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Sample records for protonated nanoparticle surface

  1. Surface modification of Fe2TiO5 nanoparticles by silane coupling agent: Synthesis and application in proton exchange composite membranes.

    PubMed

    Salarizadeh, Parisa; Javanbakht, Mehran; Pourmahdian, Saeed; Bagheri, Ahmad; Beydaghi, Hossein; Enhessari, Morteza

    2016-06-15

    Modifying surfaces of nanoparticles with silane coupling agent provides a simple method to alter their surface properties and improve their dispersibility in organic solvents and polymer matrix. Fe2TiO5 nanoparticles (IT) were modified with 3-aminopropyltriethoxysilane (APTES) as novel reinforcing filler for proton exchange membranes. The main operating parameters such as reaction time (R.T), APTES/IT and triethylamine (TEA)/IT ratios have been optimized for maximum grafting efficiency. The optimum conditions for R.T, APTES/IT and TEA/IT ratios were 6h, 4 and 0.3 respectively. It was observed that the APTES/IT and TEA/IT ratios were the most significant parameters affecting the grafting percentage. Modified nanoparticles were characterized using FT-IR, TGA, SEM, TEM and XRD techniques. Effects of modified nanoparticles in proton exchange membrane fuel cells (PEMFC) were evaluated. The resulting nanocomposite membranes exhibited higher proton conductivity in comparison with pristine SPPEK and SPPEK/IT membranes. This increase is attributed to connectivity of the water channels which creates more direct pathways for proton transport. Composite membrane with 3% AIT (6.46% grafting amount) showed 0.024Scm(-1) proton conductivity at 25°C and 149mWcm(-2) power density (at 0.5V) at 80°C which were about 243% and 51%, respectively higher than that of pure SPPEK. PMID:27023633

  2. Improving the proton conductivity and water uptake of polybenzimidazole-based proton exchange nanocomposite membranes with TiO2 and SiO2 nanoparticles chemically modified surfaces

    NASA Astrophysics Data System (ADS)

    Namazi, Hassan; Ahmadi, Hossein

    2011-03-01

    Poly [2,2‧-(m-pyrazolidene)-5,5‧-bibenzimidazole] (PPBI) was synthesized from pyrazole-3,5-dicarboxylic acid and 3,3‧,4,4‧-tetraaminobiphenyle (TAB) through polycondensation reaction in polyphosphoric acid (PPA) as reaction solvent. And polymer-grafted SiO2 and TiO2 nanoparticles were prepared through radical polymerization of 1-vinylimidazole and sulfonated vinylbenzene on the surface-vinylated nanoparticles. The polymer-grafted SiO2 and TiO2 nanoparticles were utilized as a functional additive to prepare PPBI/polymer-grafted SiO2 and TiO2 nanocomposite membranes. Imidazole and sulfonated vinylbenzene groups on the surface of modified nanoparticles forming linkages with PPBI chains, improved the compatibility between PPBI and nanoparticles, and enhanced the mechanical strength of the prepared nanocomposite membranes. The prepared nanocomposite membranes showed higher water uptake and acid doping levels comparing to PPBI. Also, after acid doping with phosphoric acid, nanocomposite membranes exhibited enhanced proton conductivity in comparison to the pristine PPBI and PPBI/un-modified SiO2 and TiO2 nanocomposite membranes. The enhancement in proton conductivity of nanocomposite membranes resulted from modified SiO2 nanoparticles showed higher conductivity than modified TiO2 nanoparticles. The above results indicated that the PPBI/modified SiO2 and TiO2 nanocomposite membranes could be utilized as proton exchange membranes for medium temperature fuel cells.

  3. Composite proton exchange membrane based on sulfonated organic nanoparticles

    NASA Astrophysics Data System (ADS)

    Pitia, Emmanuel Sokiri

    As the world sets its sight into the future, energy remains a great challenge. Proton exchange membrane (PEM) fuel cell is part of the solution to the energy challenge because of its high efficiency and diverse application. The purpose of the PEM is to provide a path for proton transport and to prevent direct mixing of hydrogen and oxygen at the anode and the cathode, respectively. Hence, PEMs must have good proton conductivity, excellent chemical stability, and mechanical durability. The current state-of-the-art PEM is a perfluorosulfonate ionomer, Nafion®. Although Nafion® has many desirable properties, it has high methanol crossover and it is expensive. The objective of this research was to develop a cost effective two-phase, composite PEM wherein a dispersed conductive organic phase preferentially aligned in the transport direction controls proton transport, and a continuous hydrophobic phase provides mechanical durability to the PEM. The hypothesis that was driving this research was that one might expect better dispersion, higher surface to volume ratio and improved proton conductivity of a composite membrane if the dispersed particles were nanometer in size and had high ion exchange capacity (IEC, = [mmol sulfonic acid]/gram of polymer). In view of this, considerable efforts were employed in the synthesis of high IEC organic nanoparticles and fabrication of a composite membrane with controlled microstructure. High IEC, ~ 4.5 meq/g (in acid form, theoretical limit is 5.4 meq/g) nanoparticles were achieved by emulsion copolymerization of a quaternary alkyl ammonium (QAA) neutralized-sulfonated styrene (QAA-SS), styrene, and divinylbenzene (DVB). The effects of varying the counterion of the sulfonated styrene (SS) monomer (alkali metal and QAA cations), SS concentration, and the addition of a crosslinking agent (DVB) on the ability to stabilize the nanoparticles to higher IECs were assessed. The nanoparticles were ion exchanged to acid form. The extent of ion

  4. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    SciTech Connect

    Dixon, David Adams

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  5. Proton transport via the membrane surface.

    PubMed Central

    Georgievskii, Yuri; Medvedev, Emile S; Stuchebrukhov, Alexei A

    2002-01-01

    Some proton pumps, such as cytochrome c oxidase (C(c)O), translocate protons across biological membranes at a rate that considerably exceeds the rate of proton transport to the entrance of the proton-conducting channel via bulk diffusion. This effect is usually ascribed to a proton-collecting antenna surrounding the channel entrance. In this paper, we consider a realistic phenomenological model of such an antenna. In our model, a homogeneous membrane surface, which can mediate proton diffusion toward the channel entrance, is populated with protolytic groups that are in dynamic equilibrium with the solution. Equations that describe coupled surface-bulk proton diffusion are derived and analyzed. A general expression for the rate constant of proton transport via such a coupled surface-bulk diffusion mechanism is obtained. A rigorous criterion is formulated of when proton diffusion along the surface enhances the transport. The enhancement factor is found to depend on the ratio of the surface and bulk diffusional constants, pK(a) values of surface protolytic groups, and their concentration. A capture radius for a proton on the surface and an effective size of the antenna are found. The theory also predicts the effective distance that a proton can migrate on the membrane surface between a source (such as CcO) and a sink (such as ATP synthase) without fully equilibrating with the bulk. In pure aqueous solutions, protons can travel over long distances (microns). In buffered solutions, the travel distance is much shorter (nanometers); still the enhancement effect of the surface diffusion on the proton flow to a target on the surface can be tens to hundreds at physiological buffer concentrations. These results are discussed in a general context of chemiosmotic theory. PMID:12023208

  6. Improving proton therapy by metal-containing nanoparticles: nanoscale insights

    PubMed Central

    Schlathölter, Thomas; Eustache, Pierre; Porcel, Erika; Salado, Daniela; Stefancikova, Lenka; Tillement, Olivier; Lux, Francois; Mowat, Pierre; Biegun, Aleksandra K; van Goethem, Marc-Jan; Remita, Hynd; Lacombe, Sandrine

    2016-01-01

    The use of nanoparticles to enhance the effect of radiation-based cancer treatments is a growing field of study and recently, even nanoparticle-induced improvement of proton therapy performance has been investigated. Aiming at a clinical implementation of this approach, it is essential to characterize the mechanisms underlying the synergistic effects of nanoparticles combined with proton irradiation. In this study, we investigated the effect of platinum- and gadolinium-based nanoparticles on the nanoscale damage induced by a proton beam of therapeutically relevant energy (150 MeV) using plasmid DNA molecular probe. Two conditions of irradiation (0.44 and 3.6 keV/μm) were considered to mimic the beam properties at the entrance and at the end of the proton track. We demonstrate that the two metal-containing nanoparticles amplify, in particular, the induction of nanosize damages (>2 nm) which are most lethal for cells. More importantly, this effect is even more pronounced at the end of the proton track. This work gives a new insight into the underlying mechanisms on the nanoscale and indicates that the addition of metal-based nanoparticles is a promising strategy not only to increase the cell killing action of fast protons, but also to improve tumor targeting. PMID:27143877

  7. Proton NMR studies of functionalized nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Tataurova, Yulia Nikolaevna

    in high-resolution NMR spectra. This technique is selective for protons on the surface organic functional groups due to their motional averaging in solution. In this study, 1H solution NMR spectroscopy was used to investigate the interface of the organic functional groups in D2O. The pKa for these functional groups covalently bound to the surface of nanoparticles was determined using an NMR-pH titration method based on the variation in the proton chemical shift for the alkyl group protons closest to the amine group with pH. The adsorption of toxic contaminants (chromate and arsenate anions) on the surface of functionalized silicalite-1 and mesoporous silica nanoparticles has been studied by 1H solution NMR spectroscopy. With this method, the surface bound contaminants are detected. The analysis of the intensity and position of these peaks allows quantitative assessment of the relative amounts of functional groups with adsorbed metal ions. These results demonstrate the sensitivity of solution NMR spectroscopy to the electronic environment and structure of the surface functional groups on porous nanomaterials.

  8. Proton Dynamics on Goethite Nanoparticles and Coupling to Electron Transport.

    PubMed

    Zarzycki, Piotr; Smith, Dayle M; Rosso, Kevin M

    2015-04-14

    The surface chemistry of metal oxide particles is governed by the charge that develops at the interface with aqueous solution. Mineral transformation, biogeochemical reactions, remediation, and sorption dynamics are profoundly affected in response. Here we report implementation of replica-exchange constant-pH molecular dynamics simulations that use classical molecular dynamics for exploring configurational space and Metropolis Monte Carlo walking through protonation space with a simulated annealing escape route from metastable configurations. By examining the archetypal metal oxide, goethite (α-FeOOH), we find that electrostatic potential gradients spontaneously arise between intersecting low-index crystal faces and across explicitly treated oxide nanoparticles at a magnitude exceeding the Johnson-Nyquist voltage fluctuation. Fluctuations in adsorbed proton density continuously repolarize the surface potential bias between edge-sharing crystal faces, at a rate slower than the reported electron-polaron hopping rate in goethite interiors. This suggests that these spontaneous surface potential fluctuations will control the net movement of charge carriers in the lattice. PMID:26574382

  9. Gold Nanoparticles-Enhanced Proton Exchange Membrane (PEM) Fuel Cell

    NASA Astrophysics Data System (ADS)

    Li, Hongfei; Pan, Cheng; Liu, Ping; Zhu, Yimei; Adzic, Radoslav; Rafailovich, Miriam

    Proton exchange membrane fuel cells have drawn great attention and been taken as a promising alternated energy source. One of the reasons hamper the wider application of PEM fuel cell is the catalytic poison effect from the impurity of the gas flow. Haruta has predicted that gold nanoparticles that are platelet shaped and have direct contact with the metal oxide substrate to be the perfect catalysts of the CO oxidization, yet the synthesis method is difficult to apply in the Fuel Cell. In our approach, thiol-functionalized gold nanoparticles were synthesized through two-phase method developed by Brust et al. We deposit these Au particles with stepped surface directly onto the Nafion membrane in the PEM fuel cell by Langmuir-Blodgett method, resulting in over 50% enhancement of the efficiency of the fuel cell. DFT calculations were conducted to understand the theory of this kind of enhancement. The results indicated that only when the particles were in direct surface contact with the membrane, where AuNPs attached at the end of the Nafion side chains, it could reduce the energy barrier for the CO oxidation that could happen at T<300K.

  10. Biological modeling of gold nanoparticle enhanced radiotherapy for proton therapy

    NASA Astrophysics Data System (ADS)

    Lin, Yuting; McMahon, Stephen J.; Paganetti, Harald; Schuemann, Jan

    2015-05-01

    Gold nanoparticles (GNPs) have shown potential as a radiosensitizer for radiation therapy using photon beams. Recently, experimental studies have been carried out using proton beams showing the GNP enhanced responses in proton therapy. In this work, we established a biological model to investigate the change in survival of irradiated cells due to the radiosensitizing effect of gold nanoparticles. Results for proton, megavoltage (MV) photon and kilovoltage (kV) photon beams are compared. For each particle source, we assessed various treatment depths, GNP cellular uptakes and sizes. We showed that kilovoltage photons caused the highest enhancement due to the high interaction probability between GNPs and kV photons. The cell survival fraction can be significantly reduced for both proton and MV photon irradiations if GNPs accumulate in the cell. For instance, the sensitizer enhancement ratio (SER) is 1.33 for protons in the middle of a spread out Bragg peak for 1 µM of internalized 50 nm GNPs. If the GNPs can all be internalized into the cell nucleus, the SER for proton therapy increases from 1.33 to 1.81. The results also show that for the same mass of GNPs in the cells, one can expect the greatest sensitization by smaller GNPs, i.e. a SER of 1.33 for 1 µM of internalized 50 nm GNPs and a SER of 3.98 for the same mass of 2 nm GNPs. We concluded that if the GNPs cannot be internalized into the cytoplasm, no GNP enhancement will be observed for proton treatment. Meanwhile, proton radiotherapy can potentially be enhanced with GNPs if they can be internalized into cells, and especially the cell nucleus.

  11. AQUEOUS PROTONATION PROPERTIES OF AMPHOTERIC NANOPARTICLES

    EPA Science Inventory

    A divergence is predicted between the acidity behavior of charged sites on micron sized colloidal particles and nanoparticles. Utilizing the approximate analytical solution to the Poisson-Boltzmann equation published by Ohshima et al. (1982), findings from the work included: 1):...

  12. Protonation and Deprotonation on Water's Surface

    NASA Astrophysics Data System (ADS)

    Colussi, A. J.; Enami, S.; Stewart, L.; Hoffmann, M. R.

    2010-12-01

    How the acidity of bulk water (pHbulk) regulates the degree of protonation of Brönsted acids and bases on water surfaces facing hydrophobic media is a key unresolved issue in chemistry and biology. We addressed experimentally the important case of the air/water interface and report the strikingly dissimilar pHbulk-dependences of the protonation/deprotonation of aqueous versus gaseous n-hexanoic acid (HxOH) determined on the surface of aqueous microjets by online electrospray mass spectrometry. We confirm that HxOH(aq) is deprotonated at pHbulk > pKa(HxOH) = 4.8, but find that the deprotonation of HxOH(g) into interfacial HxO-(s) displays two equivalence points at pHbulk ~ 2.5 and ~ 10.0. The weak base HxOH(aq) (pKa(HxOH2+) < - 4) is barely protonated at pHbulk > 1, whereas HxOH(g) is significantly protonated to HxOH2+(s) on pHbulk < 4 water, as expected from the proton affinities PA(HxOH) > PA(H2O) of gas-phase species. The exceptionally large kinetic isotope effect for the protonation of HxOH(g) on D2O/H2O: KIE = HxOH2+/HxODH+ ~ 100, is ascribed to a desolvated transition state. Since ion creation at the interface via proton transfer between H2O itself and neutral species is thermodynamically disallowed i.e., HxOH(g) is actually deprotonated by interfacial OH-(s), whereas Me3N(g) is hardly protonated by H3O+(s) on pHbulk ~ 4 - 8 water (Enami et al., J. Phys. Chem. Lett. 2010, 1, 1599) we conclude that [OH-(s)] > [H3O+(s)] above pHbulk ~ 4, at variance with inferences drawn from spectroscopic signatures or model calculations of water’s surface.

  13. Surface modification of silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Ranjan, Rajesh

    Surface modification of nanosized silica particles by polymer grafting is gaining attention. This can be attributed to the fact that it provides a unique opportunity to engineer the interfacial properties of these modified particles; at the same time the mechanical and thermal properties of the polymers can be improved. Controlled free radical polymerization is a versatile technique which affords control over molecular weight, molecular weight distribution, architecture and functionalities of the resulting polymer. Three commonly used controlled free radical polymerizations include nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer (RAFT) polymerization. ATRP and RAFT polymerization were explored in order to modify the silica surface with well-defined polymer brushes. A novel click-functionalized RAFT chain transfer agent (RAFT CTA) was synthesized which opened up the possibility of using RAFT polymerization and click chemistry together in surface modification. Using this RAFT CTA, the surface of silica nanoparticles was modified with polystyrene and polyacrylamide brushes via the "grafting to" approach. Both tethered polystyrene and polyacrylamide chains were found in the brush regime. The combination of ATRP and click chemistry was also explored for surface modification. A combination of RAFT polymerization and click chemistry was also studied to modify the surface via the "grafting from" approach. Our strategy included the (1) "grafting from" approach for brush formation (2) facile click reaction to immobilize the RAFT agent (3) synthesis of R-supported chain transfer agent and (4) use of the more active trithiocarbonate RAFT agent. Grafting density obtained by this method was significantly higher than reported values in the literature. Polystyrene (PS) grafted silica nanoparticles were also prepared by a tandem process that simultaneously employs reversible addition fragmentation

  14. Water-soluble core/shell nanoparticles for proton therapy through particle-induced radiation

    NASA Astrophysics Data System (ADS)

    Park, Jeong Chan; Jung, Myung-Hwan; Kim, Maeng Jun; Kim, Kye-Ryung

    2015-02-01

    Metallic nanoparticles have been used in biomedical applications such as magnetic resonance imaging (MRI), therapy, and drug delivery systems. Metallic nanoparticles as therapeutic tools have been demonstrated using radio-frequency magnetic fields or near-infrared light. Recently, therapeutic applications of metallic nanomaterials combined with proton beams have been reported. Particle-induced radiation from metallic nanoparticles, which can enhance the therapeutic effects of proton therapy, was released when the nanoparticles were bombarded by a high-energy proton beam. Core/shell nanoparticles, especially Au-coated magnetic nanoparticles, have drawn attention in biological applications due to their attractive characteristics. However, studies on the phase transfer of organic-ligand-based core/shell nanoparticles into water are limited. Herein, we demonstrated that hydrophobic core/shell structured nanomaterials could be successfully dispersed in water through chloroform/surfactant mixtures. The effects of the core/shell nanomaterials and the proton irradiation on Escherichia coli (E. coli) were also explored.

  15. Evaluation of the local dose enhancement in the combination of proton therapy and nanoparticles

    SciTech Connect

    Martínez-Rovira, I. Prezado, Y.

    2015-11-15

    Purpose: The outcome of radiotherapy can be further improved by combining irradiation with dose enhancers such as high-Z nanoparticles. Since 2004, spectacular results have been obtained when low-energy x-ray irradiations have been combined with nanoparticles. Recently, the same combination has been explored in hadron therapy. In vitro studies have shown a significant amplification of the biological damage in tumor cells charged with nanoparticles and irradiated with fast ions. This has been attributed to the increase in the ionizations and electron emissions induced by the incident ions or the electrons in the secondary tracks on the high-Z atoms, resulting in a local energy deposition enhancement. However, this subject is still a matter of controversy. Within this context, the main goal of the authors’ work was to provide new insights into the dose enhancement effects of nanoparticles in proton therapy. Methods: For this purpose, Monte Carlo calculations (GATE/GEANT4 code) were performed. In particular, the GEANT4-DNA toolkit, which allows the modeling of early biological damages induced by ionizing radiation at the DNA scale, was used. The nanometric radial energy distributions around the nanoparticle were studied, and the processes (such as Auger deexcitation or dissociative electron attachment) participating in the dose deposition of proton therapy treatments in the presence of nanoparticles were evaluated. It has been reported that the architecture of Monte Carlo calculations plays a crucial role in the assessment of nanoparticle dose enhancement and that it may introduce a bias in the results or amplify the possible final dose enhancement. Thus, a dosimetric study of different cases was performed, considering Au and Gd nanoparticles, several nanoparticle sizes (from 4 to 50 nm), and several beam configurations (source-nanoparticle distances and source sizes). Results: This Monte Carlo study shows the influence of the simulations’ parameters on the local

  16. Surface effects in zinc oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Combe, Nicolas; Chassaing, Pierre-Marie; Demangeot, François

    2009-01-01

    Structural properties of zinc oxide nanoparticles are theoretically studied focusing on the effects induced by the surfaces. In this aim, we compare two models: an atomistic and an elastic model. Atomistic model uses a semiempirical potential: the shell model. Effects of surface relaxation and surface stress are taken into account in this model while they were not in the elastic model. Studying nanoparticles with sizes varying from 1.5 to 4.5 nm, we show that surface relaxation occurs on a typical length of about 1 nm in the vicinity of surfaces within the atomistic model. This significant length is due to the existence of long-range interaction forces in zinc oxide which is an ionocovalent material. Because this typical length is comparable to nanoparticle size, elasticity fails to reproduce correctly structural properties of the nanoparticles. As an illustration of structural properties changes by decreasing nanoparticles sizes, we study the nanoparticles acoustic vibrations eigenfrequencies focusing on the mostly observable modes by vibration spectroscopy. Differences between elasticity and atomistic calculations are attributed to surface effects. If elasticity acceptably provides vibration frequencies of most studied nanoparticles, it fails to reproduce them for nanoparticles with a size below an approximate value of 2.5 nm. We expect such effects to be experimentally observable.

  17. Platinum Attachments on Iron Oxide Nanoparticle Surfaces

    SciTech Connect

    Palchoudhury, Soubantika; Xu, Yaolin; An, Wei; Turner, C. H.; Bao, Yuping

    2010-04-30

    Platinum nanoparticles supported on metal oxide surfaces have shown great potential as heterogeneous catalysts to accelerate electrochemical processes, such as the oxygen reduction reaction in fuel cells. Recently, the use of magnetic supports has become a promising research topic for easy separation and recovery of catalysts using magnets, such as Pt nanoparticles supported on iron oxide nanoparticles. The attachment of Pt on iron oxide nanoparticles is limited by the wetting ability of the Pt (metal) on ceramic surfaces. A study of Pt nanoparticle attachment on iron oxide nanoparticle surfaces in an organic solvent is reported, which addresses the factors that promote or inhibit such attachment. It was discovered that the Pt attachment strongly depends on the capping molecules of the iron oxide seeds and the reaction temperature. For example, the attachment of Pt nanoparticles on oleic acid coated iron oxide nanoparticles was very challenging, because of the strong binding between the carboxylic groups and iron oxide surfaces. In contrast, when nanoparticles are coated with oleic acid/tri-n-octylphosphine oxide or oleic acid/oleylamine, a significant increase in Pt attachment was observed. Electronic structure calculations were then applied to estimate the binding energies between the capping molecules and iron ions, and the modeling results strongly support the experimental observations.

  18. Surface functionalized selenium nanoparticles for biomedical applications.

    PubMed

    Chaudhary, Savita; Umar, Ahmad; Mehta, S K

    2014-10-01

    Selenium nanoparticles present an enhanced genetic actions and possess superior adsorptive capacity due to the interaction between the nanoparticles and NH, C=O, COO- and C-N groups of proteins. This review is focused on the biomedical applications of surafce funtionalized selenium nanoparticles. The engineering of exterior surface of the selenium nanoparticles has further emphasizing on the recent progresses in regulating monolayer structures for competent delivery of drugs and biomolecules. Crucial queries of transport, uptake, and clearance are discussed and illustrated through the prospects of selenium nanoparticles. The work presents an insight of how biomedical research can evolve with selenium nanoparticles and where we see the field is heading in the near future. PMID:25992427

  19. Impact of nanoparticle size and shape on selective surface segregation in polymer nanocomposites

    SciTech Connect

    Mutz, M; Holley, Daniel W; Baskaran, Durairaj; Mays, Jimmy; Dadmun, Mark D

    2012-01-01

    A study of the impact of the size and shape of a nanoparticle on the evolution of structure and surface segregation in polymer nanocomposite thin films is presented. This is realized by monitoring the evolution of structure with thermal annealing and equilibrium depth profile of a deuterated polystyrene/ protonated polystyrene bilayer in the presence and absence of various nanoparticles. For the three shapes examined, sheet-like graphene, cylindrical carbon nanotubes, and spherical soft nanoparticles, the presence of the nanoparticles slowed the inter-diffusion of the polymers in the thin film. The larger nanoparticles slowed the polymer motion the most, while the smaller spherical nanoparticles also significantly inhibited polymer chain diffusion. At equilibrium, the soft spherical nanoparticles, which are highly branched, segregate to the air surface, resulting in a decrease in the excess deuterated PS at the surface. The graphene sheets and single walled carbon nanotubes, on the other hand, enhanced the dPS segregation to the air surface. The graphene sheets were found to segregate to the silicon surface, due to their higher surface energy. Interpretation of these results indicates that entropic factors drive the structural development in the nanocomposite thin films containing the spherical nanoparticles, while a balance of the surface energies of the various components (i.e. enthalpy) controls the thin film structure formation in the polymer-carbon nanoparticle nanocomposites.

  20. Enhanced relative biological effectiveness of proton radiotherapy in tumor cells with internalized gold nanoparticles

    SciTech Connect

    Polf, Jerimy C.; Gillin, Michael; Bronk, Lawrence F.; Driessen, Wouter H. P.; Arap, Wadih; Pasqualini, Renata

    2011-05-09

    The development and use of sensitizing agents to improve the effectiveness of radiotherapy have long been sought to improve our ability to treat cancer. In this letter, we have studied the relative biological effectiveness of proton beam radiotherapy on prostate tumor cells with and without internalized gold nanoparticles. The effectiveness of proton radiotherapy for the killing of prostate tumor cells was increased by approximately 15%-20% for those cells containing internalized gold nanoparticles.

  1. Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

    NASA Astrophysics Data System (ADS)

    Kwon, Kideok D.; Refson, Keith; Sposito, Garrison

    2010-12-01

    Natural hexagonal birnessite is a poorly crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO 2OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists in

  2. Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

    SciTech Connect

    Kwon, K.; Refson, K.; Sposito, G.

    2010-10-15

    Natural hexagonal birnessite is a poorly-crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO{sub 2}OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly-coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists

  3. Transmutable nanoparticles with reconfigurable surface ligands.

    PubMed

    Kim, Youngeun; Macfarlane, Robert J; Jones, Matthew R; Mirkin, Chad A

    2016-02-01

    Unlike conventional inorganic materials, biological systems are exquisitely adapted to respond to their surroundings. Proteins and other biological molecules can process a complex set of chemical binding events as informational inputs and respond accordingly via a change in structure and function. We applied this principle to the design and synthesis of inorganic materials by preparing nanoparticles with reconfigurable surface ligands, where interparticle bonding can be programmed in response to specific chemical cues in a dynamic manner. As a result, a nascent set of "transmutable nanoparticles" can be driven to crystallize along multiple thermodynamic trajectories, resulting in rational control over the phase and time evolution of nanoparticle-based matter. PMID:26912697

  4. Nanoparticle Based Surface-Enhanced Raman Spectroscopy

    SciTech Connect

    Talley, C E; Huser, T R; Hollars, C W; Jusinski, L; Laurence, T; Lane, S M

    2005-01-03

    Surface-enhanced Raman scattering is a powerful tool for the investigation of biological samples. Following a brief introduction to Raman and surface-enhanced Raman scattering, several examples of biophotonic applications of SERS are discussed. The concept of nanoparticle based sensors using SERS is introduced and the development of these sensors is discussed.

  5. Mercury's Surface Magnetic Field Determined from Proton-Reflection Magnetometry

    NASA Technical Reports Server (NTRS)

    Winslow, Reka M.; Johnson, Catherine L.; Anderson, Brian J.; Gershman, Daniel J.; Raines, Jim M.; Lillis, Robert J.; Korth, Haje; Slavin, James A.; Solomon, Sean C.; Zurbuchen, Thomas H.; Zuber, Maria T.

    2014-01-01

    Solar wind protons observed by the MESSENGER spacecraft in orbit about Mercury exhibit signatures of precipitation loss to Mercury's surface. We apply proton-reflection magnetometry to sense Mercury's surface magnetic field intensity in the planet's northern and southern hemispheres. The results are consistent with a dipole field offset to the north and show that the technique may be used to resolve regional-scale fields at the surface. The proton loss cones indicate persistent ion precipitation to the surface in the northern magnetospheric cusp region and in the southern hemisphere at low nightside latitudes. The latter observation implies that most of the surface in Mercury's southern hemisphere is continuously bombarded by plasma, in contrast with the premise that the global magnetic field largely protects the planetary surface from the solar wind.

  6. Nanoparticle-based PARACEST agents: the quenching effect of silica nanoparticles on the CEST signal from surface-conjugated chelates.

    PubMed

    Evbuomwan, Osasere M; Merritt, Matthew E; Kiefer, Garry E; Dean Sherry, A

    2012-01-01

    Silica nanoparticles of average diameter 53 ± 3 nm were prepared using standard water-in-oil microemulsion methods. After conversion of the surface Si-OH groups to amino groups for further conjugation, the PARACEST agent, EuDOTA-(gly)₄ (-) was coupled to the amines via one or more side-chain carboxyl groups in an attempt to trap water molecules in the inner-sphere of the complex. Fluorescence and ICP analyses showed that approximately 1200 Eu(3+) complexes were attached to each silica nanoparticle, leaving behind excess protonated amino groups. CEST spectra of the modified silica nanoparticles showed that attachment of the EuDOTA-(gly)₄ (-) to the surface of the nanoparticles did not result in a decrease in water exchange kinetics as anticipated, but rather resulted in a complete elimination of the normal Eu(3+) -bound water exchange peak and broadening of the bulk water signal. This observation was traced to catalysis of proton exchange from the Eu(3+) -bound water molecule by excess positively charged amino groups on the surface of the nanoparticles. PMID:22344876

  7. Immobilization of Polymeric Luminophor on Nanoparticles Surface

    NASA Astrophysics Data System (ADS)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-04-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor.

  8. Transmutable nanoparticles with reconfigurable surface ligands

    NASA Astrophysics Data System (ADS)

    Kim, Youngeun; Macfarlane, Robert J.; Jones, Matthew R.; Mirkin, Chad A.

    2016-02-01

    Unlike conventional inorganic materials, biological systems are exquisitely adapted to respond to their surroundings. Proteins and other biological molecules can process a complex set of chemical binding events as informational inputs and respond accordingly via a change in structure and function. We applied this principle to the design and synthesis of inorganic materials by preparing nanoparticles with reconfigurable surface ligands, where interparticle bonding can be programmed in response to specific chemical cues in a dynamic manner. As a result, a nascent set of “transmutable nanoparticles” can be driven to crystallize along multiple thermodynamic trajectories, resulting in rational control over the phase and time evolution of nanoparticle-based matter.

  9. Surface track potential created by fast protons at LiF surfaces

    NASA Astrophysics Data System (ADS)

    Arnau, A.; Gravielle, M. S.; Miraglia, J. E.; Ponce, V. H.

    2003-06-01

    A model based on atomic ionization of F- sites at the surface is used to calculate the surface track potential created by fast protons at LiF surfaces. For 100-keV protons at grazing incidence, we find that the track potential close to the surface plays a significant role in determining the shift to lower energies of the convoy electron peak with respect to the unperturbed cusp value.

  10. Sulfated zirconia nanoparticles as a proton conductor for fuel cell electrodes

    NASA Astrophysics Data System (ADS)

    Tominaka, Satoshi; Akiyama, Naohisa; Croce, Fausto; Momma, Toshiyuki; Scrosati, Bruno; Osaka, Tetsuya

    Sulfated zirconia nanoparticles are evaluated as a possible alternative for a solid proton conductor in a fuel-cell catalyst layer. Two methods are applied for the synthesis of the nanoparticles, i.e.: (i) a conventional method treating ZrO 2 particles in sulfuric acid, and (ii) a solvent-free method directly synthesizing sulfated zirconia nanoparticles through the thermal decomposition of a mixture of ZrOCl 2 and (NH 4) 2SO 4. The nanoparticles synthesized by the solvent-free method have a size of 5-10 nm and an amorphous structure, and moreover their properties are promising in view of the application. In particular, the proton conductivity of the nanoparticles is high enough, i.e. of the 10 -2 S cm -1 order, to be comparable to that of Nafion. Even though they possibly reduce the activity of Pt catalyst, layers containing sulfated zirconia as a proton conductor prove to be active as catalyst in fuel cell prototypes. Compared with conventional, Nafion-based cells, the maximum power density of the cells using sulfated zirconia is about one third. We believe that improvement in the preparation procedures for catalyst layers and membrane electrode assemblies will improve the cell performance. Therefore sulfated zirconia can be a valid proton conductor for fuel cell application.

  11. Surface geometry of tryptophan adsorbed on gold colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Hussain, Shafqat; Pang, Yoonsoo

    2015-09-01

    Two distinct surface-enhanced Raman (SER) spectra of tryptophan depending on the surface adsorption geometry were obtained by using colloidal gold nanoparticles reduced by borohydride and citrate ions. According to the vibrational assignments based on DFT simulations, the SER spectra of tryptamine and 3-indolepropionic acid, and the pH dependence of tryptophan SER spectrum, we found that some indole ring vibrations are very sensitive to the surface adsorption geometry of the molecules. With citrate-reduced gold colloids, tryptophan and related molecules mainly adsorb via the protonated amine group while maintaining a perpendicular geometry of the indole ring to the surface. However, a flat geometry of the indole ring to the surface is preferred on the borohydride-reduced gold colloids where the surface adsorption occurs mainly through the indole ring π electrons. By comparing our results with previous reports on the SER spectra of tryptophan on various silver and gold surfaces, we propose a general adsorption model of tryptophan on metal nanosurfaces.

  12. Cobalt silica magnetic nanoparticles with functional surfaces

    NASA Astrophysics Data System (ADS)

    Vadala, Michael L.; Zalich, Michael A.; Fulks, David B.; St. Pierre, Tim G.; Dailey, James P.; Riffle, Judy S.

    2005-05-01

    Cobalt nanoparticles encased in polysiloxane block copolymers have been heated at 600-700 °C to form protective shells around the particles, which contain crosslinked Si-O structures, and to anneal the cobalt. Methods to functionalize and modify the surfaces of the pyrolyzed/annealed silica-cobalt complexes with amines, isocyanates, poly(ethylene oxide), poly( L-lactide) and polydimethylsiloxane (PDMS) are presented.

  13. Surface, structural and tensile properties of proton beam irradiated zirconium

    NASA Astrophysics Data System (ADS)

    Rafique, Mohsin; Chae, San; Kim, Yong-Soo

    2016-02-01

    This paper reports the surface, structural and tensile properties of proton beam irradiated pure zirconium (99.8%). The Zr samples were irradiated by 3.5 MeV protons using MC-50 cyclotron accelerator at different doses ranging from 1 × 1013 to 1 × 1016 protons/cm2. Both un-irradiated and irradiated samples were characterized using Field Emission Scanning Electron Microscope (FESEM), X-ray Diffraction (XRD) and Universal Testing Machine (UTM). The average surface roughness of the specimens was determined by using Nanotech WSxM 5.0 develop 7.0 software. The FESEM results revealed the formation of bubbles, cracks and black spots on the samples' surface at different doses whereas the XRD results indicated the presence of residual stresses in the irradiated specimens. Williamson-Hall analysis of the diffraction peaks was carried out to investigate changes in crystallite size and lattice strain in the irradiated specimens. The tensile properties such as the yield stress, ultimate tensile stress and percentage elongation exhibited a decreasing trend after irradiation in general, however, an inconsistent behavior was observed in their dependence on proton dose. The changes in tensile properties of Zr were associated with the production of radiation-induced defects including bubbles, cracks, precipitates and simultaneous recovery by the thermal energy generated with the increase of irradiation dose.

  14. Paper surfaces for metal nanoparticle inkjet printing

    NASA Astrophysics Data System (ADS)

    Öhlund, Thomas; Örtegren, Jonas; Forsberg, Sven; Nilsson, Hans-Erik

    2012-10-01

    The widespread usage of paper and board offer largely unexploited possibilities for printed electronics applications. Reliability and performance of printed devices on comparatively rough and inhomogenous surfaces of paper does however pose challenges. Silver nanoparticle ink has been deposited on ten various paper substrates by inkjet printing. The papers are commercially available, and selected over a range of different types and construction. A smooth nonporous polyimide film was included as a nonporous reference substrate. The substrates have been characterized in terms of porosity, absorption rate, apparent surface energy, surface roughness and material content. The electrical conductivity of the resulting printed films have been measured after drying at 60 °C and again after additional curing at 110 °C. A qualitative analysis of the conductivity differences on the different substrates based on surface characterization and SEM examination is presented. Measurable parameters of importance to the final conductivity are pointed out, some of which are crucial to achieve conductivity. When certain criteria of the surfaces are met, paper media can be used as low cost, but comparably high performance substrates for metal nanoparticle inks in printed electronics applications.

  15. Pt nanoparticle-dispersed graphene-wrapped MWNT composites as oxygen reduction reaction electrocatalyst in proton exchange membrane fuel cell.

    PubMed

    Aravind, S S Jyothirmayee; Ramaprabhu, Sundara

    2012-08-01

    Chemical and electrical synergies between graphite oxide and multiwalled carbon nanotube (MWNT) for processing graphene wrapped-MWNT hybrids has been realized by chemical vapor deposition without any chemical functionalization. Potential of the hybrid composites have been demonstrated by employing them as electrocatalyst supports in proton exchange membrane fuel cells. The defects present in the polyelectrolyte, which have been wrapped over highly dispersed MWNT, act as anchoring sites for the homogeneous deposition of platinum nanoparticles. Single-cell proton exchange membrane fuel cells show that the power density of the hybrid composite-based fuel cells is higher compared to the pure catalyst-support-based fuel cells, because of enhanced electrochemical reactivity and good surface area of the nanocomposites. PMID:22850438

  16. Immobilization of Polymeric Luminophor on Nanoparticles Surface.

    PubMed

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-12-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor. PMID:27090657

  17. Surface Charge Controls the Suborgan Biodistributions of Gold Nanoparticles.

    PubMed

    Elci, Sukru Gokhan; Jiang, Ying; Yan, Bo; Kim, Sung Tae; Saha, Krishnendu; Moyano, Daniel F; Yesilbag Tonga, Gulen; Jackson, Liam C; Rotello, Vincent M; Vachet, Richard W

    2016-05-24

    Surface chemistry plays a deciding role in nanoparticle biodistribution, yet very little is known about how surface chemistry influences the suborgan distributions of nanomaterials. Here, using quantitative imaging based on laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), we demonstrate that surface charge dictates the suborgan distributions of nanoparticles in the kidney, liver, and spleen of mice intravenously injected with functionalized gold nanoparticles. Images of the kidney show that positively charged nanoparticles accumulate extensively in the glomeruli, the initial stage in filtering for the nephron, suggesting that these nanoparticles may be filtered by the kidney at a different rate than the neutral or negatively charged nanoparticles. We find that positively and negatively charged nanoparticles accumulate extensively in the red pulp of the spleen. In contrast, uncharged nanoparticles accumulate in the white pulp and marginal zone of the spleen to a greater extent than the positively or negatively charged nanoparticles. Moreover, these uncharged nanoparticles are also more likely to be found associated with Kupffer cells in the liver. Positively charged nanoparticles accumulate extensively in liver hepatocytes, whereas negatively charged nanoparticles show a broader distribution in the liver. Together these observations suggest that neutral nanoparticles having 2 nm cores may interact with the immune system to a greater extent than charged nanoparticles, highlighting the value of determining the suborgan distributions of nanomaterials for delivery and imaging applications. PMID:27164169

  18. Water-Mediated Proton Hopping on an Iron Oxide Surface

    SciTech Connect

    Merte, L. R.; Peng, Guowen; Bechstein, Ralf; Rieboldt, Felix; Farberow, Carrie A.; Grabow, Lars C.; Kudernatsch, Wilhelmine; Wendt, Stefen; Laegsgaard, E.; Mavrikakis, Manos; Besenbacher, Fleming

    2012-05-18

    The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H3O+-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO2(110), where water dissociation is a key step in proton diffusion.

  19. Surface spin polarization induced ferromagnetic Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Shih, Po-Hsun; Li, Wen-Hsien; Wu, Sheng Yun

    2016-05-01

    We report on the observation of ferromagnetic spin polarized moments in 4.5 nm Ag nanoparticles. Both ferromagnetic and diamagnetic responses to an applied magnetic field were detected. The spin polarized moments shown under non-linear thermoinduced magnetization appeared on the surface atoms, rather than on all the atoms in particles. The saturation magnetization departed substantially from the Bloch T3/2-law, showing the existence of magnetic anisotropy. The Heisenberg ferromagnetic spin wave model for Ha-aligned moments was then employed to identify the magnetic anisotropic energy gap of ~0.12 meV. Our results may be understood by assuming the surface magnetism model, in which the surface atoms give rise to polarized moments while the core atoms produce diamagnetic responses.

  20. Nanoparticle-based etching of silicon surfaces

    SciTech Connect

    Branz, Howard; Duda, Anna; Ginley, David S.; Yost, Vernon; Meier, Daniel; Ward, James S.

    2011-12-13

    A method (300) of texturing silicon surfaces (116) such to reduce reflectivity of a silicon wafer (110) for use in solar cells. The method (300) includes filling (330, 340) a vessel (122) with a volume of an etching solution (124) so as to cover the silicon surface 116) of a wafer or substrate (112). The etching solution (124) is made up of a catalytic nanomaterial (140) and an oxidant-etchant solution (146). The catalytic nanomaterial (140) may include gold or silver nanoparticles or noble metal nanoparticles, each of which may be a colloidal solution. The oxidant-etchant solution (146) includes an etching agent (142), such as hydrofluoric acid, and an oxidizing agent (144), such as hydrogen peroxide. Etching (350) is performed for a period of time including agitating or stirring the etching solution (124). The etch time may be selected such that the etched silicon surface (116) has a reflectivity of less than about 15 percent such as 1 to 10 percent in a 350 to 1000 nanometer wavelength range.

  1. WE-G-BRE-02: Biological Modeling of Gold Nanoparticle Radiosensitization for Proton Therapy

    SciTech Connect

    Lin, Y; Paganetti, H; Schuemann, J

    2014-06-15

    Purpose: The aim of this work is to investigate the radiosensitization effect of gold nanoparticles (GNP) in a proton beam. A computational model was built using the Local Effect Model (LEM) to predict the biological outcome of gold nanoparticle (GNP) sensitization. We present the results using a clinical proton beam, 6MV photon beam and two kilovoltage photon beams. Methods: First, Monte Carlo simulations were carried out using TOPAS (TOol for PArticle Simulation) to obtain the spatial dose distribution in the vicinity of GNPs. The dose distribution was then used as an input for LEM, which predicts dose-response curves for high linear energy transfer radiation using the track structure. The cell survival curves were evaluated for three particle sources (proton beam, MV photon beam and kV photon beam), various treatment depths for each particle source, various GNP uptakes and two different GNP sizes. Results: For proton therapy, the GNP sensitization effect is highly dependent on the treatment depth due to the energy-dependent interaction probability. We predict that if GNPs can be taken up by the cell nucleus, proton therapy can be significantly enhanced. If GNPs are only internalized into the cytoplasm, proton therapy can still be enhanced by GNPs and if GNPs are not internalized into cells, there will be no direct damage to the nucleus. For the same GNP uptake and concentration, the cell survival at 2Gy is reduced by 80% using kilovoltage photons, 50% using protons and only 2% using clinical MV photons. Finally, for the same weight of GNPs taken up by the cells, 10 nm GNPs causes 3 times more damage than 50 nm GNPs. Conclusion: We showed that GNPs have potential to be used to enhance radiation therapy for clinical proton beams.

  2. Surface free energy of alkali and transition metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Aqra, Fathi; Ayyad, Ahmed

    2014-09-01

    This paper addresses an interesting issue on the surface free energy of metallic nanoparticles as compared to the bulk material. Starting from a previously reported equation, a theoretical model, that involves a specific term for calculating the cohesive energy of nanoparticle, is established in a view to describe the behavior of surface free energy of metallic nanoparticles (using different shapes of particle: sphere, cube and disc). The results indicate that the behavior of surface energy is very appropriate for spherical nanoparticle, and thus, it is the most realistic shape of a nanoparticle. The surface energy of copper, silver, gold, platinum, tungsten, molybdenum, tantalum, paladium and alkali metallic nanoparticles is only prominent in the nanoscale size, and it decreases with the decrease of nanoparticle size. Thus, the surface free energy plays a more important role in determining the properties of nanoparticles than in bulk materials. It differs from shape to another, and falls down as the number of atoms (nanoparticle size) decreases. In the case of spherical nanoparticles, the onset of the sharp decrease in surface energy is observed at about 110 atom. A decrease of 16% and 45% in surface energy is found by moving from bulk to 110 atom and from bulk to 5 atom, respectively. The predictions are consistent with the reported data.

  3. The impacts of surface polarity on the solubility of nanoparticle.

    PubMed

    Zhu, Jianzhuo; Ou, Xinwen; Su, Jiguo; Li, Jingyuan

    2016-07-28

    In order to study the dependence of water solubility and hydration behavior of nanoparticles on their surface polarity, we designed polar nanoparticles with varying surface polarity by assigning atomic partial charge to the surface of C60. The water solubility of the nanoparticle is enhanced by several orders of magnitude after the introduction of surface polarity. Nevertheless, when the atomic partial charge grows beyond a certain value (qM), the solubility continuously decreases to the level of nonpolar nanoparticle. It should be noted that such qM is comparable with atomic partial charge of a variety of functional groups. The hydration behaviors of nanoparticles were then studied to investigate the non-monotonic dependence of solubility on the surface polarity. The interaction between the polar nanoparticle and the hydration water is stronger than the nonpolar counterpart, which should facilitate the dissolution of the nanoparticles. On the other hand, the surface polarity also reduces the interaction of hydration water with the other water molecules and enhances the interaction between the nanoparticles which may hinder their dispersion. Besides, the introduction of surface polarity disturbs and even rearranges the hydration structure of nonpolar nanoparticle. Interestingly, the polar nanoparticle with less ordered hydration structure tends to have higher water solubility. PMID:27475378

  4. The impacts of surface polarity on the solubility of nanoparticle

    NASA Astrophysics Data System (ADS)

    Zhu, Jianzhuo; Ou, Xinwen; Su, Jiguo; Li, Jingyuan

    2016-07-01

    In order to study the dependence of water solubility and hydration behavior of nanoparticles on their surface polarity, we designed polar nanoparticles with varying surface polarity by assigning atomic partial charge to the surface of C60. The water solubility of the nanoparticle is enhanced by several orders of magnitude after the introduction of surface polarity. Nevertheless, when the atomic partial charge grows beyond a certain value (qM), the solubility continuously decreases to the level of nonpolar nanoparticle. It should be noted that such qM is comparable with atomic partial charge of a variety of functional groups. The hydration behaviors of nanoparticles were then studied to investigate the non-monotonic dependence of solubility on the surface polarity. The interaction between the polar nanoparticle and the hydration water is stronger than the nonpolar counterpart, which should facilitate the dissolution of the nanoparticles. On the other hand, the surface polarity also reduces the interaction of hydration water with the other water molecules and enhances the interaction between the nanoparticles which may hinder their dispersion. Besides, the introduction of surface polarity disturbs and even rearranges the hydration structure of nonpolar nanoparticle. Interestingly, the polar nanoparticle with less ordered hydration structure tends to have higher water solubility.

  5. Nanoparticles of mesoporous SO3H-functionalized Si-MCM-41 with superior proton conductivity.

    PubMed

    Marschall, Roland; Bannat, Inga; Feldhoff, Armin; Wang, Lianzhou; Lu, Gao Qing Max; Wark, Michael

    2009-04-01

    Nanometer-sized mesoporous silica particles of around 100-nm diameter functionalized with a large amount of sulfonic acid groups are prepared using a simple and fast in situ co-condensation procedure. A highly ordered hexagonal pore structure is established by applying a pre-hydrolysis step in a high-dilution synthesis approach, followed by adding the functionalization agent to the reaction mixture. The high-dilution approach is advantageous for the in situ functionalization since no secondary reagents for an effective particle and framework formation are needed. Structural data are determined via electron microscopy, nitrogen adsorption, and X-ray diffraction, proton conductivity values of the functionalized samples are measured via impedance spectroscopy. The obtained mesoporous SO(3)H-MCM-41 nanoparticles demonstrate superior proton conductivity than their equally loaded micrometer-sized counterparts, up to 5 x 10(-2) S cm(-1). The mesoporosity of the particles turns out to be very important for effective proton transport since non-porous silica nanoparticles exhibit worse efficient proton transport, and the obtained particle size dependence might open up a new route in rational design of highly proton conductive materials. PMID:19226596

  6. Surface-enhanced Raman scattering of coumarin 343 on silver colloidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Hussain, Shafqat; Pang, Yoonsoo

    2016-09-01

    Surface-enhanced Raman scattering (SERS) of coumarin 343 (C343) adsorbed on silver colloidal nanoparticles reduced by sodium citrate was investigated and the surface adsorption geometry of C343 on Ag was sought by optimizing C343-Ag complexes for neutral and deprotonated C343 molecules in the DFT simulations. The SERS of C343 showed a number of spectral changes upon solution pH change. We found that deprotonated C343 adsorbs on the Ag nanoparticles through the carboxylate group keeping a perpendicular geometry to the surface. When protonated, the adsorption geometry of C343 is changed into more or less flat to the surface as the cyclic ester group becomes a preferred surface adsorption site.

  7. Surface-enhanced Raman scattering of coumarin 343 on silver colloidal nanoparticles.

    PubMed

    Hussain, Shafqat; Pang, Yoonsoo

    2016-09-01

    Surface-enhanced Raman scattering (SERS) of coumarin 343 (C343) adsorbed on silver colloidal nanoparticles reduced by sodium citrate was investigated and the surface adsorption geometry of C343 on Ag was sought by optimizing C343-Ag complexes for neutral and deprotonated C343 molecules in the DFT simulations. The SERS of C343 showed a number of spectral changes upon solution pH change. We found that deprotonated C343 adsorbs on the Ag nanoparticles through the carboxylate group keeping a perpendicular geometry to the surface. When protonated, the adsorption geometry of C343 is changed into more or less flat to the surface as the cyclic ester group becomes a preferred surface adsorption site. PMID:27224016

  8. Surface modification of magnetic nanoparticles in biomedicine

    NASA Astrophysics Data System (ADS)

    Chu, Xin; Yu, Jing; Hou, Yang-Long

    2015-01-01

    Progress in surface modification of magnetic nanoparticles (MNPs) is summarized with regard to organic molecules, macromolecules and inorganic materials. Many researchers are now devoted to synthesizing new types of multi-functional MNPs, which show great application potential in both diagnosis and treatment of disease. By employing an ever-greater variety of surface modification techniques, MNPs can satisfy more and more of the demands of medical practice in areas like magnetic resonance imaging (MRI), fluorescent marking, cell targeting, and drug delivery. Project supported by the National Natural Science Foundation of China (Grant Nos. 51125001 and 51172005), the Natural Science Foundation of Beijing,China (Grant No. 2122022), the Science Fund for Creative Research Groups of the National Natural Science Foundation of China (Grant No. 81421004), and the Doctoral Program of the Education Ministry of China (Grant No. 20120001110078).

  9. Surface-modified multifunctional MIP nanoparticles

    NASA Astrophysics Data System (ADS)

    Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; Perez de Vargas Sansalvador, Isabel; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J.; Piletsky, Sergey

    2013-04-01

    The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinylferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors.The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as a protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity

  10. Investigation of gold nanoparticle radiosensitization mechanisms using a free radical scavenger and protons of different energies.

    PubMed

    Jeynes, J C G; Merchant, M J; Spindler, A; Wera, A-C; Kirkby, K J

    2014-11-01

    Gold nanoparticles (GNPs) have been shown to sensitize cancer cells to x-ray radiation, particularly at kV energies where photoelectric interactions dominate and the high atomic number of gold makes a large difference to x-ray absorption. Protons have a high cross-section for gold at a large range of relevant clinical energies, and so potentially could be used with GNPs for increased therapeutic effect.Here, we investigate the contribution of secondary electron emission to cancer cell radiosensitization and investigate how this parameter is affected by proton energy and a free radical scavenger. We simulate the emission from a realistic cell phantom containing GNPs after traversal by protons and x-rays with different energies. We find that with a range of proton energies (1-250 MeV) there is a small increase in secondaries compared to a much larger increase with x-rays. Secondary electrons are known to produce toxic free radicals. Using a cancer cell line in vitro we find that a free radical scavenger has no protective effect on cells containing GNPs irradiated with 3 MeV protons, while it does protect against cells irradiated with x-rays. We conclude that GNP generated free radicals are a major cause of radiosensitization and that there is likely to be much less dose enhancement effect with clinical proton beams compared to x-rays. PMID:25296027

  11. Investigation of gold nanoparticle radiosensitization mechanisms using a free radical scavenger and protons of different energies

    NASA Astrophysics Data System (ADS)

    Jeynes, J. C. G.; Merchant, M. J.; Spindler, A.; Wera, A.-C.; Kirkby, K. J.

    2014-10-01

    Gold nanoparticles (GNPs) have been shown to sensitize cancer cells to x-ray radiation, particularly at kV energies where photoelectric interactions dominate and the high atomic number of gold makes a large difference to x-ray absorption. Protons have a high cross-section for gold at a large range of relevant clinical energies, and so potentially could be used with GNPs for increased therapeutic effect. Here, we investigate the contribution of secondary electron emission to cancer cell radiosensitization and investigate how this parameter is affected by proton energy and a free radical scavenger. We simulate the emission from a realistic cell phantom containing GNPs after traversal by protons and x-rays with different energies. We find that with a range of proton energies (1-250 MeV) there is a small increase in secondaries compared to a much larger increase with x-rays. Secondary electrons are known to produce toxic free radicals. Using a cancer cell line in vitro we find that a free radical scavenger has no protective effect on cells containing GNPs irradiated with 3 MeV protons, while it does protect against cells irradiated with x-rays. We conclude that GNP generated free radicals are a major cause of radiosensitization and that there is likely to be much less dose enhancement effect with clinical proton beams compared to x-rays.

  12. Cell Surface-based Sensing with Metallic Nanoparticles

    PubMed Central

    Jiang, Ziwen; Rotello, Vincent M.

    2015-01-01

    Metallic nanoparticles provide versatile scaffolds for biosensing applications. In this review, we focus on the use of metallic nanoparticles for cell surface sensings. Examples of the use of both specific recognition and array-based “chemical nose” approaches to cell surface sensing will be discussed. PMID:25853985

  13. Surface-modified multifunctional MIP nanoparticles

    PubMed Central

    Moczko, Ewa; Poma, Alessandro; Guerreiro, Antonio; de Vargas Sansalvador, Isabel Perez; Caygill, Sarah; Canfarotta, Francesco; Whitcombe, Michael J.; Piletsky, Sergey

    2015-01-01

    The synthesis of core-shell molecularly imprinted polymer nanoparticles (MIP NPs) has been performed using a novel solid-phase approach on immobilised templates. The same solid phase also acts as protective functionality for high affinity binding sites during subsequent derivatisation/shell formation. This procedure allows for the rapid synthesis, controlled separation and purification of high-affinity materials, with each production cycle taking just 2 hours. The aim of this approach is to synthesise uniformly-sized imprinted materials at the nanoscale which can be readily grafted with various polymers without affecting their affinity and specificity. For demonstration purposes we grafted anti-melamine MIP NPs with coatings which introduce the following surface characteristics: high polarity (PEG methacrylate); electro-activity (vinyl ferrocene); fluorescence (eosin acrylate); thiol groups (pentaerythritol tetrakis(3-mercaptopropionate)). The method has broad applicability and can be used to produce multifunctional imprinted nanoparticles with potential for further application in the biosensors, diagnostics and biomedical fields and as an alternative to natural receptors. PMID:23503559

  14. Acellular assessments of engineered-manufactured nanoparticle biological surface reactivity

    EPA Science Inventory

    It is critical to assess the surface properties and reactivity of engineered-manufactured nanoparticles (NPs) as these will influence their interactions with biological systems, biokinetics and toxicity. We examined the physicochemical properties and surface reactivity of metal o...

