Thermal co-reduction approach to vary size of silver nanoparticle: its microbial and cellular toxicology

In recent years, silver nanoparticles (AgNPs) have attracted considerable interest in the field of food, agriculture and pharmaceuticals mainly due to its antibacterial activity. AgNPs have also been reported to possess toxic behavior. The toxicological behavior of nanomaterials largely depends on its size and shape which ultimately depend on synthetic protocol. A systematic and detailed analysis for size variation of AgNP by thermal co-reduction approach and its efficacy toward microbial and cellular toxicological behavior is presented here. With the focus to explore the size-dependent toxicological variation, two different-sized NPs have been synthesized, i.e., 60 nm (Ag60) and 85 nm (Ag85). A detailed microbial toxicological evaluation has been performed by analyzing minimum inhibitory concentration (MIC), minimum bactericidal concentration (MBC), diameter of inhibition zone (DIZ), growth kinetics (GrK), and death kinetics (DeK). Comparative cytotoxicological behavior was analyzed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. It has been concluded by this study that the size of AgNPs can be varied, by varying the concentration of reactants and temperature called as ``thermal co-reduction'' approach, which is one of the suitable approaches to meet the same. Also, the smaller AgNP has shown more microbial and cellular toxicity.

Combustion and heat transfer characteristics of nanofluid fuel droplets: A short review

With the pressing need to meet an ever-increasing energy demand, the combustion systems utilizing fossil fuels have been the major contributors to carbon footprint. As the combustion of conventional energy resources continue to produce significant Green House gas (GHG) emissions, there is a strong emphasis to either upgrade or find an energy-efficient eco-friendly alternative to the traditional hydrocarbon fuels. With recent developments in nanotechnology, the ability to manufacture materials with custom tailored properties at nanoscale has led to the discovery of a new class of high energy density fuels containing reactive metallic nanoparticles (NPs). Due to the high reactive interfacial area and enhanced thermal and mass transport properties of nanomaterials, the high heat of formation of these metallic fuels can now be released rapidly, thereby saving on specific fuel consumption and hence reducing GHG emissions. In order to examine the efficacy of nanofuels in energetic formulations, it is imperative to first study their combustion characteristics at the droplet scale that form the fundamental building block for any combustion system utilizing liquid fuel spray. During combustion of such multiphase, multicomponent droplets, the phenomenon of diffusional entrapment of high volatility species leads to its explosive boiling (at the superheat limit) thereby leading to an intense internal pressure build-up. This pressure upsurge causes droplet fragmentation either in form of a microexplosion or droplet puffing followed by atomization (with formation of daughter droplets) featuring disruptive burning. Both these atomization modes represent primary mechanisms for extracting the high oxidation energies of metal NP additives by exposing them to the droplet flame (with daughter droplets acting as carriers of NPs). Atomization also serves as a natural mechanism for uniform distribution and mixing of the base fuel and enhancing burning rates (due to increase in specific surface area through formation of smaller daughter droplets). However, the efficiency of atomization depends on the thermo-physical properties of the base fuel, NP concentration and type. For instance, at dense loading NP agglomeration may lead to shell formation which would sustain the pressure upsurge and hence suppress atomization thereby reducing droplet gasification rate. Contrarily, the NPs may act as nucleation sites and aid boiling and the radiation absorption by NPs (from the flame) may lead to enhanced burning rates. Thus, nanoadditives may have opposing effects on the burning rate depending on the relative dominance of processes occurring at the droplet scale. The fundamental idea in this study is to: First, review different thermo-physical processes that occur globally at the droplet and sub-droplet scale such as surface regression, shell formation due to NP agglomeration, internal boiling, atomization/NP transport to flame zone and flame acoustic interaction that occur at the droplet scale and second, understand how their interaction changes as a function of droplet size, NP type, NP concentration and the type of base fuel. This understanding is crucial for obtaining phenomenological insights on the combustion behavior of novel nanofluid fuels that show great promise for becoming the next-generation fuels. (C) 2016 Elsevier Ltd. All rights reserved.

High Loading of Pd Nanoparticles by Interior Functionalization of MOFs for Heterogeneous Catalysis

In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd2+ (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs. The loading amount of Pd NPs was increased monotonically without altering their size distribution on a particular MOF. Importantly, the distinct role of alkyne groups for Pe(2+) stabilization has also been demonstrated by performing a control experiment considering a MOF without an alkyne moiety. The preparation of NPs involved two distinct steps viz. adsorption of metal ions inside MOFs and reduction of metal ions. Both of these steps were monitored by microscopic techniques. This report also demonstrates the applicability of Pd@MOF NPs as extremely efficient heterogeneous catalysts for Heck-coupling and hydrogenation reactions of aryl bromides or iodides and alkenes, respectively.

