marked and initially surveyed in 2007/2008. Surveys were conducted within a 50 x 4 m transect for a total survey area of 200 square meters. All debris was removed and detailed information was taken on the types of debris, quantity, and associations with benthic fauna. Information on associations with benthic fauna included degree of entanglement, type of organism with which it is entangled or resting on, degree of fouling, and visible impacts such as tissue abrasions. Sites were re-surveyed approximately one year later to quantify new accumulation. During the initial survey, a total of ten debris items, totaling 16.3 kg in weight, were removed from two monitoring stations, both “tall” sites within the area of high boat use. Year-one accumulation totaled five items and approximately 7 kg in weight. Similar to the initial survey, all debris was found at sites in the area of high boat use. However, in contrast to the initial survey, two of these items were found on medium-height ledges. Removed items included fishing line, leaders, rope, plastic, and fabric. Although items were often encrusted in benthic biota or entangled on the ledge, impacts such as abrasions or other injuries were not observed. During the 2009 monitoring efforts, volunteer divers were trained to conduct the survey. Monitoring protocols were documented for GRNMS staff and included as an appendix of this report to enable long-term monitoring of sites. Additionally, national reconnaissance data (e.g. satellite, radar, aerial surveys) and other information on known fishing locations were examined for patterns of resource use and correlations with debris occurrence patterns. A previous model predicting the density of marine debris based on ledge features and boat use was refined and the results were used to generate a map of predicted debris density for all ledges.

Using wildlife activity and antibiotic resistance analysis to model bacterial water quality in coastal ponds

Models that help predict fecal coliform bacteria (FCB) levels in environmental waters can be important tools for resource managers. In this study, we used animal activity along with antibiotic resistance analysis (ARA), land cover, and other variables to build models that predict bacteria levels in coastal ponds that discharge into an estuary. Photographic wildlife monitoring was used to estimate terrestrial and aquatic wildlife activity prior to sampling. Increased duck activity was an important predictor of increased FCB in coastal ponds. Terrestrial animals like deer and raccoon, although abundant, were not significant in our model. Various land cover types, rainfall, tide, solar irradiation, air temperature, and season parameters, in combination with duck activity, were significant predictors of increased FCB. It appears that tidal ponds allow for settling of bacteria under most conditions. We propose that these models can be used to test different development styles and wildlife management techniques to reduce bacterial loading into downstream shellfish harvesting and contact recreation areas.

Characterizing Jobos Bay, Puerto Rico: a watershed modeling analysis and monitoring plan

Land-based pollution is commonly identified as a major contributor to the observed deterioration of shallow-water coral reef ecosystem health. Human activity on the coastal landscape often induces nutrient enrichment, hypoxia, harmful algal blooms, toxic contamination and other stressors that have degraded the quality of coastal waters. Coral reef ecosystems throughout Puerto Rico, including Jobos Bay, are under threat from coastal land uses such as urban development, industry and agriculture. The objectives of this report were two-fold: 1. To identify potentially harmful land use activities to the benthic habitats of Jobos Bay, and 2. To describe a monitoring plan for Jobos Bay designed to assess the impacts of conservation practices implemented on the watershed. This characterization is a component of the partnership between the U.S. Department of Agriculture (USDA) and the National Oceanic and Atmospheric Administration (NOAA) established by the Conservation Effects Assessment Project (CEAP) in Jobos Bay. CEAP is a multi-agency effort to quantify the environmental benefits of conservation practices used by private landowners participating in USDA programs. The Jobos Bay watershed, located in southeastern Puerto Rico, was selected as the first tropical CEAP Special Emphasis Watershed (SEW). Both USDA and NOAA use their respective expertise in terrestrial and marine environments to model and monitor Jobos Bay resources. This report documents NOAA activities conducted in the first year of the three-year CEAP effort in Jobos Bay. Chapter 1 provides a brief overview of the project and background information on Jobos Bay and its watershed. Chapter 2 implements NOAA’s Summit to Sea approach to summarize the existing resource conditions on the watershed and in the estuary. Summit to Sea uses a GIS-based procedure that links patterns of land use in coastal watersheds to sediment and pollutant loading predictions at the interface between terrestrial and marine environments. The outcome of Summit to Sea analysis is an inventory of coastal land use and predicted pollution threats, consisting of spatial data and descriptive statistics, which allows for better management of coral reef ecosystems. Chapters 3 and 4 describe the monitoring plan to assess the ecological response to conservation practices established by USDA on the watershed. Jobos Bay is the second largest estuary in Puerto Rico, but has more than three times the shoreline of any other estuarine area on the island. It is a natural harbor protected from offshore wind and waves by a series of mangrove islands and the Punta Pozuelo peninsula. The Jobos Bay marine ecosystem includes 48 km² of mangrove, seagrass, coral reef and other habitat types that span both intertidal and subtidal areas. Mapping of Jobos Bay revealed 10 different benthic habitats of varying prevalence, and a large area of unknown bottom type covering 38% of the entire bay. Of the known benthic habitats, submerged aquatic vegetation, primarily seagrass, is the most common bottom type, covering slightly less than 30% of the bay. Mangroves are the dominant shoreline feature, while coral reefs comprise only 4% of the total benthic habitat. However, coral reefs are some of the most productive habitats found in Jobos Bay, and provide important habitat and nursery grounds for fish and invertebrates of commercial and recreational value.