  15. Effects of surface chemistry and size on iron oxide nanoparticle delivery of oligonucleotides

    NASA Astrophysics Data System (ADS)

    Shen, Christopher

    The discovery of RNA interference and the increasing understanding of disease genetics have created a new class of potential therapeutics based on oligonucleotides. This therapeutic class includes antisense molecules, small interfering RNA (siRNA), and microRNA modulators such as antagomirs (antisense directed against microRNA) and microRNA mimics, all of which function by altering gene expression at the translational level. While these molecules have the promise of treating a host of diseases from neurological disorders to cancer, a major hurdle is their inability to enter cells on their own, where they may render therapeutic effect. Nanotechnology is the engineering of materials at the nanometer scale and has gained significant interest for nucleic acid delivery due to its biologically relevant length-scale and amenability to multifunctionality. While a number of nanoparticle vehicles have shown promise for oligonucleotide delivery, there remains a lack of understanding of how nanoparticle coating and size affect these delivery processes. This dissertation seeks to elucidate some of these factors by evaluating oligonucleotide delivery efficiencies of a panel of iron oxide nanoparticles with varying cationic coatings and sizes. A panel of uniformly-sized nanoparticles was prepared with surface coatings comprised of various amine groups representing high and low pKas. A separate panel of nanoparticles with sizes of 40, 80, 150, and 200 nm but with the same cationic coating was also prepared. Results indicated that both nanoparticle surface coating and nanoparticle hydrodynamic size affect transfection efficiency. Specific particle coatings and sizes were identified that gave superior performance. The intracellular fate of iron oxide nanoparticles was also tracked by electron microscopy and suggests that they function via the proton sponge effect. The research presented in this dissertation may aid in the rational design of improved nanoparticle delivery vectors for

  16. WE-G-BRE-04: Gold Nanoparticle Induced Vasculature Damage for Proton Therapy: Monte Carlo Simulation

    SciTech Connect

    Lin, Y; Paganetti, H; Schuemann, J

    2014-06-15

    Purpose: The aim of this work is to investigate the gold nanoparticle (GNP) induced vasculature damage in a proton beam. We compared the results using a clinical proton beam, 6MV photon beam and two kilovoltage photon beams. Methods: Monte Carlo simulations were carried out using TOPAS (TOol for PArticle Simulation) to obtain the spatial dose distribution in close proximity to GNPs up to 20μm distance. The spatial dose distribution was used as an input to calculate the additional dose deposited to the blood vessels. For this study, GNP induced vasculature damage is evaluated for three particle sources (proton beam, MV photon beam and kV photon beam), various treatment depths for each particle source, various GNP uptakes and three different vessel diameters (8μm, 14μm and 20μm). Results: The result shows that for kV photon, GNPs induce more dose in the vessel wall for 150kVp photon source than 250kVp. For proton therapy, GNPs cause more dose in the vessel wall at shallower treatment depths. For 6MV photons, GNPs induce more dose in the vessel wall at deeper treatment depths. For the same GNP concentration and prescribed dose, the additional dose at the inner vessel wall is 30% more than the prescribed dose for the kVp photon source, 15% more for the proton source and only 2% more for the 6MV photon source. In addition, the dose from GNPs deceases sharper for proton therapy than kVp photon therapy as the distance from the vessel inner wall increases. Conclusion: We show in this study that GNPs can potentially be used to enhance radiation therapy by causing vasculature damage using clinical proton beams. The GNP induced damage for proton therapy is less than for the kVp photon source but significantly larger than for the clinical MV photon source.

  17. Proton-Resistant Quantum Dots: Stability in Gastrointestinal Fluids and Implications for Oral Delivery of Nanoparticle Agents.

    PubMed

    Mohs, Aaron M; Duan, Hongwei; Kairdolf, Brad A; Smith, Andrew M; Nie, Shuming

    2009-06-01

    Semiconductor quantum dots (QDs) have shown great promise as fluorescent probes for molecular, cellular and in-vivo imaging. However, the fluorescence of traditional polymer-encapsulated QDs is often quenched by proton-induced etching in acidic environments. This is a major problem for QD applications in the gastrointestinal tract because the gastric (stomach) environment is strongly acidic (pH 1-2). Here we report the use of proton-resistant surface coatings to stabilize QD fluorescence under acidic conditions. Using both hyperbranched polyethylenimine (PEI) and its polyethylene glycol derivative (PEG grafted PEI), we show that the fluorescence of core-shell CdSe/CdS/ZnS QDs is effectively protected from quenching in simulated gastric fluids. In comparison, amphiphilic lipid or polymer coatings provide no protection under similarly acidic conditions. The proton-resistant QDs are found to cause moderate membrane damage to cultured epithelial cells, but PEGylation (PEG grafting) can be used to reduce cellular toxicity and to improved nanoparticle stability. PMID:20379372

  18. Protein Binding for Detection of Small Changes on Nanoparticle Surface

    PubMed Central

    Zeng, Shang; Huang, Yu-ming M.; Chang, Chia-en A.; Zhong, Wenwan

    2014-01-01

    Protein adsorption on nanoparticles is closely associated with the physicochemical properties of particles, in particular, their surface property. We synthesized two batches of polyacrylic acid-coated nanoparticles under almost identical conditions except for heating duration and found differences in the head-group structure of the polyacrylic acid. The structure change was confirmed by NMR and MS. The two batches of particles had varied binding affinities to a selected group of proteins. Computational work confirmed that the head group of the polymer on the surface of a nanoparticle could directly interact with a protein, and small structural changes in the head group were sufficient to result in a significant difference in the free energy of binding. Our results demonstrate that protein adsorption is so sensitive to the surface property of particles that it can reveal even small variations in the structure of a nanoparticle surface ligand, and should be useful for quick assessment of nanoparticle properties. PMID:24482794

  19. The electrochemisty of surface modified <10 nm metal oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Roberts, Joseph J. P.

    Chapter One provides a general introduction of the research on metal oxide nanoparticles (MOx), highlighting their synthesis, surface modification, and functionalization. Emphasis is given to the different synthetic route for producing small (<10 nm) MOx nanoparticles with narrow size distributions. Different methods for modifying their surface with small organic molecules are discussed with focus given to silanes and phosphates. Furthermore, functionalizing surface modified nanoparticles for specific functions is addressed, with markers for analytically relevant nanoscale quantification being the primary focus. Chapter Two describes in detail the thermal degradation synthesis used for the generation of small MOx nanoparticles. It demonstrates the versatile of the synthesis by successfully synthesizing ZrO 2 and IrO2 nanoparticles. Preliminary work involving the formation of Bi2S3, Bi2O3, and RuO2 nanomaterials is also addressed. The solvothermal synthesis of indium tin oxide (ITO) is also shown for comparison to ITO produced by thermal degradation. Chapter Three details the surface modification of ITO nanoparticles and subsequent electrochemical tagging with a ferrocene moiety. ITO nanoparticles were synthesized via thermal degradation. These nanoparticles underwent a ligand exchange with a covalently binding mondentate silane terminated with a primary amine. Acyl chloride coupling between the amine and chlorocarbonylferrocene provided an electrochemical tag to quantify the level of surface modification. Electrochemisty of the quasi-diffusing nanoparticles was evaluated via cyclic voltammetry (CV), chronoamperometry (CA), and mircodisk electrode (microE) experiments. Chapter Four investigates spectroscopic tagging of ITO and ZrO2 nanoparticles as well as electrochemical tagging of ZrO 2 and IrO2 nanoparticles. An unbound azo-dye was synthesized and attempts were made to attach the dye to the surface of ITO nanoparticles. Imine couple between a spectroscopic tag

  20. Antibacterial releasing titanium surface using albumin nanoparticle carriers.

    PubMed

    Kim, Da Hye; Kim, Kyo-Han; Kwon, Tae-Yub; Choi, Seok Hwa; Kang, Seong Soo; Kwon, Soon-Taek; Cho, Dae-Hyun; Kim, Hee Dong; Son, Jun Sik

    2014-11-01

    We developed a simple and highly efficient method for delivery from titanium (Ti) surfaces using albumin nanoparticle carriers. A Ti disc with a resorbable blasting media surface was used as a metal implant with a localized drug delivery structure. Human serum albumin (HSA) nanoparticles loaded with chlorhexidine (CHX) diacetate salt hydrate as the model drug were fabricated using a desolvation technique. The CHX-loaded HSA nanoparticles produced were cross linked with glutaraldehyde (GA). The nanoparticles were pre-coated with positively-charged polyethylenimine (PEI) molecules and then immobilized via electrical interactions on the negatively charged Ti disc surface. Our results suggested that the PEI-coated HSA nanoparticles loaded with CHX (PEI-CHX-HSA) were incorporated successfully and well-dispersed on the Ti disc surfaces. The agar diffusion test on the Ti surface treated with PEI-CHX-HSA nanoparticles showed a larger growth inhibition zone of Streptococcus mutans versus the control Ti surface, suggesting that this innovative delivery platform imparts potent antibacterial activity to the Ti surface. Thus, CHX, which inhibits the growth of oral bacteria, can be efficiently incorporated onto Ti surfaces by using HSA nanoparticles. PMID:25958539

  1. Interaction of surface-modified silica nanoparticles with clay minerals

    NASA Astrophysics Data System (ADS)

    Omurlu, Cigdem; Pham, H.; Nguyen, Q. P.

    2016-05-01

    In this study, the adsorption of 5-nm silica nanoparticles onto montmorillonite and illite is investigated. The effect of surface functionalization was evaluated for four different surfaces: unmodified, surface-modified with anionic (sulfonate), cationic (quaternary ammonium (quat)), and nonionic (polyethylene glycol (PEG)) surfactant. We employed ultraviolet-visible spectroscopy to determine the concentration of adsorbed nanoparticles in conditions that are likely to be found in subsurface reservoir environments. PEG-coated and quat/PEG-coated silica nanoparticles were found to significantly adsorb onto the clay surfaces, and the effects of electrolyte type (NaCl, KCl) and concentration, nanoparticle concentration, pH, temperature, and clay type on PEG-coated nanoparticle adsorption were studied. The type and concentration of electrolytes were found to influence the degree of adsorption, suggesting a relationship between the interlayer spacing of the clay and the adsorption ability of the nanoparticles. Under the experimental conditions reported in this paper, the isotherms for nanoparticle adsorption onto montmorillonite at 25 °C indicate that adsorption occurs less readily as the nanoparticle concentration increases.

  2. Water at hydrophobic interfaces delays proton surface-to-bulk transfer and provides a pathway for lateral proton diffusion.

    PubMed

    Zhang, Chao; Knyazev, Denis G; Vereshaga, Yana A; Ippoliti, Emiliano; Nguyen, Trung Hai; Carloni, Paolo; Pohl, Peter

    2012-06-19

    Fast lateral proton migration along membranes is of vital importance for cellular energy homeostasis and various proton-coupled transport processes. It can only occur if attractive forces keep the proton at the interface. How to reconcile this high affinity to the membrane surface with high proton mobility is unclear. Here, we tested whether a minimalistic model interface between an apolar hydrophobic phase (n-decane) and an aqueous phase mimics the biological pathway for lateral proton migration. The observed diffusion span, on the order of tens of micrometers, and the high proton mobility were both similar to the values previously reported for lipid bilayers. Extensive ab initio simulations on the same water/n-decane interface reproduced the experimentally derived free energy barrier for the excess proton. The free energy profile G(H(+)) adopts the shape of a well at the interface, having a width of two water molecules and a depth of 6 ± 2RT. The hydroniums in direct contact with n-decane have a reduced mobility. However, the hydroniums in the second layer of water molecules are mobile. Their in silico diffusion coefficient matches that derived from our in vitro experiments, (5.7 ± 0.7) 10(-5) cm(2) s(-1). Conceivably, these are the protons that allow for fast diffusion along biological membranes. PMID:22675120

  3. Water at hydrophobic interfaces delays proton surface-to-bulk transfer and provides a pathway for lateral proton diffusion

    PubMed Central

    Zhang, Chao; Knyazev, Denis G.; Vereshaga, Yana A.; Ippoliti, Emiliano; Nguyen, Trung Hai; Carloni, Paolo; Pohl, Peter

    2012-01-01

    Fast lateral proton migration along membranes is of vital importance for cellular energy homeostasis and various proton-coupled transport processes. It can only occur if attractive forces keep the proton at the interface. How to reconcile this high affinity to the membrane surface with high proton mobility is unclear. Here, we tested whether a minimalistic model interface between an apolar hydrophobic phase (n-decane) and an aqueous phase mimics the biological pathway for lateral proton migration. The observed diffusion span, on the order of tens of micrometers, and the high proton mobility were both similar to the values previously reported for lipid bilayers. Extensive ab initio simulations on the same water/n-decane interface reproduced the experimentally derived free energy barrier for the excess proton. The free energy profile GH+ adopts the shape of a well at the interface, having a width of two water molecules and a depth of 6 ± 2RT. The hydroniums in direct contact with n-decane have a reduced mobility. However, the hydroniums in the second layer of water molecules are mobile. Their in silico diffusion coefficient matches that derived from our in vitro experiments, (5.7 ± 0.7) × 10-5 cm2 s-1. Conceivably, these are the protons that allow for fast diffusion along biological membranes. PMID:22675120

  4. Nanoshells made easy: improving Au layer growth on nanoparticle surfaces.

    PubMed

    Brinson, Bruce E; Lassiter, J Britt; Levin, Carly S; Bardhan, Rizia; Mirin, Nikolay; Halas, Naomi J

    2008-12-16

    The growth of a continuous, uniform Au layer on a dielectric nanoparticle is the critical step in the synthesis of nanoparticles such as nanoshells or nanorice, giving rise to their unique geometry-dependent plasmon resonant properties. Here, we report a novel, streamlined method for Au layer metallization on prepared nanoparticle surfaces using carbon monoxide as the reducing agent. This approach consistently yields plasmonic nanoparticles with highly regular shell layers and is immune to variations in precursor or reagent preparation. Single particle spectroscopy combined with scanning electron microscopy reveal that thinner, more uniform shell layers with correspondingly red-shifted optical resonances are achievable with this approach. PMID:19360963

  5. Surface Characterization of Nanoparticles: Critical Needs and Significant Challenges.

    SciTech Connect

    Baer, Donald R.

    2011-03-01

    There is a growing recognition that nanoparticles and other nanostructured materials are sometimes inadequately characterized and that this may limit or even invalidate some of the conclusions regarding particle properties and behavior. A number of international organizations are working to establish the essential measurement requirements that enable adequate understanding of nanoparticle properties for both technological applications and for environmental health issues. Our research on the interaction of iron metal-core oxide-shell nanoparticles with environmental contaminants and studies of the behaviors of ceria nanoparticles, with a variety of medical, catalysis and energy applications, have highlighted a number of common nanoparticle characterization challenges that have not been fully recognized by parts of the research community. This short review outlines some of these characterization challenges based on our research observations and using other results reported in the literature. Issues highlighted include: 1) the importance of surfaces and surface characterization, 2) nanoparticles are often not created equal - subtle differences in synthesis and processing can have large impacts; 3) nanoparticles frequently change with time having lifetime implications for products and complicating understanding of health and safety impacts; 4) the high sensitivity of nanoparticles to their environment complicates characterization and applications in many ways; 5) nanoparticles are highly unstable and easily altered (damaged) during analysis.

  6. Tuning of nanoparticle biological functionality through controlled surface chemistry and characterisation at the bioconjugated nanoparticle surface

    NASA Astrophysics Data System (ADS)

    Hristov, Delyan R.; Rocks, Louise; Kelly, Philip M.; Thomas, Steffi S.; Pitek, Andrzej S.; Verderio, Paolo; Mahon, Eugene; Dawson, Kenneth A.

    2015-12-01

    We have used a silica - PEG based bionanoconjugate synthetic scheme to study the subtle connection between cell receptor specific recognition and architecture of surface functionalization chemistry. Extensive physicochemical characterization of the grafted architecture is capable of capturing significant levels of detail of both the linker and grafted organization, allowing for improved reproducibility and ultimately insight into biological functionality. Our data suggest that scaffold details, propagating PEG layer architecture effects, determine not only the rate of uptake of conjugated nanoparticles into cells but also, more significantly, the specificity of pathways via which uptake occurs.

  7. Application of Surface Chemical Analysis Tools for Characterization of Nanoparticles

    SciTech Connect

    Baer, Donald R.; Gaspar, Daniel J.; Nachimuthu, Ponnusamy; Techane, Sirnegeda D.; Castner, David G.

    2010-02-01

    The important role that surface chemical analysis methods can and should play in the characterization of nanoparticles is described. The types of information that can be obtained from analysis of nanoparticles using Auger electron spectroscopy (AES); X-ray photoelectron spectroscopy (XPS); time of flight secondary ion mass spectrometry (TOF-SIMS); low energy ion scattering (LEIS); and scanning probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), are briefly summarized. Examples describing the characterization of engineered nanoparticles are provided. Specific analysis considerations and issues associated with using surface analysis methods for the characterization of nanoparticles are discussed and summarized, along with the impact that shape instability, environmentally induced changes, deliberate and accidental coating, etc., have on nanoparticle properties.

  8. Application of Surface Chemical Analysis Tools for Characterization of Nanoparticles

    PubMed Central

    Baer, DR; Gaspar, DJ; Nachimuthu, P; Techane, SD; Castner, DG

    2010-01-01

    The important role that surface chemical analysis methods can and should play in the characterization of nanoparticles is described. The types of information that can be obtained from analysis of nanoparticles using Auger electron spectroscopy (AES); X-ray photoelectron spectroscopy (XPS); time of flight secondary ion mass spectrometry (TOF-SIMS); low energy ion scattering (LEIS); and scanning probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), are briefly summarized. Examples describing the characterization of engineered nanoparticles are provided. Specific analysis considerations and issues associated with using surface analysis methods for the characterization of nanoparticles are discussed and summarized, along with the impact that shape instability, environmentally induced changes, deliberate and accidental coating, etc., have on nanoparticle properties. PMID:20052578

  9. Surface controlled magnetic properties of Fe3O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Mohapatra, Jeotikanta; Mitra, Arijit; Bahadur, D.; Aslam, M.

    2013-02-01

    To understand the influence of surface organic-inorganic interactions on the magnetic properties of magnetic nanoparticles, magnetite (Fe3O4) of mean size 4-16 nm (standard deviation σ ≤ 15 %) are synthesized by three different thermolysis techniques. The surface functionality is controlled through either amine or amine-acid both taking as surfactant for Fe3O4 nanoparticles synthesis. Magnetic investigations revealed that samples prepared using amine as a multifunctional agent (only one surfactant) shows superior magnetic properties than the nanoparticles produced by the approach utilizing oleic acid and oleylamine.

  10. Cowpea mosaic virus nanoparticles target surface vimentin on cancer cells

    PubMed Central

    Steinmetz, Nicole F; Cho, Choi-Fong; Ablack, Amber; Lewis, John D; Manchester, Marianne

    2011-01-01

    Aims Vimentin, a type III intermediate filament, is upregulated during epithelial–mesenchymal transition and tumor progression. Vimentin is surface-expressed on cells involved in inflammation; the function remains unknown. We investigated the expression of surface vimentin on cancer cells and evaluated targeting nanoparticles to tumors exploiting vimentin. Materials & methods Cowpea mosaic virus nanoparticles that interact with surface vimentin were used as probes. Tumor homing was tested using the chick chorioallantoic membrane model with human tumor xenografts. Results & discussion Surface vimentin levels varied during cell cycle and among the cell lines tested. Surface vimentin expression correlated with cowpea mosaic virus uptake, underscoring the utility of cowpea mosaic virus to detect invasive cancer cells. Targeting to tumor xenografts was observed; homing was based on the enhanced permeability and retention effect. Our data provide novel insights into the role of surface vimentin in cancer and targeting nanoparticles in vivo. PMID:21385137

  11. Facile preparation of superhydrophobic surfaces based on metal oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Bao, Xue-Mei; Cui, Jin-Feng; Sun, Han-Xue; Liang, Wei-Dong; Zhu, Zhao-Qi; An, Jin; Yang, Bao-Ping; La, Pei-Qing; Li, An

    2014-06-01

    A novel method for fabrication of superhydrophobic surfaces was developed by facile coating various metal oxide nanoparticles, including ZnO, Al2O3 and Fe3O4, on various substrates followed by treatment with polydimethylsiloxane (PDMS) via chemical vapor deposition (CVD) method. Using ZnO nanoparticles as a model, the changes in the surface chemical composition and crystalline structures of the metal oxide nanoparticles by PDMS treatment were investigated by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) analysis. The results show that the combination of the improved surface roughness generated from of the nanoparticles aggregation with the low surface-energy of silicon-coating originated from the thermal pyrolysis of PDMS would be responsible for the surface superhydrophobicity. By a simple dip-coating method, we show that the metal oxide nanoparticles can be easily coated onto the surfaces of various textural and dimensional substrates, including glass slide, paper, fabric or sponge, for preparation of superhydrophobic surfaces for different purpose. The present strategy may provide an inexpensive and new route to surperhydrophobic surfaces, which would be of technological significance for various practical applications especially for separation of oils or organic contaminates from water.

  12. Asymmetric light reflectance from metal nanoparticle arrays on dielectric surfaces

    PubMed Central

    Huang, K.; Pan, W.; Zhu, J. F.; Li, J. C.; Gao, N.; Liu, C.; Ji, L.; Yu, E. T.; Kang, J.Y.

    2015-01-01

    Asymmetric light reflectance associated with localized surface plasmons excited in metal nanoparticles on a quartz substrate is observed and analyzed. This phenomenon is explained by the superposition of two waves, the wave reflected by the air/quartz interface and that reflected by the metal nanoparticles, and the resulting interference effects. Far field behavior investigation suggests that zero reflection can be achieved by optimizing the density of metal nanoparticles. Near field behavior investigation suggests that the coupling efficiency of localized surface plasmon can be additionally enhanced by separating the metal NPs from substrates using a thin film with refractive index smaller than the substrate. The latter behavior is confirmed via surface-enhanced Raman spectroscopy studies using metal nanoparticles on Si/SiO2 substrates. PMID:26679353

  13. Molecular dynamics study of proton binding to silica surfaces

    SciTech Connect

    Rustad, J.R.; Wasserman, E.; Felmy, A.R.; Wilke, C.

    1998-02-01

    Molecular statics calculations on gas-phase and solvated clusters and on gas-phase and solvated slabs representing aqueous species and surfaces were applied to investigate acid/base reactions on silica surfaces. The gas-phase approach, which was previously applied to goethite, predicts a surface pK{sub a} of 8.5 for the reaction > SiOH {yields} > SiO{sup {minus}} + H{sup +} which is in good agreement with estimates based on potentiometric titration. However, the model gives an unrealistically large pK{sub a} for the reaction > SiOH{sub 2}{sup +} {yields} > SiOH + H{sup +}. The model dependence of this result was checked by using two different types of interaction potentials, one based on quantum mechanical calculations on H{sub 4}SiO{sub 4} clusters, and another empirical model fitted to the structure and elastic properties of {alpha}-quartz. Because these models gave similar results, the authors hypothesize that the failure of the gas-phase models is due to intrinsic solvation effects not accounted for by previously developed correlations. They tested this idea by carrying out energy minimization calculations on gas-phase clusters with one hydration shell as well as molecular dynamics simulations on fully-solvated H{sub 5}SiO{sub 4}{sup +} and a fully solvated (0001) surface of {beta}-quartz. Though the authors are unable to establish a quantitative measure of the pK{sub a} of SiOH{sub 2} groups, the solvated systems do indicate that SiOH groups do not protonate in any of the solvated models.

  14. Neutralization of a proton at adsorbate-covered metal surfaces

    NASA Astrophysics Data System (ADS)

    Kato, M.; O'Connor, D. J.; Yamamoto, K.; Souda, R.

    1996-08-01

    Charge exchange between a proton and adatoms on the metal substrates has been studied theoretically. The neutral fraction may increase or decrease, depending on the electronic environments of the adatom. The neutral yield of a proton depends significantly on the interaction between the adatom and the substrate metal. One remarkable aspect is the creative or destructive interference between two charge-exchange processes: one is the neutralization between the proton and the adatom, and the other is the neutralization between the proton and the substrate metal. Using the parameter values derived from molecular orbital calculations for cluster atoms, the remarkable interference effect is demonstrated.

  15. Mapping and Quantifying Surface Charges on Clay Nanoparticles.

    PubMed

    Liu, Jun; Gaikwad, Ravi; Hande, Aharnish; Das, Siddhartha; Thundat, Thomas

    2015-09-29

    Understanding the electrical properties of clay nanoparticles is very important since they play a crucial role in every aspect of oil sands processing, from bitumen extraction to sedimentation in mature fine tailings (MFT). Here, we report the direct mapping and quantification of surface charges on clay nanoparticles using Kelvin probe force microscopy (KPFM) and electrostatic force microscopy (EFM). The morphology of clean kaolinite clay nanoparticles shows a layered structure, while the corresponding surface potential map shows a layer-dependent charge distribution. More importantly, a surface charge density of 25 nC/cm(2) was estimated for clean kaolinite layers by using EFM measurements. On the other hand, the EFM measurements show that the clay particles obtained from the tailings demonstrate a reduced surface charge density of 7 nC/cm(2), which may be possibly attributed to the presence of various bituminous compounds residing on the clay surfaces. PMID:26352908

  16. Assembly of surface engineered nanoparticles for functional materials

    NASA Astrophysics Data System (ADS)

    Yu, Xi

    Nanoparticles are regarded as exciting new building blocks for functional materials due to their fascinating physical properties because of the nano-confinement. Organizing nanoparticles into ordered hierarchical structures are highly desired for constructing novel optical and electrical artificial materials that are different from their isolated state or thermodynamics random ensembles. My research integrates the surface chemistry of nanoparticles, interfacial assembly and lithography techniques to construct nanoparticle based functional structures. We designed and synthesized tailor-made ligands for gold, semiconductor and magnetic nanoparticle, to modulate the assembly process and collective properties of the assembled structures, by controlling the key parameters such as particle-interface interaction, dielectric environments and inter-particle coupling etc. Top-down technologies such as micro contact printing, photolithography and nanoimprint lithography are used to guide the assembly into arbitrarily predesigned structures for potential device applications.

  17. Fundamental and applied localized surface plasmon resonance spectroscopy studies from nanoparticle arrays to single nanoparticles

    NASA Astrophysics Data System (ADS)

    Bingham, Julia Marie

    The overarching theme of this work is to understand how the localized surface plasmon resonance (LSPR) of metallic nanoparticles can be utilized for sensing applications. The work presented here describes the use of both nanoparticle arrays and single nanoparticles. Specifically, nanoparticle arrays demonstrate sensing capabilities for inhibin A, prostate specific antigen (PSA), gas and vapors, and the dye, Nile Red. A new wide-field imaging apparatus is developed to characterize multiple single nanoparticles simultaneously as well as correlate the nanoparticle structural details using transmission electron microscopy (TEM), ultimately to develop single nanoparticle sensors. From these studies, LSPR spectroscopy is shown to be a valuable tool for sensor development. In the studies utilizing nanoparticle arrays, LSPR spectroscopy proves to be a feasible technique to detect inhibin A and PSA using a sandwich assay format. However, binding constants are determined to be several orders of magnitude lower than expected for PSA. It is hypothesized that the method to immobilize the capture antibody affected the affinity for PSA. Using a high resolution LSPR spectrometer, gas and vapor sensing on the basis of small refractive index (RI) changes is demonstrated. Nile Red is used to investigate the interaction between the polarity-dependent dye absorbance and the RI dependent LSPR of Ag nanoparticles. A wide-field LSPR imaging method using a liquid crystal tunable filter is used to measure the scattering spectra of multiple Ag nanoparticles in parallel and the RI response of multiple single nanoparticles is determined. This method also provides the ability to characterize moving Ag nanoparticles by measuring the scattering spectra of the particles while simultaneously tracking their motion. Consequently, single particle diffusion coefficients are determined. As an example, several single Ag nanoprisms are tracked, the LSPR scattering spectrum of each moving particle is

  18. SU-E-J-247: A Simulation of X-Ray Emission with Gold Nanoparticle Irradiated by Energetic Proton Beam

    SciTech Connect

    Newpower, M; Ahmad, S; Chen, Y

    2014-06-01

    Purpose: To investigate the proton induced X-ray emissions in gold-water mixture materials. Methods: In this study a Monte Carlo simulation was created using the GEANT4 toolkit (version 4.9.6). The geometry in this setup includes a 2 cm × 2 cm × 2 cm target, a scoring sphere (radius = 10 cm) and a 65 MeV planar proton source (2 cm × 2 cm). Four concentrations of a gold-water solution were irradiated with 5×10{sup 5} incident protons at a distance of 0.5 cm perpendicular to the surface of the target. The solutions of gold-water mixture had 10%, 5%, 1% and 0.5% of gold by mass, respectively. The number of photon emitting for the target was counted in the scoring sphere for the energy range of 0-86.0 keV in 0.1 keV bins. For this study the reference physics list PhysListEmStandard was used together with the x-ray fluorescence, Auger electron and PIXE (particle induced xray emission) options enabled. The range cuts for photons and electrons were set at 0.5 mm and 1.0 mm, respectively. Results: In the energy spectra of emitting X-ray fluorescence, peaks from gold K shell characteristic x-rays (68.8 and 66.9 keV) were observed. The number of counts under the peaks of Ka1 and Ka2 was found to increase with the increasing of the gold concentrations in the mixture materials. The X-ray yields (for both Ka1 and Ka2) when fitted with least-square method as a function of gold concentration demonstrate a linear dependency with R{sup 2} > 0.96. The Ka1yield per incident proton was found to be 0.0016 for 10% gold-water mixture solutions. Conclusion: This preliminary study with PIXE technique with gold nanoparticle has demonstrated potentials for its utilization in the development of range and dose verification methodology that is currently of great interest in the field of proton radiation therapy.

  19. Exogenous control over intracellular acidification: Enhancement via proton caged compounds coupled to gold nanoparticles.

    PubMed

    Carbone, Marilena; Sabbatella, Gianfranco; Antonaroli, Simonetta; Remita, Hynd; Orlando, Viviana; Biagioni, Stefano; Nucara, Alessandro

    2015-11-01

    The pH regulation has a fundamental role in several intracellular processes and its variation via exogenous compounds is a potential tool for intervening in the intracellular processes. Proton caged compounds (PPCs) release protons upon UV irradiation and may efficiently provoke intracellular on-command acidification. Here, we explore the intracellular pH variation, when purposely synthesized PCCs are coupled to gold nanoparticles (AuNPs) and dosed to HEK-293 cells. We detected the acidification process caused by the UV irradiation by monitoring the intensity of the asymmetric stretching mode of the CO(2) molecule at 2343 cm(-1). The comparison between free and AuNPs functionalized proton caged compound demonstrates a highly enhanced CO(2) yield, hence pH variation, in the latter case. Finally, PCC functionalized AuNPs were marked with a purposely synthesized fluorescent marker and dosed to HEK-293 cells. The corresponding fluorescence optical images show green grains throughout the whole cytoplasm. PMID:26235337

  20. A bioinspired strategy for surface modification of silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Tian, Jianwen; Zhang, Haoxuan; Liu, Meiying; Deng, Fengjie; Huang, Hongye; Wan, Qing; Li, Zhen; Wang, Ke; He, Xiaohui; Zhang, Xiaoyong; Wei, Yen

    2015-12-01

    Silica nanoparticles have become one of the most promising nanomaterials for a vast of applications. In this work, a novel strategy for surface modification of silica nanoparticles has been developed for the first time via combination of mussel inspired chemistry and Michael addition reaction. In this procedure, thin polydopamine (PDA) films were first coated on the bare silica nanoparticles via self-polymerization of dopamine in alkaline condition. And then amino-containing polymers were introduced onto the PDA coated silica nanoparticles through Michael addition reaction, that are synthesized from free radical polymerization using poly(ethylene glycol) methyl methacrylate (PEGMA) and N-(3-aminopropyl) methacrylamide (NAPAM) as monomers and ammonium persulfate as the initiator. The successful modification of silica nanoparticles was evidenced by a series of characterization techniques. As compared with the bare silica nanoparticles, the polymers modified silica nanoparticles showed remarkable enhanced dispersibility in both aqueous and organic solution. This strategy is rather simple, effective and versatile. Therefore, it should be of specific importance for further applications of silica nanoparticles and will spark great research attention of scientists from different fields.

  1. Nanosensors based on functionalized nanoparticles and surface enhanced raman scattering

    DOEpatents

    Talley, Chad E.; Huser, Thomas R.; Hollars, Christopher W.; Lane, Stephen M.; Satcher, Jr., Joe H.; Hart, Bradley R.; Laurence, Ted A.

    2007-11-27

    Surface-Enhanced Raman Spectroscopy (SERS) is a vibrational spectroscopic technique that utilizes metal surfaces to provide enhanced signals of several orders of magnitude. When molecules of interest are attached to designed metal nanoparticles, a SERS signal is attainable with single molecule detection limits. This provides an ultrasensitive means of detecting the presence of molecules. By using selective chemistries, metal nanoparticles can be functionalized to provide a unique signal upon analyte binding. Moreover, by using measurement techniques, such as, ratiometric received SERS spectra, such metal nanoparticles can be used to monitor dynamic processes in addition to static binding events. Accordingly, such nanoparticles can be used as nanosensors for a wide range of chemicals in fluid, gaseous and solid form, environmental sensors for pH, ion concentration, temperature, etc., and biological sensors for proteins, DNA, RNA, etc.

  2. Surface segregation phenomena in extended and nanoparticle surfaces of Cu-Au alloys

    NASA Astrophysics Data System (ADS)

    Li, Jonathan; Wang, Guofeng; Zhou, Guangwen

    2016-07-01

    Using density functional theory (DFT) and Monte Carlo (MC) simulations, we studied the surface segregation phenomena of Au atoms in the extended and nanoparticle surfaces of Cu-Au alloys. Our MC simulations predicted significant Au enrichment in the outermost layer of (111) and (100) extended surfaces, and Au enrichment in the two outermost layers of (110) extended surfaces. The equilibrium Cu-Au nanoparticles were predicted to develop into an Au-enriched shell structure, where Au atoms preferably segregate to the (100) facets while Cu atoms are mainly located on the (111) facet of the nanoparticles. Our simulation predictions agree with experimental measurements.

  3. Exogenous control over intracellular acidification: Enhancement via proton caged compounds coupled to gold nanoparticles and an alternative pathway with DMSO

    PubMed Central

    Carbone, Marilena; Sabbatella, Gianfranco; Antonaroli, Simonetta; Remita, Hynd; Orlando, Viviana; Biagioni, Stefano; Nucara, Alessandro

    2016-01-01

    Proton caged compounds exhibit a characteristic behavior when directly dosed into cells or being coupled to gold nanoparticles prior to the dosing. When irradiated in the near ultraviolet region, they release protons that interact with intracellular HCO3− to yield H2CO3. The dissociation of carbonic acid, then, releases CO2 that can be distinctively singled out in infrared spectra. In the process of searching a pathway to augment the intracellular uptake of proton caged compounds, we probed the association of 1-(2-nitrophenyl)-ethylhexadecyl sulfonate (HDNS) with DMSO, an agent to enhance the membrane permeability. We found out a different UV-induced protonation mechanism that opens up to new conduits of employing of proton caged compounds. Here, we report the infrared data we collected in this set of experiments. PMID:26870760

  4. Exogenous control over intracellular acidification: Enhancement via proton caged compounds coupled to gold nanoparticles and an alternative pathway with DMSO.

    PubMed

    Carbone, Marilena; Sabbatella, Gianfranco; Antonaroli, Simonetta; Remita, Hynd; Orlando, Viviana; Biagioni, Stefano; Nucara, Alessandro

    2016-03-01

    Proton caged compounds exhibit a characteristic behavior when directly dosed into cells or being coupled to gold nanoparticles prior to the dosing. When irradiated in the near ultraviolet region, they release protons that interact with intracellular HCO3 (-) to yield H2CO3. The dissociation of carbonic acid, then, releases CO2 that can be distinctively singled out in infrared spectra. In the process of searching a pathway to augment the intracellular uptake of proton caged compounds, we probed the association of 1-(2-nitrophenyl)-ethylhexadecyl sulfonate (HDNS) with DMSO, an agent to enhance the membrane permeability. We found out a different UV-induced protonation mechanism that opens up to new conduits of employing of proton caged compounds. Here, we report the infrared data we collected in this set of experiments. PMID:26870760

  5. Chemical analysis of surface oxygenated moieties of fluorescent carbon nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, Jie; Deming, Christopher P.; Song, Yang; Kang, Xiongwu; Zhou, Zhi-You; Chen, Shaowei

    2012-01-01

    Water-soluble carbon nanoparticles were prepared by refluxing natural gas soot in concentrated nitric acid. The surface of the resulting nanoparticles was found to be decorated with a variety of oxygenated species, as suggested by spectroscopic measurements. Back potentiometric titration of the nanoparticles was employed to quantify the coverage of carboxylic, lactonic, and phenolic moieties on the particle surface by taking advantage of their vast difference of acidity (pKa). The results were largely consistent with those reported in previous studies with other carbonaceous (nano)materials. Additionally, the presence of ortho- and para-quinone moieties on the nanoparticle surface was confirmed by selective labelling with o-phenylenediamine, as manifested in X-ray photoelectron spectroscopy, photoluminescence, and electrochemical measurements. The results further supported the arguments that the surface functional moieties that were analogous to 9,10-phenanthrenequinone were responsible for the unique photoluminescence of the nanoparticles and the emission might be regulated by surface charge state, as facilitated by the conjugated graphitic core matrix.

  6. Encapsulation of silica nanoparticles by redox-initiated graft polymerization from the surface of silica nanoparticles.

    PubMed

    Wang, Huijun; Peng, Mao; Zheng, Jun; Li, Peng

    2008-10-01

    This study describes a facile and versatile method for preparing polymer-encapsulated silica particles by 'grafting from' polymerization initiated by a redox system comprising ceric ion (Ce(4+)) as an oxidant and an organic reductant immobilized on the surface of silica nanoparticles. The silica nanoparticles were firstly modified by 3-aminopropyltriethoxysilane, then reacted with poly(ethylene glycol) acrylate through the Michael addition reaction, so that hydroxyl-terminated poly(ethylene glycol) (PEG) were covalently attached onto the nanoparticle surface and worked as the reductant. Poly(methyl methacrylate) (PMMA), a common hydrophobic polymer, and poly(N-isopropylacrylamide) (PNIPAAm), a thermosensitive polymer, were successfully grafted onto the surface of silica nanoparticles by 'grafting from' polymerization initiated by the redox reaction of Ce(4+) with PEG on the silica surface in acid aqueous solutions. The polymer-encapsulated silica nanoparticles (referred to as silica@PMMA and silica@PNIPAAm, respectively) were characterized by infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. On the contrary, graft polymerization did not occur on bare silica nanoparticles. In addition, during polymerization, sediments were observed for PMMA and for PNIPAAm at a polymerization temperature above its low critical solution temperature (LCST). But the silica@PNIPAAm particles obtained at a polymerization temperature below the LCST can suspend stably in water throughout the polymerization process. PMID:18684468

  7. Protonation Dynamics on Lipid Nanodiscs: Influence of the Membrane Surface Area and External Buffers.

    PubMed

    Xu, Lei; Öjemyr, Linda Näsvik; Bergstrand, Jan; Brzezinski, Peter; Widengren, Jerker

    2016-05-10

    Lipid membrane surfaces can act as proton-collecting antennae, accelerating proton uptake by membrane-bound proton transporters. We investigated this phenomenon in lipid nanodiscs (NDs) at equilibrium on a local scale, analyzing fluorescence fluctuations of individual pH-sensitive fluorophores at the membrane surface by fluorescence correlation spectroscopy (FCS). The protonation rate of the fluorophores was ∼100-fold higher when located at 9- and 12-nm diameter NDs, compared to when in solution, indicating that the proton-collecting antenna effect is maximal already for a membrane area of ∼60 nm(2). Fluorophore-labeled cytochrome c oxidase displayed a similar increase when reconstituted in 12 nm NDs, but not in 9 nm NDs, i.e., an acceleration of the protonation rate at the surface of cytochrome c oxidase is found when the lipid area surrounding the protein is larger than 80 nm(2), but not when below 30 nm(2). We also investigated the effect of external buffers on the fluorophore proton exchange rates at the ND membrane-water interfaces. With increasing buffer concentrations, the proton exchange rates were found to first decrease and then, at millimolar buffer concentrations, to increase. Monte Carlo simulations, based on a simple kinetic model of the proton exchange at the membrane-water interface, and using rate parameter values determined in our FCS experiments, could reconstruct both the observed membrane-size and the external buffer dependence. The FCS data in combination with the simulations indicate that the local proton diffusion coefficient along a membrane is ∼100 times slower than that observed over submillimeter distances by proton-pulse experiments (Ds ∼ 10(-5)cm(2)/s), and support recent theoretical studies showing that proton diffusion along membrane surfaces is time- and length-scale dependent. PMID:27166807

  8. Magnetic Nanoparticles: Surface Effects and Properties Related to Biomedicine Applications

    PubMed Central

    Issa, Bashar; Obaidat, Ihab M.; Albiss, Borhan A.; Haik, Yousef

    2013-01-01

    Due to finite size effects, such as the high surface-to-volume ratio and different crystal structures, magnetic nanoparticles are found to exhibit interesting and considerably different magnetic properties than those found in their corresponding bulk materials. These nanoparticles can be synthesized in several ways (e.g., chemical and physical) with controllable sizes enabling their comparison to biological organisms from cells (10–100 μm), viruses, genes, down to proteins (3–50 nm). The optimization of the nanoparticles’ size, size distribution, agglomeration, coating, and shapes along with their unique magnetic properties prompted the application of nanoparticles of this type in diverse fields. Biomedicine is one of these fields where intensive research is currently being conducted. In this review, we will discuss the magnetic properties of nanoparticles which are directly related to their applications in biomedicine. We will focus mainly on surface effects and ferrite nanoparticles, and on one diagnostic application of magnetic nanoparticles as magnetic resonance imaging contrast agents. PMID:24232575

  9. Microscale Heat Transfer Transduced by Surface Plasmon Resonant Gold Nanoparticles

    PubMed Central

    Roper, D. Keith; Ahn, W.; Hoepfner, M.

    2008-01-01

    Visible radiation at resonant frequencies is transduced to thermal energy by surface plasmons on gold nanoparticles. Temperature in ≤10-microliter aqueous suspensions of 20-nanometer gold particles irradiated by a continuous wave Ar+ ion laser at 514 nm increased to a maximum equilibrium value. This value increased in proportion to incident laser power and in proportion to nanoparticle content at low concentration. Heat input to the system by nanoparticle transduction of resonant irradiation equaled heat flux outward by conduction and radiation at thermal equilibrium. The efficiency of transducing incident resonant light to heat by microvolume suspensions of gold nanoparticles was determined by applying an energy balance to obtain a microscale heat-transfer time constant from the transient temperature profile. Measured values of transduction efficiency were increased from 3.4% to 9.9% by modulating the incident continuous wave irradiation. PMID:19011696

  10. Self-assembled nanoparticle patterns on carbon nanowall surfaces.

    PubMed

    Suetin, N V; Evlashin, S A; Egorov, A V; Mironovich, K V; Dagesyan, S A; Yashina, L V; Goodilin, E A; Krivchenko, V A

    2016-04-28

    We observed that thermally treated carbon nanowalls serve efficiently as templates governing the formation of quasiperiodic patterns for nanoparticles deposited. Here we report self-assembled quasi-regular structures of diverse nanoparticles on a freestanding multilayer graphene-like material, i.e. carbon nanowalls. Metallic (Ag, Al, Co, Mo, Ni, and Ta) and semiconductor (Si) nanoparticles form coaxial polygonal closed loop structures or parallel equidistant rows, which evolve upon further deposition into bead-like structures and, finally, into nanowires. Weakly bonded nanoparticles decorate atomic steps, wrinkles and other extended defects on the carbon nanowalls as a result of anisotropic diffusion of atoms or clusters along the hexagonal sp(2)-carbon network followed by their aggregation and agglomeration. The decorated carbon nanowalls are found to be promising materials for surface enhanced Raman scattering (SERS) analysis. PMID:27086716

  11. Nanoparticle Surface Affinity as a Predictor of Trophic Transfer.

    PubMed

    Geitner, Nicholas K; Marinakos, Stella M; Guo, Charles; O'Brien, Niall; Wiesner, Mark R

    2016-07-01

    Nanoscale materials, whether natural, engineered, or incidental, are increasingly acknowledged as important components in large, environmental systems with potential implications for environmental impact and human health. Mathematical models are a useful tool for handling the rapidly increasing complexity and diversity of these materials and their exposure routes. Presented here is a mathematical model of trophic transfer driven by nanomaterial surface affinity for environmental and biological surfaces, developed in tandem with an experimental functional assay for determining these surface affinities. We found that nanoparticle surface affinity is a strong predictor of uptake through predation in a simple food web consisting of the algae Chlorella vulgaris and daphnid Daphnia magna. The mass of nanoparticles internalized by D. magna through consuming nanomaterial-contaminated algae varied linearly with surface-attachment efficiency. Internalized quantities of gold nanoparticles in D. magna ranged from 8.3 to 23.6 ng/mg for nanoparticle preparations with surface-attachment efficiencies ranging from 0.07 to 1. This model, coupled with the functional-assay approach, may provide a useful screening tool for existing materials as well as a predictive model for their development. PMID:27249534

  12. Surface segregations in platinum-based alloy nanoparticles

    NASA Astrophysics Data System (ADS)

    Yamakawa, Shunsuke; Asahi, Ryoji; Koyama, Toshiyuki

    2014-04-01

    A phase-field model that describes the radial distributions of the ordered-disordered phase and surface segregation in a single-alloy nanoparticle is introduced to clarify the overall behavior of surface segregation of various Pt-based alloy nanoparticles. One of the obstacles to apply a platinum-transition metal alloy as a cathode electro-catalyst of a polymer electrolyte fuel cell is the need to ensure the retention of the designed surface composition in an alloy nanoparticle against the alloy combinations, a particle size, and heat treatment. From the results of calculations for CrPt, FePt, CoPt, NiPt, CuPt, PdPt, IrPt, and AuPt binary nanoparticles with diameters below 10 nm at 973.15 K, the compositional variation within a single particle was found to depend on the balance between the atomic interaction within particles and the surface free energy. In addition, the obtained specific steady-state composition of the surface varied significantly with alloy combination and particle diameter. Based on the general tendencies of a binary system to exhibit segregation, attempts to control the amount of platinum segregation on the surface using a ternary-alloy system were examined.

  13. Investigation of Surface Coatings on Silver Nanoparticles by Surface Enhanced Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kühn, Melanie; Ivleva, Natalia P.; Niessner, Reinhard; Baumann, Thomas

    2013-04-01

    The behavior of engineered inorganic nanoparticles (EINP) in the environment is strongly affected by their surface properties. Once introduced in the aquatic or terrestric environment, the nanoparticle surface may be altered by weathering or the formation of a coating. These changes influence the interactions of the nanoparticle with natural surfaces or interfaces as well as with other particles. Natural organic matter for example is known to have a stabilizing effect on most nanoparticles. Therefore the assessment of the fate and transport of nanoparticles in the environment requires a precise knowledge of the influence of the coating and its modifications under natural conditions. A suitable tool for the investigation of coatings on silver nanoparticles is surface enhanced Raman spectroscopy (SERS). Although silver nanoparticles themselves do not have a distinct Raman signal, the Raman signal of adsorbed or nearby substances is enhanced by a factor of 103 - 106. This leads to a considerably higher sensitivity of SERS in comparison to normal Raman microscopy. Therefore, coatings on silver nanoparticles should be accessible via the SERS effect. As a first step, plain and citrate stabilized silver nanoparticles were mixed with different natural coating substances (polygalacturonic acid, seaweed extract, and humic substances) and filtered with a polycarbonate filter to remove excessive coating material. Afterwards, the nanoparticles were redispersed from the filter by ultrasonification. This washing procedure was repeated three times while always maintaining the same concentration of nanoparticles. SERS spectra were recorded after each washing step with a LabRAM HR Raman mircospectrometer (Horiba Scientific, Japan, ? = 633 nm, 20x water-immersion-objective, measurement time 10 s). First results indicate the formation of a stabilizing layer around the nanoparticles after contact with humic substances, thus providing experimental evidence to the stabilization of EINP

  14. Proton Radii of B12-17 Define a Thick Neutron Surface in B17

    NASA Astrophysics Data System (ADS)

    Estradé, A.; Kanungo, R.; Horiuchi, W.; Ameil, F.; Atkinson, J.; Ayyad, Y.; Cortina-Gil, D.; Dillmann, I.; Evdokimov, A.; Farinon, F.; Geissel, H.; Guastalla, G.; Janik, R.; Kimura, M.; Knöbel, R.; Kurcewicz, J.; Litvinov, Yu. A.; Marta, M.; Mostazo, M.; Mukha, I.; Nociforo, C.; Ong, H. J.; Pietri, S.; Prochazka, A.; Scheidenberger, C.; Sitar, B.; Strmen, P.; Suzuki, Y.; Takechi, M.; Tanaka, J.; Tanihata, I.; Terashima, S.; Vargas, J.; Weick, H.; Winfield, J. S.

    2014-09-01

    The first determination of radii of point proton distribution (proton radii) of B12-17 from charge-changing cross sections (σCC) measurements at the FRS, GSI, Darmstadt is reported. The proton radii are deduced from a finite-range Glauber model analysis of the σCC. The radii show an increase from B13 to B17 and are consistent with predictions from the antisymmetrized molecular dynamics model for the neutron-rich nuclei. The measurements show the existence of a thick neutron surface with neutron-proton radius difference of 0.51(0.11) fm in B17.

  15. A universal surface complexation framework for modeling proton binding onto bacterial surfaces in geologic settings

    USGS Publications Warehouse

    Borrok, D.; Turner, B.F.; Fein, J.B.

    2005-01-01

    Adsorption onto bacterial cell walls can significantly affect the speciation and mobility of aqueous metal cations in many geologic settings. However, a unified thermodynamic framework for describing bacterial adsorption reactions does not exist. This problem originates from the numerous approaches that have been chosen for modeling bacterial surface protonation reactions. In this study, we compile all currently available potentiometric titration datasets for individual bacterial species, bacterial consortia, and bacterial cell wall components. Using a consistent, four discrete site, non-electrostatic surface complexation model, we determine total functional group site densities for all suitable datasets, and present an averaged set of 'universal' thermodynamic proton binding and site density parameters for modeling bacterial adsorption reactions in geologic systems. Modeling results demonstrate that the total concentrations of proton-active functional group sites for the 36 bacterial species and consortia tested are remarkably similar, averaging 3.2 ?? 1.0 (1??) ?? 10-4 moles/wet gram. Examination of the uncertainties involved in the development of proton-binding modeling parameters suggests that ignoring factors such as bacterial species, ionic strength, temperature, and growth conditions introduces relatively small error compared to the unavoidable uncertainty associated with the determination of cell abundances in realistic geologic systems. Hence, we propose that reasonable estimates of the extent of bacterial cell wall deprotonation can be made using averaged thermodynamic modeling parameters from all of the experiments that are considered in this study, regardless of bacterial species used, ionic strength, temperature, or growth condition of the experiment. The average site densities for the four discrete sites are 1.1 ?? 0.7 ?? 10-4, 9.1 ?? 3.8 ?? 10-5, 5.3 ?? 2.1 ?? 10-5, and 6.6 ?? 3.0 ?? 10-5 moles/wet gram bacteria for the sites with pKa values of 3

  16. Quantitatively Probing the Means of Controlling Nanoparticle Assembly on Surfaces

    SciTech Connect

    Patete, J.m.; Wong, S.; Peng, X.; Serafin, J.M.

    2011-05-17

    As a means of developing a simple, cost-effective, and reliable method for probing nanoparticle behavior, we have used atomic force microscopy to gain a quantitative 3D visual representation of the deposition patterns of citrate-capped Au nanoparticles on a substrate as a function of (a) sample preparation, (b) the choice of substrate, (c) the dispersion solvent, and (d) the number of loading steps. Specifically, we have found that all four parameters can be independently controlled and manipulated in order to alter the resulting pattern and quantity of as-deposited nanoparticles. From these data, the sample preparation technique appears to influence deposition patterns most broadly, and the dispersion solvent is the most convenient parameter to use in tuning the quantity of nanoparticles deposited onto the surface under spin-coating conditions. Indeed, we have quantitatively measured the effect of surface coverage for both mica and silicon substrates under preparation techniques associated with (i) evaporation under ambient air, (ii) heat treatment, and (iii) spin-coating preparation conditions. In addition, we have observed a decrease in nanoparticle adhesion to a substrate when the ethylene glycol content of the colloidal dispersion solvent is increased, which had the effect of decreasing interparticle-substrate interactions. Finally, we have shown that substrates prepared by these diverse techniques have potential applicability in surface-enhanced Raman spectroscopy.

  17. Quantitative investigation of physical factors contributing to gold nanoparticle-mediated proton dose enhancement.

    PubMed

    Cho, Jongmin; Gonzalez-Lepera, Carlos; Manohar, Nivedh; Kerr, Matthew; Krishnan, Sunil; Cho, Sang Hyun

    2016-03-21

    Some investigators have shown tumor cell killing enhancement in vitro and tumor regression in mice associated with the loading of gold nanoparticles (GNPs) before proton treatments. Several Monte Carlo (MC) investigations have also demonstrated GNP-mediated proton dose enhancement. However, further studies need to be done to quantify the individual physical factors that contribute to the dose enhancement or cell-kill enhancement (or radiosensitization). Thus, the current study investigated the contributions of particle-induced x-ray emission (PIXE), particle-induced gamma-ray emission (PIGE), Auger and secondary electrons, and activation products towards the total dose enhancement. Specifically, GNP-mediated dose enhancement was measured using strips of radiochromic film that were inserted into vials of cylindrical GNPs, i.e. gold nanorods (GNRs), dispersed in a saline solution (0.3 mg of GNRs/g or 0.03% of GNRs by weight), as well as vials containing water only, before proton irradiation. MC simulations were also performed with the tool for particle simulation code using the film measurement setup. Additionally, a high-purity germanium detector system was used to measure the photon spectrum originating from activation products created from the interaction of protons and spherical GNPs present in a saline solution (20 mg of GNPs/g or 2% of GNPs by weight). The dose enhancement due to PIXE/PIGE recorded on the films in the GNR-loaded saline solution was less than the experimental uncertainty of the film dosimetry (<2%). MC simulations showed highly localized dose enhancement (up to a factor 17) in the immediate vicinity (<100 nm) of GNRs, compared with hypothetical water nanorods (WNRs), mostly due to GNR-originated Auger/secondary electrons; however, the average dose enhancement over the entire GNR-loaded vial was found to be minimal (0.1%). The dose enhancement due to the activation products from GNPs was minimal (<0.1%) as well. In conclusion, under the currently

  18. Quantitative investigation of physical factors contributing to gold nanoparticle-mediated proton dose enhancement

    NASA Astrophysics Data System (ADS)

    Cho, Jongmin; Gonzalez-Lepera, Carlos; Manohar, Nivedh; Kerr, Matthew; Krishnan, Sunil; Cho, Sang Hyun

    2016-03-01

    Some investigators have shown tumor cell killing enhancement in vitro and tumor regression in mice associated with the loading of gold nanoparticles (GNPs) before proton treatments. Several Monte Carlo (MC) investigations have also demonstrated GNP-mediated proton dose enhancement. However, further studies need to be done to quantify the individual physical factors that contribute to the dose enhancement or cell-kill enhancement (or radiosensitization). Thus, the current study investigated the contributions of particle-induced x-ray emission (PIXE), particle-induced gamma-ray emission (PIGE), Auger and secondary electrons, and activation products towards the total dose enhancement. Specifically, GNP-mediated dose enhancement was measured using strips of radiochromic film that were inserted into vials of cylindrical GNPs, i.e. gold nanorods (GNRs), dispersed in a saline solution (0.3 mg of GNRs/g or 0.03% of GNRs by weight), as well as vials containing water only, before proton irradiation. MC simulations were also performed with the tool for particle simulation code using the film measurement setup. Additionally, a high-purity germanium detector system was used to measure the photon spectrum originating from activation products created from the interaction of protons and spherical GNPs present in a saline solution (20 mg of GNPs/g or 2% of GNPs by weight). The dose enhancement due to PIXE/PIGE recorded on the films in the GNR-loaded saline solution was less than the experimental uncertainty of the film dosimetry (<2%). MC simulations showed highly localized dose enhancement (up to a factor 17) in the immediate vicinity (<100 nm) of GNRs, compared with hypothetical water nanorods (WNRs), mostly due to GNR-originated Auger/secondary electrons; however, the average dose enhancement over the entire GNR-loaded vial was found to be minimal (0.1%). The dose enhancement due to the activation products from GNPs was minimal (<0.1%) as well. In conclusion, under the

  19. Surface functionalized magnetic nanoparticles for cancer therapy applications

    NASA Astrophysics Data System (ADS)

    Wydra, Robert John

    Despite recent advances, cancer remains the second leading cause of deaths in the United States. Magnetic nanoparticles have found various applications in cancer research as drug delivery platforms, enhanced contrast agents for improved diagnostic imaging, and the delivery of thermal energy as standalone therapy. Iron oxide nanoparticles absorb the energy from an alternating magnetic field and convert it into heat through Brownian and Neel relaxations. To better utilize magnetic nanoparticles for cancer therapy, surface functionalization is essential for such factors as decreasing cytotoxicity of healthy tissue, extending circulation time, specific targeting of cancer cells, and manage the controlled delivery of therapeutics. In the first study, iron oxide nanoparticles were coated with a poly(ethylene glycol) (PEG) based polymer shell. The PEG coating was selected to prevent protein adsorption and thus improve circulation time and minimize host response to the nanoparticles. Thermal therapy application feasibility was demonstrated in vitro with a thermoablation study on lung carcinoma cells. Building on the thermal therapy demonstration with iron oxide nanoparticles, the second area of work focused on intracellular delivery. Nanoparticles can be appropriately tailored to enter the cell and deliver energy on the nanoscale eliminating individual cancer cells. The underlying mechanism of action is still under study, and we were interested in determining the role of reactive oxygen species (ROS) catalytically generated from the surface of iron oxide nanoparticles in this measured cytotoxicity. When exposed to an AMF, the nanoscale heating effects are capable of enhancing the Fenton-like generation of ROS determined through a methylene blue degradation assay. To deliver this enhanced ROS effect to cells, monosaccharide coated nanoparticles were developed and successfully internalized by colon cancer cell lines. Upon AMF exposure, there was a measured increase in

  20. Single-electron induced surface plasmons on a topological nanoparticle

    NASA Astrophysics Data System (ADS)

    Siroki, G.; Lee, D. K. K.; Haynes, P. D.; Giannini, V.