Dual Drug Conjugate Loaded Nanoparticles for the Treatment of Cancer

Two antineoplastic agents, Imatinib (IM) and 5-Fluorouracil (FU) were conjugated by hydrolysable linkers through an amide bond and entrapped in polymeric Human Serum Albumin (HSA) nanoparticles. The presence of dual drugs in a common carrier has the advantage of reaching the site of action simultaneously and acting at different phases of the cell cycle to arrest the growth of cancer cells before they develop chemoresistance. The study has demonstrated an enhanced anticancer activity of the conjugate, and conjugate loaded stealth HSA nanoparticles (NPs) in comparison to the free drug in A-549 human lung carcinoma cell line and Zebra fish embryos (Danio rerio). Hydrolysability of the conjugate has also been demonstrated with complete hydrolysis being observed after 12 h. In vivo pharmacodynamics study in terms of tumor volume and pharmacokinetics in mice for conjugate (IM-SC-FU) and conjugate loaded nanoparticles showed significant anti-cancer activity. The other parameters evaluated were particle size (86nm), Poly Dispersive Index (PDI) (0.209), zeta potential (-49mV), drug entrapment efficiency (96.73%) and drug loading efficiency (89%). Being in stealth mode gives the potential for the NPs to evade Reticulo-Endothelial system (RES), achieve passive targeting by Enhanced Permeation Retention (EPR) effect with controlled release of the therapeutic agent. As the conjugate cleaves into individual drugs in the tumor environment, this promises better suppression of cancer chemoresistance by delivering dual drugs with different modes of action at the same site, thereby synergistically inhibiting the growth of cancerous tissue.

Nitrogen-assisted electroless assembling of 3D nanodendrites consisting of Pd and N-doped carbon nanoparticles as bifunctional catalysts

We report a facile synthesis of three-dimensional (3D) nanodendrites of Pd nanoparticles (NPs) and nitrogen-doped carbon NPs (N-CNPs) by electroless deposition of Pd2+ ions. N-CNPs being an electron-enriched material act as a reducing agent. Moreover, the availability of a variety of nitrogen species in N-CNPs promotes the open arm structure as well as stabilizes the oriented 3D assembly of primary Pd NPs. The dendrites exhibit superior catalytic activity for methanol (0.5 M) oxidation in alkaline media (1 M NaOH) which is ascribed to the large electrochemical active surface area and the enhanced mass activity with repeated use. Further mass activity improvement has been realized after acid-treatment of dendrites which is attributed to the increment in the -OH group. The dendrites show higher mass activity (J(f) similar to 653 A g(-1)) in comparison with a commercial Pt-carbon/Pd-carbon (Pt-C/Pd-C) catalyst (J(f) similar to 46 and 163 A g(-1), respectively), better operational stability, superior CO tolerance with I-f/I-b (similar to 3.7) over a commercial Pt-C/Pd-C catalyst (I-f/I-b similar to 1.6 and 1.75, respectively) and may serve as a promising alternative to commercial Pt-C catalysts for anode application in alkaline fuel cells. To ensure the adaptability of our 3D-nanodendrites for other catalytic activities, we studied 4-nitrophenol reduction at room temperature. The 3D-nanodendrites show excellent catalytic activity toward 4-nitrophenol reduction, as well.

Density control of ZnO nanowires grown using Au-PMMA nanoparticles and their growth behavior.

Au nanoparticles stabilized by poly(methyl methacrylate) (PMMA) were used as a catalyst to grow vertically aligned ZnO nanowires (NWs). The density of ZnO NWs with very uniform diameter was controlled by changing the concentration of Au-PMMA nanoparticles (NPs). The density was in direct proportion to the concentration of Au-PMMA NPs. Furthermore, the growth process of ZnO NWs using Au-PMMA NPs was systematically investigated through comparison with that using Au thin film as a catalyst. Au-PMMA NPs induced polyhedral-shaped bases of ZnO NWs separated from each other, while Au thin film formed a continuous network of bases of ZnO NWs. This approach provides a facile and cost-effective catalyst density control method, allowing us to grow high-quality vertically aligned ZnO NWs suitable for many viable applications.