Environment monitoring technical report for the SON cage fish culture site at Bugungu, Napoleon Gulf, northern Lake Victoria, September 2013

Source of the Nile Fish farm (SON) is located in northern Lake Victoria close to the headwaters of the River Nile. The proprietors of the farm have established a collaborative agreement with the National Fisheries Resources Research Institute (NaFIRRI) to undertake quarterly environment monitoring surveys of the fish cage site at Bugungu in the Napoleon Gulf. This activity is a mandatory requirement of the National Environment Management Authority (NEMA) of Uganda. Therefore NAFIRRI undertakes monitoring surveys once every quarter covering selected physical‐chemical parameters including water column depth, water transparency, water column temperature, dissolved oxygen, pH, conductivity and nutrient status; algal, zooplankton, macro‐benthos and fish communities. While the first quarter survey of 2013 (January‐March) was missed out due to late decision, the second quarter monitoring survey was dully undertaken in May 2013 and a technical report was compiled and submitted to the client. The present report covers the third quarter survey (July‐September) undertaken in September 2013. Results/observations made are presented in this technical report along with a scientific interpretation and discussion of the results with reference to possible impacts of the cage facilities to the water environment quality and selected aquatic biota.

Reflex contributions to the directional tuning of arm stiffness

It has been shown that during arm movement, humans selectively change the endpoint stiffness of their arm to compensate for the instability in an unstable environment. When the direction of the instability is rotated with respect to the direction of movement, it was found that humans modify the antisymmetric component of their endpoint stiffness. The antisymmetric component of stiffness arises due to reflex responses suggesting that the subjects may have tuned their reflex responses as part of the feedforward adaptive control. The goal of this study was to examine whether the CNS modulates the gain of the reflex response for selective tuning of endpoint impedance. Subjects performed reaching movements in three unstable force fields produced by a robotic manipulandum, each field differing only in the rotational component. After subjects had learned to compensate for the field, allowing them to make unperturbed movements to the target, the endpoint stiffness of the arm was estimated in the middle of the movements. At the same time electromyographic activity (EMG) of six arm muscles was recorded. Analysis of the EMG revealed differences across force fields in the reflex gain of these muscles consistent with stiffness changes. This study suggests that the CNS modulates the reflex gain as part of the adaptive feedforward command in which the endpoint impedance is selectively tuned to overcome environmental instability. © 2008 Springer-Verlag Berlin Heidelberg.

Application of polyurethane foam units and calorimetry to microbial monitoring in Lake Donghu

Combined with the national standard biomonitoring method (polyurethane foam units method), calorimetry was applied to study the metabolic activities of PFU microbial communities in fresh water to determine the effects of anthropotgenic stresses on the activity of the microbial community. Comparisons were made at four sampling stations with different eutrophic status in Lake Donghu. Water quality variables, species number of protozoa, abundances of microorganisms, biomass, heterotrophy indexes and diversity indexes are reported. The heat rate-time curves of the native and concentrated PFU microbial communities were determined at 28 degrees C. Growth rate, measured maximum power output and total heat were calculated from the heat rate-time curves. The values of metabolic variables are higher at the more eutrophic stations, which suggests that organic pollution increases the activity of PFU microbial communities. The metabolic variables are in good agreement with chemical and biotic variables. And calorimetry will be useful for biomonitoring of the PFU microbial community. (C) 2005 Elsevier B.V. All rights reserved.

Investigation of the polyetherketone guest-host DR1/PEK-c polymer films by real-time monitoring of the second-harmonic generation

The real-time monitoring of the second-harmonic generation (SHG) was used to optimize the poling condition and to study the nonlinear optical (NLO) properties of the polyetherketone (PEK-c) guest-host polymer films. The high second-order NLO coefficient chi(33)((2)) = 11.02 pm/v measured at 1.064 mu m was achieved when the weight percent of DR1 guest in the polymer system is 20%. The NLO activity of the poled DR1/PEK-c polymer film can maintain more than 80% of its initial value when temperature is under 100 degrees C, and the normalized second-order NLO coefficient can maintain more than 85% after 2400 s at 80 degrees C. (C) 2000 Elsevier Science Ltd. All rights reserved.

Monitoring catalytic degradation of dye molecules on silver-coated ZnO nanowire arrays by surface-enhanced Raman spectroscopy

Catalytic degradation of organic dye molecules has attracted extensive attention due to their high toxicity to water resources. In this paper, we propose a novel method for the fabrication of uniform silver-coated ZnO nanowire arrays. The degradation of typical dye molecule rhodamine 6G (R6G), as an example, is investigated in the presence of the as-prepared silver-coated ZnO nanowire arrays. The experimental results show that such composite nanostructures exhibit high catalytic activity, and the reaction follows pseudo-first-order kinetics. Furthermore, these nanowire arrays are desirable SERS substrates for monitoring the catalytic degradation of dye molecules. Compared with traditional UV-visible spectroscopy, SERS technology can reflect more truly the catalytic degradation process occurring on the surface of the catalysts.

A Simple, Universal Colorimetric Assay for Endonuclease/Methyltransferase Activity and Inhibition Based on an Enzyme-Responsive Nanoparticle System

An enzyme responsive nanoparticle system that uses a DNA-gold nanoparticle (AuNP) assembly as the substrate has been developed for the simple, sensitive, and universal monitoring of restriction endonucleases in real time. This new assay takes advantage of the palindromic recognition sequence of the restriction nucleases and the unique optical properties of AuNPs and is simpler than the procedure previously described by by Xu et al. (Angew. Chem. Int. Ed. Engl. 2007, 46, 3468-3470). Because it involves only one type of ssDNA modified AuNPs, this assay can be directed toward most of the endonucleases by simply changing the recognition sequence found within the linker DNA. In addition, the endonuclease activity could be quantitatively analyzed by the value of the reciprocal of hydrolysis half time (t(1/2)(-1). Furthermore, our new design could also be applied to the assay of methyltransferase activity since the methylation of DNA inhibits its cleavage by the corresponding restriction endonuclease, and thus, this new methodology can be easily adapted to high-throughput screening of methyltransferase inhibitors.