    2016-08-01

    It is rarely the case that a single electron affects the behaviour of several hundred thousands of atoms. Here we demonstrate a phenomenon where this happens. The key role is played by topological insulators--materials that have surface states protected by time-reversal symmetry. Such states are delocalized over the surface and are immune to its imperfections in contrast to ordinary insulators. For topological insulators, the effects of these surface states will be more strongly pronounced in the case of nanoparticles. Here we show that under the influence of light a single electron in a topologically protected surface state creates a surface charge density similar to a plasmon in a metallic nanoparticle. Such an electron can act as a screening layer, which suppresses absorption inside the particle. In addition, it can couple phonons and light, giving rise to a previously unreported topological particle polariton mode. These effects may be useful in the areas of plasmonics, cavity electrodynamics and quantum information.

  1. Sustainable environmental nanotechnology using nanoparticle surface modification.

    EPA Science Inventory

    Reactive nanomaterials used for environmental remediation require surface modification to make them mobile in the subsurface. Nanomaterials released into the environment inadvertently without an engineered surface coating will acquire one (e.g. adsorption of natural organic matt...

  2. Mechanism of near-threshold stimulated desorption of protons from transition-metal surfaces

    SciTech Connect

    Melius, C.F.; Stulen, R.H.; Noell, J.O.

    1982-05-17

    The mechanism for near threshold electron and photon stimulated desorption of protons from transition-metal surfaces has been investigated with use of configuration-interaction techniques on finite clusters. The calculations indicate that the protons arise from repulsive states involving double excitations from the metal-hydrogen bonding orbitals and suggest that the process may occur via a surface predissociation mechanism. The calculations are compared to experimental electron stimulated desorption results for Ni<111>.

  3. Molecular Statics Calculations of Proton Binding to Goethite Surfaces: Thermodynamic Modeling of the Surface Charging and Protonation of Goethite in Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Felmy, Andrew R.; Rustad, James R.

    1998-01-01

    Molecular statics calculations of proton binding at the hydroxylated faces of goethite are used to guide the development of a thermodynamic model which describes the surface charging properties of goethite in electrolyte solutions. The molecular statics calculations combined with a linear free energy relation between the energies of the hydroxylated surface and the aqueous solvated surface predict that the acidity constants for most singly (aqua or hydroxo), doubly (μ-hydroxo), and triply (μ 3-hydroxo or μ 3-oxo) coordinated surface sites all have similar values. This model which binds protons to the goethite 110 and 021 faces satisfactorily describes the surface charging behavior of goethite, if pair formation between bulk electrolyte species, i.e., Na +, Cl -, and NO 3-, is included in the model. Inclusion of minor species of quite different charging behavior (designed to describe the possible presence of defect species) did not improve our predictions of surface charge since the protonation of the major surface sites changed when these minor species were introduced into the calculations thereby negating the effect of small amounts of defect species on the overall charging behavior. The final thermodynamic model is shown to be consistent with the surface charging properties of goethite over a range of pH values, NaNO 3, and NaCl concentrations.

  4. Surface Modified Gadolinium Phosphate Nanoparticles as MRI Contrast Agents

    NASA Astrophysics Data System (ADS)

    Dumont, Matthieu F.; Baligand, Celine; Knowles, Elisabeth S.; Meisel, Mark W.; Walter, Glenn A.; Talham, Daniel R.

    2012-02-01

    Nanoparticles of GdPO4H2O were synthesized in a water/oil microemulsion using IGEPAL CO-520 as surfactant resulting in 50 nm to 100 nm particles that are dispersible and stable in water. Using surface modification chemistry previously established for zirconium phosphonate surfaces,ootnotetext J. Monot et al., J. Am. Chem. Soc. 130 (2008) 6243. the particles are directly modified with 5'-phosphate terminated oligonucleotides, and the specific interaction of the divalent phosphate with Gd^3+ sites at the surface is demonstrated. The ability of the modified nanoparticles to act as MRI contrast agents was determined by performing MR relaxivity measurements at 14 T. Solutions of nanopure water, Feridex and Omniscan (FDA cleared contrast agents) in 0.25% agarose were used for comparison and control purposes. MRI data confirm that GdPO4H2O nanoparticles have relaxivities (r1,r2) comparable to commercially available contrast agents.ootnotetext H. Hifumi et al., J. Am. Chem. Soc. 128 (2006) 15090. In addition, biofunctionalization of the surface of the nanoparticles does not prevent their function as MRI contrast agents.

  5. Gold nanoparticle induced vasculature damage in radiotherapy: Comparing protons, megavoltage photons, and kilovoltage photons

    SciTech Connect

    Lin, Yuting Paganetti, Harald; Schuemann, Jan; McMahon, Stephen J.

    2015-10-15

    Purpose: The purpose of this work is to investigate the radiosensitizing effect of gold nanoparticle (GNP) induced vasculature damage for proton, megavoltage (MV) photon, and kilovoltage (kV) photon irradiation. Methods: Monte Carlo simulations were carried out using tool for particle simulation (TOPAS) to obtain the spatial dose distribution in close proximity up to 20 μm from the GNPs. The spatial dose distribution from GNPs was used as an input to calculate the dose deposited to the blood vessels. GNP induced vasculature damage was evaluated for three particle sources (a clinical spread out Bragg peak proton beam, a 6 MV photon beam, and two kV photon beams). For each particle source, various depths in tissue, GNP sizes (2, 10, and 20 nm diameter), and vessel diameters (8, 14, and 20 μm) were investigated. Two GNP distributions in lumen were considered, either homogeneously distributed in the vessel or attached to the inner wall of the vessel. Doses of 30 Gy and 2 Gy were considered, representing typical in vivo enhancement studies and conventional clinical fractionation, respectively. Results: These simulations showed that for 20 Au-mg/g GNP blood concentration homogeneously distributed in the vessel, the additional dose at the inner vascular wall encircling the lumen was 43% of the prescribed dose at the depth of treatment for the 250 kVp photon source, 1% for the 6 MV photon source, and 0.1% for the proton beam. For kV photons, GNPs caused 15% more dose in the vascular wall for 150 kVp source than for 250 kVp. For 6 MV photons, GNPs caused 0.2% more dose in the vascular wall at 20 cm depth in water as compared to at depth of maximum dose (Dmax). For proton therapy, GNPs caused the same dose in the vascular wall for all depths across the spread out Bragg peak with 12.7 cm range and 7 cm modulation. For the same weight of GNPs in the vessel, 2 nm diameter GNPs caused three times more damage to the vessel than 20 nm diameter GNPs. When the GNPs were attached

  6. Gold nanoparticle induced vasculature damage in radiotherapy: Comparing protons, megavoltage photons, and kilovoltage photons

    PubMed Central

    Lin, Yuting; Paganetti, Harald; McMahon, Stephen J.; Schuemann, Jan

    2015-01-01

    Purpose: The purpose of this work is to investigate the radiosensitizing effect of gold nanoparticle (GNP) induced vasculature damage for proton, megavoltage (MV) photon, and kilovoltage (kV) photon irradiation. Methods: Monte Carlo simulations were carried out using tool for particle simulation (TOPAS) to obtain the spatial dose distribution in close proximity up to 20 μm from the GNPs. The spatial dose distribution from GNPs was used as an input to calculate the dose deposited to the blood vessels. GNP induced vasculature damage was evaluated for three particle sources (a clinical spread out Bragg peak proton beam, a 6 MV photon beam, and two kV photon beams). For each particle source, various depths in tissue, GNP sizes (2, 10, and 20 nm diameter), and vessel diameters (8, 14, and 20 μm) were investigated. Two GNP distributions in lumen were considered, either homogeneously distributed in the vessel or attached to the inner wall of the vessel. Doses of 30 Gy and 2 Gy were considered, representing typical in vivo enhancement studies and conventional clinical fractionation, respectively. Results: These simulations showed that for 20 Au-mg/g GNP blood concentration homogeneously distributed in the vessel, the additional dose at the inner vascular wall encircling the lumen was 43% of the prescribed dose at the depth of treatment for the 250 kVp photon source, 1% for the 6 MV photon source, and 0.1% for the proton beam. For kV photons, GNPs caused 15% more dose in the vascular wall for 150 kVp source than for 250 kVp. For 6 MV photons, GNPs caused 0.2% more dose in the vascular wall at 20 cm depth in water as compared to at depth of maximum dose (Dmax). For proton therapy, GNPs caused the same dose in the vascular wall for all depths across the spread out Bragg peak with 12.7 cm range and 7 cm modulation. For the same weight of GNPs in the vessel, 2 nm diameter GNPs caused three times more damage to the vessel than 20 nm diameter GNPs. When the GNPs were attached

  7. Surface Sites in Cu-Nanoparticles: Chemical Reactivity or Microscopy?

    PubMed

    Larmier, Kim; Tada, Shohei; Comas-Vives, Aleix; Copéret, Christophe

    2016-08-18

    Copper nanoparticles are widely used in catalysis and electrocatalysis, and the fundamental understanding of their activity requires reliable methods to assess the number of potentially reactive atoms exposed on the surface. Herein, we provide a molecular understanding of the difference observed in addressing surface site titration using prototypical methods: transmission electron micrscopy (TEM), H2 chemisorption, and N2O titration by a combination of experimental and theoretical study. We show in particular that microscopy does not allow assessing the amount of reactive surface sites, while H2 and N2O chemisorptions can, albeit with slightly different stoichiometries (1 O/2CuS and 1 H2/2.2CuS), which can be rationalized by density functional theory calculations. High-resolution TEM shows that the origin of the observed difference between microscopy and titration methods is due to the strong metal support interaction experienced by small copper nanoparticles with the silica surface. PMID:27490121

  8. Tribological Behaviour of Surface Modified Copper Nanoparticles as lubricating Additives

    NASA Astrophysics Data System (ADS)

    Shi, P. J.; Yu, H. L.; Wang, H. M.; Xu, B. S.

    A special kind of surface modified copper nanoparticles was selected as the auto-reconditioning materials to in situ generate a copperized protective film on iron-base metal surfaces under designed tribological conditions. The morphologies and element distributions of the formed film were observed and determined by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). The micro mechanical properties and tribological behaviors were investigated by nano test system and ball- on-disc tribotester. The results show that the morphology of the protective film is smooth, the nano-hardness decreases by 46% and the friction coefficient of the copperized protective film is about 0.10. The forming mechanism of the auto-reconditioning film can be described that the copper nanoparticles deposit on the worn surfaces and form iron-copper alloy film with lower hardness and shear strength, which has better friction-reducing, antiwear and surface-optimizing behaviors.

  9. Surface Bonding Effects in Compound Semiconductor Nanoparticles: II

    SciTech Connect

    Helen H. Farrell

    2008-07-01

    Small nanoparticles have a large proportion of their atoms either at or near the surface, and those in clusters are essentially all on the surface. As a consequence, the details of the surface structure are of paramount importance in governing the overall stability of the particle. Just as with bulk materials, factors that determine this stability include “bulk” structure, surface reconstruction, charge balance and hybridization, ionicity, strain, stoichiometry, and the presence of adsorbates. Needless to say, many of these factors, such as charge balance, hybridization and strain, are interdependent. These factors all contribute to the overall binding energy of clusters and small nanoparticles and play a role in determining the deviations from an inverse size dependence that we have previously reported for compound semiconductor materials. Using first-principles density functional theory calculations, we have explored how these factors influence particle stability under a variety of conditions.

  10. Approach and Coalescence of Gold Nanoparticles Driven by Surface Thermodynamic Fluctuations and Atomic Interaction Forces.

    PubMed

    Wang, Jiadao; Chen, Shuai; Cui, Kai; Li, Dangguo; Chen, Darong

    2016-02-23

    The approach and coalescence behavior of gold nanoparticles on a silicon surface were investigated by experiments and molecular dynamics simulations. By analyzing the behavior of the atoms in the nanoparticles in the simulations, it was found that the atoms in a single isolated nanoparticle randomly fluctuated and that the surface atoms showed greater fluctuation. The fluctuation increased as the temperature increased. When there were two or more neighboring nanoparticles, the fluctuating surface atoms of the nanoparticles "flowed" toward the neighboring nanoparticle because of atomic interaction forces between the nanoparticles. With the surface atoms "flowing", the gold nanoparticles approached and finally coalesced. The simulation results were in good agreement with the experimental results. It can be concluded that surface thermodynamic fluctuations and atomic interaction forces are the causes of the approach and coalescence behavior of the gold nanoparticles. PMID:26756675

  11. Controlling the hydrophilicity and contact resistance of fuel cell bipolar plate surfaces using layered nanoparticle assembly

    NASA Astrophysics Data System (ADS)

    Wang, Feng

    Hybrid nanostructured coatings exhibiting the combined properties of electrical conductivity and surface hydrophilicity were obtained by using Layer-by-Layer (LBL) assembly of cationic polymer, silica nanospheres, and carbon nanoplatelets. This work demonstrates that by controlling the nanoparticle zeta (zeta) potential through the suspension parameters (pH, organic solvent type and amount, and ionic content) as well as the assembly sequence, the nanostructure and composition of the coatings may be adjusted to optimize the desired properties. Two types of silica nanospheres were evaluated as the hydrophilic component: X-TecRTM 3408 from Nano-X Corporation, with a diameter of about 20 nm, and polishing silica from Electron Microscopy Supply, with diameter of about 65 nm. Graphite nanoplatelets with a thickness of 5~10nm (Aquadag RTM E from Acheson Industries) were used as electrically conductive filler. A cationic copolymer of acrylamide and a quaternary ammonium salt (SuperflocRTM C442 from Cytec Corporation) was used as the binder for the negatively charged nanoparticles. Coatings were applied to gold-coated stainless steel substrates presently used a bipolar plate material for proton exchange membrane (PEM) fuel cells. Coating thickness was found to vary nearly linearly with the number of polymer-nanoparticle layers deposited while a monotonic increase in coating contact resistance was observed for all heterogeneous and pure silica coatings. Thickness increased if the difference in the oppositely charged zeta potentials of the adsorbing components was enhanced through alcohol addition. Interestingly, an opposite effect was observed if the zeta potential difference was increased through pH variation. This previously undocumented difference in adsorption behavior is herein related to changes to the surface chemical heterogeneity of the nanoparticles. Coating contact resistance and surface wettability were found to have a more subtle dependence on the assembly

  12. Branched Hydrocarbon Low Surface Energy Materials for Superhydrophobic Nanoparticle Derived Surfaces.

    PubMed

    Alexander, Shirin; Eastoe, Julian; Lord, Alex M; Guittard, Frédéric; Barron, Andrew R

    2016-01-13

    We present a new class of superhydrophobic surfaces created from low-cost and easily synthesized aluminum oxide nanoparticles functionalized carboxylic acids having highly branched hydrocarbon (HC) chains. These branched chains are new low surface energy materials (LSEMs) which can replace environmentally hazardous and expensive fluorocarbons (FCs). Regardless of coating method and curing temperature, the resulting textured surfaces develop water contact angles (θ) of ∼155° and root-mean-square roughnesses (Rq) ≈ 85 nm, being comparable with equivalent FC functionalized surfaces (θ = 157° and Rq = 100 nm). The functionalized nanoparticles may be coated onto a variety of substrates to generate different superhydrophobic materials. PMID:26641156

  13. Platinum nanoparticles on gallium nitride surfaces: effect of semiconductor doping on nanoparticle reactivity.

    PubMed

    Schäfer, Susanne; Wyrzgol, Sonja A; Caterino, Roberta; Jentys, Andreas; Schoell, Sebastian J; Hävecker, Michael; Knop-Gericke, Axel; Lercher, Johannes A; Sharp, Ian D; Stutzmann, Martin

    2012-08-01

    Platinum nanoparticles supported on n- and p-type gallium nitride (GaN) are investigated as novel hybrid systems for the electronic control of catalytic activity via electronic interactions with the semiconductor support. In situ oxidation and reduction were studied with high pressure photoemission spectroscopy. The experiments revealed that the underlying wide-band-gap semiconductor has a large influence on the chemical composition and oxygen affinity of supported nanoparticles under X-ray irradiation. For as-deposited Pt cuboctahedra supported on n-type GaN, a higher fraction of oxidized surface atoms was observed compared to cuboctahedral particles supported on p-type GaN. Under an oxygen atmosphere, immediate oxidation was recorded for nanoparticles on n-type GaN, whereas little oxidation was observed for nanoparticles on p-type GaN. Together, these results indicate that changes in the Pt chemical state under X-ray irradiation depend on the type of GaN doping. The strong interaction between the nanoparticles and the support is consistent with charge transfer of X-ray photogenerated free carriers at the semiconductor-nanoparticle interface and suggests that GaN is a promising wide-band-gap support material for photocatalysis and electronic control of catalysis. PMID:22738117

  14. Nanoparticle-Based Antimicrobials: Surface Functionality is Critical

    PubMed Central

    Gupta, Akash; Landis, Ryan F.; Rotello, Vincent M.

    2016-01-01

    Bacterial infections cause 300 million cases of severe illness each year worldwide. Rapidly accelerating drug resistance further exacerbates this threat to human health. While dispersed (planktonic) bacteria represent a therapeutic challenge, bacterial biofilms present major hurdles for both diagnosis and treatment. Nanoparticles have emerged recently as tools for fighting drug-resistant planktonic bacteria and biofilms. In this review, we present the use of nanoparticles as active antimicrobial agents and drug delivery vehicles for antibacterial therapeutics. We further focus on how surface functionality of nanomaterials can be used to target both planktonic bacteria and biofilms. PMID:27006760

  15. Surface-molecule proton transfer in the scattering of hyperthermal DABCO from H/Pt(111)

    NASA Astrophysics Data System (ADS)

    Kuipers, E. W.; Vardi, A.; Danon, A.; Amirav, A.

    1992-01-01

    Hyperthermal DABCO is scattered from H-covered Pt(111). The ionization by electron and proton transfer is measured as a function of the incident molecular kinetic energy and the angle of incidence. The positive ions produced are energy analyzed showing hyperthermal distributions which are dependent on the incident energy. This means that no equilibration occurs at the surface and therefore protonation at hyperthermal energy is an Eley-Rideal reaction. The protonation yield depends linearly on the incident DABCO flux and the H-coverage on the Pt(111) surface. The ionization yield for both electron and proton transfer depends on the incident energy as k( Ei- Etr) n with a similar threshold energy of 1.5 eV. From this we learn that direct protonation occurs by electron transfer and a subsequent binding of an H-atom. Within the error bars we found no difference between H-atom and D-atom transfer. Protonation of other molecules with a high proton affinity such as dimethylaniline at H-covered Pt(111) was measured as well. Analytical applications for both surface analysis and molecular detection are discussed.

  16. Nanoparticle Near-Surface Electric Field.

    PubMed

    Chkhartishvili, Levan

    2016-12-01

    Theoretical studies show that surface reconstruction in some crystals involves splitting the surface atomic layer into two-upper and lower-sublayers consisting of atoms with only positive or only negative effective electric charges, respectively. In a macroscopic crystal with an almost infinite surface, the electric field induced by such a surface-dipole is practically totally concentrated between the sublayers. However, when the material is powdered and its particles are of sufficiently small sizes, an electric field of a significant magnitude can be induced outside the sublayers as well. We have calculated the distribution of the electric field and its potential induced at the surface of a disc-shaped particle. The suggested novel nanoscale effect explains the increase in physical reactivity of nanopowders with decreasing particle sizes. PMID:26831686

  17. Reducing ZnO nanoparticle cytotoxicity by surface modification

    NASA Astrophysics Data System (ADS)

    Luo, Mingdeng; Shen, Cenchao; Feltis, Bryce N.; Martin, Lisandra L.; Hughes, Anthony E.; Wright, Paul F. A.; Turney, Terence W.

    2014-05-01

    Nanoparticulate zinc oxide (ZnO) is one of the most widely used engineered nanomaterials and its toxicology has gained considerable recent attention. A key aspect for controlling biological interactions at the nanoscale is understanding the relevant nanoparticle surface chemistry. In this study, we have determined the disposition of ZnO nanoparticles within human immune cells by measurement of total Zn, as well as the proportions of extra- and intracellular dissolved Zn as a function of dose and surface coating. From this mass balance, the intracellular soluble Zn levels showed little difference in regard to dose above a certain minimal level or to different surface coatings. PEGylation of ZnO NPs reduced their cytotoxicity as a result of decreased cellular uptake arising from a minimal protein corona. We conclude that the key role of the surface properties of ZnO NPs in controlling cytotoxicity is to regulate cellular nanoparticle uptake rather than altering either intracellular or extracellular Zn dissolution.Nanoparticulate zinc oxide (ZnO) is one of the most widely used engineered nanomaterials and its toxicology has gained considerable recent attention. A key aspect for controlling biological interactions at the nanoscale is understanding the relevant nanoparticle surface chemistry. In this study, we have determined the disposition of ZnO nanoparticles within human immune cells by measurement of total Zn, as well as the proportions of extra- and intracellular dissolved Zn as a function of dose and surface coating. From this mass balance, the intracellular soluble Zn levels showed little difference in regard to dose above a certain minimal level or to different surface coatings. PEGylation of ZnO NPs reduced their cytotoxicity as a result of decreased cellular uptake arising from a minimal protein corona. We conclude that the key role of the surface properties of ZnO NPs in controlling cytotoxicity is to regulate cellular nanoparticle uptake rather than

  18. Surface plasmon enhanced quantum transport in a hybrid metal nanoparticle array

    NASA Astrophysics Data System (ADS)

    Sun, Lin; Nan, Yali; Xu, Shang; Zhang, Sishi; Han, Min

    2014-07-01

    Hybrid Pd-Ag nanoparticle arrays composed of randomly distributed Pd nanoparticles in dense packing and a small number of dispersed Ag nanoparticles were fabricated with controlled coverage. Photo-enhanced conductance was observed in the nanoparticle arrays. Largest enhancement, which can be higher than 20 folds, was obtained with 450 nm light illumination. This wavelength was found to correlate with the surface plasmon resonance of the Ag nanoparticles. Electron transport measurements showed there were significant Coulomb blockade in the nanoparticle arrays and the blockade could be overcome with the surface plasmon enhanced local field of Ag nanoparticles induced by light illumination.

  19. Sodium hydroxide catalyzed monodispersed high surface area silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Bhakta, Snehasis; Dixit, Chandra K.; Bist, Itti; Abdel Jalil, Karim; Suib, Steven L.; Rusling, James F.

    2016-07-01

    Understanding of the synthesis kinetics and our ability to modulate medium conditions allowed us to generate nanoparticles via an ultra-fast process. The synthesis medium is kept quite simple with tetraethyl orthosilicate (TEOS) as precursor and 50% ethanol and sodium hydroxide catalyst. Synthesis is performed under gentle conditions at 20 °C for 20 min Long synthesis time and catalyst-associated drawbacks are most crucial in silica nanoparticle synthesis. We have addressed both these bottlenecks by replacing the conventional Stober catalyst, ammonium hydroxide, with sodium hydroxide. We have reduced the overall synthesis time from 20 to 1/3 h, ∼60-fold decrease, and obtained highly monodispersed nanoparticles with 5-fold higher surface area than Stober particles. We have demonstrated that the developed NPs with ∼3-fold higher silane can be used as efficient probes for biosensor applications.

  20. Surface plasmon enhanced photoluminescence from copper nanoparticles: Influence of temperature

    SciTech Connect

    Yeshchenko, Oleg A. Bondarchuk, Illya S.; Losytskyy, Mykhaylo Yu.

    2014-08-07

    Anomalous temperature dependence of surface plasmon enhanced photoluminescence from copper nanoparticles embedded in a silica host matrix has been observed. The quantum yield of photoluminescence increases as the temperature increases. The key role of such an effect is the interplay between the surface plasmon resonance and the interband transitions in the copper nanoparticles occurring at change of the temperature. Namely, the increase of temperature leads to the red shift of the resonance. The shift leads to increase of the spectral overlap of the resonance with photoluminescence band of copper as well as to the decrease of plasmon damping caused by interband transitions. Such mechanisms lead to the increase of surface plasmon enhancement factor and, consequently, to increase of the quantum yield of the photoluminescence.

  1. Gold nanoparticles with different amino acid surfaces: serum albumin adsorption, intracellular uptake and cytotoxicity.

    PubMed

    Cai, Huanxin; Yao, Ping

    2014-11-01

    Gold nanoparticles with aspartate, glycine, leucine, lysine, and serine surfaces were produced from the mixed solutions of HAuCl4 and respective amino acids via UV irradiation. The amino acids bind to the nanoparticle surfaces via amine groups and their carboxylic groups extend out to stabilize the nanoparticles. The nanoparticles have diameters of 15-47 nm in pH 7.4 aqueous solution and have diameters of 62-73 nm after 48 h incubation in cell culture containing serum. The nanoparticles adsorb human and bovine serum albumins on their surfaces by specific interactions, characterized by the intrinsic fluorescence quenching of the albumins. The albumin adsorption effectively decreases the aggregation of the nanoparticles in cell culture and also decreases the intracellular uptake of the nanoparticles. The gold nanoparticles produced from leucine and lysine, which have amphiphilic groups on their surfaces, present better biocompatibility than the other gold nanoparticles. PMID:25466455

  2. Organic-inorganic hybrid proton exchange membranes based on silicon-containing polyacrylate nanoparticles with phosphotungstic acid

    NASA Astrophysics Data System (ADS)

    Cui, Xuejun; Zhong, Shuangling; Wang, Hongyan

    A series of silicon-containing polyacrylate nanoparticles (SiPANPs) were successfully synthesized by simple emulsifier-free emulsion polymerization technique. The resulting latex particles were characterized by Fourier transform infrared (FTIR) spectrometry, dynamic light scattering (DLS) analysis, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The SiPANP membranes and SiPANP/phosphotungstic acid (SiPANP/PWA) hybrid membranes were also prepared and characterized to evaluate their potential as proton exchange membranes in proton exchange membrane fuel cell (PEMFC). Compared with the pure SiPANP membrane, the hybrid membranes displayed lower thermal stability. However, the degradation temperatures were still above 190 °C, satisfying the requirement of thermal stability for PEMFC operation. In addition, the hybrid membranes showed lower water uptake but higher proton conductivity than the SiPANP precursor. The proton conductivity of the hybrid membranes was in the range of 10 -3 to 10 -2 S cm -1 and increased gradually with PWA content and temperature. The excellent hydrolytic stability was also observed in the hybrid membranes because of the existence of crosslinked silica network. The good thermal stability, reasonable water uptake, excellent hydrolytic stability, suitable proton conductivity and cost effectiveness make these hybrids quite attractive as proton exchange membranes for PEMFC applications.

  3. Immobilization of gold nanoparticles on cell culture surfaces for safe and enhanced gold nanoparticle-mediated laser transfection

    NASA Astrophysics Data System (ADS)

    Kalies, Stefan; Heinemann, Dag; Schomaker, Markus; Gentemann, Lara; Meyer, Heiko; Ripken, Tammo

    2014-07-01

    In comparison to standard transfection methods, gold nanoparticle-mediated laser transfection has proven to be a versatile alternative. This is based on its minor influence on cell viability and its high efficiency, especially for the delivery of small molecules like small interfering RNA. However, in order to transfer it to routine usage, a safety aspect is of major concern: The avoidance of nanoparticle uptake by the cells is desired. The immobilization of the gold nanoparticles on cell culture surfaces can address this issue. In this study, we achieved this by silanization of the appropriate surfaces and the binding of gold nanoparticles to them. Comparable perforation efficiencies to the previous approaches of gold nanoparticle-mediated laser transfection with free gold nanoparticles are demonstrated. The uptake of the immobilized particles by the cells is unlikely. Consequently, these investigations offer the possibility of bringing gold nanoparticle-mediated laser transfection closer to routine usage.

  4. PEG-Stabilized Core–Shell Surface-Imprinted Nanoparticles

    PubMed Central

    Moczko, Ewa; Guerreiro, Antonio; Piletska, Elena; Piletsky, Sergey

    2016-01-01

    Here we present a simple technique to produce target-specific molecularly imprinted polymeric nanoparticles (MIP NPs) and their surface modification in order to prevent the aggregation process that is ever-present in most nanomaterial suspensions/dispersions. Specifically, we studied the influence of surface modification of MIP NPs with polymerizable poly(ethylene glycol) on their degree of stability in water, in phosphate buffer, and in the presence of serum proteins. Grafting a polymer shell on the surface of nanoparticles decreases the surface energy, enhances the polarity, and as a result improves the dispersibility, storage, and colloidal stability as compared to those of core (unmodified) particles. Because of the unique solid-phase approach used for synthesis, the binding sites of MIP NPs are protected during grafting, and the recognition properties of nanoparticles are not affected. These results are significant for developing nanomaterials with selective molecular recognition, increased biocompatibility, and stability in solution. Materials synthesized this way have the potential to be used in a variety of technological fields, including in vivo applications such as drug delivery and imaging. PMID:23855734

  5. Preparation of amyloid-like fibrils containing magnetic iron oxide nanoparticles: Effect of protein aggregation on proton relaxivity

    SciTech Connect

    Viktor Andersson, B.; Skoglund, Caroline; Uvdal, Kajsa; Solin, Niclas

    2012-03-23

    Highlights: Black-Right-Pointing-Pointer Preparation of amyloid materials labeled with magnetic iron oxide nanoparticles. Black-Right-Pointing-Pointer Characterization of amyloid materials by electron tomography. Black-Right-Pointing-Pointer Influence of protein aggregation on the magnetic nanoparticle properties. -- Abstract: A method to prepare amyloid-like fibrils functionalized with magnetic nanoparticles has been developed. The amyloid-like fibrils are prepared in a two step procedure, where insulin and magnetic nanoparticles are mixed simply by grinding in the solid state, resulting in a water soluble hybrid material. When the hybrid material is heated in aqueous acid, the insulin/nanoparticle hybrid material self assembles to form amyloid-like fibrils incorporating the magnetic nanoparticles. This results in magnetically labeled amyloid-like fibrils which has been characterized by Transmission Electron Microscopy (TEM) and electron tomography. The influence of the aggregation process on proton relaxivity is investigated. The prepared materials have potential uses in a range of bio-imaging applications.

  6. SU-E-T-577: Obliquity Factor and Surface Dose in Proton Beam Therapy

    SciTech Connect

    Das, I; Andersen, A; Coutinho, L

    2015-06-15

    Purpose: The advantage of lower skin dose in proton beam may be diminished creating radiation related sequalae usually seen with photon and electron beams. This study evaluates the surface dose as a complex function of beam parameters but more importantly the effect of beam angle. Methods: Surface dose in proton beam depends on the beam energy, source to surface distance, the air gap between snout and surface, field size, material thickness in front of surface, atomic number of the medium, beam angle and type of nozzle (ie double scattering, (DS), uniform scanning (US) or pencil beam scanning (PBS). Obliquity factor (OF) is defined as ratio of surface dose in 0° to beam angle Θ. Measurements were made in water phantom at various beam angles using very small microdiamond that has shown favorable beam characteristics for high, medium and low proton energy. Depth dose measurements were performed in the central axis of the beam in each respective gantry angle. Results: It is observed that surface dose is energy dependent but more predominantly on the SOBP. It is found that as SSD increases, surface dose decreases. In general, SSD, and air gap has limited impact in clinical proton range. High energy has higher surface dose and so the beam angle. The OF rises with beam angle. Compared to OF of 1.0 at 0° beam angle, the value is 1.5, 1.6, 1,7 for small, medium and large range respectively for 60 degree angle. Conclusion: It is advised that just like range and SOBP, surface dose should be clearly understood and a method to reduce the surface dose should be employed. Obliquity factor is a critical parameter that should be accounted in proton beam therapy and a perpendicular beam should be used to reduce surface dose.

  7. The influence of edge sites on the development of surface charge on goethite nanoparticles: A molecular dynamics investigation

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Felmy, Andrew R.

    2005-03-01

    Large-scale molecular simulation of proton accumulations were carried out on (i) (110) and (021) slabs immersed in aqueous solution and (ii) a series of model goethite nanoparticles of dimension 2 to 8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15% more proton charge per unit area than the (110) surface. In the particulate systems, the acicular particles having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.

  8. The Influence of Edge Sites on the Development of Surface Charge on Goethite Nanoparticles: A Molecular Dynamics Investigation

    SciTech Connect

    Rustad, James R.; Felmy, Andrew R.

    2005-03-15

    Large-scale molecular simulation of proton accumulations were carried out on (1) (110) and (021) slabs immersed in aqueous solution and (2) a series of model goethite nanoparticles of dimension 2-8 nm with systematically varying acicularity and (110)/(021) surface areas. In the slab systems, the (021) surface exhibits 15 percent more proton charge/unit area than the (110) surface. In the particulate systems, the acicular particles, having the highest (110)/(021) ratio accumulate the most charge, opposite to the trend expected from the slab simulations, indicating that, at length scales on the order of 10 nm, the slab results are not a good indicator of the overall charging behavior of the particles. The primary reason for the discrepancy between the particulate systems and slab systems is the preferential accumulation of protons at acute (110)-(110) intersections. Charge accumulates preferentially in this region because excess proton charge at an asperity is more effectively solvated than at a flat interface.

  9. Nanoparticle-Based Surface Modifications for Microtribology Control and Superhydrophobicity

    NASA Astrophysics Data System (ADS)

    Hurst, Kendall Matthew

    2010-11-01

    The emergence of miniaturization techniques for consumer electronics has brought forth the relatively new and exciting field of microelectromechanical systems (MEMS). However, due to the inherent forces that exist between surfaces at the micro- and nanoscale, scientists and semiconductor manufacturers are still struggling to improve the lifetime and reliability of complex microdevices. Due to the extremely large surface area-to-volume ratio of typical MEMS and microstructured surfaces, dominant interfacial forces exist which can be detrimental to their operational lifetime. In particular, van der Waals, capillary, and electrostatic forces contribute to the permanent adhesion, or stiction , of microfabricated surfaces. This strong adhesion force also contributes to the friction and wear of these silicon-based systems. The scope of this work was to examine the effect of utilizing nanoparticles as the basis for roughening surfaces for the purpose of creating films with anti-adhesive and/or superhydrophobic properties. All of the studies presented in this work are focused around a gas-expanded liquid (GXL) process that promotes the deposition of colloidal gold nanoparticles (AuNPs) into conformal thin films. The GXL particle deposition process is finalized by a critical point drying step which is advantageous to the microelectromechanical systems and semiconductor (IC) industries. In fact, preliminary results illustrated that the GXL particle deposition process can easily be integrated into current MEMS microfabrication processes. Thin films of AuNPs deposited onto the surfaces of silicon-based MEMS and tribology test devices were shown to have a dramatic effect on the adhesion of microstructures. In the various investigations, the apparent work of adhesion between surfaces was reduced by 2-4 orders of magnitude. This effect is greatly attributed to the roughening of the typically smooth silicon oxide surfaces which, in turn, dramatically decreases the "real are of

  10. Rapid coating of surfaces with functionalized nanoparticles for regulation of cell behavior.

    PubMed

    Tang, Rui; Moyano, Daniel F; Subramani, Chandramouleeswaran; Yan, Bo; Jeoung, Eunhee; Tonga, Gülen Yesilbag; Duncan, Bradley; Yeh, Yi-Cheun; Jiang, Ziwen; Kim, Chaekyu; Rotello, Vincent M

    2014-05-28

    A robust monolayer of nanoparticles is formed via dip-coating of cell culture plates. These surfaces provide cell type-specific modulation of growth behavior without the uptake of nanoparticles. PMID:24677290

  11. Surface passivation of semiconducting oxides by self-assembled nanoparticles

    PubMed Central

    Park, Dae-Sung; Wang, Haiyuan; Vasheghani Farahani, Sepehr K.; Walker, Marc; Bhatnagar, Akash; Seghier, Djelloul; Choi, Chel-Jong; Kang, Jie-Hun; McConville, Chris F.

    2016-01-01

    Physiochemical interactions which occur at the surfaces of oxide materials can significantly impair their performance in many device applications. As a result, surface passivation of oxide materials has been attempted via several deposition methods and with a number of different inert materials. Here, we demonstrate a novel approach to passivate the surface of a versatile semiconducting oxide, zinc oxide (ZnO), evoking a self-assembly methodology. This is achieved via thermodynamic phase transformation, to passivate the surface of ZnO thin films with BeO nanoparticles. Our unique approach involves the use of BexZn1-xO (BZO) alloy as a starting material that ultimately yields the required coverage of secondary phase BeO nanoparticles, and prevents thermally-induced lattice dissociation and defect-mediated chemisorption, which are undesirable features observed at the surface of undoped ZnO. This approach to surface passivation will allow the use of semiconducting oxides in a variety of different electronic applications, while maintaining the inherent properties of the materials. PMID:26757827

  12. Surface passivation of semiconducting oxides by self-assembled nanoparticles

    NASA Astrophysics Data System (ADS)

    Park, Dae-Sung; Wang, Haiyuan; Vasheghani Farahani, Sepehr K.; Walker, Marc; Bhatnagar, Akash; Seghier, Djelloul; Choi, Chel-Jong; Kang, Jie-Hun; McConville, Chris F.

    2016-01-01

    Physiochemical interactions which occur at the surfaces of oxide materials can significantly impair their performance in many device applications. As a result, surface passivation of oxide materials has been attempted via several deposition methods and with a number of different inert materials. Here, we demonstrate a novel approach to passivate the surface of a versatile semiconducting oxide, zinc oxide (ZnO), evoking a self-assembly methodology. This is achieved via thermodynamic phase transformation, to passivate the surface of ZnO thin films with BeO nanoparticles. Our unique approach involves the use of BexZn1-xO (BZO) alloy as a starting material that ultimately yields the required coverage of secondary phase BeO nanoparticles, and prevents thermally-induced lattice dissociation and defect-mediated chemisorption, which are undesirable features observed at the surface of undoped ZnO. This approach to surface passivation will allow the use of semiconducting oxides in a variety of different electronic applications, while maintaining the inherent properties of the materials.

  13. Surface Proton Hopping and Coupling Pathway of Water Oxidation on Cobalt Oxide Catalyst

    NASA Astrophysics Data System (ADS)

    Pham, Hieu; Cheng, Mu-Jeng; Frei, Heinz; Wang, Lin-Wang

    We propose an oxidation pathway of water splitting on cobalt oxide surface with clear thermodynamic and kinetic details. The density-functional theory studies suggest that the coupled proton-electron transfer is not necessarily sequential and implicit in every elementary step of this mechanistic cycle. Instead, the initial O-O bond could be formed by the landing of water molecule on the surface oxos, which is then followed by the dispatch of protons through the hopping manner and subsequent release of di-oxygen. Our theoretical investigations of intermediates and transition states indicate that all chemical conversions in this pathway, including the proton transfers, are possible with low activation barriers, in addition to their favorable thermodynamics. Our hypothesis is supported by recent experimental observations of surface superoxide that is stabilized by hydrogen bonding to adjacent hydroxyl group, as an intermediate on fast-kinetics catalytic site.

  14. Surface-molecule proton transfer: A demonstration of the Eley-Rideal mechanism

    NASA Astrophysics Data System (ADS)

    Kuipers, E. W.; Vardi, A.; Danon, A.; Amirav, A.

    1991-01-01

    Hyperthermal molecular DABCO [N(C2H4)3N] is scattered from hydrogen-covered Pt(111). Some of the scattered molecules are protonated at the surface and leave with a kinetic energy which is strongly dependent on the incident energy. This means that proton abstraction is occurring immediately on collision and it serves as a clear demonstration of an Eley-Rideal mechanism. No isotope effect was observed, excluding a tunneling mechanism. The proton transfer shows a threshold energy equal to the difference between the surface work function and the molecular ionization potential. The reaction therefore proceeds via a molecule-surface electron transfer and a subsequent H-atom abstraction.

  15. Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies

    NASA Astrophysics Data System (ADS)

    Wu, Wei; He, Quanguo; Jiang, Changzhong

    2008-10-01

    Surface functionalized magnetic iron oxide nanoparticles (NPs) are a kind of novel functional materials, which have been widely used in the biotechnology and catalysis. This review focuses on the recent development and various strategies in preparation, structure, and magnetic properties of naked and surface functionalized iron oxide NPs and their corresponding application briefly. In order to implement the practical application, the particles must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of iron oxide NPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The problems and major challenges, along with the directions for the synthesis and surface functionalization of iron oxide NPs, are considered. Finally, some future trends and prospective in these research areas are also discussed.

  16. Magnetic Iron Oxide Nanoparticles: Synthesis and Surface Functionalization Strategies

    PubMed Central

    2008-01-01

    Surface functionalized magnetic iron oxide nanoparticles (NPs) are a kind of novel functional materials, which have been widely used in the biotechnology and catalysis. This review focuses on the recent development and various strategies in preparation, structure, and magnetic properties of naked and surface functionalized iron oxide NPs and their corresponding application briefly. In order to implement the practical application, the particles must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of iron oxide NPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The problems and major challenges, along with the directions for the synthesis and surface functionalization of iron oxide NPs, are considered. Finally, some future trends and prospective in these research areas are also discussed. PMID:21749733

  17. Nonlinear surface plasma wave induced target normal sheath acceleration of protons

    SciTech Connect

    Liu, C. S.; Tripathi, V. K. Shao, Xi; Liu, T. C.

    2015-02-15

    The mode structure of a large amplitude surface plasma wave (SPW) over a vacuum–plasma interface, including relativistic and ponderomotive nonlinearities, is deduced. It is shown that the SPW excited by a p-polarized laser on a rippled thin foil target can have larger amplitude than the transmitted laser amplitude and cause stronger target normal sheath acceleration of protons as reported in a recent experiment. Substantial enhancement in proton number also occurs due to the larger surface area covered by the SPW.

  18. Single-electron induced surface plasmons on a topological nanoparticle

    PubMed Central

    Siroki, G.; Lee, D.K.K.; Haynes, P. D.; Giannini, V.

    2016-01-01

    It is rarely the case that a single electron affects the behaviour of several hundred thousands of atoms. Here we demonstrate a phenomenon where this happens. The key role is played by topological insulators—materials that have surface states protected by time-reversal symmetry. Such states are delocalized over the surface and are immune to its imperfections in contrast to ordinary insulators. For topological insulators, the effects of these surface states will be more strongly pronounced in the case of nanoparticles. Here we show that under the influence of light a single electron in a topologically protected surface state creates a surface charge density similar to a plasmon in a metallic nanoparticle. Such an electron can act as a screening layer, which suppresses absorption inside the particle. In addition, it can couple phonons and light, giving rise to a previously unreported topological particle polariton mode. These effects may be useful in the areas of plasmonics, cavity electrodynamics and quantum information. PMID:27491515

  19. Single-electron induced surface plasmons on a topological nanoparticle.

    PubMed

    Siroki, G; Lee, D K K; Haynes, P D; Giannini, V

    2016-01-01

    It is rarely the case that a single electron affects the behaviour of several hundred thousands of atoms. Here we demonstrate a phenomenon where this happens. The key role is played by topological insulators-materials that have surface states protected by time-reversal symmetry. Such states are delocalized over the surface and are immune to its imperfections in contrast to ordinary insulators. For topological insulators, the effects of these surface states will be more strongly pronounced in the case of nanoparticles. Here we show that under the influence of light a single electron in a topologically protected surface state creates a surface charge density similar to a plasmon in a metallic nanoparticle. Such an electron can act as a screening layer, which suppresses absorption inside the particle. In addition, it can couple phonons and light, giving rise to a previously unreported topological particle polariton mode. These effects may be useful in the areas of plasmonics, cavity electrodynamics and quantum information. PMID:27491515

  20. Surface composition of magnetron sputtered Pt-Co thin film catalyst for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Vorokhta, Mykhailo; Khalakhan, Ivan; Václavů, Michal; Kovács, Gábor; Kozlov, Sergey M.; Kúš, Peter; Skála, Tomáš; Tsud, Natalia; Lavková, Jaroslava; Potin, Valerie; Matolínová, Iva; Neyman, Konstantin M.; Matolín, Vladimír

    2016-03-01

    Recently we have tested a magnetron sputtered Pt-Co catalyst in a hydrogen-fed proton exchange membrane fuel cell and showed its high catalytic activity for the oxygen reduction reaction. Here we present further investigation of the magnetron sputtered Pt-Co thin film catalyst by both experimental and theoretical methods. Scanning electron microscopy and transmission electron microscopy experiments confirmed the nanostructured character of the catalyst. The surface composition of as-deposited and annealed at 773 K Pt-Co films was investigated by surface analysis techniques, such as synchrotron radiation photoelectron spectroscopy and X-ray photoelectron spectroscopy. Modeling based on density functional theory showed that the surface of 6 nm large 1:1 Pt-Co nanoparticles is almost exclusively composed of Pt atoms (>90%) at typical operation conditions and the Co content does not exceed 20% at 773 K, in agreement with the experimental characterization of such films annealed in vacuum. According to experiment, the density of valence states of surface atoms in Pt-Co nanostructures is shifted by 0.3 eV to higher energies, which can be associated with their higher activity in the oxygen reduction reaction. The changes in electronic structure caused by alloying are also reflected in the measured Pt 4f, Co 3p and Co 2p photoelectron peak binding energies.

  1. The role of surface charge on the uptake and biocompatibility of hydroxyapatite nanoparticles with osteoblast cells

    PubMed Central

    Chen, Liang; Mccrate, Joseph M.; Lee, James C-M.; Li, Hao

    2011-01-01

    The objective of this study is to evaluate the effect of hydroxyapatite (HAP) nanoparticles with different surface charges on the cellular uptake behavior and in vitro cell viability and proliferation of MC3T3-E1 cell lines (osteoblast). The nanoparticles surface charge was varied by the surface modification with two carboxylic acids: 12-aminododecanoic acid (positive) and dodecanedioic acid (negative). The untreated HAP nanoparticles and dodecanoic acid modified HAP nanoparticles (neutral) were used as the control. X-ray diffraction (XRD) revealed that surface modifications by the three carboxylic acids did not change the crystal structure of HAP nanoparticles; Fourier transform infrared spectroscopy (FTIR) confirmed the adsorption and binding of the carboxylic acids on HAP nanoparticle surface; and zeta potential measurement confirmed that the chemicals successfully modified the surface charge of HAP nanoparticles in water based solution. Transmission electron microscopy (TEM) images showed that positively charged, negatively charged and untreated HAP nanoparticles, with similar size and shape, all penetrated into the cells and cells had more uptake of HAP nanoparticles with positive charge compared to those with negative charge, which might be attributed to the attractive or repulsive interaction between the negatively charged cell membrane and positively/negatively charged HAP nanoparticles. The neutral HAP nanoparticles could not penetrate cell membrane due to the larger size. MTT assay and LDH assay results indicated that as compared with the polystyrene control, greater cell viability and cell proliferation were measured on MC3T3-E1 cells treated with the three kinds of the HAP nanoparticles (neutral, positive, and untreated), among which positively charged HAP nanoparticles shows strongest improvement for cell viability and cell proliferation. In summary, the surface charge of HAP nanoparticles can be modified to influence the cellular uptake of HAP

  2. Toward tuning the surface functionalization of small ceria nanoparticles

    SciTech Connect

    Huang, Xing; Wang, Binghui; Grulke, Eric A.; Beck, Matthew J.

    2014-02-21

    Understanding and controlling the performance of ceria nanoparticle (CNP) catalysts requires knowledge of the detailed structure and property of CNP surfaces and any attached functional groups. Here we report thermogravimetric analysis results showing that hydrothermally synthesized ∼30 nm CNPs are decorated with 12.9 hydroxyl groups per nm{sup 2} of CNP surface. Quantum mechanical calculations of the density and distribution of bound surface groups imply a scaling relationship for surface group density that balances formal charges in the functionalized CNP system. Computational results for CNPs with only hydroxyl surface groups yield a predicted density of bound hydroxyl groups for ∼30 nm CNPs that is ∼33% higher than measured densities. Quantitative agreement between predicted and measured hydroxyl surface densities is achieved when calculations consider CNPs with both –OH and –O{sub x} surface groups. For this more general treatment of CNP surface functionalizations, quantum mechanical calculations predict a range of stable surface group configurations that depend on the chemical potentials of O and H, and demonstrate the potential to tune CNP surface functionalizations by varying temperature and/or partial pressures of O{sub 2} and H{sub 2}O.

  3. Influence of surface roughness on water- and oil-repellent surfaces coated with nanoparticles

    NASA Astrophysics Data System (ADS)

    Hsieh, Chien-Te; Chen, Jin-Ming; Kuo, Rong-Rong; Lin, Ta-Sen; Wu, Chu-Fu

    2005-02-01

    Various rough surfaces coated with titanium oxide nanoparticles and perfluoroalkyl methacrylic copolymer were conducted to explore the influence of surface roughness on the performance of water- and oil-repellence. Surface characteristics determined from nitrogen physisorption at -196 °C showed that the surface area and pore volume increased significantly with the extent of nanoparticle ratio, indicating an increase of surface roughness. Due to the surface nano-coating, the maximum contact angles of water and ethylene glycol (EG) droplets increased up to 56 and 48%, respectively, e.g. from 105° to 164° for water droplets and from 96° to 144° for EG droplets. The excellent water- and oil-repellence of the prepared surfaces was ascribed to this increase of surface roughness and fluorinated-contained surface. Compared with Wenzel model, the Cassie model yielded a fairly good fit to the simulation of contact angle with surface roughness. However, a derivation of 3°-10° at higher roughness still existed. This phenomenon was very likely due to the surface heterogeneity with different pore size distributions of the fractal surfaces. In this case, it was unfavorable for super repellency from rough surface with larger mesopore fraction because of its capillary condensation, reflecting that micropore provided more air resistance against wettability.

  4. Enhancing surface plasmon resonances of metallic nanoparticles by diatom biosilica.

    PubMed

    Ren, Fanghui; Campbell, Jeremy; Wang, Xiangyu; Rorrer, Gregory L; Wang, Alan X

    2013-07-01

    Diatoms are single-celled algaes that make photonic-crystal-like silica shells or frustules with hierarchical micro- & nano-scale features consisting of two-dimensional periodic pores. This article reports the use of diatom frustules as an integration platform to enhance localized surface plasmon resonances of self-assembled silver nanoparticles (NPs) on the surface of diatom frustules. Theoretical and experimental results show enhanced localized surface plasmons due to the coupling with the guided-mode resonances of the frustules. We observed 2 × stronger optical extinction and over 4 × higher sensitivity of surface-enhanced Raman scattering of Rhodmine 6G from the NPs-on-diatom than the NPs-on-glass structure. PMID:23842317

  5. SU-E-T-544: Microscopic Dose Enhancement of Gold Nanoparticles in Water for Proton Therapy: A Simulation Study

    SciTech Connect

    Newpower, M; Ahmad, S; Chen, Y

    2015-06-15

    Purpose: To quantify the microscopic dose and linear energy transfer (LET) enhancement of gold nanoparticles (GNPs) in water for proton therapy. Methods: The GEANT4 toolkit (version 10) with low energy electromagnetic classes was used to create a series of simulations where three radii (r=5, 20, 100 nm) of gold nanoparticles (GNPs) were irradiated with 5 × 106 80 MeV protons. A cubic detector (10 × 10 × 10 um, divided in 25 × 25 × 25 voxels) were placed in a water phantom where the GNP rests in the center. The size of incident proton beam was set to be same as the GNPs and perpendicularly aiming to the target. Dose deposited to each voxel were recorded to calculate the overall deposited dose and the dose-averaged LET. The emitted secondary electron spectra were also collected in a spherical customized scorer (radius = 150 nm). Results: The average dose from a single GNP in a cubic water phantom was increased by 0.12 %, 1.12% and 2.3% and the mean dose-averaged LET was increased by 5.87% and 27.67% and 0.31% for GNP radius of 5 nm, 20 nm and 100 nm, respectively. Conclusion: The dose enhancement effect from the presence of a single GNP was qualified in a water phantom. A significant increase in the mean dose-averaged LET was found for 20 nm GNP.

  6. Influence of surface spins on the magnetization of fine maghemite nanoparticles

    NASA Astrophysics Data System (ADS)

    Nadeem, K.; Krenn, H.; Szabó, D. V.

    2013-12-01

    Influence of surface spins on magnetization of maghemite nanoparticles have been studied by using SQUID measurements and also comparison done with theoretical simulations. Surface spin disorder arises in these nanoparticles due to the randomness of surface spins. A model of AC-susceptibility has been used to investigate the experimental results. The comparison between experiment and theory signifies the presence of large effective anisotropy and freezing effects on the surface of maghemite nanoparticles. The enhanced effective anisotropy constant of these nanoparticles as compared to bulk maghemite is due to presence of disordered surface spins.

  7. Influence of surface spins on the magnetization of fine maghemite nanoparticles

    SciTech Connect

    Nadeem, K.; Krenn, H.; Szabó, D. V.

    2013-12-16

    Influence of surface spins on magnetization of maghemite nanoparticles have been studied by using SQUID measurements and also comparison done with theoretical simulations. Surface spin disorder arises in these nanoparticles due to the randomness of surface spins. A model of AC-susceptibility has been used to investigate the experimental results. The comparison between experiment and theory signifies the presence of large effective anisotropy and freezing effects on the surface of maghemite nanoparticles. The enhanced effective anisotropy constant of these nanoparticles as compared to bulk maghemite is due to presence of disordered surface spins.

  8. Surface plasmon polariton scattering by finite-size nanoparticles

    NASA Astrophysics Data System (ADS)

    Evlyukhin, A. B.; Brucoli, G.; Martín-Moreno, L.; Bozhevolnyi, S. I.; García-Vidal, F. J.

    2007-08-01

    The electromagnetic Green’s tensor approach (GTA) is used to obtain the differential and total scattering cross sections of a finite-size nanoparticle located at a metal surface and illuminated with surface plasmon polaritons (SPPs). The scattering process comprehends either elastic scattering of the incident SPP into other SPPs propagating in different directions or scattering into field components propagating away from the surface, as well as the radiation absorption by the (metal) nanoparticle. Once the total electric field inside the scatterer is known, the expressions obtained allow for a comparison of the efficiency of the different scattering channels. Connection between the GTA and the point-dipole approximation (PDA) of the scattering problem is discussed, including the absorption of the SPP and the transition from the GTA to the PDA when the scatterer is approximated by a spherical particle of the same volume. SPP extinction spectra for gold cubic particles of various sizes placed in the vicinity of a flat gold surface are calculated with the GTA and compared with the results obtained using the PDA.