Fish assemblages and benthic habitats of Buck Island Reef National Monument (St. Croix, U.S. Virgin Islands) and the surrounding seascape: A characterization of spatial and temporal patterns

Since 1999, NOAA’s Biogeography Branch of the Center for Coastal Monitoring and Assessment (CCMA-BB) has been working with federal and territorial partners to characterize, monitor, and assess the status of the marine environment around northeastern St. Croix, U.S. Virgin Islands. This effort is part of the broader NOAA Coral Reef Conservation Program’s (CRCP) National Coral Reef Ecosystem Monitoring Program (NCREMP). With support from CRCP’s NCREMP, CCMA conducts the “Caribbean Coral Reef Ecosystem Monitoring project” (CREM) with goals to: (1) spatially characterize and monitor the distribution, abundance, and size of marine fauna associated with shallow water coral reef seascapes (mosaics of coral reefs, seagrasses, sand and mangroves); (2) relate this information to in situ fine-scale habitat data and the spatial distribution and diversity of habitat types using benthic habitat maps; (3) use this information to establish the knowledge base necessary for enacting management decisions in a spatial setting; (4) establish the efficacy of those management decisions; and (5) develop data collection and data management protocols. The monitoring effort in northeastern St. Croix was conducted through partnerships with the National Park Service (NPS) and the Virgin Islands Department of Planning and Natural Resources (VI-DPNR). The geographical focal point of the research is Buck Island Reef National Monument (BIRNM), a protected area originally established in 1961 and greatly expanded in 2001; however, the work also encompassed a large portion of the recently created St. Croix East End Marine Park (EEMP). Project funding is primarily provided by NOAA CRCP, CCMA and NPS. In recent decades, scientific and non-scientific observations have indicated that the structure and function of the coral reef ecosystem around northeastern St. Croix have been adversely impacted by a wide range of environmental stressors. The major stressors have included the mass Diadema die off in the early 1980s, a series of hurricanes beginning with Hurricane Hugo in 1989, overfishing, mass mortality of Acropora corals due to disease and several coral bleaching events, with the most severe mass bleaching episode in 2005. The area is also an important recreational resource supporting boating, snorkeling, diving and other water based activities. With so many potential threats to the marine ecosystem and a dramatic change in management strategy in 2003 when the park’s Interim Regulations (Presidential Proclamation No. 7392) established BIRNM as one of the first fully protected marine areas in NPS system, it became critical to identify existing marine fauna and their spatial distributions and temporal dynamics. This provides ecologically meaningful data to assess ecosystem condition, support decision making in spatial planning (including the evaluation of efficacy of current management strategies) and determine future information needs. The ultimate goal of the work is to better understand the coral reef ecosystems and to provide information toward protecting and enhancing coral reef ecosystems for the benefit of the system itself and to sustain the many goods and services that it offers society. This Technical Memorandum contains analysis of the first six years of fish survey data (2001-2006) and associated characterization of the benthos (1999-2006). The primary objectives were to quantify changes in fish species and assemblage diversity, abundance, biomass and size structure and to provide spatially explicit information on the distribution of key species or groups of species and to compare community structure inside (protected) versus outside (fished) areas of BIRNM. (PDF contains 100 pages).

Metal-Free Polymethyl Methacrylate (PMMA) Nanoparticles by Enamine "Click" Chemistry at Room Temperature

"Click" chemistry has become an efficient avenue to unimolecular polymeric nanoparticles through the self-crosslinking of individual polymer chains containing appropriate functional groups. Herein we report the synthesis of ultra-small (7 nm in size) polymethyl methacrylate (PMMA) nanoparticles (NPs) by the "metal-free" cross-linking of PMMA-precursor chains prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization containing beta-ketoester functional groups. Intramolecular collapse was performed by the one-pot reaction of beta-ketoester moieties with alkyl diamines in tetrahydrofurane at r.t. (i.e., by enamine formation). The collapsing process was followed by size exclusion chromatography and by nuclear magnetic resonance spectroscopy. The size of the resulting PMMA-NPs was determined by dynamic light scattering. Enamine "click" chemistry increases the synthetic toolbox for the efficient synthesis of metal-free, ultra-small polymeric NPs.

Temporary ponds in the UK; a critical biodiversity resource for freshwater plants and animals

The importance of ponds for biodiversity in Britain has been demonstrated by a number of studies. However, most of the research and interest has been directed at permanent waterbodies, and temporary ponds have been largely neglected. In this article the author present some preliminary findings from a project which aims to fill some of the many gaps in our knowledge of temporary ponds in Britain. The project, which runs for three years until the end of 2001, aims specifically to investigate the ecology of temporary ponds in England and Wales by describing (i) their wetland plant and macroinvertebrate communities, (ii) their physico-chemical characteristics, and (iii) their value as a biodiversity resource. The article focuses on the assessment of temporary ponds as a biodiversity resource and briefly considers aspects of species richness, rarity and distinctiveness. Where possible, temporary ponds are compared with other waterbody types, mainly permanent ponds from the National Pond Survey (NPS), to give the results a broader context.