  9. Surface reactivity of V2O5(001): Effects of vacancies, protonation, hydroxylation, and chlorination

    NASA Astrophysics Data System (ADS)

    Negreira, Ana Suarez; Aboud, Shela; Wilcox, Jennifer

    2011-01-01

    Using density-functional theory we analyze the thermodynamic stability of partially reduced, protonated, hydroxylated, and chlorinated V2O5(001) surfaces under flue gas conditions. These surfaces are characterized geometrically through surface relaxation calculations and electronically through charge distribution and density-of-states analysis to understand the change in surface reactivity under different pressure and temperature conditions, with a primary focus on coal-fired flue gas conditions. The stoichiometric surface is found to be the most favorable termination under flue gas conditions, but at low oxygen partial pressures (i.e., ultra-high-vacuum conditions) and elevated temperatures, the partially reduced V2O5(001) surfaces with one or two vanadyl oxygen vacancies are found to be stable. A surface semiconductor-to-metal transformation takes place with the addition of oxygen vacancies indicated by a decrease in the band gap. The protonation of the V2O5(001) surface only takes place at low oxygen partial pressures where the main source or sink of hydrogen atoms comes from H2. The study of the thermodynamic stability of protonated surfaces and surfaces with dissociated water with both H- and OH- groups indicated that these surfaces are not stable under flue gas conditions. Chlorinated surfaces were not stable under the flue gas and the coverage conditions tested. Larger HCl concentrations or smaller coverages may lead to stable chlorinated structures; however, the small coverages required to accurately represent the chlorine flue gas concentrations would require much larger unit-cell sizes that would be too computationally expensive. From this work it is evident that the stoichiometric surface of V2O5 is the most stable under flue gas conditions, and likely reactivity corresponding to NOx reduction, surface chlorination, and mercury oxidation stems from support effects on the vanadia catalyst, which influences the vanadium oxidation state and subsequent

  10. Detailed investigation on the possibility of nanoparticles of various metal elements for surface-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Yonezawa, Tetsu; Kawasaki, Hideya; Tarui, Akira; Watanabe, Takehiro; Arakawa, Ryuichi; Shimada, Toshihiro; Mafuné, Fumitaka

    2009-03-01

    In this paper, we describe systematic detailed considerations of the feasibility of using various metal nanoparticles for organic-matrix-free surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). In order to avoid the influence of organic molecules on the nanoparticles, stabilizer-free bare nanoparticles of Ag, Au, Cu and Pt were prepared by laser ablation. Although all metal nanoparticles absorbed N(2) laser light (337 nm) energy, the performance of desorption/ionization of a representative peptide, angiotensin I, strongly depended on the metal element. Citrate buffer was used as a proton source; it reduced the amount of alkali cation adducts present. Then, protonated molecules of analytes predominated in the mass spectra when Au and Pt nanoparticles were used. Pt nanoparticles showed the highest performance in SALDI-MS, owing to their smaller heat conductivity and higher melting temperature. The selective desorption of a cationic surfactant with longer alkyl chains and a peptide with methionine was also observed. PMID:19276588

  11. Interaction of Biofunctionalized Nanoparticles with Receptors on Cell Surfaces: MC Simulations

    NASA Astrophysics Data System (ADS)

    Dormidontova, Elena; Wang, Shihu

    2015-03-01

    One of the areas of active development of modern nanomedicine is drug/gene delivery and imaging application of nanoparticles functionalized by ligands, aptamers or antibodies capable of specific interactions with cell surface receptors. Being a complex multifunctional system different structural aspects of nanoparticles affect their interactions with cell surfaces and the surface properties of cells can be different (e.g. density, distribution and mobility of receptors). Computer simulations allow a systematic investigation of the influence of multiple factors and provide a unified platform for the comparison. Using Monte Carlo simulations we investigate the influence of the nanoparticle properties (nanoparticle size, polymer tether length, polydispersity, density, ligand energy, valence and density) on nanoparticle-cell surface interactions and make predictions regarding favorable nanoparticle design for achieving multiple ligand-receptor binding. We will also discuss the implications of nanoparticle design on the selectivity of attachment to cells with high receptor density while ``ignoring'' cells with a low density of receptors.

  12. Interfacial Structure and Proton Conductivity of Nafion at the Pt-Deposited Surface.

    PubMed

    Ono, Yutaro; Nagao, Yuki

    2016-01-12

    Understanding the Nafion-Pt interface structure is important because fuel cell reactions occur at the three-phase boundary. Infrared (IR) p-polarized multiple-angle incidence resolution spectrometry (p-MAIRS) technique was used to investigate the in-plane (IP) and out-of-plane (OP) spectra in the identical substrate. Our previous study revealed that the proton conductivity of the Nafion thin films decreased at the MgO and SiO2 surfaces. We proposed that the origin for the lower proton conductivity can be derived from the highly oriented structure at the interface. However, the interface structure of the Nafion-Pt interface remains unclear. In this study, Nafion thin films were prepared by spin-coating on a Pt-deposited MgO substrates. The IP spectrum exhibited a well-known spectrum, but the OP spectrum was quite differed considerably from the IP spectrum. Furthermore, thickness dependence of the degree of orientation for this OP band was observed at the Nafion-Pt interface. This OP band can be assigned as the vibration mode of the mixture of the CF2 and sulfonic acid groups. At the low-RH region, proton conductivity of the Nafion thin film on the Pt-deposited surface was 1 order of magnitude higher than that on the SiO2 surface. Furthermore, the activation energy was 0.4-0.5 eV, which is lower than that of the SiO2 surface. These results, which suggest that the Pt surface influenced the proton transport property of Nafion thin film, can contribute to understand the relationship between the proton transport property and thin film structure on the Pt-deposited surface at the three-phase boundary for fuel cells. PMID:26653839

  13. The effect of magnetically induced linear aggregates on proton transverse relaxation rates of aqueous suspensions of polymer coated magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Saville, Steven L.; Woodward, Robert C.; House, Michael J.; Tokarev, Alexander; Hammers, Jacob; Qi, Bin; Shaw, Jeremy; Saunders, Martin; Varsani, Rahi R.; St Pierre, Tim G.; Mefford, O. Thompson

    2013-02-01

    It has been recently reported that for some suspensions of magnetic nanoparticles the transverse proton relaxation rate, R2, is dependent on the time that the sample is exposed to an applied magnetic field. This time dependence has been linked to the formation of linear aggregates or chains in an applied magnetic field via numerical modeling. It is widely known that chain formation occurs in more concentrated ferrofluids systems and that this has an affect on the ferrofluid properties. In this work we examine the relationships between colloidal stability, the formation of these linear structures, and changes observed in the proton transverse relaxation rate of aqueous suspensions of magnetic particles. A series of iron oxide nanoparticles with varying stabilizing ligand brush lengths were synthesized. These systems were characterized with dynamic light scattering, transmission electron microscopy, dark-field optical microscopy, and proton transverse relaxation rate measurements. The dark field optical microscopy and R2 measurements were made in similar magnetic fields over the same time scale so as to correlate the reduction of the transverse relaxivity with the formation of linear aggregates. Our results indicate that varying the ligand length has a direct effect on the colloidal arrangement of the system in a magnetic field, producing differences in the rate and size of chain formation, and hence systematic changes in transverse relaxation rates over time. With increasing ligand brush length, attractive inter-particle interactions are reduced, which results in slower aggregate formation and shorter linear aggregate length. These results have implications for the stabilization, characterization and potentially the toxicity of magnetic nanoparticle systems used in biomedical applications.It has been recently reported that for some suspensions of magnetic nanoparticles the transverse proton relaxation rate, R2, is dependent on the time that the sample is exposed to

  14. NOTE: Comparison of surface doses from spot scanning and passively scattered proton therapy beams

    NASA Astrophysics Data System (ADS)

    Arjomandy, Bijan; Sahoo, Narayan; Cox, James; Lee, Andrew; Gillin, Michael

    2009-07-01

    Proton therapy for the treatment of cancer is delivered using either passively scattered or scanning beams. Each technique delivers a different amount of dose to the skin, because of the specific feature of their delivery system. The amount of dose delivered to the skin can play an important role in choosing the delivery technique for a specific site. To assess the differences in skin doses, we measured the surface doses associated with these two techniques. For the purpose of this investigation, the surface doses in a phantom were measured for ten prostate treatment fields planned with passively scattered proton beams and ten patients planned with spot scanning proton beams. The measured doses were compared to evaluate the differences in the amount of skin dose delivered by using these techniques. The results indicate that, on average, the patients treated with spot scanning proton beams received lower skin doses by an amount of 11.8% ± 0.3% than did the patients treated with passively scattered proton beams. That difference could amount to 4 CGE per field for a prescribed dose of 76 CGE in 38 fractions treated with two equally weighted parallel opposed fields.

  15. Bacterial growth on a superhydrophobic surface containing silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Heinonen, S.; Nikkanen, J.-P.; Laakso, J.; Raulio, M.; Priha, O.; Levänen, E.

    2013-12-01

    The antibacterial effect of silver can be exploited in the food and beverage industry and medicinal applications to reduce biofouling of surfaces. Very small amount of silver ions are enough to destructively affect the metabolism of bacteria. Moreover, superhydrophobic properties could reduce bacterial adhesion to the surface. In this study we fabricated superhydrophobic surfaces that contained nanosized silver particles. The superhydrophobic surfaces were manufactured onto stainless steel as combination of ceramic nanotopography and hydrophobication by fluorosilane. Silver nanoparticles were precipitated onto the surface by a chemical method. The dissolution of silver from the surface was tested in an aqueous environment under pH values of 1, 3, 5, 7, 9, 11 and 13. The pH value was adjusted with nitric acid and ammonia. It was found that dissolution rate of silver increased as the pH of the solution altered from the pH of de-ionized water to lower and higher pH values but dissolution occurred also in de-ionized water. The antimicrobial potential of this coating was investigated using bacterial strains isolated from the brewery equipment surfaces. The results showed that the number of bacteria adhering onto steel surface was significantly reduced (88%) on the superhydrophobic silver containing coating.

  16. The effect of magnetically induced linear aggregates on proton transverse relaxation rates of aqueous suspensions of polymer coated magnetic nanoparticles.

    PubMed

    Saville, Steven L; Woodward, Robert C; House, Michael J; Tokarev, Alexander; Hammers, Jacob; Qi, Bin; Shaw, Jeremy; Saunders, Martin; Varsani, Rahi R; St Pierre, Tim G; Mefford, O Thompson

    2013-03-01

    It has been recently reported that for some suspensions of magnetic nanoparticles the transverse proton relaxation rate, R(2), is dependent on the time that the sample is exposed to an applied magnetic field. This time dependence has been linked to the formation of linear aggregates or chains in an applied magnetic field via numerical modeling. It is widely known that chain formation occurs in more concentrated ferrofluids systems and that this has an affect on the ferrofluid properties. In this work we examine the relationships between colloidal stability, the formation of these linear structures, and changes observed in the proton transverse relaxation rate of aqueous suspensions of magnetic particles. A series of iron oxide nanoparticles with varying stabilizing ligand brush lengths were synthesized. These systems were characterized with dynamic light scattering, transmission electron microscopy, dark-field optical microscopy, and proton transverse relaxation rate measurements. The dark field optical microscopy and R(2) measurements were made in similar magnetic fields over the same time scale so as to correlate the reduction of the transverse relaxivity with the formation of linear aggregates. Our results indicate that varying the ligand length has a direct effect on the colloidal arrangement of the system in a magnetic field, producing differences in the rate and size of chain formation, and hence systematic changes in transverse relaxation rates over time. With increasing ligand brush length, attractive inter-particle interactions are reduced, which results in slower aggregate formation and shorter linear aggregate length. These results have implications for the stabilization, characterization and potentially the toxicity of magnetic nanoparticle systems used in biomedical applications. PMID:23389324

  17. Ferroplasmons: Intense Localized Surface Plasmons in Metal-Ferromagnetic Nanoparticles

    SciTech Connect

    Sachan, Ritesh; Malasi, Abhinav; Ge, Jingxuan; Yadavali, Sagar P; Gangopadhyay, Anup; Krishna, Dr. Hare; Garcia, Hernando; Duscher, Gerd J M; Kalyanaraman, Ramki

    2014-01-01

    Interaction of photons with matter at length scales far below their wavelengths has given rise to many novel phenomena, including localized surface plasmon resonance (LSPR). However, LSPR with narrow bandwidth (BW) is observed only in a select few noble metals, and ferromagnets are not among them. Here, we report the discovery of LSPR in ferromagnetic Co and CoFe alloy (8% Fe) in contact with Ag in the form of bimetallic nanoparticles prepared by pulsed laser dewetting. These plasmons in metal-erromagnetic nanostructures, or ferroplasmons (FP) for short, are in the visible spectrum with comparable intensity and BW to those of the LSPRs from the Ag regions. This finding was enabled by electron energy-loss mapping across individual nanoparticles in a monochromated scanning transmission electron microscope. The appearance of the FP is likely due to plasmonic interaction between the contacting Ag and Co nanoparticles. Since there is no previous evidence for materials that simultaneously show ferromagnetism and such intense LSPRs, this discovery may lead to the design of improved plasmonic materials and applications. It also demonstrates that materials with interesting plasmonic properties can be synthesized using bimetallic nanostructures in contact with each other.

  18. Surface characterization and reactivity of vanadium-tin oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, Chien-Tsung; Chen, Miao-Ting; Lai, De-Lun

    2011-03-01

    Surface state and reactivity of vanadium-tin mixed oxide nanoparticles (V/Sn ratios 0.05-0.2) were characterized by spectroscopic techniques and catalytic measurements. Analyses by X-ray photoelectron spectroscopy (XPS) and diffuse reflectance spectroscopy (DRS) revealed that the oxidation state and surface structure of vanadium oxide species and the electronic interaction between Sn and V atoms are dependent upon the vanadium content. These oxides were evaluated as catalysts for methanol oxidation in a fixed-bed reactor. Both reaction rate and formaldehyde selectivity increased with increasing the vanadium amount in catalyst. Results demonstrate that the V 5+ site in the bridging V-O-Sn structure exhibits a high redox activity to facilitate the transformation of adsorbed methoxy to formaldehyde and that the vanadium dispersion plays a crucial role in the surface reactivity. A mechanism that elucidates the catalytic redox process is proposed.

  19. Mars surface radiation exposure for solar maximum conditions and 1989 solar proton events.

    NASA Astrophysics Data System (ADS)

    Simonsen, L. C.; Nealy, J. E.

    1993-02-01

    The Langley heavy-ion/nucleon and the high-energy nucleon transport codes are used to predict the propagation of galactic cosmic rays (GCR's) and solar flare protons through the carbon dioxide atmosphere of Mars. Particle fluences and the resulting doses are estimated on the surface of Mars for GCR's during solar maximum conditions and the August, September, and October 1989 solar proton events. Surface doses are estimated with both a low-density and a high-density carbon dioxide model of the atmosphere for altitudes of 0, 4, 8, and 12 km above the surface. A solar modulation function is incorporated to estimate the GCR dose variation between solar minimum and maximum conditions over the 11-year solar cycle. By using current Mars mission scenarios, doses to the skin, eye, and blood-forming organs are predicted for short- and long-duration stay times on the Martian surface throughout the solar cycle.

  20. Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

    SciTech Connect

    He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.; Clark, Kyle; Weber, Adam Z.; Kostecki, Robert

    2011-08-01

    The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationship between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.

  1. Controlling solid lipid nanoparticle adhesion by polyelectrolyte multilayer surface modifications.

    PubMed

    Finke, Jan Henrik; Schmolke, Hannah; Klages, C-P; Müller-Goymann, Christel C

    2013-06-01

    This study addresses the tunability of polyelectrolyte multilayers (PEM) toward adsorption of solid lipid nanoparticles (SLN). In SLN production for pharmaceutical applications, repellence from production equipment is desired while targeted adsorption is necessary for the functionalization of surfaces. SLN containing triglyceride/phospholipid or wax matrices were exposed to different PEM (consisting of poly(allylamine hydrochloride) (PAH), poly(diallyldimethylammonium chloride), and poly(acrylic acid)). PEM varied regarding layer architecture and surface properties by means of deposition pH, top layer variation, PEGylation with poly(acrylic acid)-graft-poly(ethylene glycol) copolymer, and thermal crosslinking. FTIR-ATR and SEM revealed SLN adhesion depending on PEM composition. Particle adsorption was tunable toward attraction as well as repellence: PEGylated PEM displayed lowest adsorption while PEM capped with PAH provided the strongest attraction of particles. Examinations at elevated temperatures resembled production conditions of SLN where these are processed as emulsions. Crystalline triglyceride SLN displayed high anisometry and, consequently, a large specific surface area. These platelets were more adherend than spherical droplets from the same formulation as an emulsion. Wax-based nanoparticles showed spherical shape, both in crystalline and molten state. However, adsorption was fostered as the fluidity of the disperse phase increased upon melting. Additionally, coalescence of adsorbed droplets took place, further increasing adsorption. PMID:23591009

  2. The effect of protonation site and conformation on surface-induced dissociation in a small, lysine containing peptide

    NASA Astrophysics Data System (ADS)

    Shaikh, Kulsum; Blackwood, Jacob; Barnes, George L.

    2015-09-01

    Simulations of surface induced dissociation (SID) of protonated peptides have provided significant insight into the energy transfer and mechanism of SID; however, they have been limited to glycine and alanine containing peptides. The chemical simplicity of these systems forces N-terminus protonation. Here we present results from simulations involving a lysine containing peptide that allowed for multiple protonation sites and conformations. We found that when the excess proton is located on the basic lysine side chain, fragmentation dynamics are typically slower and occur through a 'charge-remote' pathway. Additionally, conformation alone has a significant effect on the observed proton transfer pathways.

  3. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    NASA Astrophysics Data System (ADS)

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-Dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-12-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.

  4. Hydrogen Adsorption Studies Using Surface Acoustic Waves on Nanoparticles

    SciTech Connect

    A.B. Phillips; G. Myneni; B.S. Shivaram

    2005-06-13

    Vanadium nanoparticles, on the order of 20 nm, were deposited on a quartz crystal surface acoustic wave resonator (SAW) using a Nd:YAG pulsed laser deposition system. Due to the high Q and resonant frequency of the SAW, mass changes on the order of 0.1 nanogram can be quantitatively measured. Roughly 60 nanogram of V was deposited on the SAW for these experiments. The SAW was then moved into a hydrogen high pressure cell.At room temperature and 1 atmosphere of hydrogen pressure, 1 wt% H, or H/V {approx} 0.5 (atomic ratio) absorption was measured.

  5. Enhanced Mn2+ emission in ZnS:Mn nanoparticles by surface plasmon resonance of gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhou, Shuyao; Chu, Xueying; Li, Jinhua; Fang, Fang; Fang, Xuan; Wei, Zhipeng; Chen, Feng; Wang, Xiaohua

    2014-07-01

    The Mn2+ emission of ZnS:Mn nanoparticles was enhanced by a simple procedure. 3-Mercaptopropionic acid was used as a complexing agent in the synthesis of ZnS:Mn nanoparticles. Sulfydryl groups of 3-mercaptopropionic acid acted as bridging groups, to form composites of ZnS:Mn and Au nanoparticles. The peak wavelength of Au surface plasmons was red-shifted by 5 nm upon compositing. The intensity of Mn2+ emission at 590 nm because of the 4T1-6A1 transition was enhanced by 469% from the effects of the surface plasmon resonance. The enhancement was greatly influenced by the ratio of ZnS:Mn and Au. Enhancement was primarily attributed to localized surface plasmon resonance on the Au nanoparticle surface.

  6. Composite Nafion/sulfonated zirconia membranes: effect of the filler surface properties on proton transport characteristics

    PubMed Central

    D’Epifanio, Alessandra; Navarra, Maria Assunta; Weise, F. Christoph; Mecheri, Barbara; Farrington, Jaime; Licoccia, Silvia; Greenbaum, Steve

    2009-01-01

    Due to their strong acidity and water affinity, sulfated zirconia nanoparticles were evaluated as inorganic additives in the formation of composite Nafion-based membranes. Two types of sulfated zirconia were obtained according to the preparation experimental conditions. Sulfated zirconia-doped Nafion membranes were prepared by a casting procedure. The properties of the composite membranes were compared with those of an unfilled Nafion membrane obtained by the same preparation method. The water uptake, measured at room temperature in a wide relative humidity range, was higher for the composite membranes, this confirming the hydrophilic nature of the selected additives. The membrane doped by zirconia particles having the highest sulphate group concentration showed the highest water diffusion coefficient in the whole range of temperature and relative humidity investigated due to the presence of SO42− providing extra acid sites for water diffusion. The proton diffusivity calculated from impedance spectroscopy measurements was compared with water self diffusion coefficients measured by NMR Spectroscopy. The difference between proton and water diffusivity became significant only at high humidification levels, highlighting the role of water in the intermolecular proton transfer mechanism. Finally, great improvements were found when using the composite membrane as electrolyte in a fuel cell working at very low relative humidity. PMID:20209115

  7. Molecular modeling of the surface charging of hematite. I. The calculation of proton affinities and acidities on a surface

    NASA Astrophysics Data System (ADS)

    Wasserman, Evgeny; Rustad, James R.; Felmy, Andrew R.

    1999-03-01

    Calculation of the energy of a charged defect on a surface in supercell geometry is discussed. An important example of such a calculation is evaluation of surface proton affinities and acidities, as adding or removing a proton creates a charged unit cell. Systems with periodic boundary conditions in three spatial directions and a vacuum gap between slabs are demonstrated to be inadequate for unit cells having non-zero ionic charge and uniform neutralizing background. In such a system the calculated energy diverges linearly with the thickness of the vacuum gap. A system periodic in two directions and finite in the direction perpendicular to the surface (2-D PBC) with the neutralizing background distributed as the surface charge density is free from this problem. Furthermore, the correction for the interaction of the charged defect with its own translational images is needed to speed up the convergence to the infinite dilution limit. The expression for the asymptotic correction for the energy of interaction of a charged defect with its translational images in 2-D PBC geometry has been developed in this study. The asymptotic correction is evaluated as the interaction energy of a 2-D translationally periodic array of point charges located above and below the plate of non-uniform dielectric. This is a generalization of the method of M. Leslie and M.J. Gillan [J. Phys. C, 18 (1985) 973] for the calculation of the energy of a charged defect in bulk crystals. The usefulness of this correction was demonstrated on two test cases involving the calculation of proton affinity and acidity at the (012) surface of hematite. The proposed method is likely to be important in ab initio calculations of the energy effect of the surface protonation reactions, where computational limitations dictate a small size for the unit cell.

  8. Synthesis of water soluble glycine capped silver nanoparticles and their surface selective interaction

    SciTech Connect

    Agasti, Nityananda; Singh, Vinay K.; Kaushik, N.K.

    2015-04-15

    Highlights: • Synthesis of water soluble silver nanoparticles at ambient reaction conditions. • Glycine as stabilizing agent for silver nanoparticles. • Surface selective interaction of glycine with silver nanoparticles. • Glycine concentration influences crystalinity and optical property of silver nanoparticles. - Abstract: Synthesis of biocompatible metal nanoparticles has been an area of significant interest because of their wide range of applications. In the present study, we have successfully synthesized water soluble silver nanoparticles assisted by small amino acid glycine. The method is primarily based on reduction of AgNO{sub 3} with NaBH{sub 4} in aqueous solution under atmospheric air in the presence of glycine. UV–vis spectroscopy, transmission electron microscopy (TEM), X–ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG) and differential thermal analysis (DTA) techniques used for characterization of resulting silver nanoparticles demonstrated that, glycine is an effective capping agent to stabilize silver nanoparticles. Surface selective interaction of glycine on (1 1 1) face of silver nanoparticles has been investigated. The optical property and crystalline behavior of silver nanoparticles were found to be sensitive to concentration of glycine. X–ray diffraction studies ascertained the phase specific interaction of glycine on silver nanoparticles. Silver nanoparticles synthesized were of diameter 60 nm. We thus demonstrated an efficient synthetic method for synthesis of water soluble silver nanoparticles capped by amino acid under mild reaction conditions with excellent reproducibility.

  9. Surface functionalization of silica nanoparticles with cysteine: a low-fouling zwitterionic surface.

    PubMed

    Rosen, Joshua E; Gu, Frank X

    2011-09-01

    Herein, we report on the functionalization of silica nanoparticles with a small molecule, the amino acid cysteine, in order to create a low-fouling zwitterionic surface for nanomedicine applications. The cysteine functionalization was shown to impart the particles with excellent stability in both salt and single-protein solutions of lysozyme (positively charged) and bovine serum albumin (negatively charged). Bare silica particles precipitated immediately in a lysozyme solution, while cysteine-functionalized particles were stable for 20 h. Furthermore, the particles displayed excellent long-term stability in solutions of human serum showing no aggregation over a period of 14 days. The functionalized particles also possess multiple reactive surface groups for further coupling reactions. We believe that the surface functionalization schemes described in this report represent a versatile and effective method of stabilizing nanoparticle systems in biological media for their use in a variety of therapeutic and diagnostic applications. PMID:21761888

  10. The influence of size, shape, and surface coating on the stability of aqueous nanoparticle suspensions

    SciTech Connect

    Mulvihill, M.J.; Habas, S.E.; La Plante, I.J.; Wan, J.; Mokari, T.

    2010-09-03

    In response to the rapid development and emerging commercialization of nanoparticles, fundamental studies concerning the fate of nanoparticles in the environment are needed. Precise control over the nanoparticle size, shape, and surface coating of cadmium selenide particles modified with thiolate ligands has been used to analyze the effects of nanoparticle design on their stability in aqueous environments. Nanoparticle stability was quantified using the concept of critical coagulation concentration (CCC) in solutions of sodium chloride. These investigations characterized the instability of the ligand coatings, which varied directly with chain length of the capping ligands. The stability of the ligand coatings were characterized as a function of time, pH, and ionic strength. Ligand dissociation has been shown to be a primary mechanism for nanoparticle aggregation when short-chain (C2-C6) ligands are used in the ligand shell. Stable nanoparticle suspensions prepared with long chain ligands (C11) were used to characterize nanoparticle stability as a function of size and shape. A linear relationship between particle surface area and the CCC was discovered and was found to be independent of nanoparticle shape. Quantitative analysis of nanoparticle size, shape, and surface coating demonstrated the importance of ligand stability and particle surface area for the prediction of nanoparticle stability.

  11. Degradation mechanisms of Platinum Nanoparticle Catalysts in Proton Exchange Membrane Fuel Cells: The Role of Particle Size

    SciTech Connect

    Yu, Kang; Groom, Daniel J.; Wang, Xiaoping; Yang, Zhiwei; Gummalla, Mallika; Ball, Sarah C.; Myers, Deborah J.; Ferreira, Paulo J.

    2014-10-14

    Five membrane-electrode assemblies (MEAs) with different average sizes of platinum (Pt) nanoparticles (2.2, 3.5, 5.0, 6.7, and 11.3 nm) in the cathode were analyzed before and after potential cycling (0.6 to 1.0 V, 50 mV/s) by transmission electron microscopy. Cathodes loaded with 2.2 nm and 3.5 nm catalyst nanoparticles exhibit the following changes during electrochemical cycling: (i) substantial broadening of the size distribution relative to the initial size distribution, (ii) presence of coalesced particles within the electrode, and (iii) precipitation of sub-micron-sized particles with complex shapes within the membrane. In contrast, cathodes loaded with 5.0 nm, 6.7 nm and 11.3 nm size catalyst nanoparticles are significantly less prone to the aforementioned effects. As a result, the electrochemically-active surface area (ECA) of MEA cathodes loaded with 2.2 nm and 3.5 nm nanoparticle catalysts degrades dramatically within 1,000 cycles of operation, while the electrochemically-active surface area of MEA cathodes loaded with 5.0 nm, 6.7 nm and 11.3 nm nanoparticle catalysts appears to be stable even after 10,000 cycles. The loss in MEA performance for cathodes loaded with 2.2 nm and 3.5 nm nanoparticle catalysts appears to be due to the loss in electrochemically-active surface area concomitant with the observed morphological changes in these nanoparticle catalysts

  12. Theory of collective proton motion at interfaces with densely packed protogenic surface groups.

    PubMed

    Golovnev, Anatoly; Eikerling, Michael

    2013-01-30

    We present a theoretical study of collective proton transport at a 2D array of end-grafted protogenic surface groups with sulfonic acid head groups. The graft positions of the surface groups form a regular hexagonal lattice. We consider the interfacial array at a high packing density of the surface groups and under minimal hydration with one water molecule added per head group. For these conditions, the stable interfacial conformation consists of a bicomponent lattice of hexagonally ordered sulfonate anions and interstitial hydronium cations. Hydronium ion motion occurs as a travelling solitary wave. We analyse the microscopic parameters of the solitons and study the influence of different potential profiles on the proton motion created by rotation and tilting of sidechains and sulfonate anions. Using soliton solutions of the equation of motion, we establish relations between the energy and mobility of the solitons and the microscopic structural and interaction parameters of the array. PMID:23264459

  13. Mars surface radiation exposure for solar maximum conditions and 1989 solar proton events

    NASA Astrophysics Data System (ADS)

    Simonsen, Lisa C.; Nealy, John E.

    1992-02-01

    The Langley heavy-ion/nucleon transport code, HZETRN, and the high-energy nucleon transport code, BRYNTRN, are used to predict the propagation of galactic cosmic rays (GCR's) and solar flare protons through the carbon dioxide atmosphere of Mars. Particle fluences and the resulting doses are estimated on the surface of Mars for GCR's during solar maximum conditions and the Aug., Sep., and Oct. 1989 solar proton events. These results extend previously calculated surface estimates for GCR's at solar minimum conditions and the Feb. 1956, Nov. 1960, and Aug. 1972 solar proton events. Surface doses are estimated with both a low-density and a high-density carbon dioxide model of the atmosphere for altitudes of 0, 4, 8, and 12 km above the surface. A solar modulation function is incorporated to estimate the GCR dose variation between solar minimum and maximum conditions over the 11-year solar cycle. By using current Mars mission scenarios, doses to the skin, eye, and blood-forming organs are predicted for short- and long-duration stay times on the Martian surface throughout the solar cycle.

  14. Mars surface radiation exposure for solar maximum conditions and 1989 solar proton events

    NASA Technical Reports Server (NTRS)

    Simonsen, Lisa C.; Nealy, John E.

    1992-01-01

    The Langley heavy-ion/nucleon transport code, HZETRN, and the high-energy nucleon transport code, BRYNTRN, are used to predict the propagation of galactic cosmic rays (GCR's) and solar flare protons through the carbon dioxide atmosphere of Mars. Particle fluences and the resulting doses are estimated on the surface of Mars for GCR's during solar maximum conditions and the Aug., Sep., and Oct. 1989 solar proton events. These results extend previously calculated surface estimates for GCR's at solar minimum conditions and the Feb. 1956, Nov. 1960, and Aug. 1972 solar proton events. Surface doses are estimated with both a low-density and a high-density carbon dioxide model of the atmosphere for altitudes of 0, 4, 8, and 12 km above the surface. A solar modulation function is incorporated to estimate the GCR dose variation between solar minimum and maximum conditions over the 11-year solar cycle. By using current Mars mission scenarios, doses to the skin, eye, and blood-forming organs are predicted for short- and long-duration stay times on the Martian surface throughout the solar cycle.

  15. Modulation of Immune Response Using Engineered Nanoparticle Surfaces.

    PubMed

    Moyano, Daniel F; Liu, Yuanchang; Peer, Dan; Rotello, Vincent M

    2016-01-01

    Nanoparticles (NPs) coated with a monolayer of ligands can be recognized by different components of the immune system, opening new doors for the modulation of immunological responses. By the use of different physical or chemical properties at the NP surface (such as charge, functional groups, and ligand density), NPs can be designed to have distinct cellular uptake, cytokine secretion, and immunogenicity, factors that influence the distribution and clearance of these particles. Understanding these immunological responses is critical for the development of new NP-based carriers for the delivery of therapeutic molecules, and as such several studies have been performed to understand the relationships between immune responses and NP surface functionality. In this review, we will discuss recent reports of these structure-activity relationships, and explore how these motifs can be controlled to elicit therapeutically useful immune responses. PMID:26618755

  16. Ultrasonic-assisted synthesis of ZrO2 nanoparticles and their application to improve the chemical stability of Nafion membrane in proton exchange membrane (PEM) fuel cells.

    PubMed

    Taghizadeh, Mohammad Taghi; Vatanparast, Morteza

    2016-12-01

    Zirconium dioxide (ZrO2) nanoparticles were fabricated successfully via ultrasonic-assisted method using ZrO(NO3)2·H2O, ethylenediamine and hydrazine as precursors in aqueous solution. Morphology, structure and composition of the obtained products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance spectroscopy (DRS). Then, the synthesized nanoparticles were used to prepare Nafion/ZrO2 nanocomposite membranes. The properties of the membranes were studied by ion exchange capacity (IEC) proton conductivity (σ), thermal stability and water uptake measurements. The ex-situ Fenton's test was used to investigate the chemical stability of the membranes. From our results, compared with Nafion membrane, the nanocomposite membrane exhibited lower fluoride release and weight loss. Therefore, it can concluded that Nafion/ZrO2 nanocomposite exhibit more chemical stability than the pure Nafion membrane. ATR-FTIR spectra and SEM surface images of membranes also confirm these results. PMID:27544443

  17. An impact of the ring substitution in nicorandil on its adsorption on silver nanoparticles. Surface-enhanced Raman spectroscopy studies.

    PubMed

    Jaworska, Aleksandra; Malek, Kamilla; Marzec, Katarzyna M; Baranska, Malgorzata

    2014-08-14

    The substituent effect on structure and surface activity of biologically active nicorandil was investigated by means of surface-enhanced Raman spectroscopy (SERS). Vibrational characterization was a basis for investigation of the adsorption profile of nicorandil and 1-methylnicorandil on silver nanoparticles. An assignment of SERS bands was performed by the comparison of the Raman spectra of both compounds in the solid state and in solutions, complemented by DFT calculations. Even though the nitro group was found to be the most attractive to the silver surface, the strong impact of the methyl substituent changed this preferable adsorption mechanism in 1-methylnicorandil. Protonation of the nitrogen atom in the pyridinium ring was also found to have an impact on absorption mechanism. PMID:24759187

  18. Producing ultra-thin silica coatings on iron-oxide nanoparticles to improve their surface reactivity

    NASA Astrophysics Data System (ADS)

    Kralj, Slavko; Makovec, Darko; Čampelj, Stanislav; Drofenik, Miha

    2010-07-01

    The reactivity of the relatively inert surfaces of iron-oxide magnetic nanoparticles can be significantly improved by coating the surfaces with silica. Unfortunately, however, this nonmagnetic silica layer tends to dilute the magnetic properties of the nanoparticles. Therefore, the silica layer should be as continuous, homogeneous, and as thin as possible. In this investigation we coated superparamagnetic maghemite nanoparticles by hydrolysis and the polycondensation of tetraethyl orthosilicate (TEOS), with the ethanol solution of TEOS being added to a stable suspension of citric acid-coated nanoparticles. The influences of the various parameters of the procedure on the quality of the coatings were systematically evaluated. The quality of the silica layer was characterized using electron microscopy and by performing leaching of the nanoparticles in HCl, while the surface reactivity was tested by grafting (3-aminopropyl) triethoxysilane (APS) onto the nanoparticles. We observed that the surface concentration of the grafted APS strongly increased when the nanoparticles were coated with a silica layer. The choice of experimental conditions for the coating procedure that favors the heterogeneous nucleation of silica on the surfaces of the nanoparticles enabled the preparation of very thin silica layers, less than 2 nm thick. By decreasing the amount of added TEOS to correspond to a monolayer of -Si-OH at the nanoparticles' surfaces, their surface reactivity could be very much improved, and with a reduction in their magnetization of only ˜10%.

  19. Functionalization of Ag nanoparticles using local hydrophilic pool segment designed on their particle surface

    NASA Astrophysics Data System (ADS)

    Iijima, Motoyuki; Kurumiya, Aki; Esashi, Junki; Miyazaki, Hayato; Kamiya, Hidehiro

    2014-10-01

    The preparation of SiO2-coated Ag nanoparticles dispersible in various organic solvents has been achieved using a solgel reaction of tetraethylorthosilicate (TEOS), in the localized hydrophilic pool segments designed on Ag nanoparticle surfaces. First, oleylamine-capped core Ag nanoparticles were synthesized, followed by ligand exchange with polyethyleneimine (PEI) and further adsorption of an anionic surfactant comprising hydrophilic polyethylene glycol (PEG) chains and hydrophobic alkyl chains, which has previously been reported to improve the stability of nanoparticles in various solvents. Then, a reaction of TEOS with the localized hydrophilic PEI layer on the Ag nanoparticles' surface was conducted by stirring a toluene/TEOS solution of surface-modified Ag nanoparticles at various temperatures. It was found that a SiO2 layer was successfully formed on Ag nanoparticles when the reaction temperature was increased to 60 °C. It was also found, however, that at this elevated temperature, the primary particle size of Ag nanoparticles increased to several tens of nm, attributable to the dissolution and re-reduction of Ag+. Because the surface modifier, PEI and anionic surfactant all remained on the nanoparticle surface during the SiO2 coating process, the prepared SiO2-coated Ag nanoparticles were found to be dispersible in various organic solvents near to their primary particle size.

  20. In situ surface characterization and oxygen reduction reaction on shape-controlled gold nanoparticles.

    PubMed

    Hernández, J; Solla-Gullón, J; Herrero, E; Feliu, J M; Aldaz, A

    2009-04-01

    Gold nanoparticles of different shapes/surface structures were synthesized and electrochemically characterized. An in-situ surface characterization of the Au nanoparticles, which was able to obtain qualitative information about the type and relative sizes of the different facets present in the surface of the Au nanoparticles, was carried out by using Pb Under Potential Deposition (UPD) in alkaline solutions as a surface sensitive tool. The results obtained show that the final atomic arrangement on the surface can be different from that expected from the bulk structure of the well-defined shape Au nanoparticles. In this way, the development of precise in-situ methods to measure the distribution of the different sites on the nanoparticle surface, as lead UPD on gold surfaces, is highlighted. Oxygen Reduction Reaction (ORR) was performed on the different Au nanoparticles. In agreement with the particular sensitivity of the oxygen reduction to the presence of Au(100) surface domains, cubic Au nanoparticles show much better electrocatalytic activity for ORR than small spherical particles and long nanorods, in agreement with the presence of a great fraction of (100) terrace sites on the surface of cubic gold nanoparticles. PMID:19437963

  1. Tuning surface plasmon resonance by the plastic deformation of Au nanoparticles within a diamond anvil cell

    NASA Astrophysics Data System (ADS)

    Bao, Yongjun; Zhao, Bin; Tang, Xinyu; Hou, Dongjie; Cai, Jian; Tang, Shan; Liu, Junsong; Wang, Fei; Cui, Tian

    2015-11-01

    In this work, surface plasmon resonance (SPR) is tuned by controlling the deformation of Au nanoparticles within a diamond anvil cell (DAC). Colloidal Au nanoparticles were loaded into a DAC and pressurized into a mixture of ice and Au nanoparticles. The Au nanoparticles were reshaped by their anisotropic compression of surrounding ice, which leads to the spectral variations of absorption peaks, broadening or red-shifting. These spectral features are well tuned by controlling the deformation process of Au nanoparticle with choosing the initial intended thickness of DAC gasket. The mechanical properties of Au nanoparticles are also revealed by the shape-dependent SPR in nanometer scale. This result provides us a way to fabricate Au nanoparticles into new shapes and tune SPR of metallic nanoparticles with pressure.

  2. Surface mineralization and characterization of tobacco mosaic virus biotemplated nanoparticles

    NASA Astrophysics Data System (ADS)

    Freer, Alexander S.

    The genetically engineered tobacco mosaic virus (TMV) has been utilized as a biotemplate in the formation of nanoparticles with the intent of furthering the understanding of the biotemplated nanoparticles formed in the absence of an external reducing agent. Specifically, the work aims to provide better knowledge of the final particle characteristics and how these properties could be altered to better fit the need of functional devices. Three achievements have been accomplished including a method for controlling final particle size, characterizing the resistivity of palladium coated TMV, and the application of TMV as an additive in nanometric calcium carbonate synthesis. Until the last 5 years, formation of metal nanoparticles on the surface of TMV has always occurred with the addition of an external reducing agent. The surface functionalities of genetically engineered TMV allow for the reduction of palladium in the absence of an external reducing agent. This process has been furthered to understand how palladium concentration affects the final coating uniformity and thickness. By confirming an ideal ratio of palladium and TMV concentrations, a uniform coat of palladium is formed around the viral nanorod. Altering the number of palladium coating cycles at these concentrations allows for a controllable average diameter of the final nanorods. The average particle diameter was determined by small angle x-ray scattering (SAXS) analysis by comparing the experimental results to the model of scattering by an infinitely long cylinder. The SAXS results were confirmed through transmission electron microscopy images of individual Pd-TMV nanorods. Secondly, methodologies to determine the electrical resistivity of the genetically engineered TMV biotemplated palladium nanoparticles were created to provide valuable previously missing information. Two fairly common nanoelectronic characterization techniques were combined to create the novel approach to obtain the desired

  3. Surface Charge-Switching Polymeric Nanoparticles for Bacterial Cell Wall-Targeted Delivery of Antibiotics

    PubMed Central

    Radovic-Moreno, Aleksandar F.; Lu, Timothy K.; Puscasu, Vlad A.; Yoon, Chris J.; Langer, Robert; Farokhzad, Omid C.

    2013-01-01

    Bacteria have shown a remarkable ability to overcome drug therapy if there is a failure to achieve sustained bactericidal concentration or if there is a reduction in activity in situ. The latter can be caused by localized acidity, a phenomenon that can occur as a result of the combined actions of bacterial metabolism and the host immune response. Nanoparticles (NP) have shown promise in treating bacterial infections, but a significant challenge has been to develop antibacterial NPs that may be suitable for systemic administration. Herein we develop drug-encapsulated, pH-responsive, surface charge-switching poly(D, L-lactic-co-glycolic acid)-b-poly(L-histidine)-b-poly(ethylene glycol) (PLGA-PLH-PEG) nanoparticles for treating bacterial infections. These NP drug carriers are designed to shield nontarget interactions at pH 7.4 but bind avidly to bacteria in acidity, delivering drugs and mitigating in part the loss of drug activity with declining pH. The mechanism involves pH-sensitive NP surface charge-switching, which is achieved by selective protonation of the imidazole groups of PLH at low pH. NP binding studies demonstrate pH-sensitive NP binding to bacteria with a 3.5±0.2 to 5.8±0.1 fold increase in binding to bacteria at pH 6.0 compared to 7.4. Further, PLGA-PLH-PEG-encapsulated vancomycin demonstrates reduced loss of efficacy at low pH, with an increase in minimum inhibitory concentration of 1.3-fold as compared to 2.0-fold and 2.3-fold for free- and PLGA-PEG-encapsulated vancomycin, respectively. The PLGA-PLH-PEG NPs described herein are a first step towards developing systemically administered drug carriers that can target and potentially treat Gram-positive, Gram-negative, or polymicrobial infections associated with acidity. PMID:22471841

  4. Beauty is Skin Deep: A Surface Monolayer Perspective on Nanoparticle Interactions with Cells and Biomacromolecules**

    PubMed Central

    Saha, Krishnendu; Bajaj, Avinash; Duncan, Bradley; Rotello, Vincent M.

    2012-01-01

    Surface recognition of biosystems is a critical component in the development of novel biosensors, delivery vehicles and for the therapeutic regulation of biological processes. Monolayer-protected nanoparticles present a highly versatile scaffold for selective interaction with biomacromolecules and cells. Through engineering of the monolayer surface, nanoparticles can be tailored for surface recognition of biomolecules and cells. This review highlights recent progress in nanoparticle-biomacromolecule/cellular interactions, emphasizing the effect of the surface monolayer structure on the interactions with proteins, DNA and cell surfaces. The extension of these tailored interactions to hybrid nanomaterials, biosensing platforms and delivery vehicles is also discussed. PMID:21671432

  5. Salicylate effects on proton gradient dissipation by isolated gastric mucosal surface cells.

    PubMed

    Olender, E J; Woods, D; Kozol, R; Fromm, D

    1986-11-01

    The effects of salicylate were examined on Na+/H+ exchange by isolated gastric mucosal surface cells loaded with H+ and resuspended in a buffered medium. Choline salicylate (pH 7.4) increases the dissipation of an intracellular proton gradient which was measured using acridine orange. The exchange of extracellular Na+ with intracellular H+ by surface cells not only remains intact but also is enhanced upon exposure to salicylate. This was confirmed by cellular uptake of 22Na and titration of cellular H+ efflux. Salicylate increases Na+/H+ exchange via a pathway predominantly sensitive to amiloride. However, the data also suggest that salicylate dissipates an intracellular proton gradient by an additional mechanism. The latter is independent of extracellular Na+ and not due to a generalized increase in cellular permeability. PMID:3020564

  6. Nanoparticles and intracellular applications of surface-enhanced Raman spectroscopy.

    PubMed

    Taylor, Jack; Huefner, Anna; Li, Li; Wingfield, Jonathan; Mahajan, Sumeet

    2016-08-15

    Surface-enhanced Raman spectrocopy (SERS) offers ultrasensitive vibrational fingerprinting at the nanoscale. Its non-destructive nature affords an ideal tool for interrogation of the intracellular environment, detecting the localisation of biomolecules, delivery and monitoring of therapeutics and for characterisation of complex cellular processes at the molecular level. Innovations in nanotechnology have produced a wide selection of novel, purpose-built plasmonic nanostructures capable of high SERS enhancement for intracellular probing while microfluidic technologies are being utilised to reproducibly synthesise nanoparticle (NP) probes at large scale and in high throughput. Sophisticated multivariate analysis techniques unlock the wealth of previously unattainable biomolecular information contained within large and multidimensional SERS datasets. Thus, with suitable combination of experimental techniques and analytics, SERS boasts enormous potential for cell based assays and to expand our understanding of the intracellular environment. In this review we trace the pathway to utilisation of nanomaterials for intracellular SERS. Thus we review and assess nanoparticle synthesis methods, their toxicity and cell interactions before presenting significant developments in intracellular SERS methodologies and how identified challenges can be addressed. PMID:27479539

  7. Formation and properties of metallic nanoparticles on compound semiconductor surfaces

    NASA Astrophysics Data System (ADS)

    Kang, Myungkoo

    When electromagnetic radiation is incident upon metallic nanoparticles (NPs), a collective oscillation, termed a surface plasmon resonance (SPR), is generated. Recently, metallic NPs on semiconductor surfaces have enabled the generation of SPR, promising for enhanced light emission, efficient solar energy harvesting, biosensing, and metamaterials. Metallic NPs have been fabricated by focused ion beam (FIB) which has an advantage of cost-effectiveness over conventional lithography process requiring multi-step processes. Here, we report formation and properties of FIB-induced metallic NPs on compound semiconductor surfaces. Results presented in this thesis study suggest that FIB-induced Ga NPs can be a promising alternative plasmonic material. In particular, using a combined experimental-computational approach, we discovered a universal mechanism for ion-induced NP formation, which is governed by the sputtering yield of semiconductor surfaces. We also discovered a governing mechanism for ion-induced NP motion, which is driven by thermal fluctuation and anisotropic mass transport. Furthermore, we demonstrated Ga NP arrays with plasmon resonances with performance comparable to those of traditionally-used silver and gold NPs. We then finally demonstrated the Ga NP plasmoninduced enhancement of light emission from GaAs, which is the first ever combination of a new plasmonic material (Ga) and a new fabrication method (FIB) for the plasmon-enhanced light emission.

  8. Membrane mimetic surface functionalization of nanoparticles: Methods and applications

    PubMed Central

    Weingart, Jacob; Vabbilisetty, Pratima; Sun, Xue-Long

    2013-01-01

    Nanoparticles (NPs), due to their size-dependent physical and chemical properties, have shown remarkable potential for a wide range of applications over the past decades. Particularly, the biological compatibilities and functions of NPs have been extensively studied for expanding their potential in areas of biomedical application such as bioimaging, biosensing, and drug delivery. In doing so, surface functionalization of NPs by introducing synthetic ligands and/or natural biomolecules has become a critical component in regards to the overall performance of the NP system for its intended use. Among known examples of surface functionalization, the construction of an artificial cell membrane structure, based on phospholipids, has proven effective in enhancing biocompatibility and has become a viable alternative to more traditional modifications, such as direct polymer conjugation. Furthermore, certain bioactive molecules can be immobilized onto the surface of phospholipid platforms to generate displays more reminiscent of cellular surface components. Thus, NPs with membrane-mimetic displays have found use in a range of bioimaging, biosensing, and drug delivery applications. This review herein describes recent advances in the preparations and characterization of integrated functional NPs covered by artificial cell membrane structures and their use in various biomedical applications. PMID:23688632

  9. Self assembly of magnetic nanoparticles at silicon surfaces.

    PubMed

    Theis-Bröhl, Katharina; Gutfreund, Philipp; Vorobiev, Alexei; Wolff, Max; Toperverg, Boris P; Dura, Joseph A; Borchers, Julie A

    2015-06-21

    Neutron reflectometry was used to study the assembly of magnetite nanoparticles in a water-based ferrofluid close to a silicon surface. Under three conditions, static, under shear and with a magnetic field, the depth profile is extracted. The particles have an average diameter of 11 nm and a volume density of 5% in a D2O-H2O mixture. They are surrounded by a 4 nm thick bilayer of carboxylic acid for steric repulsion. The reflectivity data were fitted to a model using a least square routine based on the Parratt formalism. From the scattering length density depth profiles the following behavior is concluded: the fits indicate that excess carboxylic acid covers the silicon surface and almost eliminates the water in the densely packed wetting layer that forms close to the silicon surface. Under constant shear the wetting layer persists but a depletion layer forms between the wetting layer and the moving ferrofluid. Once the flow is stopped, the wetting layer becomes more pronounced with dense packing and is accompanied by a looser packed second layer. In the case of an applied magnetic field the prolate particles experience a torque and align with their long axes along the silicon surface which leads to a higher particle density. PMID:25971712

  10. Antibacterial activity of silver nanoparticles grafted on stone surface.

    PubMed

    Bellissima, F; Bonini, M; Giorgi, R; Baglioni, P; Barresi, G; Mastromei, G; Perito, B

    2014-12-01

    Microbial colonization has a relevant impact on the deterioration of stone materials with consequences ranging from esthetic to physical and chemical changes. Avoiding microbial growth on cultural stones therefore represents a crucial aspect for their long-term conservation. The antimicrobial properties of silver nanoparticles (AgNPs) have been extensively investigated in recent years, showing that they could be successfully applied as bactericidal coatings on surfaces of different materials. In this work, we investigated the ability of AgNPs grafted to Serena stone surfaces to inhibit bacterial viability. A silane derivative, which is commonly used for stone consolidation, and Bacillus subtilis were chosen as the grafting agent and the target bacterium, respectively. Results show that functionalized AgNPs bind to stone surface exhibiting a cluster disposition that is not affected by washing treatments. The antibacterial tests on stone samples revealed a 50 to 80 % reduction in cell viability, with the most effective AgNP concentration of 6.7 μg/cm(2). To our knowledge, this is the first report on antimicrobial activity of AgNPs applied to a stone surface. The results suggest that AgNPs could be successfully used in the inhibition of microbial colonization of stone artworks. PMID:24151026

  11. Surface modification of PLGA nanoparticles via human serum albumin conjugation for controlled delivery of docetaxel

    PubMed Central

    2013-01-01

    Background Poly lactic-co-glycolic acid (PLGA) based nanoparticles are considered to be a promising drug carrier in tumor targeting but suffer from the high level of opsonization by reticuloendothelial system due to their hydrophobic structure. As a result surface modification of these nanoparticles has been widely studied as an essential step in their development. Among various surface modifications, human serum albumin (HSA) possesses advantages including small size, hydrophilic surface and accumulation in leaky vasculature of tumors through passive targeting and a probable active transport into tumor tissues. Methods PLGA nanoparticles of docetaxel were prepared by emulsification evaporation method and were surface conjugated with human serum albumin. Fourier transform infrared spectrum was used to confirm the conjugation reaction where nuclear magnetic resonance was utilized for conjugation ratio determination. In addition, transmission electron microscopy showed two different contrast media in conjugated nanoparticles. Furthermore, cytotoxicity of free docetaxel, unconjugated and conjugated PLGA nanoparticles was studied in HepG2 cells. Results Size, zeta potential and drug loading of PLGA nanoparticles were about 199 nm, −11.07 mV, and 4%, respectively where size, zeta potential and drug loading of conjugated nanoparticles were found to be 204 nm, −5.6 mV and 3.6% respectively. Conjugated nanoparticles represented a three-phasic release pattern with a 20% burst effect for docetaxel on the first day. Cytotoxicity experiment showed that the IC50 of HSA conjugated PLGA nanoparticles (5.4 μg) was significantly lower than both free docetaxel (20.2 μg) and unconjugated PLGA nanoparticles (6.2 μg). Conclusion In conclusion surface modification of PLGA nanoparticles through HSA conjugation results in more cytotoxicity against tumor cell lines compared with free docetaxel and unconjugated PLGA nanoparticles. Albumin conjugated PLGA nanoparticles may

  12. Size dependence of surface thermodynamic properties of nanoparticles and its determination method by reaction rate constant

    NASA Astrophysics Data System (ADS)

    Li, Wenjiao; Xue, Yongqiang; Cui, Zixiang

    2016-08-01

    Surface thermodynamic properties are the fundamental properties of nanomaterials, and these properties depend on the size of nanoparticles. In this paper, relations of molar surface thermodynamic properties and surface heat capacity at constant pressure of nanoparticles with particle size were derived theoretically, and the method of obtaining the surface thermodynamic properties by reaction rate constant was put forward. The reaction of nano-MgO with sodium bisulfate solution was taken as a research system. The influence regularities of the particle size on the surface thermodynamic properties were discussed theoretically and experimentally, which show that the experimental regularities are in accordance with the corresponding theoretical relations. With the decreasing of nanoparticle size, the molar surface thermodynamic properties increase, while the surface heat capacity decreases (the absolute value increases). In addition, the surface thermodynamic properties are linearly related to the reciprocal of nanoparticle diameter, respectively.

  13. Nuclear microprobe analysis of solar proton implantation profiles in lunar rock surfaces

    NASA Technical Reports Server (NTRS)

    Stauber, M. C.; Padawer, G. M.; D'Agostino, M. D.; Kamykowski, E.; Brandt, W.; Young, D. A.

    1973-01-01

    Discussion of the results of hydrogen (proton) depth profile concentration analyses conducted on selected Apollo 16 rocks. A modeling of solar particle implantation profiles in lunar rocks is shown to trace the evolvement of these profiles under the combined influence of diffusion of atomic particles implanted in the rock, and rock surface erosion. It is also demonstrated that such diffusion may have a significant effect on the shape of the implantation profiles in certain rock materials.

  14. First-principles computation of surface segregation in L10 CoPt magnetic nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Zhenyu; Lei, Yinkai; Wang, Guofeng

    2016-07-01

    In this study, we have employed the first-principles density functional theory (DFT) computational method to predict the influence of surface segregation on the magnetic properties of small L10 CoPt nanoparticles. For both the modelled cuboidal (with a chemical formula of Co26Pt12) and cuboctahedral (with a chemical formula of Co18Pt20) CoPt nanoparticles, the DFT calculations predict that Pt surface segregation should occur thermodynamically. Associated with this Pt surface segregation, the surface-segregated CoPt magnetic nanoparticles are predicted to have significantly reduced magnetic moments and magnetic anisotropy energies than those of the corresponding bulk-terminated (i.e. non-segregated) nanoparticles. Hence, our study suggests that surface segregation could deteriorate the magnetic properties of CoPt nanoparticles.

  15. Reaction efficiency and retention of poly(styrene-co-maleimide) nanoparticles deposited on fibrillated cellulose surfaces.

    PubMed

    Rastogi, Vibhore Kumar; Stanssens, Dirk; Samyn, Pieter

    2016-05-01

    Surface modification of micro- and nanofibrillated cellulose (MFC and NFC) under aqueous environment was performed by deposition of poly(styrene-co-maleimide) nanoparticles synthesized by imidization of poly(styrene-co-maleic anhydride) in presence of wax and ammonium hydroxide in variable amounts. Specifically, the influences of fiber fibrillation on nanoparticle formation (i.e., reaction efficiency) and permanent nanoparticle deposition on the fiber surface (i.e., retention) were investigated. The surface modification was mainly governed by the fiber diameter, surface charges and amount of wax. As such, the MFC affected the imidization reaction to a smaller extent (i.e., high reaction efficiency) and was more densely deposited by nanoparticles than NFC (i.e., high retention). Moreover, wax protected the fibers against fibrillation and peeling-off at high temperature and favored nanoparticle deposition. As a result, water contact angles of 142° were obtained for modified MFC in parallel with a surface coverage of 92%. PMID:26877019

  16. First-principles computation of surface segregation in L10 CoPt magnetic nanoparticles.

    PubMed

    Liu, Zhenyu; Lei, Yinkai; Wang, Guofeng

    2016-07-01

    In this study, we have employed the first-principles density functional theory (DFT) computational method to predict the influence of surface segregation on the magnetic properties of small L10 CoPt nanoparticles. For both the modelled cuboidal (with a chemical formula of Co26Pt12) and cuboctahedral (with a chemical formula of Co18Pt20) CoPt nanoparticles, the DFT calculations predict that Pt surface segregation should occur thermodynamically. Associated with this Pt surface segregation, the surface-segregated CoPt magnetic nanoparticles are predicted to have significantly reduced magnetic moments and magnetic anisotropy energies than those of the corresponding bulk-terminated (i.e. non-segregated) nanoparticles. Hence, our study suggests that surface segregation could deteriorate the magnetic properties of CoPt nanoparticles. PMID:27194486

  17. Effect of thermodiffusion on pH-regulated surface charge properties of nanoparticle.

    PubMed

    Das, Pradipta Kr

    2016-01-01

    Surface properties of nanoparticle are of high importance in the field of biotechnology, drug delivery and micro/nanofabrication. In this article, we developed a comprehensive theoretical model and subsequently solved that numerically to study the effect of thermodiffusion of ions on surface charge properties of nanoparticle. The theoretical study has been done considering silica nanoparticle for two aqueous solutions NaCl and KCl. The effect of solution pH in conjunction with nanoparticle temperature on surface charge density has been obtained for different salt concentrations (1, 10 and 100 mM) and nanoparticle size (diameter of 2 and 100 nm). It is observed from the results that with increasing temperature of the nanoparticle, the negative surface charge density gets higher due to increasing thermodiffusion effect. It is also found out that the magnitude of surface charge density is higher for KCl solution than NaCl solution under same condition which is attributed mostly due to less thermodiffusion of counterions for KCl than NaCl. Present study also shows that magnitude of surface charge density decreases with increasing nanoparticle size until it reaches a limiting value (called critical size) above which the effect of nanoparticle size on surface charge density is insignificant. PMID:26530465

  18. Upconversion Nanoparticles: Synthesis, Surface Modification, and Biological Applications

    PubMed Central

    Wang, Meng; Abbineni, Gopal; Clevenger, April; Mao, Chuanbin; Xu, Shukun

    2011-01-01

    New generation fluorophores, also termed upconversion nanoparticles (UCNPs), have the ability to convert near infrared radiations with lower energy into visible radiations with higher energy via a non-linear optical process. Recently, these UCNPs have evolved as alternative fluorescent labels to traditional fluorophores, showing great potential for imaging and biodetection assays in both in vitro and in vivo applications. UCNPs exhibit unique luminescent properties, including high penetration depth into tissues, low background signals, large Stokes shifts, sharp emission bands, and high resistance to photo-bleaching, making UCNPs an attractive alternative source for overcoming current limitations in traditional fluorescent probes. In this review, we discuss the recent progress in the synthesis and surface modification of rare earth doped UCNPs with a specific focus on their biological applications. PMID:21419877

  19. Self-organization of gold nanoparticles on silanated surfaces

    PubMed Central

    Kyaw, Htet H; Sellai, Azzouz; Dutta, Joydeep

    2015-01-01

    Summary The self-organization of monolayer gold nanoparticles (AuNPs) on 3-aminopropyltriethoxysilane (APTES)-functionalized glass substrate is reported. The orientation of APTES molecules on glass substrates plays an important role in the interaction between AuNPs and APTES molecules on the glass substrates. Different orientations of APTES affect the self-organization of AuNps on APTES-functionalized glass substrates. The as grown monolayers and films annealed in ultrahigh vacuum and air (600 °C) were studied by water contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, UV–visible spectroscopy and ultraviolet photoelectron spectroscopy. Results of this study are fundamentally important and also can be applied for designing and modelling of surface plasmon resonance based sensor applications. PMID:26734526

  20. Therapeutic cell engineering with surface-conjugated synthetic nanoparticles.

    PubMed

    Stephan, Matthias T; Moon, James J; Um, Soong Ho; Bershteyn, Anna; Irvine, Darrell J

    2010-09-01

    A major limitation of cell therapies is the rapid decline in viability and function of the transplanted cells. Here we describe a strategy to enhance cell therapy via the conjugation of adjuvant drug-loaded nanoparticles to the surfaces of therapeutic cells. With this method of providing sustained pseudoautocrine stimulation to donor cells, we elicited marked enhancements in tumor elimination in a model of adoptive T cell therapy for cancer. We also increased the in vivo repopulation rate of hematopoietic stem cell grafts with very low doses of adjuvant drugs that were ineffective when given systemically. This approach is a simple and generalizable strategy to augment cytoreagents while minimizing the systemic side effects of adjuvant drugs. In addition, these results suggest therapeutic cells are promising vectors for actively targeted drug delivery. PMID:20711198

  1. Adsorption study of antibiotics on silver nanoparticle surfaces by surface-enhanced Raman scattering spectroscopy

    NASA Astrophysics Data System (ADS)

    Filgueiras, Aline Luciano; Paschoal, Diego; Dos Santos, Hélio F.; Sant'Ana, Antonio C.

    2015-02-01

    In this work the adsorption of the antibiotics levofloxacin (LV), tetracycline (TC) and benzylpenicillin (BP) on the surface of silver nanoparticles (AgNP) have been investigated through both surface-enhanced Raman scattering (SERS) and UV-VIS-NIR spectroscopies. The SERS spectra were obtained using 1064 nm exciting radiation. Theoretical models for the antibiotic molecules were obtained from DFT calculations, and used in the vibrational assignment. The adsorption geometries were proposed based on the changes in the spectral patterns. The LV compound adsorbs through carboxylate group, TC compound interacts with silver atoms through carbonyl from intermediate ring, and BP compound adsorbs by carbonyl moieties from carboxylate and acyclic amide.

  2. Surface engineering of gold nanoparticles for in vitro siRNA delivery

    NASA Astrophysics Data System (ADS)

    Zhao, Enyu; Zhao, Zhixia; Wang, Jiancheng; Yang, Chunhui; Chen, Chengjun; Gao, Lingyan; Feng, Qiang; Hou, Wenjie; Gao, Mingyuan; Zhang, Qiang

    2012-07-01

    Cellular uptake, endosomal/lysosomal escape, and the effective dissociation from the carrier are a series of hurdles for specific genes to be delivered both in vitro and in vivo. To construct siRNA delivery systems, poly(allylamine hydrochloride) (PAH) and siRNA were alternately assembled on the surface of 11.8 +/- 0.9 nm Au nanoparticles (GNP), stabilized by denatured bovine serum albumin, by the ionic layer-by-layer (LbL) self-assembly method. By manipulating the outmost PAH layer, GNP-PAH vectors with different surface electric potentials were prepared. Then, the surface potential-dependent cytotoxicity of the resultant GNP-PAH particles was evaluated via sulforhodamine B (SRB) assay, while the surface potential-dependent cellular uptake efficiency was quantitatively analyzed by using the flow cytometry method based on carboxyfluorescein (FAM)-labeled siRNA. It was revealed that the GNP-PAH particles with surface potential of +25 mV exhibited the optimal cellular uptake efficiency and cytotoxicity for human breast cancer MCF-7 cells. Following these results, two more positively charged polyelectrolytes with different protonating abilities in comparison with PAH, i.e., polyethylenimine (PEI), and poly(diallyl dimethyl ammonium chloride) (PDDA), were chosen to fabricate similarly structured vectors. Confocal fluorescence microscopy studies indicated that siRNA delivered by GNP-PAH and GNP-PEI systems was better released than that delivered by the GNP-PDDA system. Further flow cytometric assays based on immunofluorescence staining of the epidermal growth factor receptor (EGFR) revealed that EGFR siRNA delivered by GNP-PAH and GNP-PEI exhibited similar down-regulation effects on EGFR expression in MCF-7 cells. The following dual fluorescence flow cytometry assays by co-staining phosphatidylserine and DNA suggested the EGFR siRNA delivered by GNP-PAH exhibited an improved silencing effect in comparison with that delivered by the commercial transfection reagent

  3. Cell surface nucleolin serves as receptor for DNA nanoparticles composed of pegylated polylysine and DNA.

    PubMed

    Chen, Xuguang; Kube, Dianne M; Cooper, Mark J; Davis, Pamela B

    2008-02-01

    Compacted DNA nanoparticles deliver transgenes efficiently to the lung following intrapulmonary dosing. Here we show that nucleolin, a protein known to shuttle between the nucleus, cytoplasm, and cell surface, is a receptor for DNA nanoparticles at the cell surface. By using surface plasmon resonance (SPR), we demonstrate that nucleolin binds to DNA nanoparticles directly. The presence of nucleolin on the surface of HeLa and 16HBEo- cells was confirmed by surface biotinylation assay and immunofluorescence. Rhodamine-labeled DNA nanoparticles colocalize with nucleolin on the cell surface, as well as in the cytoplasm and nucleus, but not with transferrin or markers of early endosome or lysosome following cellular uptake. Reducing nucleolin on the cell surface by serum-free medium or siRNA against nucleolin treatment leads to significant reduction in luciferase reporter gene activity, while overexpressing nucleolin has the opposite effect. Competition for binding to DNA nanoparticles with exogenous purified nucleolin decreases the transfection efficiency by 60-90% in a dose-dependent manner. Therefore, the data strongly suggest that cell surface nucleolin serves as a receptor for DNA nanoparticles, and that nucleolin is essential for internalization and/or transport of the nanoparticles from cell surface to the nucleus. PMID:18059369

  4. Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces

    PubMed Central

    Liu, Guoliang; Eichelsdoerfer, Daniel J.; Rasin, Boris; Zhou, Yu; Brown, Keith A.; Liao, Xing; Mirkin, Chad A.

    2013-01-01

    Although nanoparticles with exquisite properties have been synthesized for a variety of applications, their incorporation into functional devices is challenging owing to the difficulty in positioning them at specified sites on surfaces. In contrast with the conventional synthesis-then-assembly paradigm, scanning probe block copolymer lithography can pattern precursor materials embedded in a polymer matrix and synthesize desired nanoparticles on site, offering great promise for incorporating nanoparticles into devices. This technique, however, is extremely limited from a materials standpoint. To develop a materials-general method for synthesizing nanoparticles on surfaces for broader applications, a mechanistic understanding of polymer-mediated nanoparticle formation is crucial. Here, we design a four-step synthetic process that enables independent study of the two most critical steps for synthesizing single nanoparticles on surfaces: phase separation of precursors and particle formation. Using this process, we elucidate the importance of the polymer matrix in the diffusion of metal precursors to form a single nanoparticle and the three pathways that the precursors undergo to form nanoparticles. Based on this mechanistic understanding, the synthetic process is generalized to create metal (Au, Ag, Pt, and Pd), metal oxide (Fe2O3, Co2O3, NiO, and CuO), and alloy (AuAg) nanoparticles. This mechanistic understanding and resulting process represent a major advance in scanning probe lithography as a tool to generate patterns of tailored nanoparticles for integration with solid-state devices. PMID:23277538

  5. Surface free energy of platinum nanoparticles at zero pressure: A molecular dynamic study

    NASA Astrophysics Data System (ADS)

    Akbarzadeh, Hamed; Abroshan, Hadi; Parsafar, Gholam Abbas

    2010-02-01

    Metallic nanoparticles are interesting because of their use in catalysis and sensors. The surface energy of the FCC platinum nanoparticles are investigated via molecular dynamics simulation using Quantum Sutton-Chen (QSC) potential. We have calculated the Gibbs free energy for the FCC platinum bulk and also for its nanoparticle. All calculations have been carried out at zero pressure. We have used the thermodynamic integration method to obtain the Gibbs free energy. The total Gibbs free energy is taken as the sum of its central bulk and its surface free energy. We have calculated the free energy of a platinum nanoparticle as a function of temperature.

  6. Anchoring gold nanoparticles onto a mica surface by oxygen plasma ashing for sequential nanocomponent assembly

    NASA Astrophysics Data System (ADS)

    Takagi, Akihiko; Ojima, Kaoru; Mikamo, Eriko; Matsumoto, Takuya; Kawai, Tomoji

    2007-01-01

    Water-soluble gold nanoparticles were immobilized in both polar (water) and nonpolar (chloroform) liquids on hydrophilic mica surface by oxygen plasma ashing. It is then demonstrated that a DNA with a thiol at an extremity is attached to the immobilized nanoparticles due to the gold-thiol coupling and stretched in the flow direction of the following water rinse. This technique allows a sequential integration of nanoparticles and molecules for various solutions, since the nanoparticles remain on a solid surface rather than dissolve into the solution.

  7. Anchoring gold nanoparticles onto a mica surface by oxygen plasma ashing for sequential nanocomponent assembly

    SciTech Connect

    Takagi, Akihiko; Ojima, Kaoru; Mikamo, Eriko; Matsumoto, Takuya; Kawai, Tomoji

    2007-01-22

    Water-soluble gold nanoparticles were immobilized in both polar (water) and nonpolar (chloroform) liquids on hydrophilic mica surface by oxygen plasma ashing. It is then demonstrated that a DNA with a thiol at an extremity is attached to the immobilized nanoparticles due to the gold-thiol coupling and stretched in the flow direction of the following water rinse. This technique allows a sequential integration of nanoparticles and molecules for various solutions, since the nanoparticles remain on a solid surface rather than dissolve into the solution.

  8. Gold nanoparticle based surface enhanced fluorescence for detection of organophosphorus agents

    NASA Astrophysics Data System (ADS)

    Dasary, Samuel S. R.; Rai, Uma S.; Yu, Hongtao; Anjaneyulu, Yerramilli; Dubey, Madan; Ray, Paresh Chandra

    2008-07-01

    Organophosphorus agents (OPA) represent a serious concern to public safety as nerve agents and pesticides. Here we report the development of gold nanoparticle based surface enhanced fluorescence (NSEF) spectroscopy for rapid and sensitive screening of organophosphorus agents. Fluorescent from Eu 3+ ions that are bound within the electromagnetic field of gold nanoparticles exhibit a strong enhancement. In the presence of OPA, Eu 3+ ions are released from the gold nanoparticle surface and thus a very distinct fluorescence signal change was observed. We discussed the mechanism of fluorescence enhancement and the role of OPA for fluorescence intensity change in the presence of gold nanoparticles.

  9. Surface functionalized mesoporous silica nanoparticles for intracellular drug delivery

    NASA Astrophysics Data System (ADS)

    Vivero-Escoto, Juan Luis

    Mesoporous silica nanoparticles (MSNs) are a highly promising platform for intracellular controlled release of drugs and biomolecules. Despite that the application of MSNs in the field of intracellular drug delivery is still at its infancy very exciting breakthroughs have been achieved in the last years. A general review of the most recent progress in this area of research is presented, including a description of the latest findings on the pathways of entry into live mammalian cells together with the intracellular trafficking, a summary on the contribution of MSNs to the development of site-specific drug delivery systems, a report on the biocompatibility of this material in vitro andin vivo, and a discussion on the most recent breakthroughs in the synthesis and application of stimuli-responsive mesoporous silica-based delivery vehicles. A gold nanoparticles (AuNPs)-capped MSNs-based intracellular photoinduced drug delivery system (PR-AuNPs-MSNs) for the controlled release of anticancer drug inside of human fibroblast and liver cells was synthesized and characterized. We found that the mesoporous channels of MSNs could be efficiently capped by the photoresponsive AuNPs without leaking the toxic drug, paclitaxel, inside of human cells. Furthermore, we demonstrated that the cargo-release property of this PR-AuNPs-MSNs system could be easily photo-controlled under mild and biocompatible conditions in vitro. In collaboration with Renato Mortera (a visiting student from Italy), a MSNs based intracellular delivery system for controlled release of cell membrane impermeable cysteine was developed. A large amount of cysteine molecules were covalently attached to the silica surface of MSNs through cleavable disulfide linkers. These cysteine-containing nanoparticles were efficiently endocytosed by human cervical cancer cells HeLa. These materials exhibit 450 times higher cell growth inhibition capability than that of the conventional N-acetylcysteine prodrug. The ability to

  10. Patterning of gold nanoparticles on fluoropolymer films by using patterned surface grafting and layer-by-layer deposition techniques.

    PubMed

    Jung, Chang-Hee; Hwang, In-Tae; Jung, Chan-Hee; Choi, Jae-Hak; Kwon, Oh-Sun; Shin, Kwanwoo

    2013-09-11

    The patterning of gold nanoparticles (GNPs) on the surface of a fluoropolymer substrate by using patterned surface grafting and layer-by-layer deposition techniques is described. The surface of a poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) substrate was selectively implanted with 150 keV proton ions. Peroxide groups were successfully formed on the implanted PFA surface, and their concentration depended on the fluence. Acrylic acid was graft polymerized onto the implanted regions of the PFA substrate, resulting in well-defined patterns of poly(acrylic acid) (PAA) on the PFA substrate. The surface properties of the PAA-patterned PFA surface, such as chemical compositions, wettability, and morphology, were investigated. The surface analysis results revealed that PAA was definitely present on the implanted regions of the PFA surface, and the degree of grafting was dependent on three factors: fluence, grafting time, and monomer concentration. Furthermore, GNP patterns were generated on the prepared PAA-patterned PFA surface by layer-by-layer deposition of GNPs and poly(diallyldimethyl ammonium chloride). The multilayers of GNPs were deposited only onto the PAA-grafted regions separated by bare PFA regions, and the resulting GNP patterns exhibited good electrical conductivity. PMID:23927646

  11. Bacteria-mimicking nanoparticle surface functionalization with targeting motifs

    NASA Astrophysics Data System (ADS)

    Lai, Mei-Hsiu; Clay, Nicholas E.; Kim, Dong Hyun; Kong, Hyunjoon

    2015-04-01

    In recent years, surface modification of nanocarriers with targeting motifs has been explored to modulate delivery of various diagnostic, sensing and therapeutic molecular cargo to desired sites of interest in in vitro bioengineering platforms and in vivo pathologic tissue. However, most surface functionalization approaches are often plagued by complex chemical modifications and effortful purifications. To resolve such challenges, this study demonstrates a unique method to immobilize antibodies that can act as targeting motifs on the surfaces of nanocarriers, inspired by a process that bacteria use for immobilization of the host's antibodies. We hypothesized that alkylated Staphylococcus aureus protein A (SpA) would self-assemble with micelles and subsequently induce stable coupling of antibodies to the micelles. We examined this hypothesis by using poly(2-hydroxyethyl-co-octadecyl aspartamide) (PHEA-g-C18) as a model polymer to form micelles. The self-assembly between the micelles and alkylated SpA became more thermodynamically favorable by increasing the degree of substitution of octadecyl chains to PHEA-g-C18, due to a positive entropy change. Lastly, the mixing of SpA-PA-coupled micelles with antibodies resulted in the coating of micelles with antibodies, as confirmed with a fluorescence resonance energy transfer (FRET) assay. The micelles coated with antibodies to VCAM-1 or integrin αv displayed a higher binding affinity to substrates coated with VCAM-1 and integrin αvβ3, respectively, than other controls, as evaluated with surface plasmon resonance (SPR) spectroscopy and a circulation-simulating flow chamber. We envisage that this bacteria-inspired protein immobilization approach will be useful to improve the quality of targeted delivery of nanoparticles, and can be extended to modify the surface of a wide array of nanocarriers.In recent years, surface modification of nanocarriers with targeting motifs has been explored to modulate delivery of various

  12. Au nanoparticles on graphitic petal arrays for surface-enhanced Raman spectroscopy

    SciTech Connect

    Rout, Chandra Sekhar; Kumar, Anurag; Xiong Guoping; Fisher, Timothy S.; Irudayaraj, Joseph

    2010-09-27

    We report a unique substrate for surface-enhanced Raman scattering (SERS) based on Au nanoparticle-decorated, thin graphitic petals. The petals were grown on Si substrates by microwave plasma chemical vapor deposition without catalyst, followed by Au nanoparticle decoration on the oxygen plasma-treated petals by electrodeposition. The substrates possess high surface area and sharp nanoscale features that enable high SERS sensitivity to detect 1x10{sup -7} M rhodamine 6G in methanol solution. The obtained SERS enhancement is comparable to the best values reported in the literature and is determined to result from high surface area and increased density of Au nanoparticles on the petal surfaces.

  13. Alumoxane/ferroxane nanoparticles for the removal of viral pathogens: the importance of surface functionality to nanoparticle activity

    NASA Astrophysics Data System (ADS)

    Maguire-Boyle, Samuel J.; Liga, Michael V.; Li, Qilin; Barron, Andrew R.

    2012-08-01

    A bi-functional nano-composite coating has been created on a porous Nomex® fabric support as a trap for aspirated virus contaminated water. Nomex® fabric was successively dip-coated in solutions containing cysteic acid functionalized alumina (alumoxane) nanoparticles and cysteic acid functionalized iron oxide (ferroxane) nanoparticles to form a nanoparticle coated Nomex® (NPN) fabric. From SEM and EDX the nanoparticle coating of the Nomex® fibers is uniform, continuous, and conformal. The NPN was used as a filter for aspirated bacteriophage MS2 viruses using end-on filtration. All measurements were repeated to give statistical reliability. The NPN fabrics show a large decrease as compared to Nomex® alone or alumoxane coated Nomex®. An increase in the ferroxane content results in an equivalent increase in virus retention. This suggests that it is the ferroxane that has an active role in deactivating and/or binding the virus. Heating the NPN to 160 °C results in the loss of cysteic acid functional groups (without loss of the iron nanoparticle's core structure) and the resulting fabric behaves similar to that of untreated Nomex®, showing that the surface functionalization of the nanoparticles is vital for the surface collapse of aspirated water droplets and the absorption and immobilization of the MS2 viruses. Thus, for virus immobilization, it is not sufficient to have iron oxide nanoparticles per se, but the surface functionality of a nanoparticle is vitally important in ensuring efficacy.A bi-functional nano-composite coating has been created on a porous Nomex® fabric support as a trap for aspirated virus contaminated water. Nomex® fabric was successively dip-coated in solutions containing cysteic acid functionalized alumina (alumoxane) nanoparticles and cysteic acid functionalized iron oxide (ferroxane) nanoparticles to form a nanoparticle coated Nomex® (NPN) fabric. From SEM and EDX the nanoparticle coating of the Nomex® fibers is uniform, continuous

  14. Geant4 Monte Carlo simulation of absorbed dose and radiolysis yields enhancement from a gold nanoparticle under MeV proton irradiation

    NASA Astrophysics Data System (ADS)

    Tran, H. N.; Karamitros, M.; Ivanchenko, V. N.; Guatelli, S.; McKinnon, S.; Murakami, K.; Sasaki, T.; Okada, S.; Bordage, M. C.; Francis, Z.; El Bitar, Z.; Bernal, M. A.; Shin, J. I.; Lee, S. B.; Barberet, Ph.; Tran, T. T.; Brown, J. M. C.; Nhan Hao, T. V.; Incerti, S.

    2016-04-01

    Gold nanoparticles have been reported as a possible radio-sensitizer agent in radiation therapy due to their ability to increase energy deposition and subsequent direct damage to cells and DNA within their local vicinity. Moreover, this increase in energy deposition also results in an increase of the radiochemical yields. In this work we present, for the first time, an in silico investigation, based on the general purpose Monte Carlo simulation toolkit Geant4, into energy deposition and radical species production around a spherical gold nanoparticle 50 nm in diameter via proton irradiation. Simulations were preformed for incident proton energies ranging from 2 to 170 MeV, which are of interest for clinical proton therapy.

  15. Individual Detection and Electrochemically Assisted Identification of Adsorbed Nanoparticles by Using Surface Plasmon Microscopy.

    PubMed

    Nizamov, Shavkat; Kasian, Olga; Mirsky, Vladimir M

    2016-06-13

    The increasing production and application of nanoparticles necessitates a highly sensitive analytical method for the quantification and identification of these potentially hazardous materials. We describe here an application of surface plasmon microscopy for the individual detection of each adsorbed nanoparticle and for visualization of its electrochemical conversion. Whereas the adsorption rate characterizes the number concentration of nanoparticles, the potential at which the adsorbed nanoparticles disappear during an anodic potential sweep characterizes the type of material. All the adsorbed nanoparticles are subjected to the potential sweep simultaneously; nevertheless, each of the up to a million adsorbed nanoparticles is identified individually by its electrochemical dissolution potential. The technique has been tested with silver and copper nanoparticles, but can be extended to many other electrochemically active nanomaterials. PMID:27139913

  16. Surface modification of magnetite nanoparticles using lactobionic acid and their interaction with hepatocytes.

    PubMed

    Kamruzzaman Selim, K M; Ha, Yong-Soo; Kim, Sun-Jung; Chang, Yongmin; Kim, Tae-Jeong; Ho Lee, Gang; Kang, Inn-Kyu

    2007-02-01

    In the current study, superparamagnetic magnetite nanoparticles were surface-modified with lactobionic acid (LA) to improve their intracellular uptake and ability to target hepatocytes. Maltotrionic acid (MA)-modified nanoparticles were also synthesized as a control. Cell culture experiment showed that LA-modified nanoparticles were internalized into hepatocytes and atomic absorption spectrometer (AAS) measurement indicated that the uptake amount of LA-modified magnetite into hepatocytes was higher than that of unmodified and MA-modified nanoparticles. LA-modified nanoparticle solution was injected in rabbit and the magnetic resonance (MR) images obtained showed that LA-coated nanoparticles were selectively accumulated onto the hepatocytes. This result demonstrates that the LA-modified magnetite nanoparticles have a great potential to be used as contrast agent for liver diagnosis. PMID:17049979

  17. Bacteria-mimicking nanoparticle surface functionalization with targeting motifs.

    PubMed

    Lai, Mei-Hsiu; Clay, Nicholas E; Kim, Dong Hyun; Kong, Hyunjoon

    2015-04-21

    In recent years, surface modification of nanocarriers with targeting motifs has been explored to modulate delivery of various diagnostic, sensing and therapeutic molecular cargo to desired sites of interest in in vitro bioengineering platforms and in vivo pathologic tissue. However, most surface functionalization approaches are often plagued by complex chemical modifications and effortful purifications. To resolve such challenges, this study demonstrates a unique method to immobilize antibodies that can act as targeting motifs on the surfaces of nanocarriers, inspired by a process that bacteria use for immobilization of the host's antibodies. We hypothesized that alkylated Staphylococcus aureus protein A (SpA) would self-assemble with micelles and subsequently induce stable coupling of antibodies to the micelles. We examined this hypothesis by using poly(2-hydroxyethyl-co-octadecyl aspartamide) (PHEA-g-C18) as a model polymer to form micelles. The self-assembly between the micelles and alkylated SpA became more thermodynamically favorable by increasing the degree of substitution of octadecyl chains to PHEA-g-C18, due to a positive entropy change. Lastly, the mixing of SpA-PA-coupled micelles with antibodies resulted in the coating of micelles with antibodies, as confirmed with a fluorescence resonance energy transfer (FRET) assay. The micelles coated with antibodies to VCAM-1 or integrin αv displayed a higher binding affinity to substrates coated with VCAM-1 and integrin αvβ3, respectively, than other controls, as evaluated with surface plasmon resonance (SPR) spectroscopy and a circulation-simulating flow chamber. We envisage that this bacteria-inspired protein immobilization approach will be useful to improve the quality of targeted delivery of nanoparticles, and can be extended to modify the surface of a wide array of nanocarriers. PMID:25804130

  18. Bacterium-Mimicking Nanoparticle Surface Functionalization with Targeting Motifs

    PubMed Central

    Lai, Mei-Hsiu; Clay, Nicholas E.; Kim, Dong Hyun; Kong, Hyunjoon

    2015-01-01

    In recent years, surface modification of nanocarriers with targeting motifs has been explored to modulate delivery of various diagnostic, sensing and therapeutic molecular cargos to desired sites of interest in in vitro bioengineering platforms and in vivo pathologic tissue. However, most surface functionalization approaches are often plagued by complex chemical modifications and effortful purifications. To resolve such challenges, this study demonstrates a unique method to immobilize antibodies that can act as targeting motifs on the surfaces of nanocarriers, inspired by a process that bacteria use for immobilization of the host’s antibodies. We hypothesized that alkylated Staphylococcus aureus protein A (SpA) would self-assemble with micelles and subsequently induce stable coupling of antibodies to the micelles. We examined this hypothesis by using poly(2-hydroxyethyl-co-octadecyl aspartamide) (PHEA-g-C18) as a model polymer to form micelles. The self-assembly between micelles and alkylated SpA became more thermodynamically favorable by increasing the degree of substitution of octadecyl chains to PHEA-g-C18, due to a positive entropy change. Lastly, the simple mixing of SpA-PA-coupled micelles with antibodies resulted in the micelles coated by antibodies, as confirmed with a fluorescence resonance energy transfer (FRET) assay. The micelles coated by antibodies to VCAM-1 or integrin αv displayed higher binding affinity to a substrate coated by VCAM-1 and integrin αvβ3, respectively, than other controls, as evaluated with surface plasmon resonance (SPR) spectroscopy and a circulation-simulating flow chamber. We envisage this bacterium-inspired protein immobilization approach will be useful to improving the quality of targeted delivery of nanoparticles, and can be extended to modify the surface of a wide array of nanocarriers. PMID:25804130

  19. Dynamics of water confined on the surface of titania and cassiterite nanoparticles

    SciTech Connect

    Ross, Dr. Nancy; Spencer, Elinor; Levchenko, Andrey A.; Kolesnikov, Alexander I; Abernathy, Douglas L; Boerio-Goates, Juliana; Woodfield, Brian; Navrotsky, Alexandra; Li, Guangshe; Wang, Weixing; Wesolowski, David J

    2011-01-01

    We present low-temperature inelastic neutron scattering spectra collected on two metal oxide nanoparticle systems, isostructural TiO2 rutile and SnO2 cassiterite, between 0-550 meV. Data were collected on samples with varying levels of water coverage, and in the case of SnO2, particles of different sizes. This study provides a comprehensive understanding of the structure and dynamics of the water confined on the surface of these particles. The translational movement of water confined on the surface of these nanoparticles is suppressed relative to that in ice-Ih and water molecules on the surface of rutile nanoparticles are more strongly restrained that molecules residing on the surface of cassiterite nanoparticles. The INS spectra also indicate that the hydrogen bond network within the hydration layers on rutile is more perturbed than for water on cassiterite. This result is indicative of stronger water-surface interactions between water on the rutile nanoparticles than for water confined on the surface of cassiterite nanoparticles. These differences are consistent with the recently reported differences in the surface energy of these two nanoparticle systems. The results of this study also support previous studies that suggest that water dissociation is more prevalent on the surface of SnO2 than TiO2.

  20. Removal of thiol ligands from surface-confined nanoparticles without particle growth or desorption.

    PubMed

    Elliott, Edward W; Glover, Richard D; Hutchison, James E

    2015-03-24

    Size-dependent properties of surface-confined inorganic nanostructures are of interest for applications ranging from sensing to catalysis and energy production. Ligand-stabilized nanoparticles are attractive precursors for producing such nanostructures because the stabilizing ligands may be used to direct assembly of thoroughly characterized nanoparticles on the surface. Upon assembly; however, the ligands block the active surface of the nanoparticle. Methods used to remove these ligands typically result in release of nanoparticles from the surface or cause undesired growth of the nanoparticle core. Here, we demonstrate that mild chemical oxidation (50 ppm of ozone in nitrogen) oxidizes the thiolate headgroups, lowering the ligand's affinity for the gold nanoparticle surface and permitting the removal of the ligands at room temperature by rinsing with water. XPS and TEM measurements, performed using a custom planar analysis platform that permits detailed imaging and chemical analysis, provide insight into the mechanism of ligand removal and show that the particles retain their core size and remain tethered on the surface core during treatment. By varying the ozone exposure time, it is possible to control the amount of ligand removed. Catalytic carbon monoxide oxidation was used as a functional assay to demonstrate ligand removal from the gold surface for nanoparticles assembled on a high surface area support (fumed silica). PMID:25727562

  1. Leaky-Surface-Acoustic-Wave Properties on Reverse-Proton-Exchanged LiNbO3

    NASA Astrophysics Data System (ADS)

    Kakio, Shoji; Shimizu, Hidenori; Nakagawa, Yasuhiko

    2009-07-01

    A proton-exchanged (PE) layer with an elastically soft property can be buried into a substrate by a reverse proton exchange (RPE) process. It is expected that an RPE layer with a property similar to that of bulk LiNbO3 will prevent the degradation of coupling factor, and that the buried PE layer will change the anisotropy of the substrate effectively and reduce the leaky surface acoustic wave (LSAW) attenuation as compared with bulk LN. In this study, first, a layered structure of air/bulk LN/softened LN was assumed for rotated Y-X LN and LSAW attenuation was calculated. By controlling the elastic constant of the softened LN, the rotation angle from the Y-axis giving zero attenuation shifted from 64 to 5° for a metallized surface, and the rotation angle at which the attenuation decreases as compared with bulk LN was drastically changed for a free surface. Next, the LSAW propagation loss PL was measured on 41° Y-X LN. The PL for the metallized surface was decreased by carrying out the RPE process from 0.036 dB/λ of a virgin sample to 0.015 dB/λ. The decrease in PL for the free surface was also observed.

  2. Alumoxane/ferroxane nanoparticles for the removal of viral pathogens: the importance of surface functionality to nanoparticle activity.

    PubMed

    Maguire-Boyle, Samuel J; Liga, Michael V; Li, Qilin; Barron, Andrew R

    2012-09-21

    A bi-functional nano-composite coating has been created on a porous Nomex® fabric support as a trap for aspirated virus contaminated water. Nomex® fabric was successively dip-coated in solutions containing cysteic acid functionalized alumina (alumoxane) nanoparticles and cysteic acid functionalized iron oxide (ferroxane) nanoparticles to form a nanoparticle coated Nomex® (NPN) fabric. From SEM and EDX the nanoparticle coating of the Nomex® fibers is uniform, continuous, and conformal. The NPN was used as a filter for aspirated bacteriophage MS2 viruses using end-on filtration. All measurements were repeated to give statistical reliability. The NPN fabrics show a large decrease as compared to Nomex® alone or alumoxane coated Nomex®. An increase in the ferroxane content results in an equivalent increase in virus retention. This suggests that it is the ferroxane that has an active role in deactivating and/or binding the virus. Heating the NPN to 160 °C results in the loss of cysteic acid functional groups (without loss of the iron nanoparticle's core structure) and the resulting fabric behaves similar to that of untreated Nomex®, showing that the surface functionalization of the nanoparticles is vital for the surface collapse of aspirated water droplets and the absorption and immobilization of the MS2 viruses. Thus, for virus immobilization, it is not sufficient to have iron oxide nanoparticles per se, but the surface functionality of a nanoparticle is vitally important in ensuring efficacy. PMID:22864822

  3. The Effect of Surface Treated Nanoparticles on Single and Multi-Phase Flow in Porous Media

    NASA Astrophysics Data System (ADS)

    DiCarlo, D. A.; Aminzadeh, B.; Chung, D.; Zhang, X.; Wung, R.; Huh, C.; Bryant, S. L.

    2013-12-01

    Surface treated nanoparticles have been suggested to be an additive to CO2 storage scenarios. This is because 1) the nanoparticles have been shown to freely transport through permeable media, and 2) the nanoparticles can stabilize a CO2 in water foam by adhering to the surface of CO2 bubbles/droplets preventing their coalescence. In terms of storage, The formation of CO2 foam will limit the CO2 mobility which can potentially help limit the CO2 leakage. Here, we will show how nanoparticles in porous media can have many interesting properties in single and multi-phase flow. For multi-phase CO2, we have performed experiments where high pressure liquid CO2 displaces brine and vice versa with and without nanoparticles in the brine. We measure the displacement pattern and in-situ CO2 saturation using CT scanning and measure the pressure drop using pressure transducers. We find that the flow is less preferential and the pressure drop is greater than when nanoparticles are present. This suggest the formation of in-situ foam/emulsion. We also show that on a brine chase, the residual saturation of CO2 is greater in the presence of nanoparticles. In terms of nanoparticle transport, it is observed that nanoparticles accumulate at the front of a brine/octane displacement. We hypothesize that this occurs due to the nanoparticles being size excluded from portions of the pore-space. To determine if this occurs in single phase flow, we have also performed experiments single-phase flow with the nanoparticles and tracer. We find that the nanoparticles arrive roughly 5% faster than the tracer. This also has implications for the positioning of nanoparticles in the pore space and how this can change the effective viscosity of the nanoparticle suspension.

  4. WE-G-BRE-07: Proton Therapy Enhanced by Tumor-Targeting Gold Nanoparticles: A Pilot in Vivo Experiment at The Proton Therapy Center at MD Anderson Cancer Center

    SciTech Connect

    Wolfe, T; Grant, J; Wolfe, A; Gillin, M; Krishnan, S

    2014-06-15

    Purpose: Assess tumor-growth delay and survival in a mouse model of prostate cancer treated with tumor-targeting gold nanoparticles (AuNPs) and proton therapy. Methods: We first examined the accumulation of targeting nanoparticles within prostate tumors by imaging AuNPs with ultrasound-guided photoacoustics at 24h after the intravenous administration of goserelin-conjugated AuNPs (gAuNP) in three mice. Nanoparticles were also imaged at the cellular level with TEM in PC3 cells incubated with gAuNP for 24h. Pegylated AuNPs (pAuNP) were also imaged in vivo and in vitro for comparison. PC3 cells were then implanted subcutaneously in nude mice; 51mice with 8–10mm tumors were included. AuNPs were injected intravenously at 0.2%w/w final gold concentration 24h before irradiation. A special jig was designed to facilitate tumor irradiation perpendicular to the proton beam. Proton energy was set to 180MeV, the radiation field was 18×18cm{sup 2}, and 9cm or 13.5cm thick solid-water compensators were used to position the tumors at either the beam entrance (BE) or the SOBP. Physical doses of 5Gy were delivered to all tumors on a patient beam line at MD Anderson's Proton Therapy Center. Results: The photoacoustic experiment reveled that our nanoparticles leak from the tumor-feeding vasculature and accumulate within the tumor volume over time. Additionally, TEM images showed gAuNP are internalized in cancer cells, accumulating within the cytoplasm, whereas pAuNP are not. Tumor-growth was delayed by 11 or 32days in mice receiving gAuNP irradiated at the BE or the SOBP, relative to proton radiation alone. Survival curves (ongoing experiment) reveal that gAuNPs improved survival by 36% or 74% for tumors irradiated at the BE or SOBP. Conclusion: These important, albeit preliminary, in vivo findings reveal nanoparticles to be potent sensitizers to proton therapy. Further, conjugation of AuNPs to tumor-specific antigens that promote enhanced cellular internalization improved both

  5. Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

    PubMed Central

    Chi, Miaofang; Wang, Chao; Lei, Yinkai; Wang, Guofeng; Li, Dongguo; More, Karren L.; Lupini, Andrew; Allard, Lawrence F.; Markovic, Nenad M.; Stamenkovic, Vojislav R.

    2015-01-01

    The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation; nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. This work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance. PMID:26576477

  6. Production of excitons in grazing collisions of protons with LiF surfaces: An onion model

    SciTech Connect

    Miraglia, J. E.; Gravielle, M. S.

    2011-12-15

    In this work we evaluate the production of excitons of a lithium fluoride crystal induced by proton impact in the intermediate and high energy regime (from 100 keV to 1 MeV). A simple model is proposed to account for the influence of the Coulomb grid of the target by dressing crystal ions to transform them in what we call onions. The excited states of these onions can be interpreted as excitons. Within this model, total cross section and stopping power are calculated by using the first Born and the continuum distorted-wave (CDW) eikonal initial-state (EIS) approximations. We found that between 7 and 30 excitons per incident proton are produced in grazing collisions with LiF surfaces, becoming a relevant mechanism of inelastic transitions.

  7. Fabrication of micro-prominences on PTFE surface using proton beam writing

    NASA Astrophysics Data System (ADS)

    Kitamura(Ogawa), Akane; Satoh, Takahiro; Koka, Masashi; Kobayashi, Tomohiro; Kamiya, Tomihiro

    2013-07-01

    Polytetrafluoroethylene (PTFE) is a typical fluoropolymer and it has several desirable technological properties such as electrical insulation, solid lubrication etc. However, the conventional microstructuring methods have not been well applied to PTFE due to its chemical inertness. Some effective micromachining using synchrotron radiation or ion beam irradiation has been reported. In this study, we create micro-prominences by raising the original surface using proton beam writing (PBW) without chemical etching. A conical prominence was formed by spiral drawing from the center with a 3 MeV proton beam. The body was porous, and the bulk PTFE below the prominence changed to fragmented structures. With decreasing writing speed, the prominence became taller but the height peaked. The prominence gradually reduced in size after the speed reached the optimum value. We expect that these porous projections with high aspect ratio will be versatile in medical fields and microelectromechanical systems (MEMS) technology.

  8. Colloidal microcapsules: Surface engineering of nanoparticles for interfacial assembly

    NASA Astrophysics Data System (ADS)

    Patra, Debabrata

    2011-12-01

    Colloidal Microcapsules (MCs), i.e. capsules stabilized by nano-/microparticle shells are highly modular inherently multi-scale constructs with applications in many areas of material and biological sciences e.g. drug delivery, encapsulation and microreactors. These MCs are fabricated by stabilizing emulsions via self-assembly of colloidal micro/nanoparticles at liquid-liquid interface. In these systems, colloidal particles serve as modular building blocks, allowing incorporation of the particle properties into the functional capabilities of the MCs. As an example, nanoparticles (NPs) can serve as appropriate antennae to induce response by external triggers (e.g. magnetic fields or laser) for controlled release of encapsulated materials. Additionally, the dynamic nature of the colloidal assembly at liquid-liquid interfaces result defects free organized nanostructures with unique electronic, magnetic and optical properties which can be tuned by their dimension and cooperative interactions. The physical properties of colloidal microcapsules such as permeability, mechanical strength, and biocompatibility can be precisely controlled through the proper choice of colloids and preparation conditions for their. This thesis illustrates the fabrication of stable and robust MCs through via chemical crosslinking of the surface engineered NPs at oil-water interface. The chemical crosslinking assists NPs to form a stable 2-D network structure at the emulsion interface, imparting robustness to the emulsions. In brief, we developed the strategies for altering the nature of chemical interaction between NPs at the emulsion interface and investigated their role during the self-assembly process. Recently, we have fabricated stable colloidal microcapsule (MCs) using covalent, dative as well as non-covalent interactions and demonstrated their potential applications including encapsulation, size selective release, functional devices and biocatalysts.

  9. Gold nanoparticles with externally controlled, reversible shifts of local surface plasmon resonance bands.

    PubMed

    Yavuz, Mustafa S; Jensen, Gary C; Penaloza, David P; Seery, Thomas A P; Pendergraph, Samuel A; Rusling, James F; Sotzing, Gregory A

    2009-11-17

    We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states. PMID:19839619

  10. Strategies in biomimetic surface engineering of nanoparticles for biomedical applications

    NASA Astrophysics Data System (ADS)

    Gong, Yong-Kuan; Winnik, Françoise M.

    2012-01-01

    Engineered nanoparticles (NPs) play an increasingly important role in biomedical sciences and in nanomedicine. Yet, in spite of significant advances, it remains difficult to construct drug-loaded NPs with precisely defined therapeutic effects, in terms of release time and spatial targeting. The body is a highly complex system that imposes multiple physiological and cellular barriers to foreign objects. Upon injection in the blood stream or following oral administation, NPs have to bypass numerous barriers prior to reaching their intended target. A particularly successful design strategy consists in masking the NP to the biological environment by covering it with an outer surface mimicking the composition and functionality of the cell's external membrane. This review describes this biomimetic approach. First, we outline key features of the composition and function of the cell membrane. Then, we present recent developments in the fabrication of molecules that mimic biomolecules present on the cell membrane, such as proteins, peptides, and carbohydrates. We present effective strategies to link such bioactive molecules to the NPs surface and we highlight the power of this approach by presenting some exciting examples of biomimetically engineered NPs useful for multimodal diagnostics and for target-specific drug/gene delivery applications. Finally, critical directions for future research and applications of biomimetic NPs are suggested to the readers.

  11. Surface functionalities of gold nanoparticles impact embryonic gene expression responses

    PubMed Central

    Truong, Lisa; Tilton, Susan C.; Zaikova, Tatiana; Richman, Erik; Waters, Katrina M.; Hutchison, James E.; Tanguay, Robert L.

    2012-01-01

    Incorporation of gold nanoparticles (AuNPs) into consumer products is increasing; however, there is a gap in available toxicological data to determine the safety of AuNPs. In this study, we utilised the embryonic zebrafish to investigate how surface functionalisation and charge influence molecular responses. Precisely engineered AuNPs with 1.5 nm cores were synthesised and functionalized with three ligands: 2-mercaptoethanesulfonic acid (MES), N,N,N-trimethylammoniumethanethiol (TMAT), or 2-(2-(2-mercaptoethoxy)ethoxy)ethanol. Developmental assessments revealed differential biological responses when embryos were exposed to the functionalised AuNPs at the same concentration. Using inductively coupled plasma–mass spectrometry, AuNP uptake was confirmed in exposed embryos. Following exposure to MES- and TMAT-AuNPs from 6 to 24 or 6 to 48 h post fertilisation, pathways involved in inflammation and immune response were perturbed. Additionally, transport mechanisms were misregulated after exposure to TMAT and MES-AuNPs, demonstrating that surface functionalisation influences many molecular pathways. PMID:22263968

  12. Simple, readily controllable palladium nanoparticle formation on surface-assembled viral nanotemplates.

    PubMed

    Manocchi, Amy K; Horelik, Nicholas E; Lee, Byeongdu; Yi, Hyunmin

    2010-03-01

    Transition-metal nanoparticles possess unique size-dependent optical, electronic, and catalytic properties on the nanoscale, which differ significantly from their bulk properties. In particular, palladium (Pd) nanoparticles have properties applicable to a wide range of applications in catalysis and electronics. However, predictable and controllable nanoparticle synthesis remains challenging because of harsh reaction conditions, artifacts from capping agents, and unpredictable growth. Biological supramolecules offer attractive templates for nanoparticle synthesis because of their precise structure and size. In this article, we demonstrate simple, controllable Pd nanoparticle synthesis on surface-assembled viral nanotemplates. Specifically, we exploit precisely spaced thiol functionalities of genetically modified tobacco mosaic virus (TMV1cys) for facile surface assembly and readily controllable Pd nanoparticle synthesis via simple electroless deposition under mild aqueous conditions. Atomic force microscopy (AFM) studies clearly show tunable surface assembly and Pd nanoparticle formation preferentially on the TMV1cys templates. Grazing incidence small-angle X-ray scattering (GISAXS) further provided an accurate and statistically meaningful route by which to investigate the broad size ranges and uniformity of the Pd nanoparticles formed on TMV templates by simply tuning the reducer concentration. We believe that our viral-templated bottom-up approach to tunable Pd nanoparticle formation combined with the first in-depth characterization via GISAXS represents a major advancement toward exploiting viral templates for facile nanomaterials/device fabrication. We envision that our strategy can be extended to a wide range of applications, including uniform nanostructure and nanocatalyst synthesis. PMID:19919039

  13. Surface-enhanced Raman scattering of carbon nanotubes by decoration of ZnS nanoparticles.

    PubMed

    Chang, Jingbo; Lee, Jae-Hyeok; Najeeb, Choolakadavil Khalid; Kim, Jae-Ho

    2011-07-01

    ZnS nanoparticles anchored on the single-walled carbon nanotubes (SWNTs) were fabricated by a chemical vapor deposition (CVD) method. The CVD method shows no selectivity for growth of ZnS nanoparticles on types and defects of the SWNTs, and thus ensures the uniform decoration of all SWNTs on the substrate. ZnS nanoparticles with a diameter of 10 nm were decorated on the SWNTs surface with an interparticle distance of about 20 nm. This method provides the possibility to realize the optimal configurations of ZnS nanoparticles on SWNTs for obtaining surface-enhanced Raman spectroscopy (SERS) of SWNTs. Investigations of mechanism reveal that charge transfer (a small amount of excitation electrons) from ZnS nanoparticles to SWNTs weakly affects Raman intensity, and the coupled surface plasmon resonance (SPR) formed from plenty of excitation electrons on the surface of ZnS nanoparticles contributes to the strong surface enhancement. It would be an alternative approach for SERS after metal (normally gold or silver) nanoparticles' decoration on the SWNTs surface. PMID:22121696

  14. Surface engineering of silica nanoparticles for oral insulin delivery: characterization and cell toxicity studies.

    PubMed

    Andreani, Tatiana; Kiill, Charlene P; de Souza, Ana Luiza R; Fangueiro, Joana F; Fernandes, Lisete; Doktorovová, Slavomira; Santos, Dario L; Garcia, Maria L; Gremião, Maria Palmira D; Souto, Eliana B; Silva, Amélia M

    2014-11-01

    The present work aimed at studying the interaction between insulin and SiNP surfaced with mucoadhesive polymers (chitosan, sodium alginate or polyethylene glycol) and the evaluation of their biocompatibility with HepG2 and Caco-2 cell lines, which mimic in vivo the target of insulin-loaded nanoparticles upon oral administration. Thus, a systematic physicochemical study of the surface-modified insulin-silica nanoparticles (Ins-SiNP) using mucoadhesive polymers has been described. The surfacing of nanoparticle involved the coating of silica nanoparticles (SiNP) with different mucoadhesive polymers, to achieve high contact between the systems and the gut mucosa to enhance the oral insulin bioavailability. SiNP were prepared by a modified Stöber method at room temperature via hydrolysis and condensation of tetraethyl orthosilicate (TEOS). Interaction between insulin and nanoparticles was assessed by differential scanning calorimetry (DSC), X-ray and Fourier-transform infrared (FTIR) studies. The high efficiency of nanoparticles' coating resulted in more stable system. FTIR spectra of insulin-loaded nanoparticles showed amide absorption bands which are characteristic of α-helix content. In general, all developed nanoparticles demonstrated high biocompatible, at the tested concentrations (50-500 μg/mL), revealing no or low toxicity in the two human cancer cell lines (HepG2 and Caco-2). In conclusion, the developed insulin-loaded SiNP surfaced with mucoadhesive polymers demonstrated its added value for oral administration of proteins. PMID:25466464

  15. Nanoparticle-enhanced surface plasmon resonance detection of proteins at attomolar concentrations: comparing different nanoparticle shapes and sizes.

    PubMed

    Kwon, Min Jeong; Lee, Jaeyoung; Wark, Alastair W; Lee, Hye Jin

    2012-02-01

    The application of biofunctionalized nanoparticles possessing various shapes and sizes for the enhanced surface plasmon resonance (SPR) detection of a protein biomarker at attomolar concentrations is described. Three different gold nanoparticle shapes (cubic cages, rods and quasi-spherical) with each possessing at least one dimension in the 40-50 nm range were systematically compared. Each nanoparticle (NP) was covalently functionalized with an antibody (anti-thrombin) and used as part of a sandwich assay in conjunction with a Au SPR chip modified with a DNA-aptamer probe specific to thrombin. The concentration of each NP-antibody conjugate solution was first optimized prior to establishing that the quasi-spherical nanoparticles resulted in the greatest enhancement in sensitivity with the detection of thrombin at concentrations as low as 1 aM. When nanorod and nanocage antibody conjugates were instead used, the minimum target concentrations detected were 10 aM (rods) and 1 fM (cages). This is a significant improvement (>10(3)) on previous NP-enhanced SPR studies utilizing smaller (~15 nm) gold NP conjugates and is attributed to the functionalization of both the NP and chip surfaces resulting in low nonspecific adsorption as well as a combination of density increases and plasmonic coupling inducing large shifts in the local refractive index at the chip surface upon nanoparticle adsorption. PMID:22224823

  16. Internal photoemission from plasmonic nanoparticles: comparison between surface and volume photoelectric effects.

    PubMed

    Uskov, Alexander V; Protsenko, Igor E; Ikhsanov, Renat S; Babicheva, Viktoriia E; Zhukovsky, Sergei V; Lavrinenko, Andrei V; O'Reilly, Eoin P; Xu, Hongxing

    2014-05-01

    We study the emission of photoelectrons from plasmonic nanoparticles into a surrounding matrix. We consider two mechanisms of electron emission from the nanoparticles--surface and volume ones--and use models for these two mechanisms which allow us to obtain analytical results for the photoelectron emission rate from a nanoparticle. Calculations have been carried out for a step potential at the surface of a spherical nanoparticle, and a simple model for the hot electron cooling has been used. We highlight the effect of the discontinuity of the dielectric permittivity at the nanoparticle boundary in the surface mechanism, which leads to a substantial (by ∼5 times) increase of the internal photoelectron emission rate from a nanoparticle compared to the case when such a discontinuity is absent. For a plasmonic nanoparticle, a comparison of the two photoeffect mechanisms was undertaken for the first time which showed that the surface photoeffect can in the general case be larger than the volume one, which agrees with the results obtained for a flat metal surface first formulated by Tamm and Schubin in their pioneering development of a quantum-mechanical theory of photoeffect in 1931. In accordance with our calculations, this possible predominance of the surface effect is based on two factors: (i) effective cooling of hot carriers during their propagation from the volume of the nanoparticle to its surface in the scenario of the volume mechanism and (ii) strengthening of the surface mechanism through the effect of the discontinuity of the dielectric permittivity at the nanoparticle boundary. The latter is stronger at relatively lower photon energies and correspondingly is more substantial for internal photoemission than for an external one. We show that in the general case, it is essential to take both mechanisms into account in the development of devices based on the photoelectric effect and when considering hot electron emission from a plasmonic nanoantenna. PMID

  17. Engineering plasmonic nanoparticles for surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Pinkhasova, Polina

    This dissertation focuses on the development of novel nanotags encapsulated in an intricate Au-Ag nanostructure that uniquely functions both as a reporter and ultra-sensitive substrate for surface-enhanced Raman scattering (SERS) measurements. Hollow Au-Ag alloy nanoshells with a porous wall were synthesized by galvanic replacement reaction, and were subsequently loaded with Raman-active label molecules. The open structure of the nanoshells was filled with Ag via citrate reduction, entrapping label molecules in the process. The resultant nanotags have been shown to be individually SERS-active for the entrapped label molecules and robust for SERS measurements of analytes. We have shown that the SERS intensity of the molecular beacon is insensitive to environmental variants such as an external analyte 1,2-Di-(4-pyridyl)ethylene (BPE) and can be reliably used as an internal reference for quantitative measurements. Theoretical quantum chemical calculations and experimental studies revealed that surface-adsorbed poly(vinyl pyrrolidone) (PVP) used during nanotag formation which provides steric hindrance to promote colloidal stability actually enables highly selective SERS detection of analytes of various types and surface charge with enhancement factors as high as 108, depending on pH. Fully characterized nanotags were immobilized in the cladding air channels of suspended core photonic crystal fiber (PCF) to assess critical parameters such as nanoparticle coverage density and fiber length, both of which play an important role in the competitive interplay between accumulative Raman signal gain and attenuation loss, in order for the development of optimal SERS-active PCF optofluidic platform. We show that in the region where accumulative Raman gain dominates, the length of PCF can be exploited for enhanced measurement sensitivity.

  18. Molecular Surface Chemistry by Metal Single Crystals and Nanoparticles from Vacuum to High Pressure.

    SciTech Connect

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-04-05

    Model systems for studying molecular surface chemistry have evolved from single crystal surfaces at low pressure to colloidal nanoparticles at high pressure. Low pressure surface structure studies of platinum single crystals using molecular beam surface scattering and low energy electron diffraction techniques probe the unique activity of defects, steps and kinks at the surface for dissociation reactions (H-H, C-H, C-C, O{double_bond}O bonds). High-pressure investigations of platinum single crystals using sum frequency generation vibrational spectroscopy have revealed the presence and the nature of reaction intermediates. High pressure scanning tunneling microscopy of platinum single crystal surfaces showed adsorbate mobility during a catalytic reaction. Nanoparticle systems are used to determine the role of metal-oxide interfaces, site blocking and the role of surface structures in reactive surface chemistry. The size, shape and composition of nanoparticles play important roles in determining reaction activity and selectivity.

  19. Nitrate Deposition to Surface Snow at Summit, Greenland, Following the 9 November 2000 Solar Proton Event

    NASA Technical Reports Server (NTRS)

    Duderstadt, Katharine A.; Dibb, Jack E.; Schwadron, Nathan A.; Spence, Harlan E.; Jackman, Charles Herbert; Randall, Cora E.; Solomon, Stanley C.; Mills, Michael J.

    2014-01-01

    This study considers whether spurious peaks in nitrate ions in snow sampled at Summit, Greenland from August 2000 to August 2002 are related to solar proton events. After identifying tropospheric sources of nitrate on the basis of correlations with sulfate, ammonium, sodium, and calcium, we use the three-dimensional global Whole Atmosphere Community Climate Model (WACCM) to examine unaccounted for nitrate spikes. Model calculations confirm that solar proton events significantly impact HOx, NOx, and O3 levels in the mesosphere and stratosphere during the weeks and months following the major 9 November 2000 solar proton event. However, SPE-enhanced NOy calculated within the atmospheric column is too small to account for the observed nitrate ion peaks in surface snow. Instead, our WACCM results suggest that nitrate spikes not readily accounted for by measurement correlations are likely of anthropogenic origin. These results, consistent with other recent studies, imply that nitrate spikes in ice cores are not suitable proxies for individual SPEs and motivate the need to identify alternative proxies.