Microwave Resonant and Zero-Field Absorption Study of Doped Magnetite Prepared by a Co-Precipitation Method

Fe3O4 and ZnxFe3-xO4 pure and doped magnetite magnetic nanoparticles (NPs) were prepared in aqueous solution (Series A) or in a water-ethyl alcohol mixture (Series B) by the co-precipitation method. Only one ferromagnetic resonance line was observed in all cases under consideration indicating that the materials are magnetically uniform. The shortfall in the resonance fields from 3.27 kOe (for the frequency of 9.5 GHz) expected for spheres can be understood taking into account the dipolar forces, magnetoelasticity, or magnetocrystalline anisotropy. All samples show non-zero low field absorption. For Series A samples the grain size decreases with an increase of the Zn content. In this case zero field absorption does not correlate with the changes of the grain size. For Series B samples the grain size and zero field absorption behavior correlate with each other. The highest zero-field absorption corresponded to 0.2 zinc concentration in both A and B series. High zero-field absorption of Fe3O4 ferrite magnetic NPs can be interesting for biomedical applications.

Funcionalización y estudio de nanopartículas de magnetita para su aplicación en terapias de hipertermia magnética

262 p.

Mechanisms of Toxicity of Ag Nanoparticles in Comparison to Bulk and Ionic Ag on Mussel Hemocytes and Gill Cells

Silver nanoparticles (Ag NPs) are increasingly used in many products and are expected to end up in the aquatic environment. Mussels have been proposed as marine model species to evaluate NP toxicity in vitro. The objective of this work was to assess the mechanisms of toxicity of Ag NPs on mussel hemocytes and gill cells, in comparison to ionic and bulk Ag. Firstly, cytotoxicity of commercial and maltose stabilized Ag NPs was screened in parallel with the ionic and bulk forms at a wide range of concentrations in isolated mussel cells using cell viability assays. Toxicity of maltose alone was also tested. LC50 values were calculated and the most toxic Ag NPs tested were selected for a second step where sublethal concentrations of each Ag form were tested using a wide array of mechanistic tests in both cell types. Maltose-stabilized Ag NPs showed size-dependent cytotoxicity, smaller (20 nm) NPs being more toxic than larger (40 and 100 nm) NPs. Maltose alone provoked minor effects on cell viability. Ionic Ag was the most cytotoxic Ag form tested whereas bulk Ag showed similar cytotoxicity to the commercial Ag NPs. Main mechanisms of action of Ag NPs involved oxidative stress and genotoxicity in the two cell types, activation of lysosomal AcP activity, disruption of actin cytoskeleton and stimulation of phagocytosis in hemocytes and increase of MXR transport activity and inhibition of Na-K-ATPase in gill cells. Similar effects were observed after exposure to ionic and bulk Ag in the two cell types, although generally effects were more marked for the ionic form. In conclusion, results suggest that most observed responses were due at least in part to dissolved Ag.

Cellular and molecular responses of zebrafish to legacy and emerging pollutants: the specific cases of PAHs and metal oxide nanoparticles

270 p.

Mytillus galloprovinciallis muskuiluaren aklaramendu tasa eta NPSen azterketa gazitasun ezberdinen aurrean

Mytillus galloprovincialis muskuilua gazitasun ezberdinetara jarri da aklaramendu tasan honek duen efektua ikusteko asmoz. Erabilitako gazitasunak ur gazia %100ean, %70ean eta %40an izan dira eta hiru esperimentu ezberdin jarraituz atera dira ondorioak. Hiru esperimentu hauetan muskuiluen aklaramendu tasak neurtu dira baldintza desberdinetan eta hirugarren esperimentuan NPS kontzentrazioaren neurketa kolorimetrikoa ere egin da. Ikusi da %70ko diluzioak ez duela aklaramendu tasan eraginik sortzen kasu guztietan eta %40ko diluzioak ere ez duela eraginik sortzen soilik aldaketa graduala bada. %40 gazitasunean, aldaketa gradualik gabe, mantendu diren muskuiluen berehalako erantzuna balbaren itxiera izan da, aklaratzeari utziz, baina denborarekin aklaratzeko gaitasuna berreskuratu dute. Aklimatazio horren arrazoia aurkitzeko asmoz, azkeneko esperimentuan NPS edo aminoazido askeen determinazioa egin da, bai brankian bai muskulu abduktorean. Gazitasuna jaisten denean NPSen kontzentrazioa behera egiten duela ikusi da muskuiluetan, bolumen zelularra erregulatuz. Efektu hau muskulu abduktorean adierazgarritasun handiagoarekin nabaritu da.

Effect of surface plasmon resonance in TiO2/Au thin films on the fluorescence of self-assembled CdTe QDs structure

23rd Congress of the International Comission for Optics (ICO 23)