  20. Accelerated CO2 transport on surface of AgO nanoparticles in ionic liquid BMIMBF4

    PubMed Central

    Ji, Dahye; Kang, Yong Soo; Kang, Sang Wook

    2015-01-01

    The AgO nanoparticles were utilized for a CO2 separation membrane. The AgO nanoparticles were successfully generated in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIMBF4) by favorable interaction between the surface of particles and the counteranion of BMIMBF4. The generated AgO nanoparticles were confirmed by TEM, and the average size was 20 nm. Coordinative interactions of dissociated AgO particles with BMIM+BF4− were investigated by FT-Raman spectroscopy. When the ionic liquid BMIMBF4 containing AgO nanoparticles was utilized as a CO2 separation membrane, the separation performance was largely enhanced. PMID:26549605

  1. Effects of surface functional groups on the formation of nanoparticle-protein corona

    PubMed Central

    Podila, R.; Chen, R.; Ke, P. C.; Brown, J. M.; Rao, A. M.

    2012-01-01

    Herein, we examined the dependence of protein adsorption on the nanoparticle surface in the presence of functional groups. Our UV-visible spectrophotometry, transmission electron microscopy, infrared spectroscopy, and dynamic light scattering measurements evidently suggested that the functional groups play an important role in the formation of nanoparticle-protein corona. We found that uncoated and surfactant-free silver nanoparticles derived from a laser ablation process promoted a maximum protein (bovine serum albumin) coating due to increased changes in entropy. On the other hand, bovine serum albumin displayed a relatively lower affinity for electrostatically stabilized nanoparticles due to the constrained entropy changes. PMID:23341687

  2. Refractive index measurement of nanoparticles by immersion refractometry based on a surface plasmon resonance sensor

    NASA Astrophysics Data System (ADS)

    Kano, Hiroshi; Iseda, Ayumu; Ohenoja, Katja; Niskanen, Ilpo

    2016-06-01

    Accurate determination of the refractive index of nanoparticles has important ramifications for applications, such as pharmaceuticals, cosmetics, paints, textiles, and inks. We describe a new method to determine the refractive index of nanoparticles by immersion refractometry with a surface plasmon resonance sensor. With this method, the refractive index of the nanoparticles is perfectly matched with that of the surrounding liquid. We demonstrate this method for calcium fluoride nanoparticles that have an average diameter of 100 nm; the results achieve an accuracy of better than 0.002 refractive index units.

  3. Self-assembly of nanoparticles on the surface of ionic crystals: Structural properties

    NASA Astrophysics Data System (ADS)

    Nikolic, K.; Murugesan, M.; Forshaw, M.; Cunningham, D.; Martinez-Albertos, J.-L.; Moore, B. D.

    2007-07-01

    With a suitable combination of ligand-stabilised nanoparticle suspension and ionic salt solutions, it is possible to produce microcrystals that are coated with nanoparticles. The self-assembly process of coating microcrystals by gold nanoparticles (NP) is mediated by the crystal lattice. This is the so-called CLAMS process - a generic process for self-organisation of nanoparticles on the surface of crystals [M. Murugeshan, D. Cunningham, J.-L. Martnez-Albertos, R. Vrcelj, B.D. Moore, Chem. Commun. (2005) 2677]. We are exploring here the structural properties of these self-assembled structures by using different imaging techniques.

  4. Surface chemistry : a non-negligible parameter in determining optical properties of small colloidal metal nanoparticles.

    SciTech Connect

    Sun, Y.; Gray, S. K.; Peng, S.

    2011-01-01

    Surface chemistry can become pronounced in determining the optical properties of colloidal metal nanoparticles as the nanoparticles become so small (diameters <20 nm) that the surface atoms, which can undergo chemical interactions with the environment, represent a significant fraction of the total number of atoms although this effect is often ignored. For instance, formation of chemical bonds between surface atoms of small metal nanoparticles and capping molecules that help stabilize the nanoparticles can reduce the density of conduction band electrons in the surface layer of metal atoms. This reduced electron density consequently influences the frequency-dependent dielectric constant of the metal atoms in the surface layer and, for sufficiently high surface to volume ratios, the overall surface plasmon resonance (SPR) absorption spectrum. The important role of surface chemistry is highlighted here by carefully analyzing the classical Mie theory and a multi-layer model is presented to produce more accurate predictions by considering the chemically reduced density of conduction band electrons in the outer shell of metal atoms in nanoparticles. Calculated absorption spectra of small Ag nanoparticles quantitatively agree with the experimental results for our monodispersed Ag nanoparticles synthesized via a well-defined chemical reduction process, revealing an exceptional size-dependence of absorption peak positions: the peaks first blue-shift followed by a turnover and a dramatic red-shift as the particle size decreases. A comprehensive understanding of the relationship between surface chemistry and optical properties is beneficial to exploit new applications of small colloidal metal nanoparticles, such as colorimetric sensing, electrochromic devices, and surface enhanced spectroscopies.

  5. The Ligand Shell as an Energy Barrier in Surface Reactions on Transition Metal Nanoparticles.

    PubMed

    Smith, Jeremy G; Jain, Prashant K

    2016-06-01

    Transition metal nanoparticles, including those employed in catalytic, electrocatalytic, and photocatalytic conversions, have surfaces that are typically coated with a layer of short or long-chain ligands. There is little systematic understanding of how much this ligand layer affects the reactivity of the underlying surface. We show for Ag nanoparticles that a surface-adsorbed thiol layer greatly impedes the kinetics of an ionic chemical reaction taking place on the Ag surface. The model reaction studied is the galvanic exchange of Ag with Au(3+) ions, the kinetics of which is measured on individual thiol-coated nanoparticles using in situ optical scattering spectroscopy. We observe a systematic lowering of the reactivity of the nanoparticle as the chain length of the thiol is increased, from which we deduce that the ligand layer serves as an energy barrier to the transport of incoming/outgoing reactive ions. This barrier effect can be decreased by light irradiation, resulting from weakened binding of the thiol layer to the metal surface. We find that the influence of the surface ligand layer on reactivity is much stronger than factors such as nanoparticle size, shape, or crystallinity. These findings provide improved understanding of the role of ligand or adsorbates in colloidal catalysis and photocatalysis and have important implications for the transport of reactants and ions to surfaces and for engineering the reactivity of nanoparticles using surface passivation. PMID:27152595

  6. Tuning surface hydrophilicity/hydrophobicity of hydrocarbon proton exchange membranes (PEMs).

    PubMed

    He, Chenfeng; Mighri, Frej; Guiver, Michael D; Kaliaguine, Serge

    2016-03-15

    The effect of annealing on the surface hydrophilicity of various representative classes of hydrocarbon-based proton exchange membranes (PEMs) is investigated. In all cases, a more hydrophilic membrane surface develops after annealing at elevated temperatures. The annealing time also had some influence, but in different ways depending on the class of PEM. Longer annealing times resulted in more hydrophilic membrane surfaces for copolymerized sulfonated poly(ether ether ketone) (SPEEK-HQ), while the opposite behavior occurred in sulfonated poly(aryl ether ether ketone) (Ph-SPEEK), sulfonated poly(aryl ether ether ketone ketone) (Ph-m-SPEEKK) and sulfonated poly (aryl ether ether nitrile) (SPAEEN-B). Increased surface hydrophilicity upon annealing results from ionic cluster decomposition, according to the "Eisenberg-Hird-Moore model" (EHM). The increased surface hydrophilicity is supported by contact angle (CA) measurements, and the cluster decomposition is auxiliarily supported by probing the level of atomic sulfur (sulfonic acid) within different surface depths using angle-dependent XPS as well as ATR-FTIR. Membrane acidification leads to more hydrophilic surfaces by elimination of the hydrogen bonding that occurs between strongly-bound residual solvent (dimethylacetamide, DMAc) and PEM sulfonic acid groups. The study of physicochemical tuning of surface hydrophilicity/hydrophobicity of PEMs by annealing and acidification provides insights for improving membrane electrode assembly (MEA) fabrication in fuel cell (FC). PMID:26722798

  7. Synthesis, Magnetic Properties, Map Images, and Water Proton Relaxivities of D-Glucuronic Acid Coated Ln2O3 Nanoparticles (Ln = Ho and Er).

    PubMed

    Kattel, Krishna; Kim, Cho Rong; Xu, Wenlong; Kim, Tae Jeong; Park, Jang Woo; Chang, Yongmin; Lee, Gang Ho

    2015-09-01

    T2 MRI contrast agents cannot be synthesized by using molecules but nanoparticles because appreciable magnetic moments at room temperature are needed. Recently, some of lanthanide (Ln) oxide nanoparticles have shown decent magnetic moments at room temperature and even at ultrasmall particle diameters. In this study, we explored D-glucuronic acid coated Ln2O3 nanoparticles (Ln = Ho and Er) with ultrasmall particle diameters. They showed decent magnetic moments at room temperature and as a result, appreciable transverse water proton relaxivities (r2s) at 1.5 tesla MR field. Clear dose-dependent contrast enhancements in R2 map images were observed in both samples. These results showed that D-glucuronic acid coated Ln2O3 nanoparticles (Ln = Ho and Er) would be potential T2 MRI contrast agents at high MR fields. PMID:26716328

  8. Surface charge of gold nanoparticles mediates mechanism of toxicity

    NASA Astrophysics Data System (ADS)

    Schaeublin, Nicole M.; Braydich-Stolle, Laura K.; Schrand, Amanda M.; Miller, John M.; Hutchison, Jim; Schlager, John J.; Hussain, Saber M.

    2011-02-01

    Recently gold nanoparticles (Au NPs) have shown promising biological and military applications due to their unique electronic and optical properties. However, little is known about their biocompatibility in the event that they come into contact with a biological system. In the present study, we have investigated whether modulating the surface charge of 1.5 nm Au NPs induced changes in cellular morphology, mitochondrial function, mitochondrial membrane potential (MMP), intracellular calcium levels, DNA damage-related gene expression, and of p53 and caspase-3 expression levels after exposure in a human keratinocyte cell line (HaCaT). The evaluation of three different Au NPs (positively charged, neutral, and negatively charged) showed that cell morphology was disrupted by all three NPs and that they demonstrated a dose-dependent toxicity; the charged Au NPs displayed toxicity as low as 10 µg ml-1 and the neutral at 25 µg ml-1. Furthermore, there was significant mitochondrial stress (decreases in MMP and intracellular Ca2+ levels) following exposure to the charged Au NPs, but not the neutral Au NPs. In addition to the differences observed in the MMP and Ca2+ levels, up or down regulation of DNA damage related gene expression suggested a differential cell death mechanism based on whether or not the Au NPs were charged or neutral. Additionally, increased nuclear localization of p53 and caspase-3 expression was observed in cells exposed to the charged Au NPs, while the neutral Au NPs caused an increase in both nuclear and cytoplasmic p53 expression. In conclusion, these results indicate that surface charge is a major determinant of how Au NPs impact cellular processes, with the charged NPs inducing cell death through apoptosis and neutral NPs leading to necrosis.Recently gold nanoparticles (Au NPs) have shown promising biological and military applications due to their unique electronic and optical properties. However, little is known about their biocompatibility in the

  9. The thermodynamics of proton hydration and the electrochemical surface potential of water

    SciTech Connect

    Pollard, Travis P.; Beck, Thomas L.

    2014-11-14

    The free energy change for transferring a single ion across the water liquid/vapor interface includes an electrochemical surface potential contribution. Since this potential is not directly accessible to thermodynamic measurement, several extra-thermodynamic approaches have been employed to infer its sign and magnitude, with a resulting wide spread of values. Here, we examine further the thermodynamics of proton hydration and the electrochemical surface potential of water along three directions: (1) a basic relation of interfacial electrostatics and experimental results on ion distributions near a water/organic interface are employed to infer a solvent contribution to the electrochemical surface potential, (2) a re-analysis is performed of the existing bulk and cluster ion hydration data, and (3) extensive computational modeling is conducted to examine the size dependence of hydration enthalpy differences for the NaF ion pair between the small cluster and the converged bulk limits. The computational studies include classical polarizable models and high-level quantum chemical methods. The new theoretical analysis of existing experimental data and the combined classical/quantum modeling lead to results consistent with our previously derived proton hydration quantities.

  10. Aluminum Nitride Hydrolysis Enabled by Hydroxyl-Mediated Surface Proton Hopping.

    PubMed

    Bartel, Christopher J; Muhich, Christopher L; Weimer, Alan W; Musgrave, Charles B

    2016-07-20

    Aluminum nitride (AlN) is used extensively in the semiconductor industry as a high-thermal-conductivity insulator, but its manufacture is encumbered by a tendency to degrade in the presence of water. The propensity for AlN to hydrolyze has led to its consideration as a redox material for solar thermochemical ammonia (NH3) synthesis applications where AlN would be intentionally hydrolyzed to produce NH3 and aluminum oxide (Al2O3), which could be subsequently reduced in nitrogen (N2) to reform AlN and reinitiate the NH3 synthesis cycle. No quantitative, atomistic mechanism by which AlN, and more generally, metal nitrides react with water to become oxidized and generate NH3 yet exists. In this work, we used density-functional theory (DFT) to examine the reaction mechanisms of the initial stages of AlN hydrolysis, which include: water adsorption, hydroxyl-mediated proton diffusion to form NH3, and NH3 desorption. We found activation barriers (Ea) for hydrolysis of 330 and 359 kJ/mol for the cases of minimal adsorbed water and additional adsorbed water, respectively, corroborating the high observed temperatures for the onset of steam AlN hydrolysis. We predict AlN hydrolysis to be kinetically limited by the dissociation of strong Al-N bonds required to accumulate protons on surface N atoms to form NH3. The hydrolysis mechanism we elucidate is enabled by the diffusion of protons across the AlN surface by a hydroxyl-mediated Grotthuss mechanism. A comparison between intrinsic (Ea = 331 kJ/mol) and mediated proton diffusion (Ea = 89 kJ/mol) shows that hydroxyl-mediated proton diffusion is the predominant mechanism in AlN hydrolysis. The large activation barrier for NH3 generation from AlN (Ea = 330 or 359 kJ/mol, depending on water coverage) suggests that in the design of materials for solar thermochemical ammonia synthesis, emphasis should be placed on metal nitrides with less covalent metal-nitrogen bonds and, thus, more-facile NH3 liberation. PMID:27341277

  11. Protons migrate along interfacial water without significant contributions from jumps between ionizable groups on the membrane surface

    PubMed Central

    Springer, Andreas; Hagen, Volker; Cherepanov, Dmitry A.; Antonenko, Yuri N.; Pohl, Peter

    2011-01-01

    Proton diffusion along membrane surfaces is thought to be essential for many cellular processes such as energy transduction. Commonly, it is treated as a succession of jumps between membrane-anchored proton-binding sites. Our experiments provide evidence for an alternative model. We released membrane-bound caged protons by UV flashes and monitored their arrival at distant sites by fluorescence measurements. The kinetics of the arrival is probed as a function of distance for different membranes and for different water isotopes. We found that proton diffusion along the membrane is fast even in the absence of ionizable groups in the membrane, and it decreases strongly in D2O as compared to H2O. We conclude that the fast proton transport along the membrane is dominated by diffusion via interfacial water, and not via ionizable lipid moieties. PMID:21859952

  12. Protons migrate along interfacial water without significant contributions from jumps between ionizable groups on the membrane surface.

    PubMed

    Springer, Andreas; Hagen, Volker; Cherepanov, Dmitry A; Antonenko, Yuri N; Pohl, Peter

    2011-08-30

    Proton diffusion along membrane surfaces is thought to be essential for many cellular processes such as energy transduction. Commonly, it is treated as a succession of jumps between membrane-anchored proton-binding sites. Our experiments provide evidence for an alternative model. We released membrane-bound caged protons by UV flashes and monitored their arrival at distant sites by fluorescence measurements. The kinetics of the arrival is probed as a function of distance for different membranes and for different water isotopes. We found that proton diffusion along the membrane is fast even in the absence of ionizable groups in the membrane, and it decreases strongly in D(2)O as compared to H(2)O. We conclude that the fast proton transport along the membrane is dominated by diffusion via interfacial water, and not via ionizable lipid moieties. PMID:21859952

  13. Surface functionalization of silica-coated magnetic nanoparticles for covalent attachment of cholesterol oxidase

    NASA Astrophysics Data System (ADS)

    Šulek, Franja; Drofenik, Miha; Habulin, Maja; Knez, Željko

    2010-01-01

    A systematic approach towards the fabrication of highly functionalized silica shell magnetic nanoparticles, presently used for enzyme immobilization, is herein fully presented. The synthesis of bare maghemite (γ-Fe 2O 3) nanoparticles was accomplished by thermal co-precipitation of iron ions in ammonia alkaline solution at harsh reaction conditions, respectively. Primary surface engineering of maghemite nanoparticles was successfully performed by the proper deposition of silica onto nanoparticles surface under strictly regulated reaction conditions. Next, the secondary surface functionalization of the particles was achieved by coating the particles with organosilane followed by glutaraldehyde activation in order to enhance protein immobilization. Covalent immobilization of cholesterol oxidase was attempted afterwards. The structural and magnetic properties of magnetic silica nanocomposites were characterized by TEM and vibrating sample magnetometer (VSM) instruments. X-ray diffraction measurements confirmed the spinel structure and average size of uncoated maghemite nanoparticles to be around 20 nm in diameter. SEM-EDS spectra indicated a strong signal for Si, implying the coating procedure of silica onto the particles surface to be successfully accomplished. Fourier transform infrared (FT-IR) spectra analysis confirmed the binding of amino silane molecules onto the surface of the maghemite nanoparticles mediated Si-O-Si chemical bonds. Compared to the free enzyme, the covalently bound cholesterol oxidase retained 50% of its activity. Binding of enzyme onto chemically modified magnetic nanoparticles via glutaraldehyde activation is a promising method for developing biosensing components in biomedicine.

  14. Surface Structures of Cubo-octahedral Pt-Mo Catalyst Nanoparticles from Monte Carlo Simulations

    SciTech Connect

    Wang, Guofeng; Van Hove, M.A.; Ross, P.N.; Baskes, M.I.

    2005-03-31

    The surface structures of cubo-octahedral Pt-Mo nanoparticles have been investigated using the Monte Carlo method and modified embedded atom method potentials that we developed for Pt-Mo alloys. The cubo-octahedral Pt-Mo nanoparticles are constructed with disordered fcc configurations, with sizes from 2.5 to 5.0 nm, and with Pt concentrations from 60 to 90 at. percent. The equilibrium Pt-Mo nanoparticle configurations were generated through Monte Carlo simulations allowing both atomic displacements and element exchanges at 600 K. We predict that the Pt atoms weakly segregate to the surfaces of such nanoparticles. The Pt concentrations in the surface are calculated to be 5 to 14 at. percent higher than the Pt concentrations of the nanoparticles. Moreover, the Pt atoms preferentially segregate to the facet sites of the surface, while the Pt and Mo atoms tend to alternate along the edges and vertices of these nanoparticles. We found that decreasing the size or increasing the Pt concentration leads to higher Pt concentrations but fewer Pt-Mo pairs in the Pt-Mo nanoparticle surfaces.

  15. Retention of in-situ surface modified silica nanoparticles for carbon dioxide foam stabilization in sandpack

    NASA Astrophysics Data System (ADS)

    Adil, Muhammad

    2014-10-01

    Nanoparticle-stabilized CO2 foams have been used for mobility control for CO2 flooding; however, raw nanosilica particles which are hydrophilic in nature tend to develop unstable CO2 foam under certain reservoir conditions. The unstable foam leads to particles aggregation resulting in complete retention while propagating in a long distance, deep into the reservoir. This can be avoided by the application of a particular coating of a specific surfactant, polymer or their combination to the surface of the nanoparticles. The in-situ surface activation of unmodified SiO2 nanoparticles by interaction with mixed surfactant (TX100:SDBS) in aqueous media has been studied with extensive experiments using variable volumetric ratios. The retention of in-situ surface-modified nanoparticles was evaluated by the injection of the dispersion of nanoparticles through a sandpack. The loading of nanoparticles in dispersion was ranging from concentrated (5 wt %) to dilute (0.1 wt %). Effluent nanoparticles concentration histories were measured to determine the retained particles in the sandpack. Little retention (< 10% of particles injected over two pore volumes) was attained for 0.5% SiO2 and volumetric ratio of 2:1 (TX100:SDBS). These results were concluded in terms of surface charges, adsorption isotherm, surface adsorption, and DLVO theory between particles and rock.

  16. nanoparticles

    NASA Astrophysics Data System (ADS)

    Andreu-Cabedo, Patricia; Mondragon, Rosa; Hernandez, Leonor; Martinez-Cuenca, Raul; Cabedo, Luis; Julia, J. Enrique

    2014-10-01

    Thermal energy storage (TES) is extremely important in concentrated solar power (CSP) plants since it represents the main difference and advantage of CSP plants with respect to other renewable energy sources such as wind, photovoltaic, etc. CSP represents a low-carbon emission renewable source of energy, and TES allows CSP plants to have energy availability and dispatchability using available industrial technologies. Molten salts are used in CSP plants as a TES material because of their high operational temperature and stability of up to 500°C. Their main drawbacks are their relative poor thermal properties and energy storage density. A simple cost-effective way to improve thermal properties of fluids is to dope them with nanoparticles, thus obtaining the so-called salt-based nanofluids. In this work, solar salt used in CSP plants (60% NaNO3 + 40% KNO3) was doped with silica nanoparticles at different solid mass concentrations (from 0.5% to 2%). Specific heat was measured by means of differential scanning calorimetry (DSC). A maximum increase of 25.03% was found at an optimal concentration of 1 wt.% of nanoparticles. The size distribution of nanoparticle clusters present in the salt at each concentration was evaluated by means of scanning electron microscopy (SEM) and image processing, as well as by means of dynamic light scattering (DLS). The cluster size and the specific surface available depended on the solid content, and a relationship between the specific heat increment and the available particle surface area was obtained. It was proved that the mechanism involved in the specific heat increment is based on a surface phenomenon. Stability of samples was tested for several thermal cycles and thermogravimetric analysis at high temperature was carried out, the samples being stable.

  17. Dual surface plasmon resonances in Ni nanoparticles in silica

    SciTech Connect

    Majhi, Jayanta K.; Kuiri, Probodh K.

    2015-06-24

    We report the observations of two broad absorption bands (at ∼3.5 and ∼6.0 eV) in the optical absorption (OA) spectra of Ni nanoparticles (NPs) in silica. For the calculations of the OA spectra, Maxwell-Garnett type effective medium theory has been used with NP radii in the range of 1 – 50 nm. The peak positions of both the OA bands have been found to shift towards higher energy (blue-shift) with decrease in NP radius. In addition, the OA spectra are found to more sensitive for smaller NPs as compare to larger NPs. These observations are argued as due to the confinement of the mean free path of free electrons in Ni NPs. Based on this, we conclude that the observed OA bands are due to the surface plasmon resonance (SPR) absorptions irrespective of the satisfaction of the criteria of the SPR conditions, thus resolving the unclear understanding of the appearance of two absorption bands in Ni NPs.

  18. Surface Plasmon-Driven Water Reduction: Gold Nanoparticle Size Matters

    SciTech Connect

    Qian, Kun; Sweeny, Brendan C.; Johnston-Peck, Aaron C.; Niu, Wenxin; Graham, Jeremy O.; DuChene, Joseph S.; Qiu, Jingjing; Wang, Yi-Chung; Engelhard, Mark H.; Su, Dong; Stach, Eric A.; Wei, Wei

    2014-07-16

    Water reduction under two visible light ranges (λ > 400 and λ > 435 nm) was investigated using gold-loaded titanium dioxide (Au-TiO2) with different sizes of Au nanoparticles (NPs). Two different mechanisms have been determined to clarify the specific role of Au NPs in visible light-induced photocatalytic reactions. Our study provides solid evidences showing that Au NPs sizes are essential for the surface plasmon-driven water reduction under λ > 435 nm. More specifically, we have demonstrated that the Au NPs sizes are vital for the SPR mediated electron transfer efficiency and play a critical role in determining the reduction potential of the transferred electrons in the TiO2 conduction band (CB) and their following activities. Our discovery provides a facile way to manipulate the reduction potential of transferred electrons by simply varying the Au NPs sizes, which will greatly facilitate the design of suitable plasmonic photocatalysts for water reduction and other valuable solar-to-fuel reactions.

  19. Enzyme sensitive, surface engineered nanoparticles for enhanced delivery of camptothecin.

    PubMed

    Yu, Hongliang; Chen, Jiao; Liu, Sen; Lu, Qian; He, Jian; Zhou, Zhengyang; Hu, Yong

    2015-10-28

    To achieve a drug delivery system combining the programmable long circulation and targeting ability, surface engineering nanoparticles (NPs), having a sandwich structure consisting of a long circulating outmost layer, a targeting middle layer and a hydrophobic innermost core were constructed by mixing a matrix metalloproteinase MMP2 and MMP9-sensitive copolymers (mPEG-Pep-PCL) and folate receptor targeted copolymers (FA-PEG-PCL). Their physiochemical traits including morphology, particle size, drug loading content, and in vitro release profiles were studied. In vitro studies validated that the inhibition efficiency of tumor cells was effectively correlated with NP concentrations. Furthermore, The PEG layer would detach from the NPs due to the up-regulated extracellular MMP2 and MMP9 in tumors, resulting in the exposure of folate to enhance the cellular internalization via folate receptor mediated endocytosis, which accelerated the release rate of CPT in vivo. The antitumor efficacy, tumor targeting ability and bio-distribution of the NPs were examined in a B16 melanoma cells xenograft mouse model. These NPs showed improved tumor target ability and enhanced aggregation of camptothecin (CPT) in tumor site and prominent suppression of tumor growth. Thus this mPEG-Pep-PCL@FA-PEG-PCL core-shell structure NP could be a better candidate for the tumor specific delivery of hydrophobic drug. PMID:26282096

  20. Surface-Directed Synthesis of Erbium-Doped Yttrium Oxide Nanoparticles within Organosilane Zeptoliter Containers

    PubMed Central

    2015-01-01

    We introduce an approach to synthesize rare earth oxide nanoparticles using high temperature without aggregation of the nanoparticles. The dispersity of the nanoparticles is controlled at the nanoscale by using small organosilane molds as reaction containers. Zeptoliter reaction vessels prepared from organosilane self-assembled monolayers (SAMs) were used for the surface-directed synthesis of rare earth oxide (REO) nanoparticles. Nanopores of octadecyltrichlorosilane were prepared on Si(111) using particle lithography with immersion steps. The nanopores were filled with a precursor solution of erbium and yttrium salts to confine the crystallization step to occur within individual zeptoliter-sized organosilane reaction vessels. Areas between the nanopores were separated by a matrix film of octadecyltrichlorosilane. With heating, the organosilane template was removed by calcination to generate a surface array of erbium-doped yttria nanoparticles. Nanoparticles synthesized by the surface-directed approach retain the periodic arrangement of the nanopores formed from mesoparticle masks. While bulk rare earth oxides can be readily prepared by solid state methods at high temperature (>900 °C), approaches for preparing REO nanoparticles are limited. Conventional wet chemistry methods are limited to low temperatures according to the boiling points of the solvents used for synthesis. To achieve crystallinity of REO nanoparticles requires steps for high-temperature processing of samples, which can cause self-aggregation and dispersity in sample diameters. The facile steps for particle lithography address the problems of aggregation and the requirement for high-temperature synthesis. PMID:25163977

  1. Surface-directed synthesis of erbium-doped yttrium oxide nanoparticles within organosilane zeptoliter containers.

    PubMed

    Englade-Franklin, Lauren E; Morrison, Gregory; Verberne-Sutton, Susan D; Francis, Asenath L; Chan, Julia Y; Garno, Jayne C

    2014-09-24

    We introduce an approach to synthesize rare earth oxide nanoparticles using high temperature without aggregation of the nanoparticles. The dispersity of the nanoparticles is controlled at the nanoscale by using small organosilane molds as reaction containers. Zeptoliter reaction vessels prepared from organosilane self-assembled monolayers (SAMs) were used for the surface-directed synthesis of rare earth oxide (REO) nanoparticles. Nanopores of octadecyltrichlorosilane were prepared on Si(111) using particle lithography with immersion steps. The nanopores were filled with a precursor solution of erbium and yttrium salts to confine the crystallization step to occur within individual zeptoliter-sized organosilane reaction vessels. Areas between the nanopores were separated by a matrix film of octadecyltrichlorosilane. With heating, the organosilane template was removed by calcination to generate a surface array of erbium-doped yttria nanoparticles. Nanoparticles synthesized by the surface-directed approach retain the periodic arrangement of the nanopores formed from mesoparticle masks. While bulk rare earth oxides can be readily prepared by solid state methods at high temperature (>900 °C), approaches for preparing REO nanoparticles are limited. Conventional wet chemistry methods are limited to low temperatures according to the boiling points of the solvents used for synthesis. To achieve crystallinity of REO nanoparticles requires steps for high-temperature processing of samples, which can cause self-aggregation and dispersity in sample diameters. The facile steps for particle lithography address the problems of aggregation and the requirement for high-temperature synthesis. PMID:25163977

  2. Surface functionalization of thin-film composite membranes with copper nanoparticles for antimicrobial surface properties.

    PubMed

    Ben-Sasson, Moshe; Zodrow, Katherine R; Genggeng, Qi; Kang, Yan; Giannelis, Emmanuel P; Elimelech, Menachem

    2014-01-01

    Biofouling is a major operational challenge in reverse osmosis (RO) desalination, motivating a search for improved biofouling control strategies. Copper, long known for its antibacterial activity and relatively low cost, is an attractive potential biocidal agent. In this paper, we present a method for loading copper nanoparticles (Cu-NPs) on the surface of a thin-film composite (TFC) polyamide RO membrane. Cu-NPs were synthesized using polyethyleneimine (PEI) as a capping agent, resulting in particles with an average radius of 34 nm and a copper content between 39 and 49 wt.%. The positive charge of the Cu-NPs imparted by the PEI allowed a simple electrostatic functionalization of the negatively charged RO membrane. We confirmed functionalization and irreversible binding of the Cu-NPs to the membrane surface with SEM and XPS after exposing the membrane to bath sonication. We also demonstrated that Cu-NP functionalization can be repeated after the Cu-NPs dissolve from the membrane surface. The Cu-NP functionalization had minimal impact on the intrinsic membrane transport parameters. Surface hydrophilicity and surface roughness were also maintained, and the membrane surface charge became positive after functionalization. The functionalized membrane exhibited significant antibacterial activity, leading to an 80-95% reduction in the number of attached live bacteria for three different model bacterial strains. Challenges associated with this functionalization method and its implementation in RO desalination are discussed. PMID:24308843

  3. Surface Engineering of Core/Shell Iron/Iron Oxide Nanoparticles from Microemulsions for Hyperthermia

    PubMed Central

    Zhang, Guandong; Liao, Yifeng; Baker, Ian

    2011-01-01

    This paper describes the synthesis and surface engineering of core/shell-type iron/iron oxide nanoparticles for magnetic hyperthermia cancer therapy. Iron/iron oxide nanoparticles were synthesized from microemulsions of NaBH4 and FeCl3, followed by surface modification in which a thin hydrophobic hexamethyldisilazane layer - used to protect the iron core - replaced the CTAB coating on the particles. Phosphatidylcholine was then assembled on the nanoparticle surface. The resulting nanocomposite particles have a biocompatible surface and show good stability in both air and aqueous solution. Compared to iron oxide nanoparticles, the nanocomposites show much better heating in an alternating magnetic field. They are good candidates for both hyperthermia and magnetic resonance imaging applications. PMID:21833157

  4. Synthesis of polydopamine at the femtoliter scale and confined fabrication of Ag nanoparticles on surfaces.

    PubMed

    Guardingo, M; Esplandiu, M J; Ruiz-Molina, D

    2014-10-25

    Nanoscale polydopamine motifs are fabricated on surfaces by deposition of precursor femtolitre droplets using an AFM tip and employed as confined reactors to fabricate Ag nanoparticle patterns by in situ reduction of a Ag(+) salt. PMID:25195667

  5. Air stable colloidal copper nanoparticles: Synthesis, characterization and their surface-enhanced Raman scattering properties

    NASA Astrophysics Data System (ADS)

    Ramani, Thekkathu; Leon Prasanth, K.; Sreedhar, Bojja

    2016-03-01

    Air stable colloidal copper nanoparticles are synthesized by a simple chemical reduction method using octadecylsilane as a reducing agent and octadecylamine as a stabilizing agent in toluene without any inert gas. The formation of nanosized copper was confirmed by its characteristic surface plasmon absorption peaks in UV-visible spectra. The transmission electron microscopic (TEM) images show that the resulting copper nanoparticles are distributed uniformly with a narrow size distribution. The X-ray diffraction (XRD) demonstrated that the obtained copper nanoparticles are single crystalline nanoparticles. Fourier transform infra-red (FT-IR) spectroscopic data suggested that the silane Si-H is responsible for the reduction of copper ions. And also the resulting colloidal copper nanoparticles exhibit large surface-enhanced Raman scattering (SERS) signals.

  6. Highly stable gelatin layer-protected gold nanoparticles as surface-enhanced Raman scattering substrates.

    PubMed

    Lee, Changwon; Zhang, Peng

    2014-06-01

    Amine and carboxylic groups rich gelatin was used as reducing and stabilizing agent to form highly stable gold nanoparticles for surface-enhanced Raman scattering (SERS) applications. The size of the particle was determined to be 13 nm by TEM with mono-dispersity. The size of the gold nanoparticles was little affected by the initial gelatin concentration. The gelatin-gold nanoparticles show strong SERS activity with Rhodamine 6G and Ruthenium bipyridine as reporter molecules. Both carboxylic acid groups and amine groups were identified by FT-IR to be present on the gelatin-gold nanoparticle surface, providing the possibility of further conjugation with other molecules. The gelatin-protected gold nanoparticles prepared by this simple, green, method displayed very good solubility and stability in many solvents, and good monodispersity, all desirable features as good SERS substrates. PMID:24738391

  7. High-performance heterogeneous catalysis with surface-exposed stable metal nanoparticles

    PubMed Central

    Huang, Ning; Xu, Yanhong; Jiang, Donglin

    2014-01-01

    Protection of metal nanoparticles from agglomeration is critical for their functions and applications. The conventional method for enhancing their stability is to cover them with passivation layers to prevent direct contact. However, the presence of a protective shell blocks exposure of the metal species to reactants, thereby significantly impeding the nanoparticles' utility as catalysts. Here, we report that metal nanoparticles can be prepared and used in a surface-exposed state that renders them inherently catalytically active. This strategy is realised by spatial confinement and electronic stabilisation with a dual-module mesoporous and microporous three-dimensional π-network in which surface-exposed nanoparticles are crystallised upon in situ reduction. The uncovered palladium nanoparticles serve as heterogeneous catalysts that are exceptionally active in water, catalyse unreactive aryl chlorides for straightforward carbon–carbon bond formation and are stable for repeated use in various types of cross couplings. Therefore, our results open new perspectives in developing practical heterogeneous catalysts. PMID:25427425

  8. Dynamics of Protonated Peptide Ion Collisions with Organic Surfaces: Consonance of Simulation and Experiment.

    PubMed

    Pratihar, Subha; Barnes, George L; Laskin, Julia; Hase, William L

    2016-08-18

    In this Perspective, mass spectrometry experiments and chemical dynamics simulations are described that have explored the atomistic dynamics of protonated peptide ions, peptide-H(+), colliding with organic surfaces. These studies have investigated the energy transfer and fragmentation dynamics for peptide-H(+) surface-induced dissociation (SID), peptide-H(+) physisorption on the surface, soft landing (SL), and peptide-H(+) reaction with the surface, reactive landing (RL). SID provides primary structures of biological ions and information regarding their fragmentation pathways and energetics. Two SID mechanisms are found for peptide-H(+) fragmentation. A traditional mechanism in which peptide-H(+) is vibrationally excited by its collision with the surface, rebounds off the surface and then dissociates in accord with the statistical, RRKM unimolecular rate theory. The other, shattering, is a nonstatistical mechanism in which peptide-H(+) fragments as it collides with the surface, dissociating via many pathways and forming many product ions. Shattering is important for collisions with diamond and perfluorinated self-assembled monolayer (F-SAM) surfaces, increasing in importance with the peptide-H(+) collision energy. Chemical dynamics simulations also provide important mechanistic insights on SL and RL of biological ions on surfaces. The simulations indicate that SL occurs via multiple mechanisms consisting of sequences of peptide-H(+) physisorption on and penetration in the surface. SL and RL have a broad range of important applications including preparation of protein or peptide microarrays, development of biocompatible substrates and biosensors, and preparation of novel synthetic materials, including nanomaterials. An important RL mechanism is intact deposition of peptide-H(+) on the surface. PMID:27467857

  9. Surface-enhanced Raman scattering enhancement factor distribution for nanoparticles of arbitrary shapes using surface integral equation method

    NASA Astrophysics Data System (ADS)

    Ying Huang, Shao; Wu, Bae-Ian; Foong, Shaohui

    2013-01-01

    Poggio-Miller-Chang-Harrington-Wu-Tsai (PMCHWT) surface integral equation method is applied for the first time to accurately estimate the surface-enhanced Raman scattering (SERS) enhancement factor distribution for arbitrary nanoparticles and nano-aggregates. It is the first time in literature that the distributions of SERS enhancement factors of nanoparticles of a large variety are reported. It is shown that not every SERS substrate exhibits a long-tail distribution as a dimer consisting of two spheres in close proximity. Generic methods are proposed to evaluate the performance of nanoparticles on SERS substrates. A cumulative distribution is proposed to examine the contributions of hot and warm spots around the nanoparticles. It is used to identify the importance of warm spots on a SERS substrate. A parameter q is proposed to describe the likelihood of a randomly positioned molecule that can be activated. This study provides guidance and insights for the optimization of SERS substrate fabrication techniques.

  10. Study of proton acceleration at the target front surface in laser-solid interactions by neutron spectroscopy

    SciTech Connect

    Youssef, A.; Kodama, R.; Tampo, M.

    2006-03-15

    Proton acceleration inside solid LiF and CH-LiF targets irradiated by a 450-fs, 20-J, 1053-nm laser at an intensity of 3x10{sup 18} W/cm{sup 2} has been studied via neutron spectroscopy. Neutron spectra produced through the {sup 7}Li(p,n){sup 7}Be reaction that occurs between accelerated protons, at the front surface, and background {sup 7}Li ions inside the target. From measured and calculated spectra, by three-dimensional Monte Carlo code, the maximum energy, total number, and slope temperature of the accelerated protons are investigated. The study indicates that protons originate at the front surface and are accelerated to a maximum energy that is reasonably consistent with the calculated one due to the ponderomotive force.

  11. Molecular modeling of the surface charging of hematite. II. Optimal proton distribution and simulation of surface charge versus pH relationships

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Wasserman, Evgeny; Felmy, Andrew R.

    1999-03-01

    A parameterized classical potential model for the interaction of water and hydroxide with iron oxide was used to calculate the optimal proton arrangement and proton binding energies on the (012) surface of hematite. Energy minimization calculations with the parameterized potential model indicate that approximately 75% of adsorbed water molecules are dissociated on this surface, in agreement with recent TPD and HREELS measurements. Surface protonation/deprotonation energies were calculated from the predicted optimal arrangement of protons on the neutral (012) surface. A supercell geometry with translational symmetry in two dimensions and finite in the third dimension (2-D PBC) was assumed. The calculated surface protonation energies were then used to model the experimentally observed surface-charging curve of hematite in aqueous solution. Excellent agreement was found between the calculated and measured surface charge for ionic strengths ranging from 0.001 to 0.1 M. Our calculations favor the value of 8.5 for the pH of zero charge of hematite over the more recent result of 6.7.

  12. Magnetic iron oxide nanoparticles: Synthesis and surface coating techniques for biomedical applications

    NASA Astrophysics Data System (ADS)

    Sun, Sheng-Nan; Wei, Chao; Zhu, Zan-Zan; Hou, Yang-Long; Subbu, S. Venkatraman; Xu, Zhi-Chuan

    2014-03-01

    Iron oxide nanoparticles are the most popular magnetic nanoparticles used in biomedical applications due to their low cost, low toxicity, and unique magnetic property. Magnetic iron oxide nanoparticles, including magnetite (Fe3O4) and maghemite (γ-Fe2O3), usually exhibit a superparamagnetic property as their size goes smaller than 20 nm, which are often denoted as superparamagnetic iron oxide nanoparticles (SPIONs) and utilized for drug delivery, diagnosis, therapy, and etc. This review article gives a brief introduction on magnetic iron oxide nanoparticles in terms of their fundamentals of magnetism, magnetic resonance imaging (MRI), and drug delivery, as well as the synthesis approaches, surface coating, and application examples from recent key literatures. Because the quality and surface chemistry play important roles in biomedical applications, our review focuses on the synthesis approaches and surface modifications of iron oxide nanoparticles. We aim to provide a detailed introduction to readers who are new to this field, helping them to choose suitable synthesis methods and to optimize the surface chemistry of iron oxide nanoparticles for their interests.

  13. Synthesis and Characterization of Biodegradable Lignin Nanoparticles with Tunable Surface Properties.

    PubMed

    Richter, Alexander P; Bharti, Bhuvnesh; Armstrong, Hinton B; Brown, Joseph S; Plemmons, Dayne; Paunov, Vesselin N; Stoyanov, Simeon D; Velev, Orlin D

    2016-06-28

    Lignin nanoparticles can serve as biodegradable carriers of biocidal actives with minimal environmental footprint. Here we describe the colloidal synthesis and interfacial design of nanoparticles with tunable surface properties using two different lignin precursors, Kraft (Indulin AT) lignin and Organosolv (high-purity lignin). The green synthesis process is based on flash precipitation of dissolved lignin polymer, which enabled the formation of nanoparticles in the size range of 45-250 nm. The size evolution of the two types of lignin particles is fitted on the basis of modified diffusive growth kinetics and mass balance dependencies. The surface properties of the nanoparticles are fine-tuned by coating them with a cationic polyelectrolyte, poly(diallyldimethylammonium chloride). We analyze how the colloidal stability and dispersion properties of these two types of nanoparticles vary as a function of pH and salinities. The data show that the properties of the nanoparticles are governed by the type of lignin used and the presence of polyelectrolyte surface coating. The coating allows the control of the nanoparticles' surface charge and the extension of their stability into strongly basic regimes, facilitating their potential application at extreme pH conditions. PMID:27268077

  14. Using light to covalently immobilize and pattern nanoparticles onto surfaces.

    PubMed

    Park, Ellane J; Wagenaar, Tina; Zhang, Siyan; Link, A James; Prud'homme, Robert K; Koberstein, Jeffrey T; Turro, Nicholas J

    2012-07-24

    There is considerable current interest in developing methods to integrate nanoparticles into optical, electronic, and biological systems due to their unique size-dependent properties and controllable shape. We report herein a versatile new approach for covalent immobilization of nanoparticles onto substrates modified with photoactive, phthalimide-functional, self-assembled monolayers. Upon illumination with UV radiation, the phthalimide group abstracts a hydrogen atom from a neighboring organic molecule, leading to radical-based photografting reactions. The approach is potentially "universal" since virtually any polymeric or organic-inorganic hybrid nanoparticle can be covalently immobilized in this fashion. Because grafting is confined to illuminated regions that undergo photoexcitation, masking provides a simple and direct method for nanoparticle patterning. To illustrate the technique, nanoparticles formed from diblock copolymers of poly(styrene-b-polyethylene oxide) and laden with Hostasol Red dye are photografted and patterned onto glass and silicon substrates modified with photoactive phthalimide-silane self-assembled monolayers. Atomic force microscopy and X-ray photoelectron spectroscopy are applied to characterize the grafted nanoparticle films while confocal fluorescence microscopy is used to image patterned nanoparticle deposition. PMID:22746532

  15. Synergetic effect of size and morphology of cobalt ferrite nanoparticles on proton relaxivity.

    PubMed

    N, Venkatesha; Srivastava, Chandan; Hegde, Veena

    2014-12-01

    Cobalt ferrite nanoparticles with average sizes of 14, 9 and 6 nm were synthesised by the chemical co-precipitation technique. Average particle sizes were varied by changing the chitosan surfactant to precursor molar ratio in the reaction mixture. Transmission electron microscopy images revealed a faceted and irregular morphology for the as-synthesised nanoparticles. Magnetic measurements revealed a ferromagnetic nature for the 14 and 9 nm particles and a superparamagnetic nature for the 6 nm particles. An increase in saturation magnetisation with increasing particle size was noted. Relaxivity measurements were carried out to determine T2 value as a function of particle size using nuclear magnetic resonance measurements. The relaxivity coefficient increased with decrease in particle size and decrease in the saturation magnetisation value. The observed trend in the change of relaxivity value with particle size was attributed to the faceted nature of as-synthesised nanoparticles. Faceted morphology results in the creation of high gradient of magnetic field in the regions adjacent to the facet edges increasing the relaxivity value. The effect of edges in increasing the relaxivity value increases with decrease in the particle size because of an increase in the total number of edges per particle dispersion. PMID:25429495

  16. Novel mechanochemical approaches for the synthesis of surface-functionalized metal nanoparticles

    NASA Astrophysics Data System (ADS)

    McMahon, Brandon Wade

    A novel mechanochemical milling technique, homogeneous media milling (HMM) is used to generate copious nanoparticles from a metal, parent media. Through the addition of surface-active capping agents, this method removes material from inch-scale parent material, via spallation and abrasion, resulting in gram-scale quantities of nanoparticles. Based on the principal of lowering a materials surface free energy through the chemisorption of a liquid or gaseous reagent, ductile and malleable metals can now be effectively and efficiently reduced to the nano scale. Acetonitrile was discovered to be an exceptionally good reagent for producing active aluminum nanoparticles, and oleic acid could be used to subsequently functionalize the particle surface, rendering them air-stable and hydrocarbon-fuel dispersible. In the interest of generality this process was used to make iron and copper nanoparticles via a similar method. It was discovered that acetonitrile decomposes on the surface of aluminum during HMM, resulting in the liberation of methyl group and hydrogen, which was detected as H2, CH4, and C2H6 in the headspace of the milling jar. Ammonia and methylamine, in gaseous form, are also reported to be highly effective surface-active milling agents for the production of aluminum nanoparticles. Methylamine, in particular, produced active, pyrophoric nanoparticles. For both acetonitrile and methylamine evidence of a stable surface adduct can be detected post milling using X-Ray photoelectron spectroscopy.

  17. Influence of surface potential on aggregation and transport of titania nanoparticles.

    PubMed

    Guzman, Katherine A Dunphy; Finnegan, Michael P; Banfield, Jillian F

    2006-12-15

    To investigate the effect of pH on nanoparticle aggregation and transport in porous media, we quantified nanoparticle transport in two-dimensional structures. Titania was used as a model compound to explore the effects of surface potential on particle mobility in the subsurface. Results show that pH, and therefore, surface potential and aggregate size, dominate nanoparticle interactions with each other and surfaces. In each solution, nanoparticle aggregate size distributions were bimodal or trimodal, and aggregate sizes increased as the pH approached the pH of the point of zero charge (pHzpc). Over 80% of suspended particles and aggregates were mobile over the pH range of 1-12, except close to the pHzpc of the surfaces, where the particles are highly aggregated. The effect of pH on transport is not symmetric around the pHzpc of the particles due to charging of the channel surfaces. However, transport speed of nanoparticle aggregates did not vary with pH. The surface element integration technique, which takes into account the effect of curvature of particles on interaction energy, was used to evaluate the ability of theory to predict nanoparticle transport. PMID:17256514

  18. Deposition of corrosion products from dowels on human dental root surfaces measured with proton microprobe technique

    NASA Astrophysics Data System (ADS)

    Brune, D.; Brunell, G.; Lindh, U.

    1982-06-01

    Distribution of copper, mercury and zinc on human teeth root surfaces adjacent to dowels of gold alloy or brass as well as dowels of brass in conjunction with an amalgam crown has been measured with a proton microprobe using PIXE techniques. Upper limits of the contents of gold and silver on the root surfaces were established. Pronounced concentration profiles of copper and zinc were observed on the root surfaces of teeth prepared with dowels of brass. The dowel of gold alloy revealed only zinc deposition. The major part of copper on the root surfaces is assumed to arise from corrosion of the dowels, and has been transported to the surface by diffusion through the dential tubuli. Zinc in the volume analysed is a constituent of dentin tissue as well as a corrosion product of the brass dowel. Part of the zinc level could also be ascribed to erosion of the zinc phosphate cement matrix. The volumes analysed were (25×25×25)μm 3. The levels of copper, mercury and zinc on the tooth root surfaces attained values up to about 200, 20 and 600 ppm, respectively.

  19. Solar-Wind Protons and Heavy Ions Sputtering of Lunar Surface Materials

    SciTech Connect

    Barghouty, N.; Meyer, Fred W; Harris, Peter R

    2011-01-01

    Lunar surface materials are exposed to {approx}1 keV/amu solar-wind protons and heavy ions on almost continuous basis. As the lunar surface consists of mostly oxides, these materials suffer, in principle, both kinetic and potential sputtering due to the actions of the solar-wind ions. Sputtering is an important mechanism affecting the composition of both the lunar surface and its tenuous exosphere. While the contribution of kinetic sputtering to the changes in the composition of the surface layer of these oxides is well understood and modeled, the role and implications of potential sputtering remain unclear. As new potential-sputtering data from multi-charged ions impacting lunar regolith simulants are becoming available from Oak Ridge National Laboratory's MIRF, we examine the role and possible implications of potential sputtering of Lunar KREEP soil. Using a non-equilibrium model we demonstrate that solar-wind heavy ions induced sputtering is critical in establishing the timescale of the overall solar-wind sputtering process of the lunar surface. We also show that potential sputtering leads to a more pronounced and significant differentiation between depleted and enriched surface elements. We briefly discuss the impacts of enhanced sputtering on the composition of the regolith and the exosphere, as well as of solar-wind sputtering as a source of hydrogen and water on the moon.

  20. Energy loss of MeV protons specularly reflected from metal surfaces

    SciTech Connect

    Juaristi, J.I.

    1996-05-01

    A parameter-free model is presented to study the energy loss of fast protons specularly reflected from metal surfaces. The contributions to the energy loss from excitation of valence-band electrons and ionization of localized target-atom electronic states are calculated separately. The former is calculated from the induced surface wake potential using linear response theory and the specular-reflection model, while the latter is calculated in the first Born approximation. The results obtained are in good agreement with available experimental data. However, the experimental qualitative trend of the energy loss as a function of the angle of incidence is obtained when the valence-band electron model is replaced by localized target atom electron states, though with a worse quantitative agreement. {copyright} {ital 1996 The American Physical Society.}

  1. High surface area graphite as alternative support for proton exchange membrane fuel cell catalysts

    NASA Astrophysics Data System (ADS)

    Ferreira-Aparicio, P.; Folgado, M. A.; Daza, L.

    The suitability of a high surface area graphite (HSAG) as proton exchange membrane fuel cell (PEMFC) catalyst support has been evaluated and compared with that of the most popular carbon black: the Vulcan XC72. It has been observed that Pt is arranged on the graphite surface resulting in different structures which depend on the catalysts synthesis conditions. The influence that the metal particle size and the metal-support interaction exert on the catalysts degradation rate is analyzed. Temperature programmed oxidation (TPO) under oxygen containing streams has been shown to be a useful method to assess the resistance of PEMFC catalysts to carbon corrosion. The synthesized Pt/HSAG catalysts have been evaluated in single cell tests in the cathode catalytic layer. The obtained results show that HSAG can be a promising alternative to the traditionally used Vulcan XC72 carbon black when suitable catalysts synthesis conditions are used.

  2. Pattern formation in fatty acid-nanoparticle and lipid-nanoparticle mixed monolayers at water surface

    NASA Astrophysics Data System (ADS)

    Choudhuri, M.; Datta, A.; Iyengar, A. N. Sekar; Janaki, M. S.

    2015-06-01

    Dodecanethiol-capped gold nanoparticles (AuNPs) are self-organized in two different amphiphilic monolayers one of which is a single-tailed fatty acid Stearic acid (StA) and the other a double-tailed lipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). In the StA-AuNP film the AuNPs self-organize to form an interconnected network of nanoclusters on compression while in the DMPC-AuNP film the AuNPs aggregate to form random, isolated clusters in the film. The long time evolution of the films at constant surface pressure reveals ring structures in the former and diffusion limited aggregates in the latter that with time evolve into an irregular porous maze of AuNPs in the DMPC film. The difference in structure of the AuNP patterns in the two films can be attributed to a difference in the lipophilic interactions between the NPs and the amphiphilic molecules. The mean square intensity fluctuations f(ln) calculated along a typical line for the 2D structures in both the films at initial and final stages of long time evolution reflect the structural changes in the films over time.

  3. Surface functionalization of titanium dioxide nanoparticles: Photo-stability and reactive oxygen species (ROS) generation

    NASA Astrophysics Data System (ADS)

    Louis, Kacie M.

    Metal oxide nanoparticles are becoming increasingly prevalent in society for applications of sunscreens, cosmetics, paints, biomedical imaging, and photovoltaics. Due to the increased surface area to volume ratio of nanoparticles compared to bulk materials, it is important to know the health and safety impacts of these materials. One mechanism of toxicity of nominally "safe" materials such as TiO 2 is through the photocatalytic generation of reactive oxygen species (ROS). ROS production and ligand degradation can affect the bioavailability of these particles in aqueous organisms. We have investigated ROS generation by functionalized TiO2 nanoparticles and its influence on aggregation and bioavailability and toxicity to zebrafish embryos/larvae. For these studies we investigated anatase TiO2 nanoparticles. For application purposes and solution stability, the TiO2 nanoparticles were functionalized with a variety of ligands such as citrate, 3,4-dihydroxybenzaldehyde, and ascorbate. We quantitatively examined the amount of ROS produced in aqueous solution using fluorescent probes and see that more ROS is produced under UV light than in the dark control. Our measurements show that TiO2 toxicity reaches a maximum for nanoparticles with smaller diameters, and is correlated with surface area dependent changes in ROS generation. In an effort to reduce toxicity through control of the surface and surface ligands, we synthesized anatase nanoparticles of different sizes, functionalized them with different ligands, and examined the resulting ROS generation and ligand stability. Using a modular ligand containing a hydrophobic inner region and a hydrophilic outer region, we synthesized water-stable nanoparticles, via two different chemical reactions, having much-reduced ROS generation and thus reduced toxicity. These results suggest new strategies for making safer nanoparticles while still retaining their desired properties. We also examine the degradation of the different ligands

  4. Preparation of transition metal nanoparticles and surfaces modified with (CO) polymers synthesized by RAFT

    DOEpatents

    McCormick, III, Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

    2006-10-25

    A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surface modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a collidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as fuctionalization with a variety of different chemical groups, expanding their utility and application.

  5. Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

    DOEpatents

    McCormick, III, Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

    2011-12-27

    A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

  6. Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

    DOEpatents

    McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

    2006-11-21

    A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

  7. Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces.

    PubMed

    Hu, Peiguang; Chen, Limei; Deming, Christopher P; Lu, Jia-En; Bonny, Lewis W; Chen, Shaowei

    2016-06-01

    Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 ± 0.3 nm, 1.3 ± 0.2 nm, and 1.1 ± 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species. PMID:27242019

  8. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    PubMed Central

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-01-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

  9. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes.

    PubMed

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-01-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [Co(II)(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

  10. Preliminary investigations into surface molecularly imprinted nanoparticles for Helicobacter pylori eradication

    PubMed Central

    Han, Jiaying; Sun, Yinjing; Hou, Jiapeng; Wang, Yuyan; Liu, Yu; Xie, Cao; Lu, Weiyue; Pan, Jun

    2015-01-01

    This paper reports investigations into the preparation and characterization of surface molecularly imprinted nanoparticles (SMINs) designed to adhere to Helicobacter pylori (H. pylori). Imprinted nanoparticles were prepared by the inverse microemulsion polymerization method. A fraction of Lpp20, an outer membrane protein of H. pylori known as NQA, was chosen as template and modified with myristic acid to facilitate its localization on the surface of the nanoparticles. The interaction between these SMINs with the template NQA were evaluated using surface plasmon resonance (SPR), change in zeta potential and fluorescence polarization (FP). The results were highly consistent in demonstrating a preferential recognition of the template NQA for SMINs compared with the control nanoparticles. In vitro experiments also indicate that such SMINs are able to adhere to H. pylori and may be useful for H. pylori eradication. PMID:26713273

  11. Discontinuous variation of the surface plasmon linewidth of small sodium nanoparticles with electron temperatures

    NASA Astrophysics Data System (ADS)

    Wang, Guozhong; Zheng, Yizhuang; Zi, Jian

    2015-05-01

    We found a novel behavior of the surface plasmon linewidth of small sodium nanoparticles, which monotonically decreases with the electron temperature and bears a sudden drop or rise at high electron temperatures. Our calculation is based on the model constructed by splitting the total Hamiltonian of all valence electrons of a metallic nanoparticle into two sub-Hamiltonians and the coupling between them. This novel behavior of the surface plasma resonance linewidth can be verified by pump-probe femtosecond spectroscopy experiments and is able to take place for metallic particles with sizes less than few nanometers. In addition, we propose that it is the size uncertainty of small nanoparticles that yields the intrinsic linewidth of the surface plasmon resonance, which is supported by experimental and theoretical results of nanoparticles Na8 and Na20.

  12. Controlling optical properties of metallic multi-shell nanoparticles through suppressed surface plasmon resonance.

    PubMed

    Acapulco, Jesus A I; Hong, Soonchang; Kim, Seong Kyu; Park, Sungho

    2016-01-01

    Herein, we report the surface plasmon resonance of plasmonic multi-shell nanoparticles compared to bimetallic Ag/Au hollow nanospheres of similar final size, shape, and percent composition. The surface plasmon resonance of solid and hollow nanoparticles exhibited a quadrupole mode that was particularly prominent around the 100 nm size regime, while multi-shell nanoparticles did not show a quadrupole mode at a similar size. In the latter case, the quadrupole mode of the outermost nanoshell was suppressed by the dipole modes of the inner shells, and the suppression of the quadrupole mode was not affected by the shape of the inner nanostructures. Light interaction of the multi-shell nanoparticle was investigated through simulated electromagnetic field distribution obtained by finite-difference time domain (FDTD) calculations which were in a good agreement with the results of surface-enhanced Raman spectroscopy (SERS). PMID:26414420

  13. Probing protein adsorption on a nanoparticle surface using second harmonic light scattering.

    PubMed

    Das, A; Chakrabarti, A; Das, P K

    2016-09-21

    A new application of second harmonic light scattering to probe protein physisorption on a gold nanoparticle surface in aqueous buffer is reported. The free energies of adsorption, the number of protein molecules adsorbed on the surface and the binding affinity of a moderate size protein, alcohol dehydrogenase (ADH), and a small protein, insulin, have been determined using the change in the second harmonic scattered light signal as a function of binding. Four different size gold nanoparticles from 15 to 60 nm were used to determine the effect of size on the free energy change, the affinity constant and the number of protein molecules adsorbed on the surface. All were shown to increase with an increase in size. The binding can be reversed by centrifugation, and the protein molecules can be desorbed quantitatively. The application of this method for studying thermodynamic parameters of weakly interacting biomolecules with nanoparticles for nanoparticle based diagnostic and therapeutic formulations is important. PMID:27530608

  14. Synthesis and surface functionalization of silica nanoparticles for nanomedicine

    PubMed Central

    Liberman, Alexander; Mendez, Natalie; Trogler, William C.; Kummel, Andrew C.

    2014-01-01

    There are a wide variety of silica nanoformulations being investigated for biomedical applications. Silica nanoparticles can be produced using a wide variety of synthetic techniques with precise control over their physical and chemical characteristics. Inorganic nanoformulations are often criticized or neglected for their poor tolerance; however, extensive studies into silica nanoparticle biodistributions and toxicology have shown that silica nanoparticles may be well tolerated, and in some case are excreted or are biodegradable. Robust synthetic techniques have allowed silica nanoparticles to be developed for applications such as biomedical imaging contrast agents, ablative therapy sensitizers, and drug delivery vehicles. This review explores the synthetic techniques used to create and modify an assortment of silica nanoformulations, as well as several of the diagnostic and therapeutic applications. PMID:25364083

  15. Synthesis and surface functionalization of silica nanoparticles for nanomedicine

    NASA Astrophysics Data System (ADS)

    Liberman, Alexander; Mendez, Natalie; Trogler, William C.; Kummel, Andrew C.

    2014-09-01

    There are a wide variety of silica nanoformulations being investigated for biomedical applications. Silica nanoparticles can be produced using a wide variety of synthetic techniques with precise control over their physical and chemical characteristics. Inorganic nanoformulations are often criticized or neglected for their poor tolerance; however, extensive studies into silica nanoparticle biodistributions and toxicology have shown that silica nanoparticles may be well tolerated, and in some case are excreted or are biodegradable. Robust synthetic techniques have allowed silica nanoparticles to be developed for applications such as biomedical imaging contrast agents, ablative therapy sensitizers, and drug delivery vehicles. This review explores the synthetic techniques used to create and modify an assortment of silica nanoformulations, as well as several of the diagnostic and therapeutic applications.

  16. Surface modified carbon nanoparticle papers and applications on polymer composites

    NASA Astrophysics Data System (ADS)

    Ouyang, Xilian

    Free-standing paper like materials are usually employed as protective layers, chemical filters, components of electrical batteries or supercapacitors, adhesive layers, and electronic or optoelectric components. Free-standing papers made from carbon nanoparticles have drawn increased interest because they have a variety of superior chemical and physical characteristics, such as light weight, high intrinsic mechanical properties, and extraordinary high electrical conductivity. Nanopapers fabricated from 1- D shape carbon nanofibers (CNFs) and carbon nanotubes (CNTs) are promising reinforcing materials for polymer composites, because the highly porous CNF and CNT nanopapers (porosity ˜80% and ˜70% respectively) can be impregnated with matrix polymers. In the first part of this work, polyaniline (PANI) was used to functionalize the surface of CNFs, and the resultant carbon nanopapers presented impressive mechanical strength and electrical conductivity that it could be used in the in-mold coating (IMC)/ injection molding process to achieve high electromagnetic interference (EMI) shielding effectiveness. Aniline modified (AF) CNT nanopapers were used as a 3D network in gas separation membranes. The resultant composite membranes demonstrated better and stable CO2 permeance and CO 2/H2 selectivity in a high temperature (107°C) and high pressure (15-30 atm) gas separation process, not achievable by conventional polymer membranes. In the second part, we demonstrated that 2-D graphene (GP) or graphene oxide (GO) nanosheets could be tightly packed into a film which was impermeable to most gases and liquids. GP or GO nanopapers could be coated on polymer composites. In order to achieve well-dispersed single-layer graphene in aqueous medium, we developed a facile approach to synthesize functional GP bearing benzenesulfonic acid groups which allow the preparation of nanopapers by water based assembly. With the optimized processing conditions, our best GP nanopapers could reach

  17. SU-E-J-139: One Institution’s Experience with Surface Imaging in Proton Therapy

    SciTech Connect

    Zhao, L; Singh, H; Zheng, Y

    2015-06-15

    Purpose: X-ray system is commonly used for IGRT in proton therapy, however image acquisition not only increases treatment time but also adds imaging dose. We studied a 3D surface camera system (AlignRT) performance for proton therapy. Methods: System accuracy was evaluated with rigid phantom under two different camera location configurations. For initial clinical applications, post mastectomy chest wall and partial breast treatments were studied. X-ray alignment was used as our ground truth. Our studies included: 1) comparison of daily patient setup shifts between X-ray alignment and SI calculation; 2) interfractional breast surface position variation when aligning to bony landmark on X-ray; 3) absolute positioning using planning CT DICOM data; 4) shifts for multi-isocenter treatment plan; 5) couch isocentric rotation accuracy. Results: Camera locations affected the system performance. After camera relocation, the accuracy of the system for the rigid phantom was within 1 mm (fixed couch), and 1.5 mm (isocentric rotation). For intrafractional patient positioning, X-ray and AlignRT shifts were highly correlated (r=0.99), with the largest difference (mean ± SD) in the longitudinal direction (2.14 ± 1.02 mm). For interfractional breast surface variation and absolute positioning, there were still larger disagreements between the two modalities due to different focus on anatomical landmarks, and 95% of the data lie within 5mm with some outliers at 7 mm–9 mm. For multi-isocenter shifts, the difference was 1 ± 0.56 mm over an 11 cm shift in longitudinal direction. For couch rotation study, the differences was 1.36 ± 1.0 mm in vertical direction, 3.04 ± 2.11 mm in longitudinal direction, and 2.10 ± 1.66 mm in lateral direction, with all rotation differences < 1.5 degree. Conclusion: Surface imaging is promising for intrafractional treatment application in proton therapy to reduce X-ray frequency. However the interfractional discrepancy between the X-ray and SI

  18. Ectoenzyme switches the surface of magnetic nanoparticles for selective binding of cancer cells.

    PubMed

    Du, Xuewen; Zhou, Jie; Xu, Bing

    2015-06-01

    Enzymatic switch, such as phosphorylation and dephosphorylation of proteins, is the most important mechanism for cellular signal transductions. Inspired by Nature and encouraged by our recent unexpected observation of the dephosphorylation of d-tyrosine phosphate-contain small peptides, we modify the surface of magnetic nanoparticles (MNP) with d-tyrosine phosphate that is a substrate of alkaline phosphatase (ALP). Our studies find that ALP is able to remove the phosphate groups from the magnetic nanoparticles. Most importantly, placental alkaline phosphatase (ALPP), an ectoenzyme that locates on cell surface with catalytic domains outside the plasma membrane and is overexpressed on many cancer cells, dephosphorylate the d-tyrosine phosphates on the surface of the magnetic nanoparticle and enable the magnetic nanoparticles to adhere selectively to the cancer cells, such as HeLa cells. Unlikely commonly used antibodies, the selectivity of the magnetic nanoparticles to cancer cells originates from the enzymatic reaction catalyzed by ALPP. The use of enzymatic reaction to modulate the surface of various nanostructures may lead to a general method to broadly target cancer cells without relying on specific ligand-receptor interactions (e.g., antibodies). This work, thus, illustrates a fundamentally new concept to allow cells to actively engineer the surface of colloids materials, such as magnetic nanoparticles, for various applications. PMID:25586118

  19. Secondary structure of corona proteins determines the cell surface receptors used by nanoparticles.

    PubMed

    Fleischer, Candace C; Payne, Christine K

    2014-12-11

    Nanoparticles used for biological and biomedical applications encounter a host of extracellular proteins. These proteins rapidly adsorb onto the nanoparticle surface, creating a protein corona. Poly(ethylene glycol) can reduce, but not eliminate, the nonspecific adsorption of proteins. As a result, the adsorbed proteins, rather than the nanoparticle itself, determine the cellular receptors used for binding, the internalization mechanism, the intracellular transport pathway, and the subsequent immune response. Using fluorescence microscopy and flow cytometry, we first characterize a set of polystyrene nanoparticles in which the same adsorbed protein, bovine serum albumin, leads to binding to two different cell surface receptors: native albumin receptors and scavenger receptors. Using a combination of circular dichroism spectroscopy, isothermal titration calorimetry, and fluorescence spectroscopy, we demonstrate that the secondary structure of the adsorbed bovine serum albumin protein controls the cellular receptors used by the protein-nanoparticle complexes. These results show that protein secondary structure is a key parameter in determining the cell surface receptor used by a protein-nanoparticle complex. We expect this link between protein structure and cellular outcomes will provide a molecular basis for the design of nanoparticles for use in biological and biomedical applications. PMID:24779411

  20. Nanoparticle generation and interactions with surfaces in vacuum systems

    NASA Astrophysics Data System (ADS)

    Khopkar, Yashdeep

    Extreme ultraviolet lithography (EUVL) is the most likely candidate as the next generation technology beyond immersion lithography to be used in high volume manufacturing in the semiconductor industry. One of the most problematic areas in the development process is the fabrication of mask blanks used in EUVL. As the masks are reflective, there is a chance that any surface aberrations in the form of bumps or pits could be printed on the silicon wafers. There is a strict tolerance to the number density of such defects on the mask that can be used in the final printing process. Bumps on the surface could be formed when particles land on the mask blank surface during the deposition of multiple bi-layers of molybdenum and silicon. To identify, and possibly mitigate the source of particles during mask fabrication, SEMATECH investigated particle generation in the VEECO Nexus deposition tool. They found several sources of particles inside the tool such as valves. To quantify the particle generation from vacuum components, a test bench suitable for evaluating particle generation in the sub-100 nm particle size range was needed. The Nanoparticle test bench at SUNY Polytechnic Institute was developed as a sub-set of the overall SEMATECH suite of metrology tools used to identify and quantify sources of particles inside process tools that utilize these components in the semiconductor industry. Vacuum valves were tested using the test bench to investigate the number, size and possible sources of particles inside the valves. Ideal parameters of valve operation were also investigated using a 300-mm slit valve with the end goal of finding optimized parameters for minimum particle generation. SEMATECH also pursued the development of theoretical models of particle transport replicating the expected conditions in an ion beam deposition chamber assuming that the particles were generated. In the case of the ion beam deposition tool used in the mask blank fabrication process, the ion

  1. Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

    2015-05-01

    Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this

  2. Effects of surface coordination chemistry on the magnetic properties of MnFe(2)O(4) spinel ferrite nanoparticles.

    PubMed

    Vestal, Christy R; Zhang, Z John

    2003-08-13

    To understand the influence of surface interactions upon the magnetic properties of magnetic nanoparticles, the surface of manganese ferrite, MnFe(2)O(4), nanoparticles have been systematically modified with a series of para-substituted benzoic acid ligands (HOOC-C(6)H(4)-R; R = H, CH(3), Cl, NO(2), OH) and substituted benzene ligands (Y-C(6)H(5), Y = COOH, SH, NH(2), OH, SO(3)H). The coercivity of magnetic nanoparticles decreases up to almost 50% upon the coordination of the ligands on the nanoparticle surface, whereas the saturation magnetization has increased. The percentage coercivity decrease of the modified nanoparticles with respect to the native nanoparticles strongly correlates with the crystal field splitting energy (CFSE) Delta evoked by the coordination ligands. The ligand inducing largest CFSE results in the strongest effect on the coercivity of magnetic nanoparticles. The change in magnetic properties of nanoparticles also correlates with the specific coordinating functional group bound onto the nanoparticle surface. The correlations suggest the decrease in spin-orbital couplings and surface anisotropy of magnetic nanoparticles due to the surface coordination. Such surface effects clearly show the dependence on the size of nanoparticles. PMID:12904049

  3. Size dependent thermalization time of Ag nanoparticles and the surface density profile

    NASA Astrophysics Data System (ADS)

    Lopez-Bastidas, Catalina

    2009-03-01

    It is well known that the lack of d-electron screening in the s-electron spill-out region at the surface of Ag nanoparticles increases the electron-electron interaction in this region compared to the bulk. Therefore when comparing the electron-electron interaction contribution to the thermalization time of Ag nanoparticles of varying radius, smaller particles thermalize faster due to the increased surface to bulk ratio. One aspect which has not been addressed is the effect of the spatial distribution of charge at the surface of the nanoparticle. In this work it is shown that the size dependence of the thermalization time is very sensitive to the surface density profile. The electron thermalization time of conduction electrons in Ag nanoparticles as a function of the radius is calculated. The sensitivity of the scattering rate to the spatial distribution of charge at the surface of the nanostructure is analyzed using several model surface profiles. The change in surface charge distribution via charging or coating of the nanospheres is shown to be a tool for control and probing of the ultra-fast electron-electron dynamics in metallic nanoparticles.

  4. On nanoparticle surface growth: MgO nanoparticle formation during a Mg particle combustion

    NASA Astrophysics Data System (ADS)

    Altman, Igor S.; Agranovski, Igor E.; Choi, Mansoo

    2004-06-01

    It is demonstrated that formation of MgO nanoparticles during a Mg particle combustion occurs in the vapor adsorption regime and the particle coagulation and coalescence do not play any significant role in the process in question. Analysis of the particle size distributions shows that the rate of the nanoparticle condensation growth strongly depends on the actual particle size. The revealed dependence of the growth rate upon the size is consistent with the exponential law recently predicted. This finding can shed light on the long-standing general problem of gas-phase nanotechnology—the origin of lognormal size distribution behavior of generated nanoparticles.

  5. Surface modification of nanoparticles enables selective evasion of phagocytic clearance by distinct macrophage phenotypes

    NASA Astrophysics Data System (ADS)

    Qie, Yaqing; Yuan, Hengfeng; von Roemeling, Christina A.; Chen, Yuanxin; Liu, Xiujie; Shih, Kevin D.; Knight, Joshua A.; Tun, Han W.; Wharen, Robert E.; Jiang, Wen; Kim, Betty Y. S.

    2016-05-01

    Nanomedicine is a burgeoning industry but an understanding of the interaction of nanomaterials with the immune system is critical for clinical translation. Macrophages play a fundamental role in the immune system by engulfing foreign particulates such as nanoparticles. When activated, macrophages form distinct phenotypic populations with unique immune functions, however the mechanism by which these polarized macrophages react to nanoparticles is unclear. Furthermore, strategies to selectively evade activated macrophage subpopulations are lacking. Here we demonstrate that stimulated macrophages possess higher phagocytic activities and that classically activated (M1) macrophages exhibit greater phagocytic capacity than alternatively activated (M2) macrophages. We show that modification of nanoparticles with polyethylene-glycol results in decreased clearance by all macrophage phenotypes, but importantly, coating nanoparticles with CD47 preferentially lowers phagocytic activity by the M1 phenotype. These results suggest that bio-inspired nanoparticle surface design may enable evasion of specific components of the immune system and provide a rational approach for developing immune tolerant nanomedicines.

  6. Surface enhanced Raman scattering, antibacterial and antifungal active triangular gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Smitha, S. L.; Gopchandran, K. G.

    2013-02-01

    Shape controlled syntheses of gold nanoparticles have attracted a great deal of attention as their optical, electronic, magnetic and biological properties are strongly dependent on the size and shape of the particles. Here is a report on the surface enhanced Raman scattering (SERS) activity of Cinnamomum zeylanicum leaf broth reduced gold nanoparticles consisting of triangular and spherical like particles, using 2-aminothiophenol (2-ATP) and crystal violet (CV) as probe molecules. Nanoparticles prepared with a minimum leaf broth concentration, having a greater number of triangular like particles exhibit a SERS activity of the order of 107. The synthesized nanoparticles exhibit efficient antibacterial activity against the tested gram negative bacterium Escherichia coli and gram positive bacterium Staphylococcus aureus. Investigations on the antifungal activity of the synthesized nanoparticles against Aspergillus niger and Fusarium oxysporum positive is also discussed.

  7. 2.6 MeV proton irradiation effects on the surface integrity of depleted UO2

    NASA Astrophysics Data System (ADS)

    Pakarinen, J.; He, L.; Gupta, M.; Gan, J.; Nelson, A.; El-Azab, A.; Allen, T. R.

    2014-01-01

    The effect of low temperature proton irradiation in depleted uranium dioxide was examined as a function of fluence. With 2.6 MeV protons, the fluence limit for preserving a good surface quality was found to be relatively low, about 1.4 and 7.0 × 1017 protons/cm2 for single and poly crystalline samples, respectively. Upon increasing the fluence above this threshold, severe surface flaking and disintegration of samples was observed. Based on scanning electron microscopy (SEM) and X-ray diffraction (XRD) observations the causes of surface failure were associated to high H atomic percent at the peak damage region due to low solubility of H in UO2. The resulting lattice stress is believed to exceed the fracture stress of the crystal at the observed fluencies. The oxygen point defects from the displacement damage may hinder the H diffusion and further increase the lattice stress, especially at the peak damage region.

  8. Active Tumor Permeation and Uptake of Surface Charge-Switchable Theranostic Nanoparticles for Imaging-Guided Photothermal/Chemo Combinatorial Therapy

    PubMed Central

    Hung, Chia-Chian; Huang, Wen-Chia; Lin, Yi-Wen; Yu, Ting-Wei; Chen, Hsin-Hung; Lin, Sung-Chyr; Chiang, Wen-Hsuan; Chiu, Hsin-Cheng

    2016-01-01

    To significantly promote tumor uptake and penetration of therapeutics, a nanovehicle system comprising poly(lactic-co-glycolic acid) (PLGA) as the hydrophobic cores coated with pH-responsive N-acetyl histidine modified D-α-tocopheryl polyethylene glycol succinate (NAcHis-TPGS) is developed in this work. The nanocarriers with switchable surface charges in response to tumor extracellular acidity (pHe) were capable of selectively co-delivering indocyanine green (ICG), a photothermal agent, and doxorubicin (DOX), a chemotherapy drug, to tumor sites. The in vitro cellular uptake of ICG/DOX-loaded nanoparticles by cancer cells and macrophages was significantly promoted in weak acidic environments due to the increased protonation of the NAcHis moieties. The results of in vivo and ex vivo biodistribution studies demonstrated that upon intravenous injection the theranostic nanoparticles were substantially accumulated in TRAMP-C1 solid tumor of tumor-bearing mice. Immunohistochemical examination of tumor sections confirmed the active permeation of the nanoparticles into deep tumor hypoxia due to their small size, pHe-induced near neutral surface, and the additional hitchhiking transport via tumor-associated macrophages. The prominent imaging-guided photothermal therapy of ICG/DOX-loaded nanoparticles after tumor accumulation induced extensive tumor tissue/vessel ablation, which further promoted their extravasation and DOX tumor permeation, thus effectively suppressing tumor growth. PMID:26909107

  9. Active Tumor Permeation and Uptake of Surface Charge-Switchable Theranostic Nanoparticles for Imaging-Guided Photothermal/Chemo Combinatorial Therapy.

    PubMed

    Hung, Chia-Chian; Huang, Wen-Chia; Lin, Yi-Wen; Yu, Ting-Wei; Chen, Hsin-Hung; Lin, Sung-Chyr; Chiang, Wen-Hsuan; Chiu, Hsin-Cheng

    2016-01-01

    To significantly promote tumor uptake and penetration of therapeutics, a nanovehicle system comprising poly(lactic-co-glycolic acid) (PLGA) as the hydrophobic cores coated with pH-responsive N-acetyl histidine modified D-α-tocopheryl polyethylene glycol succinate (NAcHis-TPGS) is developed in this work. The nanocarriers with switchable surface charges in response to tumor extracellular acidity (pHe) were capable of selectively co-delivering indocyanine green (ICG), a photothermal agent, and doxorubicin (DOX), a chemotherapy drug, to tumor sites. The in vitro cellular uptake of ICG/DOX-loaded nanoparticles by cancer cells and macrophages was significantly promoted in weak acidic environments due to the increased protonation of the NAcHis moieties. The results of in vivo and ex vivo biodistribution studies demonstrated that upon intravenous injection the theranostic nanoparticles were substantially accumulated in TRAMP-C1 solid tumor of tumor-bearing mice. Immunohistochemical examination of tumor sections confirmed the active permeation of the nanoparticles into deep tumor hypoxia due to their small size, pHe-induced near neutral surface, and the additional hitchhiking transport via tumor-associated macrophages. The prominent imaging-guided photothermal therapy of ICG/DOX-loaded nanoparticles after tumor accumulation induced extensive tumor tissue/vessel ablation, which further promoted their extravasation and DOX tumor permeation, thus effectively suppressing tumor growth. PMID:26909107

  10. Biosorption of nonpolar hydrophobic organic compounds to Escherichia coli facilitated by metal and proton surface binding.

    PubMed

    Xiao, Lin; Qu, Xiaolei; Zhu, Dongqiang

    2007-04-15

    We observed that the presence of transition metal ion, Ag+, Cu2+, or Fe3+, at a concentration of 3 mg L(-1) increases sorption of two nonpolar hydrophobic organic compounds (HOCs), phenanthrene (PHEN), and 1,2,4,5-tetrachlorobenzene (TeCB) by 1.5-4 times to Gram-negative bacteria Escherichia coli. Complexation of transition metals with the deprotonated functional groups (mainly carboxyl) of bacterial cell walls neutralizes the negative charge, making the bacterial surface less hydrophilic and enhancing hydrophobic partition of HOCs. This is evidenced by the fact that the zeta potential (zeta) value of bacteria becomes less negative when a transition metal is present. Furthermore, the observed higher sorption of PHEN than TeCB at low pH (3.8) cannot be fully explained by the pH-dependent hydrophobic effects. The results led us to propose two specific sorption mechanisms for pi-donor compounds: cation-pi interactions with protonated amines and pi H-bonding with protonated carboxyls. The biosorption of PHEN was best described as pi-donor compared to the biosorption of TeCB considered non-pi-donor. Results of the present study highlight that the presence of coexisting transition metals and changes on pH have a major effect on the biosorption of nonpolar HOCs. PMID:17533834

  11. Surface spin-glass in cobalt ferrite nanoparticles dispersed in silica matrix

    NASA Astrophysics Data System (ADS)

    Zeb, F.; Sarwer, W.; Nadeem, K.; Kamran, M.; Mumtaz, M.; Krenn, H.; Letofsky-Papst, I.

    2016-06-01

    Surface effects in cobalt ferrite (CoFe2O4) nanoparticles dispersed in a silica (SiO2) matrix were studied by using AC and DC magnetization. Nanoparticles with different concentration of SiO2 were synthesized by using sol-gel method. Average crystallite size lies in the range 25-34 nm for different SiO2 concentration. TEM image showed that particles are spherical and elongated in shape. Nanoparticles with higher concentration of SiO2 exhibit two peaks in the out-of-phase ac-susceptibility. First peak lies in the high temperature regime and corresponds to average blocking temperature of the nanoparticles. Second peak lies in the low temperature regime and is attributed to surface spin-glass freezing in these nanoparticles. Low temperature peak showed SiO2 concentration dependence and was vanished for large uncoated nanoparticles. The frequency dependence of the AC-susceptibility of low temperature peak was fitted with dynamic scaling law which ensures the presence of spin-glass behavior. With increasing applied DC field, the low temperature peak showed less shift as compared to blocking peak, broaden, and decreased in magnitude which also signifies its identity as spin-glass peak for smaller nanoparticles. M-H loops showed the presence of more surface disorder in nanoparticles dispersed in 60% SiO2 matrix. All these measurements revealed that surface effects become strengthen with increasing SiO2 matrix concentration and surface spins freeze in to spin-glass state at low temperatures.

  12. Quantitative Prediction of Surface Segregation in Bimetallic Pt-MAlloy Nanoparticles (M=Ni, Re, Mo)

    SciTech Connect

    Wang, Guofeng; Van Hove, Michel A.; Ross, Phil N.; Baskes,Michael I.

    2005-06-20

    This review addresses the issue of surface segregation inbimetallic alloy nanoparticles, which are relevant to heterogeneouscatalysis, in particular for electro-catalysts of fuel cells. We describeand discuss a theoretical approach to predicting surface segregation insuch nanoparticles by using the Modified Embedded Atom Method and MonteCarlo simulations. In this manner it is possible to systematicallyexplore the behavior of such nanoparticles as a function of componentmetals, composition, and particle size, among other variables. We choseto compare Pt75Ni25, Pt75Re25, and Pt80Mo20 alloys as example systems forthis discussion, due to the importance of Pt in catalytic processes andits high-cost. It is assumed that the equilibrium nanoparticles of thesealloys have a cubo-octahedral shape, the face-centered cubic lattice, andsizes ranging from 2.5 nm to 5.0 nm. By investigating the segregation ofPt atoms to the surfaces of the nanoparticles, we draw the followingconclusions from our simulations at T= 600 K. (1) Pt75Ni25 nanoparticlesform a surface-sandwich structure in which the Pt atoms are stronglyenriched in the outermost and third layers while the Ni atoms areenriched in the second layer. In particular, a nearly pure Pt outermostsurface layer can be achieved in those nanoparticles. (2) EquilibriumPt75Re25 nanoparticles adopt a core-shell structure: a nearly pure Ptshell surrounding a more uniform Pt-Re core. (3) In Pt80Mo20nanoparticles, the facets are fully occupied by Pt atoms, the Mo atomsonly appear at the edges and vertices, and the Pt and Mo atoms arrangethemselves in an alternating sequence along the edges and vertices. Oursimulations quantitatively agree with previous experimental andtheoretical results for the extended surfaces of Pt-Ni, Pt-Re, and Pt-Moalloys. We further discuss the reasons for the different types of surfacesegregation found in the different alloys, and some of theirimplications.

  13. A slowing down of proton motion from HPTS to water adsorbed on the MCM-41 surface.

    PubMed

    Alarcos, Noemí; Cohen, Boiko; Douhal, Abderrazzak

    2016-01-28

    We report on the steady-state and femtosecond-nanosecond (fs-ns) behaviour of 8-hydroxypyrene-1,3,6-trisulfonate (pyranine, HPTS) and its interaction with mesoporous silica based materials (MCM-41) in both solid-state and dichloromethane (DCM) suspensions in the absence and presence of water. In the absence of water, HPTS forms aggregates which are characterized by a broad emission spectrum and multiexponential behavior (τsolid-state/DCM = 120 ps, 600 ps, 2.2 ns). Upon interaction with MCM41, the aggregate population is found to be lower, leading to the formation of adsorbed monomers. In the presence of water (1%), HPTS with and without MCM41 materials in DCM suspensions undergoes an excited-state intermolecular proton-transfer (ESPT) reaction in the protonated form (ROH*) producing a deprotonated species (RO(-)*). The long-time emission decays of the ROH* in different systems in the presence of water are multiexponential, and are analysed using the diffusion-assisted geminate recombination model. The obtained proton-transfer and recombination rate constants for HPTS and HPTS/MCM41 complexes in DCM suspensions in the presence of water are kPT = 13 ns(-1), krec = 7.5 Å ns(-1), and kPT = 5.4 ns(-1), krec = 2.2 Å ns(-1), respectively, The slowing down of both processes in the latter case is explained in terms of specific interactions of the dye and of the water molecules with the silica surface. The ultrafast dynamics (fs-regime) of the HPTS/MCM41 complexes in DCM suspensions, without and with water, shows two components which are assigned to intramolecular vibrational-energy relaxation (IVR) (∼120 fs vs. ∼0.8 ps), and vibrational relaxation/cooling (VC), and charge transfer (CT) processes (∼2 ps without water and ∼5 ps with water) of the adsorbed ROH*. Our results provide new knowledge on the interactions and the proton-transfer reaction dynamics of HPTS adsorbed on mesoporous materials. PMID:26705542

  14. Surface-enhanced raman scattering detection of pH with silica-encapsulated 4-mercaptobenzoic acid-functionalized silver nanoparticles.

    PubMed

    Wang, Fenglin; Widejko, Ryan G; Yang, Zhiqiang; Nguyen, KhanhVan T; Chen, Hongyu; Fernando, Lawrence P; Christensen, Kenneth A; Anker, Jeffrey N

    2012-09-18

    Sensors based upon surface-enhanced Raman spectroscopy (SERS) are attractive because they have narrow, vibrationally specific spectral peaks that can be excited using red and near-infrared light which avoids photobleaching, penetrates tissue, and reduces autofluorescence. Several groups have fabricated pH nanosensors by functionalizing silver or gold nanoparticle surfaces with an acidic molecule and measuring the ratio of protonated to deprotonated Raman bands. However, a limitation of these sensors is that macromolecules in biological systems can adsorb onto the nanoparticle surface and interfere with measurements. To overcome this interference, we encapsulated pH SERS sensors in a 30 nm thick silica layer with small pores which prevented bovine serum albumin (BSA) molecules from interacting with the pH-indicating 4-mercaptobenzoic acid (4-MBA) on the silver surfaces but preserved the pH-sensitivity. Encapsulation also improved colloidal stability and sensor reliability. The noise level corresponded to less than 0.1 pH units from pH 3 to 6. The silica-encapsulated functionalized silver nanoparticles (Ag-MBA@SiO(2)) were taken up by J774A.1 macrophage cells and measured a decrease in local pH during endocytosis. This strategy could be extended for detecting other small molecules in situ. PMID:22881392

  15. Molecular statics calculations of proton binding to goethite surfaces: A new approach to estimation of stability constants for multisite surface complexation models

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Felmy, Andrew R.; Hay, Benjamin P.

    1996-05-01

    A new approach to estimating stability constants for proton binding in multisite surface complexation models is presented. The method is based on molecular statics computation of energies for the formation of proton vacancies and interstitials in ideal periodic slabs representing the (100), (110), (010), (001), and (021) surfaces of goethite. Gas-phase energies of clusters representing the hydrolysis products of ferric iron are calculated using the same potential energy functions used for the surface. These energies are linearly related to the hydrolysis constants for ferric iron in aqueous solution. Stability constants for proton binding at goethite surfaces are estimated by assuming the same log K- Δ E relationship for goethite surface protonation reactions. These stability constants predict a pH of zero charge of 8.9, in adequate agreement with measurements on CO 2-free goethite. The estimated stability constants differ significantly from previous estimations based on Pauling bond strength. We find that nearly all the surface oxide ions are reactive; nineteen of the twenty-six surface sites investigated have log Kint between 7.7 and 9.4. This implies a site density between fifteen and sixteen reactive sites/nm for crystals dominated by (110) and (021) crystal faces.

  16. Molecular statics calculations of proton binding to goethite surfaces: A new approach to estimation of stability constants for multisite surface complexation models

    SciTech Connect

    Rustad, J.R.; Felmy, A.R.; Hay, B.P.

    1996-05-01

    A new approach to estimating stability constants for proton binding in multisite surface complexation models is presented. The method is based on molecular statics computation of energies for the formation of proton vacancies and interstitials in ideal periodic slabs representing the (100), (110), (010), (001), and (021) surfaces of goethite. Gas-phase energies of clusters representing the hydrolysis products of ferric iron are calculated using the same potential energy functions used for the surface. These energies are linearly related to the hydrolysis constants for ferric iron in aqueous solution. Stability constants for proton binding at goethite surfaces are estimated by assuming the same log K-{Delta}E relationship for goethite surface protonation reactions. These stability constants predict a pH of zero charge of 8.9, in adequate agreement with measurements on CO{sub 2}-free goethite. The estimated stability constants differ significantly from previous estimations based on Pauling bond strength. We find that nearly all the surface oxide ions are reactive; nineteen of the twenty-six surface sites investigated have log K{sup int} between 7.7 and 9.4. This implies a site density between fifteen and sixteen reactive sites/nm for crystals dominated by (110) and (021) crystal faces. 39 refs., 8 figs., 4 tabs.

  17. Effect of Thickness on Surface Morphology of Silver Nanoparticle Layer During Furnace Sintering

    NASA Astrophysics Data System (ADS)

    Moon, Yoon Jae; Kang, Heuiseok; Kang, Kyungtae; Moon, Seung-Jae; Young hwang, Jun

    2015-04-01

    In printed electronics applications, specific resistances of conductive lines are critical to the performance of the devices. The specific resistance of a silver (Ag) nanoparticle electrode is affected by surface morphology of the layered nanoparticles which were sintered by the heat treatment after printing. In this work, the relationship between surface morphology and specific resistance was investigated with various sintering temperatures and various layer thicknesses of Ag nanoparticle ink. Ag nanoparticles with an average size of approximately 50 nm were spin-coated on Eagle XG glass substrates with various spin speed to change the layer thickness of Ag nanoparticles from 200 nm to 900 nm. Coated Ag nanoparticle layers were heated from 150°C to 450°C for 30 min in a furnace. The result showed that higher sintering temperature produces larger grains in an Ag layer and decreases specific resistance of the layer, but that the maximum allowable heating temperature is limited by the thickness of the layer. When grain size exceeded the thickness of the layer, the morphology of the Ag nanoparticles changed to submicron-sized islands and the Ag layers did not have electrical conductivity any more.

  18. Pure surface plasmon resonance enhancement of the first hyperpolarizability of gold core-silver shell nanoparticles.

    PubMed

    Abid, Jean-Pierre; Nappa, Jérôme; Girault, Hubert H; Brevet, Pierre-François

    2004-12-22

    We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface. PMID:15606279

  19. Modeling Nanoparticle Targeting to a Vascular Surface in Shear Flow Through Diffusive Particle Dynamics

    NASA Astrophysics Data System (ADS)

    Peng, Bei; Liu, Yang; Zhou, Yihua; Yang, Longxiang; Zhang, Guocheng; Liu, Yaling

    2015-05-01

    Nanoparticles are regarded as promising carriers for targeted drug delivery and imaging probes. A fundamental understanding of the dynamics of polymeric nanoparticle targeting to receptor-coated vascular surfaces is therefore of great importance to enhance the design of nanoparticles toward improving binding ability. Although the effects of particle size and shear flow on the binding of nanoparticles to a vessel wall have been studied at the particulate level, a computational model to investigate the details of the binding process at the molecular level has not been developed. In this research, dissipative particle dynamics simulations are used to study nanoparticles with diameters of several nanometers binding to receptors on vascular surfaces under shear flow. Interestingly, shear flow velocities ranging from 0 to 2000 s-1 had no effect on the attachment process of nanoparticles very close to the capillary wall. Increased binding energy between the ligands and wall caused a corresponding linear increase in bonding ability. Our simulations also indicated that larger nanoparticles and those of rod shape with a higher aspect ratio have better binding ability than those of smaller size or rounder shape.

  20. Challenges in Applying Surface Analysis Methods to Nanoparticles and Nanostructured Materials

    SciTech Connect

    Baer, Donald R.; Engelhard, Mark H.; Gaspar, Dan J.; Matson, Dean W.; Pecher, Klaus H.; Williams, Josh R.; Wang, Chong M.

    2005-03-01

    Nanostructured materials of various types and forms are formulated in a variety of novel ways and increasingly subject to many types of chemical and physical analysis. Since nanomaterial systems contain a relatively large amount of surface or interface area, it should be natural to characterize them using tools designed to analyze surfaces and interfaces. We have found that nanoparticles and other nanostructured materials present a variety of challenges. This paper reviews environmental effects on measurements of Ce-oxide nanoparticles and nanoporous silica films and focuses on efforts to quantify the ion damage and sputter rates for the Fe-oxide nanoparticles. We have found that nanoparticles appear more readily damaged and to have sputter rates that exceed “bulk” materials. To verify such effects, we need to know many details about size, size distribution, density, and shape that are not always easily obtained.

  1. Colloidal aluminum nanoparticles with tunable localized surface plasmon resonances for energy applications

    NASA Astrophysics Data System (ADS)

    Cheng, Yan; Smith, Kenneth; Arinze, Ebuka; Nyirjesy, Gabrielle; Bragg, Arthur; Thon, Susanna

    Localized surface plasmon resonances (LSPRs) of noble metal nanoparticles are of interest for energy applications due to their visible and near infrared wavelength sensitivity. However, application of these materials in optoelectronic devices is limited by their rarity and high cost. Earth-abundant, inexpensive and non-toxic aluminum is a promising alternative material with a plasmon resonance that can also be tuned via size-, shape- and surface-oxide-control. Here, we employ solution-processed methods to synthesize stable colloidal aluminum nanoparticles. We systematically investigate parameters in the synthesis that control size, shape and oxidation of the aluminum nanoparticles and tune their LSPRs over the ultraviolet and visible spectral regions. We optically characterize the nanoparticle solutions and evaluate their potential for future integration into photovoltaic, photocatalytic and photosensing systems.

  2. Magnetic order of Au nanoparticle with clean surface

    NASA Astrophysics Data System (ADS)

    Sato, Ryuju; Ishikawa, Soichiro; Sato, Hiroyuki; Sato, Tetsuya

    2015-11-01

    Au nanoparticles, which are kept in vacuum after the preparation by gas evaporation method, show ferromagnetism even in 1.7 nm in diameter. The intrinsic magnetism is examined by detecting the disappearance of spontaneous magnetization in Au bulk prepared by heating the nanoparticles without exposure to the air. The temperature dependence of spontaneous magnetization is not monotonic and the increase in magnetization is observed after Au nanoparticles are exposed to the air. The magnetic behavior can be interpreted by the ferrimagnetic-like core-shell structure with shell thickness of 0.16±0.01 nm and magnetic moment of (1.5±0.1)×10-2 μB/Au atom, respectively.

  3. Surface modification strategies on mesoporous silica nanoparticles for anti-biofouling zwitterionic film grafting.

    PubMed

    Khung, Yit Lung; Narducci, Dario

    2015-12-01

    In the past decade, zwitterionic-based anti-biofouling layers had gained much focus as a serious alternative to traditional polyhydrophilic films such as PEG. In the area of assembling silica nanoparticles with stealth properties, the incorporation of zwitterionic surface film remains fairly new but considering that silica nanoparticles had been widely demonstrated as useful biointerfacing nanodevice, zwitterionic film grafting on silica nanoparticle holds much potential in the future. This review will discuss on the conceivable functional chemistry approaches, some of which are potentially suitable for the assembly of such stealth systems. PMID:26589704

  4. Surface enhanced Raman scattering by graphene-nanosheet-gapped plasmonic nanoparticle arrays for multiplexed DNA detection

    NASA Astrophysics Data System (ADS)

    Duan, Bo; Zhou, Jiajing; Fang, Zheng; Wang, Chenxu; Wang, Xiujuan; Hemond, Harold F.; Chan-Park, Mary B.; Duan, Hongwei

    2015-07-01

    We have developed a new type of surface enhanced Raman scattering (SERS) substrate with thiolated graphene oxide (tGO) nanosheets sandwiched between two layers of closely packed plasmonic nanoparticles. The trilayered substrate is built up through alternative loading of interfacially assembled plasmonic nanoparticle arrays and tGO nanosheets, followed by coating the nanoparticle surfaces with poly(ethylene glycol) (PEG). Here tGO plays multifunctional roles as a 2D scaffold to immobilized interfacially assembled plasmonic nanoparticles, a nanospacer to create SERS-active nanogaps between two layers of nanoparticle arrays, and a molecule harvester to enrich molecules of interest via π-π interaction. In particular, the molecule harvesting capability of the tGO nanospacer and the stealth properties of PEG coating on the plasmonic nanoparticles collectively lead to preferential positioning of selective targets such as aromatic molecules and single-stranded DNA at the SERS-active nanogap hotspots. We have demonstrated that an SERS assay based on the PEGylated trilayered substrate, in combination with magnetic separation, allows for sensitive, multiplexed ``signal-off'' detection of DNA sequences of bacterial pathogens.We have developed a new type of surface enhanced Raman scattering (SERS) substrate with thiolated graphene oxide (tGO) nanosheets sandwiched between two layers of closely packed plasmonic nanoparticles. The trilayered substrate is built up through alternative loading of interfacially assembled plasmonic nanoparticle arrays and tGO nanosheets, followed by coating the nanoparticle surfaces with poly(ethylene glycol) (PEG). Here tGO plays multifunctional roles as a 2D scaffold to immobilized interfacially assembled plasmonic nanoparticles, a nanospacer to create SERS-active nanogaps between two layers of nanoparticle arrays, and a molecule harvester to enrich molecules of interest via π-π interaction. In particular, the molecule harvesting capability of

  5. Selectivity of Ligand-Receptor Interactions between Nanoparticle and Cell Surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Shihu; Dormidontova, Elena E.

    2012-12-01

    Selectivity of interactions between nanoparticles functionalized by tethered ligands and cell surfaces with different densities of receptors plays an essential role in biorecognition and its implementation in nanobiomedicine. We show that the onset of nanoparticle adsorption has a universal character for a range of nanoparticles: the onset receptor density decreases exponentially with the energy of ligand-receptor binding and inversely with the ligand density. We demonstrate that a bimodal tether distribution, which permits shielding ligands by longer nonfunctional tethers, leads to extra loss of entropy at the adsorption onset, enhancing the selectivity.

  6. Theoretical study of the amphoteric oxide nanoparticle surface charge during multi-particle interactions in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Alfimov, A. V.; Aryslanova, E. M.; Chivilikhin, S. A.

    2015-11-01

    Nanoparticle surface charge plays an important role in many biological applications. In this study, an analytical surface charging model for the amphoteric oxide nanoparticles has been presented. The model accounts for the particle's electric double layer self-action on the charging process and the charge regulation during multi-particle interactions in aqueous solutions. The employment of the model allows to explicitly describe the nanoparticle agglomeration process and the accompanying agglomerate surface charge variation.

  7. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

    SciTech Connect

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; Schwartz, Thomas J.; Dumesic, James A.; Shanks, Brent H.; Pruski, Marek

    2015-11-20

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticles. In addition, by offering >2500-fold time savings, the technique enabled the observation of 13C-13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  8. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR

    DOE PAGESBeta

    Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi; Schwartz, Thomas J.; Dumesic, James A.; Shanks, Brent H.; Pruski, Marek

    2015-11-20

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticles. In addition, by offering >2500-fold time savings, the technique enabled the observation of 13C-13C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface.

  9. Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR.

    PubMed

    Johnson, Robert L; Perras, Frédéric A; Kobayashi, Takeshi; Schwartz, Thomas J; Dumesic, James A; Shanks, Brent H; Pruski, Marek

    2016-01-31

    DNP-NMR spectroscopy has been applied to enhance the signal for organic molecules adsorbed on γ-Al2O3-supported Pd nanoparticle catalysts. By offering >2500-fold time savings, the technique enabled the observation of (13)C-(13)C cross-peaks for low coverage species, which were assigned to products from oxidative degradation of methionine adsorbed on the nanoparticle surface. PMID:26675287

  10. Fabrication of condensate microdrop self-propelling porous films of cerium oxide nanoparticles on copper surfaces.

    PubMed

    Luo, Yuting; Li, Juan; Zhu, Jie; Zhao, Ye; Gao, Xuefeng

    2015-04-13

    Condensate microdrop self-propelling (CMDSP) surfaces have attracted intensive interest. However, it is still challenging to form metal-based CMDSP surfaces. We design and fabricate a type of copper-based CMDSP porous nanoparticle film. An electrodeposition method based on control over the preferential crystal growth of isotropic nanoparticles and synergistic utilization of tiny hydrogen bubbles as pore-making templates is adopted for the in situ growth of cerium oxide porous nanoparticle films on copper surfaces. After characterizing their microscopic morphology, crystal structure and surface chemistry, we explore their CMDSP properties. The nanostructure can realize the efficient ejection of condensate microdrops with sizes below 50 μm. PMID:25693502

  11. Dynamic nanoproteins: self-assembled peptide surfaces on monolayer protected gold nanoparticles.

    PubMed

    Garcia Martin, Sergio; Prins, Leonard J

    2016-07-19

    Here, we demonstrate the formation of dynamic peptide surfaces through the self-assembly of small peptides on the surface of monolayer protected gold nanoparticles. The complexity of the peptide surface can be simply tuned by changing the chemical nature of the added peptides and the ratio in which these are added. The dynamic nature of the surface permits adaptation to changes in the environment. PMID:27374419

  12. Enhanced hydrophobicity of polyurethane via non-solvent induced surface aggregation of silica nanoparticles.

    PubMed

    Seyfi, Javad; Hejazi, Iman; Jafari, Seyed Hassan; Khonakdar, Hossein Ali; Simon, Frank

    2016-09-15

    Fabrication of superhydrophobic surfaces from hydrophilic polymers has always been regarded as a challenge. In this study, to achieve superhydrophobic polyurethane (PU) surfaces, silica nanoparticles and ethanol as non-solvent were simultaneously utilized during a solution casting-based process. Such modified version of phase separation process was found to be highly efficient, and also it required much lower concentration of nanoparticles to achieve superhydrophobicity as compared to the previously reported methods in the literature. According to the proposed mechanism, non-solvent induces a more profound aggregation of silica nanoparticles at the surface's top layer causing the surface energy to be highly diminished, and thus, the water repellency is improved. Morphology and topography results showed that a unique "triple-sized" structure was formed on the surface of superhydrophobic samples. X-ray photoelectron spectroscopy results proved that both PU macromolecules and silica nanoparticles were concurrently present at the surface layer of the superhydrophobic sample. It was concluded that surface composition and roughness could be regarded as competing factors in achieving superhydrophobicity. Based on the obtained results, the proposed method exhibits a promising potential in large-scale fabrication of surface layers with superhydrophobic property. Moreover, a mechanism was also presented to further explicate the physics behind the suggested method. PMID:27288577

  13. FDTD/TDSE study of surface-enhanced infrared absorption by metal nanoparticles.

    SciTech Connect

    Chang, S.-H.; Schatz, G. C.; Gray, S. K.; Chemistry; Northwestern Univ.; National Cheng-Kung Univ.

    2006-01-01

    We study surface-enhanced infrared absorption, including multiphoton processes, due to the excitation of surface plasmons on metal nanoparticles. The time-dependent Schroedinger equation and finite-difference time-domain method are self-consistently coupled to treat the problem.

  14. Antibacterial Efficacy of Iron-Oxide Nanoparticles against Biofilms on Different Biomaterial Surfaces

    PubMed Central

    Thukkaram, Monica; Sitaram, Soundarya; Kannaiyan, Sathish kumar; Subbiahdoss, Guruprakash

    2014-01-01

    Biofilm growth on the implant surface is the number one cause of the failure of the implants. Biofilms on implant surfaces are hard to eliminate by antibiotics due to the protection offered by the exopolymeric substances that embed the organisms in a matrix, impenetrable for most antibiotics and immune cells. Application of metals in nanoscale is considered to resolve biofilm formation. Here we studied the effect of iron-oxide nanoparticles over biofilm formation on different biomaterial surfaces and pluronic coated surfaces. Bacterial adhesion for 30 min showed significant reduction in bacterial adhesion on pluronic coated surfaces compared to other surfaces. Subsequently, bacteria were allowed to grow for 24 h in the presence of different concentrations of iron-oxide nanoparticles. A significant reduction in biofilm growth was observed in the presence of the highest concentration of iron-oxide nanoparticles on pluronic coated surfaces compared to other surfaces. Therefore, combination of polymer brush coating and iron-oxide nanoparticles could show a significant reduction in biofilm formation. PMID:25332720

  15. Preparation of porous polymer monoliths featuring enhanced surface coverage with gold nanoparticles

    PubMed Central

    Lv, Yongqin; Alejandro, Fernando Maya; Fréchet, Jean M. J.

    2012-01-01

    A new approach to the preparation of porous polymer monoliths with enhanced coverage of pore surface with gold nanoparticles has been developed. First, a generic poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith was reacted with cystamine followed by the cleavage of its disulfide bonds with tris(2-carboxylethyl)phosphine which liberated the desired thiol groups. Dispersions of gold nanoparticles with sizes varying from 5 to 40 nm were then pumped through the functionalized monoliths. The materials were then analyzed using both energy dispersive X-ray spectroscopy and thermogravimetric analysis. We found that the quantity of attached gold was dependent on the size of nanoparticles, with the maximum attachment of more than 60 wt% being achieved with 40 nm nanoparticles. Scanning electron micrographs of the cross sections of all the monoliths revealed the formation of a non-aggregated, homogenous monolayer of nanoparticles. The surface of the bound gold was functionalized with 1-octanethiol and 1-octadecanethiol, and these monolithic columns were used successfully for the separations of proteins in reversed phase mode. The best separations were obtained using monoliths modified with 15, 20, and 30 nm nanoparticles since these sizes produced the most dense coverage of pore surface with gold. PMID:22542442

  16. Cationic Surface Modification of PLG Nanoparticles Offers Sustained Gene Delivery to Pulmonary Epithelial Cells

    PubMed Central

    BAOUM, ABDULGADER; DHILLON, NAVNEET; BUCH, SHILPA; BERKLAND, CORY

    2010-01-01

    Biodegradable polymeric nanoparticles are currently being explored as a nonviral gene delivery system; however, many obstacles impede the translation of these nanomaterials. For example, nanoparticles delivered systemically are inherently prone to adsorbing serum proteins and agglomerating as a result of their large surface/volume ratio. What is desired is a simple procedure to prepare nanoparticles that may be delivered locally and exhibit minimal toxicity while improving entry into cells for effectively delivering DNA. The objective of this study was to optimize the formulation of poly(D,L-lactide-co-glycolide) (PLG) nanoparticles for gene delivery performance to a model of the pulmonary epithelium. Using a simple solvent diffusion technique, the chemistry of the particle surface was varied by using different coating materials that adsorb to the particle surface during formation. A variety of cationic coating materials were studied and compared to more conventional surfactants used for PLG nanoparticle fabrication. Nanoparticles (~200 nm) efficiently encapsulated plasmids encoding for luciferase (80–90%) and slowly released the same for 2 weeks. In A549 alveolar lung epithelial cells, high levels of gene expression appeared at day 5 for certain positively charged PLG particles and gene expression was maintained for at least 2 weeks. In contrast, PEI gene expression ended at day 5. PLG particles were also significantly less cytotoxic than PEI suggesting the use of these vehicles for localized, sustained gene delivery to the pulmonary epithelium. PMID:19911425

  17. Surface engineered gold nanoparticles through highly stable metal-surfactant complexes.

    PubMed

    Kim, Sunghwan; Jang, Youngjin; Yoon, Ki Youl; Park, Jongnam

    2016-02-15

    Monodispersed Au nanoparticles were synthesized by the reduction of Au-decyltrimethylammonium bromide (Au-DTAB), which was easily prepared via the reaction of HAuCl4 and DTAB. This Au-DTAB complex is highly stable in air and moisture, and suitable for large-scale synthesis of uniform-sized Au nanoparticles. The nanoparticles were characterized by transmission electron microscopy, optical absorption spectrometry, X-ray diffraction, and Fourier Transform infrared spectroscopy. The size of Au nanoparticles was controlled in the range of 5-10nm by changing the concentrations of reducing agent and Au precursor. The resulting Au nanoparticles were transferred to the aqueous phase after surface engineering using multidentate polymeric ligands with multiple imidazole functional groups. Polymeric imidazole ligands (PILs) demonstrated enhanced binding stability with the Au surface, and overcame the disadvantage of multidentate thiol ligand systems which have oxidative cross-linking and the formation of disulfide bonding. The colloidal stability of surface engineered Au nanoparticles with PILs was investigated by dynamic light scattering (DLS) characterization. PMID:26609930

  18. Directed Nanoparticle Assembly onto Random Copolymer Templates: Kinetics and Surface Considerations

    NASA Astrophysics Data System (ADS)

    McConnell, Marla; Yang, Shu; Composto, Russell

    2008-03-01

    Recent efforts have focused on the development of nanoparticle arrays with controlled spacing. In this study, poly(styrene-ran-acrylic acid) films were prepared by spin-casting poly(styrene-ran-t-butyl acrylate), followed by thermal deprotection. Silica nanoparticles (10-15 nm in diameter) coated with self-assembled monolayers (SAMs) of (3-aminopropyl)triethoxysilane were covalently attached to the PS-ran-PAA films with an EDC/NHS coupling reaction. To measure the kinetics of nanoparticle attachment, films of either 25 or 50 weight percent acrylic acid were reacted with nanoparticle suspensions from 0.005 to 0.1 weight percent for varying lengths of time. SEM imaging of the nanoparticle surfaces showed that the particles were well dispersed, and that particle coverage increased with increasing AA and nanoparticle concentration, and time. SAMs containing an acrylic acid moiety were used as a non-swelling control surface, and particle attachment to these surfaces follow different kinetics than those observed for the polymeric substrates. The swelling of the polymeric substrates under the reaction conditions was found to influence the observed coverage kinetics, so film swelling was monitored with environmental AFM.

  19. [Three-dimensional vertically aligned CNTs coated by Ag nanoparticles for surface-enhanced Raman scattering].

    PubMed

    Zhang, Xiao-Lei; Zhang, Jie; Fan, Tuo; Ren, Wen-Jie; Lai, Chun-Hong

    2014-09-01

    In order to make surface-enhanced Raman scattering (SERS) substrates contained more "hot spots" in a three-dimensional (3D) focal volume, and can be adsorbed more probe molecules and metal nanoparticles, to obtain stronger Raman spectral signal, a new structure based on vertically aligned carbon nanotubes (CNTs) coated by Ag nanoparticles for surface Raman enhancement is presented. The vertically aligned CNTs are synthesized by chemical vapor deposition (CVD). A silver film is first deposited on the vertically aligned CNTs by magnetron sputtering. The samples are then annealed at different temperature to cause the different size silver nanoparticles to coat on the surface and sidewalls of vertically aligned CNTs. The result of scanning electron microscopy(SEM) shows that Ag nanoparticles are attached onto the sidewalls and tips of the vertically aligned CNTs, as the annealing temperature is different , pitch size, morphology and space between the silver nanoparticles is vary. Rhodamine 6G is served as the probe analyte. Raman spectrum measurement indicates that: the higher the concentration of R6G, the stronger the Raman intensity, but R6G concentration increase with the enhanced Raman intensity varies nonlinearly; when annealing temperature is 450 °C, the average size of silver nanoparticles is about 100 to 120 nm, while annealing temperature is 400 °C, the average size is about 70 nm, and the Raman intensity of 450 °C is superior to the annealing temperature that of 400 °C and 350 °C. PMID:25532342

  20. Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy.

    PubMed

    DeVetter, Brent M; Mukherjee, Prabuddha; Murphy, Catherine J; Bhargava, Rohit

    2015-05-21

    Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min(-1). This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. PMID:25905515

  1. Surface Structure of Protonated R-Sapphire (1$\\bar{1}$02) Studied by Sum-Frequency Vibrational Spectroscopy

    SciTech Connect

    Sung, Jaeho; Zhang, Luning; Tian, Chuanshan; Waychunas, Glenn A.; Shen, Y. Ron

    2011-03-23

    Sum frequency vibrational spectroscopy was used to study the protonated R-plane (1$\\bar{1}$02 ) sapphire surface. The OH stretch vibrational spectra show that the surface is terminated with three hydroxyl moieties, two from AlOH2 and one from Al2OH functional groups. The observed polarization dependence allows determination of the orientations of the three OH species. The results suggest that the protonated sapphire (1$\\bar{1}$02 ) surface differs from an ideal stoichimetric termination in a manner consistent with previous X-ray surface diffraction (crystal truncation rod) studies. However, in order to best explain the observed hydrogenbonding arrangement, surface oxygen spacing determined from the X-ray diffraction study requires modification.

  2. Gold nanoparticle-catalyzed reduction in a model system: Quantitative determination of reactive heterogeneity of a supported nanoparticle surface

    SciTech Connect

    Nigra, Michael M.; Arslan, Ilke; Katz, Alexander

    2012-11-01

    Kinetic poisoning experiments employing organic ligands were conducted using a gold nanoparticle–catalyzed reaction consisting of the reduction of resazurin to resorufin. The kinetic contributions of three distinct types of sites along with the number density of each of these site types during reaction were determined. The calculated number densities of each of the three types of sites, hypothesized to be corners, edges, and terraces, correlates well with atomic-resolution micrographs of the supported gold nanoparticles, obtained using aberration-corrected transmission electron microscopy and with predictions based on geometric models of idealized gold nanoparticles. The most active sites comprising 1% of the surface atoms exhibit at least 30% of the total activity of the catalyst for resazurin reduction. The selective mechanical blocking of surface sites on nanoparticles, particularly undercoordinated sites, paves the way for novel approaches utilizing organic ligands to quantify the activity of different active sites and control catalysis on metal surfaces. This work was supported in part by the Laboratory Directed Research and Development program at the Pacific Northwest National Laboratory (PNNL). The aberration-corrected electron microscopy was performed in the William R. Wiley Environmental Molecular Sciences Laboratory, a U.S. Department of Energy (DOE) national scientific user facility located at PNNL and funded by BER. PNNL is operated by Battelle for the U.S. DOE under contract DE-AC05-76RL01830.

  3. Segregation of Fischer-Tropsch reactants on cobalt nanoparticle surfaces.

    PubMed

    Lewis, E A; Le, D; Jewell, A D; Murphy, C J; Rahman, T S; Sykes, E C H

    2014-06-21

    Using scanning tunnelling microscopy, we have visualized the segregation of carbon monoxide and hydrogen, the two reactants in Fischer-Tropsch synthesis, on cobalt nanoparticles at catalytically relevant coverages. Density functional theory was used to interrogate the relevant energetics. PMID:24825772

  4. Controlled Assembly of Viral Surface Proteins into Biological Nanoparticles

    NASA Astrophysics Data System (ADS)

    Nakatani-Webster, Eri

    In recent years, therapeutic use of engineered particles on the 1-1,000 nm scale has gained popularity; these nanoparticles have been developed for use in drug delivery, gene therapy, vaccine preparation, and diagnostics. Often, viral proteins are utilized in the design of such species, and outlined here are completed studies on the in vitro assembly of nanoparticles derived from two very different viral systems. The incorporation of the human immunodeficiency virus (HIV) envelope glycoprotein precursor gp160 into phospholipid bilayer nanodiscs is discussed as a potential platform for vaccine design; efforts were successful, however yield currently limits the practical application of this approach. The utility of bacteriophage lambda procapsids and virus-like particles in therapeutic nanoparticle design is also outlined, as are efforts toward the structural and thermodynamic characterization of a urea-triggered capsid maturation event. It is demonstrated that lambda virus-like particles can be assembled from purified capsid and scaffolding proteins, and that these particles undergo urea-triggered maturation and in vitro decoration protein addition similar to that seen in lambda procapsids. The studies on lambda provided materials for the further development of nanoparticles potentially useful in a clinical setting, as well as shedding light on critical viral assembly and maturation events as they may take place in vivo.

  5. Using flow to switch the valency of bacterial capture on engineered surfaces containing immobilized nanoparticles.

    PubMed

    Fang, Bing; Gon, Saugata; Park, Myoung-Hwan; Kumar, Kushi-Nidhi; Rotello, Vincent M; Nüsslein, Klaus; Santore, Maria M

    2012-05-22

    Toward an understanding of nanoparticle-bacterial interactions and the development of sensors and other substrates for controlled bacterial adhesion, this article describes the influence of flow on the initial stages of bacterial capture (Staphylococcus aureus) on surfaces containing cationic nanoparticles. A PEG (poly(ethylene glycol)) brush on the surface around the nanoparticles sterically repels the bacteria. Variations in ionic strength tune the Debye length from 1 to 4 nm, increasing the strength and range of the nanoparticle attractions toward the bacteria. At relatively high ionic strengths (physiological conditions), bacterial capture requires several nanoparticle-bacterial contacts, termed "multivalent capture". At low ionic strength and gentle wall shear rates (on the order of 10 s(-1)), individual bacteria can be captured and held by single surface-immobilized nanoparticles. Increasing the flow rate to 50 s(-1) causes a shift from monovalent to divalent capture. A comparison of experimental capture efficiencies with statistically determined capture probabilities reveals the initial area of bacteria-surface interaction, here about 50 nm in diameter for a Debye length κ(-1) of 4 nm. Additionally, for κ(-1) = 4 nm, the net per nanoparticle binding energies are strong but highly shear-sensitive, as is the case for biological ligand-receptor interactions. Although these results have been obtained for a specific system, they represent a regime of behavior that could be achieved with different bacteria and different materials, presenting an opportunity for further tuning of selective interactions. These finding suggest the use of surface elements to manipulate individual bacteria and nonfouling designs with precise but finite bacterial interactions. PMID:22563906

  6. Large range localized surface plasmon resonance of Ag nanoparticles films dependent of surface morphology

    NASA Astrophysics Data System (ADS)

    Yan, Lijuan; Yan, Yaning; Xu, Leilei; Ma, Rongrong; Jiang, Fengxian; Xu, Xiaohong

    2016-03-01

    Noble metal nanoparticles (NPs) have received enormous attention since it displays uniquely optical and electronic properties. In this work, we study localized surface plasmon resonances (LSPR) at different thicknesses and substrate temperatures of Ag NPs films grown by Laser Molecule Beam Epitaxy (LMBE). The LSPR wavelength can be largely tuned in the visible light range of 470 nm to 770 nm. The surface morphology is characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The average size of Ag NPs increased with the thickness increased which leading to the LSPR band broaden and wavelength red-shift. As the substrate temperature is increased from RT to 200 °C, the Ag NPs size distribution becomes homogeneous and particle shape changes from oblate spheroid to sphere, the LSPR band displays sharp, blue-shift and significantly symmetric. Obviously, the morphology of Ag NPs films is important for tuning absorption position. We obtain the cubic crystal structure of Ag NPs with a (1 1 1) main diffraction peak from the X-ray diffraction (XRD) spectra. The high resolution TEM (HR-TEM) and selected area electron diffraction (SAED) prove that Ag NPs is polycrystal structure. The Ag NPs films with large range absorption in visible light region can composite with semiconductor to apply in various optical or photoelectric devices.

  7. Effect of Surface and Salt Properties on the Ion Distribution around Spherical Nanoparticles: Monte Carlo Simulations.

    PubMed

    Clavier, Arnaud; Carnal, Fabrice; Stoll, Serge

    2016-08-18

    Nanoparticle surface charge properties represent key parameters to predict their fate, reactivity, and complexation in natural, biological, and industrial dispersions. In this context, we present here an original approach to better understand the surface charge electrostatic properties of spherical nanoparticles (NPs). The ion distribution around one nanoparticle is investigated using Monte Carlo simulations and by adjusting a wide range of parameters including NP properties (surface charge density and site distribution), salt concentration (ionic strength and cation concentration), and salt valency (mono-, di-, and trivalent salt). A canonical Metropolis Monte Carlo method is used to reach equilibrium states and a primitive Coulomb model is applied to describe the electrostatic interactions between explicit discrete sites, counterions, and salt particles. Our results show that the presence of explicit surface charges on the NP and in solution has a strong influence on the local ion distribution and on the effective surface charge of the nanoparticles. The increase of surface charge density reduces the NP effective charge by the formation of a condensation layer around the nanoparticle. However, a limit of condensation is achieved due to steric effects and electrostatic repulsions. The presence of di- and trivalent cations is also found to strongly modify the effective charge and improve condensation state as long as electrostatic repulsion between the cations close to the surface are not so strong. At high trivalent cation concentration, the NP effective charge is greatly reduced and the local environment around the nanoparticle becomes more structured with the formation of a multi layer structure composed by anions and cations. PMID:27459187

  8. Interfacial Atmospheric Chemistry: Quantum Chemical Calculations on the Mechanism of Protonation and Oligomerization of Isoprene on Aqueous Surfaces

    NASA Astrophysics Data System (ADS)

    Mishra, H.; Colussi, A. J.; Enami, S.; Nielsen, R. J.; Hoffmann, M. R.; Goddard, W. A.

    2012-12-01

    It has become increasingly apparent that atmospheric chemistry involves more than gas-phase reactions. Key processes, such as the decay of NO2 in urban plumes and the associated daytime formation of HONO, and the rapid chemistries observed in and over forest canopies at nighttime defy explanation by conventional atmospheric chemistry mechanisms. We have recently reported experimental results on several gas-liquid reactions of atmospheric interest, such as the facile protonation of gaseous isoprene on mildly acidic (pH < 4) water. Although interfacial proton transfers, such as the one involved in the protonation of gaseous isoprene, also participate in cloud and ocean acidification, bioenergetics coupling, 'on-water' catalysis, self-assembly and molecular recognition, little is known about the molecular mechanisms of such reactions. Herein we apply quantum mechanics to investigate how biogenic or anthropogenic olefins may get protonated and undergo oligomerization at the air-water interface by performing model calculations on small water clusters carrying an excess proton as surrogates for the surface of mildly acidic water as sensed by gaseous isoprene (ISO). We find that ISO binds weakly to the surface of water and accepts a proton from H+(H2O)3, leading to ISOH+ via a proton transfer hindered by a ΔG1‡ = 5.6 kcal mol-1 kinetic barrier. Subsequently, another ISO attaches loosely to this ensemble, before being attacked by the ISOH+. This process, which represents the first step of the cationic polymerization of ISO, is hindered by a similar ΔG2‡ = 5.7 kcal mol-1 barrier. Our theoretical results are consistent with experimental (~ 10-4) uptake coefficients for ISO measured on acidic water.

  9. High-resolution investigation of metal nanoparticle growth on an insulating surface

    NASA Astrophysics Data System (ADS)

    Mativetsky, Jeffrey M.; Fostner, Shawn; Burke, Sarah A.; Grutter, Peter

    2009-07-01

    The three-dimensional nanoparticle morphology and the nanoparticle-substrate relationship during the submonolayer growth of three metals (gold, tantalum, and palladium) on the alkali halide KBr (001) surface is investigated by combining in situ high-resolution noncontact atomic force microscopy and ex situ transmission electron microscopy approaches. Highly varied growth behavior between the metals is revealed. Gold produces nearly spherical multiply twinned nanoparticles at room temperature and an increasing number of epitaxial particles at elevated temperatures. In contrast, the tantalum grows as relatively flat fractal particles, despite the square symmetry of the substrate lattice, a condition which normally precludes fractal growth. The tantalum also exhibits a strong affinity for KBr surface steps, leading to one-dimensional chains of nanoparticles. The deposition of palladium results in the creation of protruding substrate distortions and monolayer-high rectangular KBr islands in addition to the growth of palladium nanoparticles. It is hypothesized that the unusual growth observed in the palladium-KBr system is caused by the interdiffusion of palladium under the KBr surface. The range of growth behavior in the three systems is described in terms of the surface and interface energies, yielding bounds on the metal/KBr interface energies.

  10. Synthesis and surface engineering of magnetic nanoparticles for environmental cleanup and pesticide residue analysis: a review.

    PubMed

    Kaur, Ranjeet; Hasan, Abshar; Iqbal, Nusrat; Alam, Samsul; Saini, Mahesh Kr; Raza, Syed Kalbe

    2014-07-01

    In recent years, water pollution and pesticide accumulation in the food chain have become a serious environmental and health hazard problem. Direct determination of these contaminants is a difficult task due to their low concentration level and the matrix interferences. Therefore, an efficient separation and preconcentration procedure is often required prior to the analysis. With the advancement in nanotechnology, various types of magnetic core-shell nanoparticles have successfully been synthesized and received considerable attention as sorbents for decontamination of diverse matrices. Magnetic core-shell nanoparticles with surface modifications have the advantages of large surface-area-to-volume ratio, high number of surface active sites, no secondary pollutant, and high magnetic properties. Due to their physicochemical properties, surface-modified magnetic core-shell nanoparticles exhibit high adsorption efficiency, high rate of removal of contaminants, and easy as well as rapid separation of adsorbent from solution via external magnetic field. Such facile separation is essential to improve the operation efficiency. In addition, reuse of nanoparticles would substantially reduce the treatment cost. In this review article, we have attempted to summarize recent studies that address the preconcentration methods of pesticide residue analysis and removal of toxic contaminants from aquatic systems using magnetic core-shell nanoparticles as adsorbents. PMID:24777942

  11. YAG laser surface densification of a zircon refractory by adding AlN nanoparticles

    SciTech Connect

    Wang, W.Y.; Wang, A.H. . E-mail: pmahwang@public.wh.hb.cn; Zeng, D.W.; Bai, Z.K.; Xie, C.S.; Song, W.L.; Zhu, X.C.

    2006-04-15

    A zircon refractory zirconium silicate was surface melted with a pulsed YAG laser to introduce AlN nanoparticles, with the aim of improving its surface density and modifying the corresponding microstructure. The microstructure and phase structure features of the refractory induced by the laser beam were studied by scanning transmission microscopy, incorporating energy dispersive X-ray and X-ray diffraction analysis. Results show that the addition of AlN nanoparticles into the refractory surface significantly reduced the laser beam energy required to melt the surface of the refractory. The laser-melted depth was increased with an increase of laser power from 133 to 200 W. The microstructure of the laser-treated zone with the addition of AlN nanoparticles has a much finer dendritic structure with undeveloped primary dendrite arms while without the addition of AlN nanoparticles, a coarser dendrite with much long primary dendrite arms was observed. The phase structure of the laser-treated layer with the addition of AlN nanoparticles was found to be composed of m-ZrO{sub 2}, c-ZrO{sub 2}, ZrSiO{sub 4} and H-AlN.

  12. Physicochemical properties of surface charge-modified ZnO nanoparticles with different particle sizes

    PubMed Central

    Kim, Kyoung-Min; Choi, Mun-Hyoung; Lee, Jong-Kwon; Jeong, Jayoung; Kim, Yu-Ri; Kim, Meyoung-Kon; Paek, Seung-Min; Oh, Jae-Min

    2014-01-01

    In this study, four types of standardized ZnO nanoparticles were prepared for assessment of their potential biological risk. Powder-phased ZnO nanoparticles with different particle sizes (20 nm and 100 nm) were coated with citrate or L-serine to induce a negative or positive surface charge, respectively. The four types of coated ZnO nanoparticles were subjected to physicochemical evaluation according to the guidelines published by the Organisation for Economic Cooperation and Development. All four samples had a well crystallized Wurtzite phase, with particle sizes of ∼30 nm and ∼70 nm after coating with organic molecules. The coating agents were determined to have attached to the ZnO surfaces through either electrostatic interaction or partial coordination bonding. Electrokinetic measurements showed that the surface charges of the ZnO nanoparticles were successfully modified to be negative (about −40 mV) or positive (about +25 mV). Although all the four types of ZnO nanoparticles showed some agglomeration when suspended in water according to dynamic light scattering analysis, they had clearly distinguishable particle size and surface charge parameters and well defined physicochemical properties. PMID:25565825

  13. Physicochemical properties of surface charge-modified ZnO nanoparticles with different particle sizes.

    PubMed

    Kim, Kyoung-Min; Choi, Mun-Hyoung; Lee, Jong-Kwon; Jeong, Jayoung; Kim, Yu-Ri; Kim, Meyoung-Kon; Paek, Seung-Min; Oh, Jae-Min

    2014-01-01

    In this study, four types of standardized ZnO nanoparticles were prepared for assessment of their potential biological risk. Powder-phased ZnO nanoparticles with different particle sizes (20 nm and 100 nm) were coated with citrate or L-serine to induce a negative or positive surface charge, respectively. The four types of coated ZnO nanoparticles were subjected to physicochemical evaluation according to the guidelines published by the Organisation for Economic Cooperation and Development. All four samples had a well crystallized Wurtzite phase, with particle sizes of ∼30 nm and ∼70 nm after coating with organic molecules. The coating agents were determined to have attached to the ZnO surfaces through either electrostatic interaction or partial coordination bonding. Electrokinetic measurements showed that the surface charges of the ZnO nanoparticles were successfully modified to be negative (about -40 mV) or positive (about +25 mV). Although all the four types of ZnO nanoparticles showed some agglomeration when suspended in water according to dynamic light scattering analysis, they had clearly distinguishable particle size and surface charge parameters and well defined physicochemical properties. PMID:25565825

  14. Surface modification of MPEG-b-PCL-based nanoparticles via oxidative self-polymerization of dopamine for malignant melanoma therapy.

    PubMed

    Xiong, Wei; Peng, Lixia; Chen, Hongbo; Li, Qin

    2015-01-01

    To enhance the therapeutic effects of chemotherapy on malignant melanoma, paclitaxel (PTX)-loaded methoxy poly(ethylene glycol)-b-poly(ε-caprolactone) nanoparticles (MPEG-b-PCL NPs) that had their surfaces modified with polydopamine (PTX-loaded MPEG-b-PCL NPs@PDA) were prepared as drug vehicles. The block copolymer MPEG-b-PCL was synthesized by ring-opening polymerization and characterized by proton nuclear magnetic resonance spectroscopy and gel permeation chromatography. The PTX-loaded NPs were prepared by a modified nanoprecipitation technique. The PTX-loaded NPs and PTX-loaded NPs@PDA were characterized in terms of size and size distribution, zeta potential, surface morphology, drug encapsulation efficiency, and drug release. Confocal laser scanning microscopy showed that coumarin-6-loaded NPs@PDA could be internalized by human melanoma cell line A875 cells. The cellular uptake efficiency of NPs was greatly enhanced after PDA modification. The antitumor efficacy of the PTX-loaded NPs@PDA was investigated in vitro by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and in vivo by a xenograft tumor model. The PTX-loaded NPs@PDA could significantly inhibit tumor growth compared to Taxol(®) and precursor PTX-loaded NPs. All the results suggested that the PTX-loaded MPEG-b-PCL NPs that had their surfaces modified with PDA are promising nanocarriers for malignant melanoma therapy. PMID:25945046

  15. Surface modification of MPEG-b-PCL-based nanoparticles via oxidative self-polymerization of dopamine for malignant melanoma therapy

    PubMed Central

    Xiong, Wei; Peng, Lixia; Chen, Hongbo; Li, Qin

    2015-01-01

    To enhance the therapeutic effects of chemotherapy on malignant melanoma, paclitaxel (PTX)-loaded methoxy poly(ethylene glycol)-b-poly(ε-caprolactone) nanoparticles (MPEG-b-PCL NPs) that had their surfaces modified with polydopamine (PTX-loaded MPEG-b-PCL NPs@PDA) were prepared as drug vehicles. The block copolymer MPEG-b-PCL was synthesized by ring-opening polymerization and characterized by proton nuclear magnetic resonance spectroscopy and gel permeation chromatography. The PTX-loaded NPs were prepared by a modified nanoprecipitation technique. The PTX-loaded NPs and PTX-loaded NPs@PDA were characterized in terms of size and size distribution, zeta potential, surface morphology, drug encapsulation efficiency, and drug release. Confocal laser scanning microscopy showed that coumarin-6-loaded NPs@PDA could be internalized by human melanoma cell line A875 cells. The cellular uptake efficiency of NPs was greatly enhanced after PDA modification. The antitumor efficacy of the PTX-loaded NPs@PDA was investigated in vitro by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and in vivo by a xenograft tumor model. The PTX-loaded NPs@PDA could significantly inhibit tumor growth compared to Taxol® and precursor PTX-loaded NPs. All the results suggested that the PTX-loaded MPEG-b-PCL NPs that had their surfaces modified with PDA are promising nanocarriers for malignant melanoma therapy. PMID:25945046

  16. Plasmofluidic single-molecule surface-enhanced Raman scattering from dynamic assembly of plasmonic nanoparticles

    NASA Astrophysics Data System (ADS)

    Patra, Partha Pratim; Chikkaraddy, Rohit; Tripathi, Ravi P. N.; Dasgupta, Arindam; Kumar, G. V. Pavan

    2014-07-01

    Single-molecule surface-enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon polariton-assisted, reversible assembly of plasmonic nanoparticles at an unstructured metal-fluid interface. One of the unique features of our method is that we use a single evanescent-wave optical excitation for nanoparticle assembly, manipulation and SM-SERS measurements. Furthermore, by utilizing dual excitation of plasmons at metal-fluid interface, we create interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures. Our work will have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms.

  17. Plasmofluidic single-molecule surface-enhanced Raman scattering from dynamic assembly of plasmonic nanoparticles.

    PubMed

    Patra, Partha Pratim; Chikkaraddy, Rohit; Tripathi, Ravi P N; Dasgupta, Arindam; Kumar, G V Pavan

    2014-01-01

    Single-molecule surface-enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon polariton-assisted, reversible assembly of plasmonic nanoparticles at an unstructured metal-fluid interface. One of the unique features of our method is that we use a single evanescent-wave optical excitation for nanoparticle assembly, manipulation and SM-SERS measurements. Furthermore, by utilizing dual excitation of plasmons at metal-fluid interface, we create interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures. Our work will have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms. PMID:25000476

  18. Controlled release study of an anti-carcinogenic agent, gallate from the surface of magnetite nanoparticles

    NASA Astrophysics Data System (ADS)

    Ghotbi, Mohammad Yeganeh; bin Hussein, Mohd Zobir

    2012-07-01

    Immobilization of gallate anion, an anti-carcinogenic, anti-mutagenic, and anti-microbial agent on the surface of magnetite nanoparticles was accomplished by adsorption technique for the formation of a core-shell nanocomposite. A simple co-precipitation technique in the presence of poly vinyl pyrrolidone was successfully applied for the preparation of magnetite nanoparticles as core beads with narrow size distribution. The powders were characterized by X-ray diffraction, particle size analysis, magnetic measurements, atomic force microscope and also infrared spectroscopy. FTIR and CHNS results indicated that the gallate anion was actually adsorbed onto the surface of the magnetite nanoparticles. The release of the anion from the surface of the nanocomposite was found to be controllable by the selection of the release media.

  19. Durable superhydrophobic and antireflective surfaces by trimethylsilanized silica nanoparticles-based sol-gel processing.

    PubMed

    Manca, Michele; Cannavale, Alessandro; De Marco, Luisa; Aricò, Antonino S; Cingolani, Roberto; Gigli, Giuseppe

    2009-06-01

    We present a robust and cost-effective coating method to fabricate long-term durable superhydrophobic andsimultaneouslyantireflective surfaces by a double-layer coating comprising trimethylsiloxane (TMS) surface-functionalized silica nanoparticles partially embedded into an organosilica binder matrix produced through a sol-gel process. A dense and homogeneous organosilica gel layer was first coated onto a glass substrate, and then, a trimethylsilanized nanospheres-based superhydrophobic layer was deposited onto it. After thermal curing, the two layers turned into a monolithic film, and the hydrophobic nanoparticles were permanently fixed to the glass substrate. Such treated surfaces showed a tremendous water repellency (contact angle = 168 degrees ) and stable self-cleaning effect during 2000 h of outdoor exposure. Besides this, nanotextured topology generated by the self-assembled nanoparticles-based top layer produced a fair antireflection effect consisting of more than a 3% increase in optical transmittance. PMID:19466786

  20. Construction of boundary-surface-based Chinese female astronaut computational phantom and proton dose estimation.

    PubMed

    Sun, Wenjuan; Jia, Xianghong; Xie, Tianwu; Xu, Feng; Liu, Qian

    2013-03-01

    With the rapid development of China's space industry, the importance of radiation protection is increasingly prominent. To provide relevant dose data, we first developed the Visible Chinese Human adult Female (VCH-F) phantom, and performed further modifications to generate the VCH-F Astronaut (VCH-FA) phantom, incorporating statistical body characteristics data from the first batch of Chinese female astronauts as well as reference organ mass data from the International Commission on Radiological Protection (ICRP; both within 1% relative error). Based on cryosection images, the original phantom was constructed via Non-Uniform Rational B-Spline (NURBS) boundary surfaces to strengthen the deformability for fitting the body parameters of Chinese female astronauts. The VCH-FA phantom was voxelized at a resolution of 2 × 2 × 4 mm(3)for radioactive particle transport simulations from isotropic protons with energies of 5000-10 000 MeV in Monte Carlo N-Particle eXtended (MCNPX) code. To investigate discrepancies caused by anatomical variations and other factors, the obtained doses were compared with corresponding values from other phantoms and sex-averaged doses. Dose differences were observed among phantom calculation results, especially for effective dose with low-energy protons. Local skin thickness shifts the breast dose curve toward high energy, but has little impact on inner organs. Under a shielding layer, organ dose reduction is greater for skin than for other organs. The calculated skin dose per day closely approximates measurement data obtained in low-Earth orbit (LEO). PMID:23135158

  1. Construction of boundary-surface-based Chinese female astronaut computational phantom and proton dose estimation

    PubMed Central

    Sun, Wenjuan; JIA, Xianghong; XIE, Tianwu; XU, Feng; LIU, Qian

    2013-01-01

    With the rapid development of China's space industry, the importance of radiation protection is increasingly prominent. To provide relevant dose data, we first developed the Visible Chinese Human adult Female (VCH-F) phantom, and performed further modifications to generate the VCH-F Astronaut (VCH-FA) phantom, incorporating statistical body characteristics data from the first batch of Chinese female astronauts as well as reference organ mass data from the International Commission on Radiological Protection (ICRP; both within 1% relative error). Based on cryosection images, the original phantom was constructed via Non-Uniform Rational B-Spline (NURBS) boundary surfaces to strengthen the deformability for fitting the body parameters of Chinese female astronauts. The VCH-FA phantom was voxelized at a resolution of 2 × 2 × 4 mm3for radioactive particle transport simulations from isotropic protons with energies of 5000–10 000 MeV in Monte Carlo N-Particle eXtended (MCNPX) code. To investigate discrepancies caused by anatomical variations and other factors, the obtained doses were compared with corresponding values from other phantoms and sex-averaged doses. Dose differences were observed among phantom calculation results, especially for effective dose with low-energy protons. Local skin thickness shifts the breast dose curve toward high energy, but has little impact on inner organs. Under a shielding layer, organ dose reduction is greater for skin than for other organs. The calculated skin dose per day closely approximates measurement data obtained in low-Earth orbit (LEO). PMID:23135158

  2. Energy transport of surface phonon polaritons propagating along a chain of spheroidal nanoparticles

    NASA Astrophysics Data System (ADS)

    Ordonez-Miranda, Jose; Tranchant, Laurent; Gluchko, Sergei; Volz, Sebastian

    2015-09-01

    We analyze in detail the energy transport of surface phonon polaritons propagating in a chain of spheroidal polar nanoparticles with both longitudinal and transversal polarizations. Explicit and closed-form expressions for the dispersion relation and propagation length are derived and used to determine the values of the nanoparticle polarizability and the interparticle distance that maximize the polariton propagation length. The thermal conductance in the ballistic regime and the thermal conductivity in the diffusive one are also determined and examined as a function of the geometry of the nanoparticles and their temperature. For a chain of cigar-shaped SiC nanoparticles in contact, an aspect ratio of 5, and surrounded by air; it is shown that: (i) The surface phonon polaritons propagate a distance of 10 μ m along a chain of 100 nanoparticles. This propagation length is one order of magnitude longer than that for spherical nanoparticles. (ii) The polariton thermal conductivity is comparable with the one of air in a wide range of temperatures and is 41 mW m-1K-1 at 500 K. (iii) The polariton thermal conductance increases with the temperature and at 500 K is 44 pW K-1 , which represents 9 % of the quantum of thermal conductance. In view of the ultralow phonon thermal conductivity of a chain of polar nanoparticles in contact and their high surface area-to-volume ratios, the proposed theoretical model and obtained results are expected to be useful to experimentally quantify the energy transport of surface phonon polaritons propagating along these nanostructures.

  3. Enhancement of surface ligand display on PLGA nanoparticles with amphiphilic ligand conjugates

    PubMed Central

    Park, Jason; Mattessich, Thomas; Jay, Steven M.; Agawu, Atu; Saltzman, W. Mark; Fahmy, Tarek M.

    2013-01-01

    Biodegradable polymeric nanoparticles are widely recognized as efficacious drug delivery vehicles, yet the rational engineering of nanoparticle surfaces in order to improve biodistribution, reduce clearance, and/or improve targeting remains a significant challenge. We have previously demonstrated that an amphiphilic conjugate of avidin and palmitic acid can be used to modify poly(lactic-co-glycolic acid) (PLGA) particle surfaces to display functional avidin groups, allowing for the facile attachment of biotinylated ligands for targeting or steric stabilization. Here, we hypothesized that the incorporation, density, and stability of surface-presented avidin could be modulated through varying the lipophilicity of its fatty acid conjugate partner. We tested this hypothesis by generating a set of novel conjugates incorporating avidin and common fatty acids. We found that conjugation to linoleic acid resulted in a ∼60% increase in the incorporation of avidin on the nanoparticle surface compared to avidin–palmitic acid, which exhibited the highest avidin incorporation in previous studies. Further, the linoleic acid–avidin conjugate yielded nanoparticles with enhanced ability to bind biotinylated ligands compared to the previous method; nanoparticles modified with avidin–linoleic acid bound ∼170% more biotin–HRP than those made with avidin–palmitic acid and ∼1300% more than particles made without conjugated avidin. Most critically, increased ligand density on anti-CD4-targeted nanoparticles formulated with the linoleic acid–avidin conjugate resulted in a 5% increase in binding of CD4+ T cells. Thus we conclude that the novel avidin–linoleic acid conjugate facilitates enhanced ligand density on PLGA nanoparticles, resulting in functional enhancement of cellular targeting. PMID:21723893

  4. Quantitative proteomics analysis of adsorbed plasma proteins classifies nanoparticles with different surface properties and size

    SciTech Connect

    Zhang, Haizhen; Burnum, Kristin E.; Luna, Maria L.; Petritis, Brianne O.; Kim, Jong Seo; Qian, Weijun; Moore, Ronald J.; Heredia-Langner, Alejandro; Webb-Robertson, Bobbie-Jo M.; Thrall, Brian D.; Camp, David G.; Smith, Richard D.; Pounds, Joel G.; Liu, Tao

    2011-12-01

    In biofluids (e.g., blood plasma) nanoparticles are readily embedded in layers of proteins that can affect their biological activity and biocompatibility. Herein, we report a study on the interactions between human plasma proteins and nanoparticles with a controlled systematic variation of properties using stable isotope labeling and liquid chromatography-mass spectrometry (LC-MS) based quantitative proteomics. Novel protocol has been developed to simplify the isolation of nanoparticle bound proteins and improve the reproducibility. Plasma proteins associated with polystyrene nanoparticles with three different surface chemistries and two sizes as well as for four different exposure times (for a total of 24 different samples) were identified and quantified by LC-MS analysis. Quantitative comparison of relative protein abundances were achieved by spiking an 18 O-labeled 'universal reference' into each individually processed unlabeled sample as an internal standard, enabling simultaneous application of both label-free and isotopic labeling quantitation across the sample set. Clustering analysis of the quantitative proteomics data resulted in distinctive pattern that classifies the nanoparticles based on their surface properties and size. In addition, data on the temporal study indicated that the stable protein 'corona' that was isolated for the quantitative analysis appeared to be formed in less than 5 minutes. The comprehensive results obtained herein using quantitative proteomics have potential implications towards predicting nanoparticle biocompatibility.

  5. Role of surface charge in cytotoxicity of charged manganese ferrite nanoparticles towards macrophages

    NASA Astrophysics Data System (ADS)

    Yang, Seung-Hyun; Heo, Dan; Park, Jinsung; Na, Sungsoo; Suh, Jin-Suck; Haam, Seungjoo; Park, Sahng Wook; Huh, Yong-Min; Yang, Jaemoon

    2012-12-01

    Amphiphilic surfactants have been used to disperse magnetic nanoparticles in biological media, because they exhibit a dual hydrophobic/hydrophilic affinity that facilitates the formation of a nanoemulsion, within which nanoparticle surfaces can be modified to achieve different physicochemical properties. For the investigation of the interactions of cells with charged magnetic nanoparticles in a biological medium, we selected the nanoemulsion method to prepare water-soluble magnetic nanoparticles using amphiphilic surfactant (polysorbate 80). The hydroxyl groups of polysorbate 80 were modified to carboxyl or amine groups. The chemical structures of carboxylated and aminated polysorbate 80 were confirmed, and water-soluble manganese ferrite nanoparticles (MFNPs) were synthesized with three types of polysorbate 80. Colloidal size, morphology, monodispersity, solubility and T2 relaxivity were found to be similar between the three types of MFNP. However, cationic MFNPs exhibited greater cytotoxicity in macrophages (RAW264.7 cells) and lower cellular membrane effective stiffness than anionic and non-ionic MFNPs. Moreover, cationic MFNPs exhibited large uptake efficiency for RAW264.7 cells compared with anionic or non-ionic MFNPs under the same conditions. Therefore, we propose that surface charge should be a key consideration factor in the design of magnetic nanoparticles for theragnostic applications.

  6. Design strategy of surface decoration for efficient delivery of nanoparticles by computer simulation

    PubMed Central

    Ding, Hong-ming; Ma, Yu-qiang

    2016-01-01

    Understanding the role of surface decoration of nanoparticles in protein adsorption and cellular uptake is of great importance in biomedicine. Here, by using dissipative particle dynamics simulations, we take two typical coating polymers (i.e., hydrophilic and zwitterionic polymers) as an example, and systematically investigate their effect on cellular delivery of hydrophobic and charged nanoparticles (in the presence of serum protein). Our results show that though two types of polymers are charge-neutral and can both reduce the protein adsorption, there exist some differences between their ability of protein resistance, especially in the case of positively charged nanoparticles. Besides, it is found that the coating polymers may also greatly decrease the cellular uptake efficiency of nanoparticles. Nevertheless, and importantly, since the zwitterionic polymers may become positively charged under low pH environments, the nanoparticle can attach onto cell membrane more firmly than that coated with hydrophilic polymers, which can further enhance the active targeting of nanoparticles. Finally, we also provide the design maps for surface decoration to achieve efficient cellular delivery. These results can help better understand how to keep the balance between protein resistance and cell targeting, which may give some useful guidelines on optimal design of future nanomaterials in drug delivery. PMID:27226273

  7. Design strategy of surface decoration for efficient delivery of nanoparticles by computer simulation

    NASA Astrophysics Data System (ADS)

    Ding, Hong-Ming; Ma, Yu-Qiang

    2016-05-01

    Understanding the role of surface decoration of nanoparticles in protein adsorption and cellular uptake is of great importance in biomedicine. Here, by using dissipative particle dynamics simulations, we take two typical coating polymers (i.e., hydrophilic and zwitterionic polymers) as an example, and systematically investigate their effect on cellular delivery of hydrophobic and charged nanoparticles (in the presence of serum protein). Our results show that though two types of polymers are charge-neutral and can both reduce the protein adsorption, there exist some differences between their ability of protein resistance, especially in the case of positively charged nanoparticles. Besides, it is found that the coating polymers may also greatly decrease the cellular uptake efficiency of nanoparticles. Nevertheless, and importantly, since the zwitterionic polymers may become positively charged under low pH environments, the nanoparticle can attach onto cell membrane more firmly than that coated with hydrophilic polymers, which can further enhance the active targeting of nanoparticles. Finally, we also provide the design maps for surface decoration to achieve efficient cellular delivery. These results can help better understand how to keep the balance between protein resistance and cell targeting, which may give some useful guidelines on optimal design of future nanomaterials in drug delivery.

  8. Design strategy of surface decoration for efficient delivery of nanoparticles by computer simulation.

    PubMed

    Ding, Hong-Ming; Ma, Yu-Qiang

    2016-01-01

    Understanding the role of surface decoration of nanoparticles in protein adsorption and cellular uptake is of great importance in biomedicine. Here, by using dissipative particle dynamics simulations, we take two typical coating polymers (i.e., hydrophilic and zwitterionic polymers) as an example, and systematically investigate their effect on cellular delivery of hydrophobic and charged nanoparticles (in the presence of serum protein). Our results show that though two types of polymers are charge-neutral and can both reduce the protein adsorption, there exist some differences between their ability of protein resistance, especially in the case of positively charged nanoparticles. Besides, it is found that the coating polymers may also greatly decrease the cellular uptake efficiency of nanoparticles. Nevertheless, and importantly, since the zwitterionic polymers may become positively charged under low pH environments, the nanoparticle can attach onto cell membrane more firmly than that coated with hydrophilic polymers, which can further enhance the active targeting of nanoparticles. Finally, we also provide the design maps for surface decoration to achieve efficient cellular delivery. These results can help better understand how to keep the balance between protein resistance and cell targeting, which may give some useful guidelines on optimal design of future nanomaterials in drug delivery. PMID:27226273

  9. Surface chemistry of surfactant AOT-stabilized SnO(2) nanoparticles and effect of temperature.

    PubMed

    Luwang, Meitram N; Ningthoujam, Raghumani S; Singh, Naorem S; Tewari, Raghvendra; Srivastava, Sri K; Vatsa, Rajesh K

    2010-09-01

    SnO(2).xH(2)O nanoparticles were prepared at room temperature by the microemulsion route. Sodium bis(2-ethylhexyl) sulfosuccinate (AOT) was used as a surfactant to stabilize the nanoparticles. These nanoparticles show green luminescence at 510nm, which has been assigned to oxygen vacancies. Infrared spectra of samples heated in the temperature range 500-900 degrees C show bond formation between SnO(2) nanoparticles and SO(4)(2-), which arises from oxidation of SO(3)(-) present in AOT. This was further supported by X-ray diffraction. Shape transformations of the particles from triangular to spherical and then to rectangular was observed as the heat-treatment temperature was increased, and this is related to the surface energy of particles. An enhancement in emission intensity of Eu(3+) was observed when Eu(3+) ions were doped into the SnO(2) nanoparticles due to significant energy transfer from SnO(2) (or Eu-O) to Eu(3+) through surface-mediated energy transfer as compared to direct excitation of Eu(3+) at 397nm. Interestingly, these nanoparticles are dispersible in water, and can be incorporated into polymer-based materials such as polyvinyl alcohol to give homogeneous films, giving rise to blue and red emissions. PMID:20557894

  10. Magnetic domains and surface effects in hollow maghemite nanoparticles

    SciTech Connect

    Cabot, Andreu; Alivisatos, A. Paul; Puntes, Victor; Balcells, Lluis; Iglesias, Oscar; Labarta, Amilcar

    2008-09-30

    In the present work, we investigate the magnetic properties of ferrimagnetic and non-interacting maghemite hollow nanoparticles obtained by the Kirkendall effect. From the experimental characterization of their magnetic behavior, we find that polycrystalline hollow maghemite nanoparticles exhibit low blocked-to-superparamagnetic transition temperatures, small magnetic moments, significant coercivities and irreversibility fields, and no magnetic saturation on external magnetic fields up to 5 T. These results are interpreted in terms of the microstructural parameters characterizing the maghemite shells by means of atomistic Monte Carlo simulations of an individual spherical shell. The model comprises strongly interacting crystallographic domains arranged in a spherical shell with random orientations and anisotropy axis. The Monte Carlo simulation allows discernment between the influence of the polycrystalline structure and its hollow geometry, while revealing the magnetic domain arranggement in the different temperataure regimes.

  11. Graphene oxide-Fe{sub 3}O{sub 4} nanoparticle composite with high transverse proton relaxivity value for magnetic resonance imaging

    SciTech Connect

    Venkatesha, N.; Srivastava, Chandan; Poojar, Pavan; Geethanath, Sairam; Qurishi, Yasrib

    2015-04-21

    The potential of graphene oxide–Fe{sub 3}O{sub 4} nanoparticle (GO-Fe{sub 3}O{sub 4}) composite as an image contrast enhancing material in magnetic resonance imaging has been investigated. Proton relaxivity values were obtained in three different homogeneous dispersions of GO-Fe{sub 3}O{sub 4} composites synthesized by precipitating Fe{sub 3}O{sub 4} nanoparticles in three different reaction mixtures containing 0.01 g, 0.1 g, and 0.2 g of graphene oxide. A noticeable difference in proton relaxivity values was observed between the three cases. A comprehensive structural and magnetic characterization revealed discrete differences in the extent of reduction of the graphene oxide and spacing between the graphene oxide sheets in the three composites. The GO-Fe{sub 3}O{sub 4} composite framework that contained graphene oxide with least extent of reduction of the carboxyl groups and largest spacing between the graphene oxide sheets provided the optimum structure for yielding a very high transverse proton relaxivity value. It was found that the GO-Fe{sub 3}O{sub 4} composites possessed good biocompatibility with normal cell lines, whereas they exhibited considerable toxicity towards breast cancer cells.

  12. Size and surface chemistry of nanoparticles lead to a variant behavior in the unfolding dynamics of human carbonic anhydrase.

    PubMed

    Nasir, Irem; Lundqvist, Martin; Cabaleiro-Lago, Celia

    2015-11-01

    The adsorption induced conformational changes of human carbonic anhydrase I (HCAi) and pseudo wild type human carbonic anhydrase II truncated at the 17th residue at the N-terminus (trHCAii) were studied in presence of nanoparticles of different sizes and polarities. Isothermal titration calorimetry (ITC) studies showed that the binding to apolar surfaces is affected by the nanoparticle size in combination with the inherent protein stability. 8-Anilino-1-naphthalenesulfonic acid (ANS) fluorescence revealed that HCAs adsorb to both hydrophilic and hydrophobic surfaces, however the dynamics of the unfolding at the nanoparticle surfaces drastically vary with the polarity. The size of the nanoparticles has opposite effects depending on the polarity of the nanoparticle surface. The apolar nanoparticles induce seconds timescale structural rearrangements whereas polar nanoparticles induce hours timescale structural rearrangements on the same charged HCA variant. Here, a simple model is proposed where the difference in the timescales of adsorption is correlated with the energy barriers for initial docking and structural rearrangements which are firmly regulated by the surface polarity. Near-UV circular dichorism (CD) further supports that both protein variants undergo structural rearrangements at the nanoparticle surfaces regardless of being "hard" or "soft". However, the conformational changes induced by the apolar surfaces differ for each HCA isoform and diverge from the previously reported effect of silica nanoparticles. PMID:26445221

  13. Effects of para-substituents of styrene derivatives on their chemical reactivity on platinum nanoparticle surfaces

    NASA Astrophysics Data System (ADS)

    Hu, Peiguang; Chen, Limei; Deming, Christopher P.; Lu, Jia-En; Bonny, Lewis W.; Chen, Shaowei

    2016-06-01

    Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent aggregation, suggesting sufficient protection of the nanoparticles by the organic capping ligands, and the average core diameter was estimated to be 2.0 +/- 0.3 nm, 1.3 +/- 0.2 nm, and 1.1 +/- 0.2 nm for the nanoparticles capped with 4-tert-butylstyrene, 4-methoxystyrene, and 4-(trifluoromethyl)styrene, respectively, as a result of the decreasing rate of dehydrogenation with the increasing Taft (polar) constant of the para-substituents. Importantly, the resulting nanoparticles exhibited unique photoluminescence, where an increase of the Hammett constant of the para-substituents corresponded to a blue-shift of the photoluminescence emission, suggesting an enlargement of the HOMO-LUMO band gap of the nanoparticle-bound acetylene moieties. Furthermore, the resulting nanoparticles exhibited apparent electrocatalytic activity towards oxygen reduction in acidic media, with the best performance among the series of samples observed with the 4-tert-butylstyrene-capped nanoparticles due to an optimal combination of the nanoparticle core size and ligand effects on the bonding interactions between platinum and oxygen species.Stable platinum nanoparticles were successfully prepared by the self-assembly of para-substituted styrene derivatives onto the platinum surfaces as a result of platinum-catalyzed dehydrogenation and transformation of the vinyl groups to the acetylene ones, forming platinum-vinylidene/-acetylide interfacial bonds. Transmission electron microscopic measurements showed that the nanoparticles were well dispersed without apparent

  14. Nanoparticle technology for treatment of Parkinson's disease: the role of surface phenomena in reaching the brain.

    PubMed

    Leyva-Gómez, Gerardo; Cortés, Hernán; Magaña, Jonathan J; Leyva-García, Norberto; Quintanar-Guerrero, David; Florán, Benjamín

    2015-07-01

    The absence of a definitive treatment for Parkinson's disease has driven the emerging investigation in the search for novel therapeutic alternatives. At present, the formulation of different drugs on nanoparticles has represented several advantages over conventional treatments. This type of multifunctional carrier, owing to its size and composition, has different interactions in biological systems that can lead to a decrease in ability to cross the blood-brain barrier. Therefore, this review focuses on the latest advances in obtaining nanoparticles for Parkinson's disease and provides an overview of technical aspects in the design of brain drug delivery of nanoparticles and an analysis of surface phenomena, a key aspect in the development of functional nanoparticles for Parkinson's disease. PMID:25701281

  15. Revisiting 30 years of biofunctionalization and surface chemistry of inorganic nanoparticles for nanomedicine

    PubMed Central

    Conde, João; Dias, Jorge T.; Grazú, Valeria; Moros, Maria; Baptista, Pedro V.; de la Fuente, Jesus M.

    2014-01-01

    In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold) nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles. PMID:25077142

  16. Using Response Surface Methodology in Synthesis of Ultrafine Copper Nanoparticles by Electrolysis

    NASA Astrophysics Data System (ADS)

    Tamilvanan, A.; Balamurugan, K.; Ponappa, K.; Madhan Kumar, B.

    2016-02-01

    Electrolysis is a method used for producing copper (Cu) nanoparticles at faster rate and at low cost in ambient conditions. The property of Cu nanoparticles prepared by electrolysis depends on their process parameters. The influence of selected process parameters such as copper sulfate (CuSo4) concentration, electrode gap and electrode potential difference on particle size was investigated. To optimize these parameters response surface methodology (RSM) was used. Cu nanoparticles prepared by electrolysis were characterized by using X-ray diffraction (XRD) and scanning electron microscope (SEM). After reviewing the results of analysis of variance (ANOVA), mathematical equation was created and optimized parameters for producing Cu nanoparticles were determined. The results confirm that the average size of Cu particle at the optimum condition was found to be 17nm and they are hexagonal in shape.

  17. Revisiting 30 years of biofunctionalization and surface chemistry of inorganic nanoparticles for nanomedicine.

    PubMed

    Conde, João; Dias, Jorge T; Grazú, Valeria; Moros, Maria; Baptista, Pedro V; de la Fuente, Jesus M

    2014-01-01

    In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold) nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles. PMID:25077142

  18. Triply surface-plasmon resonant four-wave mixing imaging of gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Masia, Francesco; Langbein, Wolfgang; Watson, Peter; Borri, Paola

    2011-03-01

    We have developed a novel multiphoton microscopy technique not relying on (and hence not limited by) fluorescence emission, which exploits the third-order nonlinearity called four-wave mixing of gold nanoparticles in resonance with their surface Plasmon. The coherent, transient and resonant nature of this signal allows its detection free from backgrounds that limit other contrast methods for gold nanoparticles. We show detection of single 10nm gold nanoparticles with low excitation intensities, corresponding to negligible average thermal heating. Owing to the the third-order nonlinearity we measure a transversal and axial resolution of 140nm and 470nm respectively, better than the one-photon diffraction limit. We also show high-contrast imaging of gold-labels down to 5nm size in Golgi structures of HepG2 cells at useful imaging speeds (10 kHz pixel rate). Thermal dissociation of gold nanoparticles from their bonding sites when varying the excitation intensity is also investigated.

  19. Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

    DOE PAGESBeta

    Chi, Miaofang; Wang, Chao; Lei, Yinkai; Wang, Guofeng; Li, Dongguo; More, Karren L.; Lupini, Andrew; Allard, Lawrence F.; Markovic, Nenad M.; Stamenkovic, Vojislav R.

    2015-11-18

    The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation; nucleation ofmore » structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. Furthermore, this work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance.« less

  20. Highly hydrophilic thin-film composite forward osmosis membranes functionalized with surface-tailored nanoparticles.

    PubMed

    Tiraferri, Alberto; Kang, Yan; Giannelis, Emmanuel P; Elimelech, Menachem

    2012-09-26

    Thin-film composite polyamide membranes are state-of-the-art materials for membrane-based water purification and desalination processes, which require both high rejection of contaminants and high water permeabilities. However, these membranes are prone to fouling when processing natural waters and wastewaters, because of the inherent surface physicochemical properties of polyamides. The present work demonstrates the fabrication of forward osmosis polyamide membranes with optimized surface properties via facile and scalable functionalization with fine-tuned nanoparticles. Silica nanoparticles are coated with superhydrophilic ligands possessing functional groups that impart stability to the nanoparticles and bind irreversibly to the native carboxyl moieties on the membrane selective layer. The tightly tethered layer of nanoparticles tailors the surface chemistry of the novel composite membrane without altering the morphology or water/solute permeabilities of the membrane selective layer. Surface characterization and interfacial energy analysis confirm that highly hydrophilic and wettable membrane surfaces are successfully attained. Lower intermolecular adhesion forces are measured between the new membrane materials and model organic foulants, indicating the presence of a bound hydration layer at the polyamide membrane surface that creates a barrier for foulant adhesion. PMID:22948042

  1. Surface Enhanced Raman Spectroscopy of Volatile Organic molecules on the surface of Zinc Nanoparticles Produced by Laser Ablation

    NASA Astrophysics Data System (ADS)

    Singh, Subhash C.; Swarnkar, Raj K.; Ankit, Preyas; Chattopadhyaya, Mahesh C.; Gopal, R.

    2008-11-01

    Surface enhanced Raman spectroscopy have provided potential tool for the detection of organic/biological molecules within the cell of living organism. This technique is suitable for in vivo as well as in vitro detection upto single molecular level. In the present work we have studied SERS activity of zinc nanoparticles on CCl4 and CHCl3 molecules. Colloidal solution of zinc nanoparticles was found as a suitable substrate for Raman signal enhancement. The applied technique may be useful for the sensing of organic/biological molecules as a trace in solid as well as in liquid media.

  2. Conducting shrinkable nanocomposite based on au-nanoparticle implanted plastic sheet: tunable thermally induced surface wrinkling.

    PubMed

    Greco, Francesco; Bellacicca, Andrea; Gemmi, Mauro; Cappello, Valentina; Mattoli, Virgilio; Milani, Paolo

    2015-04-01

    A thermally shrinkable and conductive nanocomposite material is prepared by supersonic cluster beam implantation (SCBI) of neutral Au nanoparticles (Au NPs) into a commercially available thermo-retractable polystyrene (PS) sheet. Micronanowrinkling is obtained during shrinking, which is studied by means of SEM, TEM and AFM imaging. Characteristic periodicity is determined and correlated with nanoparticle implantation dose, which permits us to tune the topographic pattern. Remarkable differences emerged with respect to the well-known case of wrinkling of bilayer metal-polymer. Wrinkled composite surfaces are characterized by a peculiar multiscale structuring that promises potential technological applications in the field of catalytic surfaces, sensors, biointerfaces, and optics, among others. PMID:25811100

  3. Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse Pt(x)Ni(1-x) Nanoparticles

    SciTech Connect

    Wang, Chao; Chi, Miaofang; Wang, Guofeng; Van der Vliet, Dennis; Li, Dongguo; More, Karren Leslie; Wang, Hsien-Hua; Schlueter, John; Markovic, Nenad; Stamenkovic, Vojislav

    2011-01-01

    Monodisperse and homogeneous Pt{sub x}Ni{sub 1-x} alloy nanoparticles of various compositions are synthesized via an organic solution approach in order to reveal the correlation between surface chemistry and their electrocatalytic properties. Atomic-level microscopic analysis of the compositional profile and modeling of nanoparticle structure are combined to follow the dependence of Ni dissolution on the initial alloy composition and formation of the Pt-skeleton nanostructures. The developed approach and acquired knowledge about surface structure-property correlation can be further generalized and applied towards the design of advanced functional nanomaterials.

  4. Effects of surface charge on the anomalous light extinction from metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Sijercic, Edin; Leung, P. T.

    2016-07-01

    The effects of extraneous surface charges on the anomalous extinction from metallic nanoparticles are studied via an application of the extended Mie theory by Bohren and Hunt. Due to the sensitivity of the higher multipolar resonance on the surface charges, it is found that quenching of the anomalous resonance can be observed with presence of only a modest amount of charges on these particles. The observed effects thus provide a rather sensitive mechanism for the monitoring of the neutrality of these nanoparticles using far field scattering approaches.

  5. Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding

    NASA Astrophysics Data System (ADS)

    Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M.; Ke, Pu Chun; Ding, Feng

    2014-06-01

    Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding.Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and

  6. Recent prospective of surface engineered Nanoparticles in the management of Neurodegenerative disorders.

    PubMed

    Singh, Devendra; Kapahi, Himani; Rashid, Muzamil; Prakash, Atish; Majeed, Abu Bakar Abdul; Mishra, Neeraj

    2016-05-01

    Clinically, the therapeutic outcomes in neurodegenerative disorders (NDs) by drug treatment are very limited, and the most insurmountable obstacle in the treatment of NDs is the blood-brain barrier (BBB), which provides the highest level of protection from xenobiotics. A great deal of attention still needs to be paid to overcome these barriers, and surface-engineered polymeric nanoparticles are emerging as innovative tools that are able to interact with the biological system at a molecular level for the desired response. The present review covers the potential importance of surface-structure-engineered nanoparticles to overcome the BBB for good bioavailability, and the evaluation of drug therapy in NDs. PMID:26107112

  7. Surface plasma resonant effect of gold nanoparticles on the photoelectrodes of dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Meen, Teen-Hang; Tsai, Jenn-Kai; Chao, Shi-Mian; Lin, Yu-Chien; Wu, Tien-Chuan; Chang, Tang-Yun; Ji, Liang-Wen; Water, Walter; Chen, Wen-Ray; Tang, I.-Tseng; Huang, Chien-Jung

    2013-10-01

    In this study, we prepared different shapes of gold nanoparticles by seed-mediated growth method and applied them on the photoelectrodes of dye-sensitized solar cells (DSSCs) to study the surface plasma resonant (SPR) effect of gold nanoparticles on the photoelectrodes of dye-sensitized solar cells. The analyses of field emission scanning electron microscopy show that the average diameter of the spherical gold nanoparticles is 45 nm, the average length and width of the short gold nanorods were 55 and 22 nm, respectively, and the average length and width of the long gold nanorods were 55 and 14 nm, respectively. The aspect ratio of the short and long gold nanorods was about 2.5 and 4, respectively. The results of ultraviolet-visible absorption spectra show that the absorption wavelength is about 540 nm for spherical gold nanoparticles, and the absorption of the gold nanorods reveals two peaks. One is about 510 to 520 nm, and the other is about 670 and 710 nm for the short and long gold nanorods, respectively. The best conversion efficiency of the dye-sensitized solar cells with spherical gold nanoparticles and short and long gold nanorods added in is 6.77%, 7.08%, and 7.29%, respectively, and is higher than that of the cells without gold nanoparticles, which is 6.21%. This result indicates that the effect of gold nanoparticles on the photoelectrodes can increase the conductivity and reduce the recombination of charges in the photoelectrodes, resulting in the increase of conversion efficiency for DSSCs. In addition, the long gold nanorods have stronger SPR effect than the spherical gold nanoparticles and short gold nanorods at long wavelength. This may be the reason for the higher conversion efficiency of DSSCs with long gold nanorods than those of the cells with spherical gold nanoparticles and short gold nanorods.

  8. The mechanisms for nanoparticle surface diffusion and chain self-assembly determined from real-time nanoscale kinetics in liquid

    SciTech Connect

    Woehl, Taylor J.; Prozorov, Tanya

    2015-08-20

    The mechanisms for nanoparticle self-assembly are often inferred from the morphology of the final nanostructures in terms of attractive and repulsive interparticle interactions. Understanding how nanoparticle building blocks are pieced together during self-assembly is a key missing component needed to unlock new strategies and mechanistic understanding of this process. Here we use real-time nanoscale kinetics derived from liquid cell transmission electron microscopy investigation of nanoparticle self-assembly to show that nanoparticle mobility dictates the pathway for self-assembly and final nanostructure morphology. We describe a new method for modulating nanoparticle diffusion in a liquid cell, which we employ to systematically investigate the effect of mobility on self-assembly of nanoparticles. We interpret the observed diffusion in terms of electrostatically induced surface diffusion resulting from nanoparticle hopping on the liquid cell window surface. Slow-moving nanoparticles self-assemble predominantly into linear 1D chains by sequential attachment of nanoparticles to existing chains, while highly mobile nanoparticles self-assemble into chains and branched structures by chain–chain attachments. Self-assembly kinetics are consistent with a diffusion-driven mechanism; we attribute the change in self-assembly pathway to the increased self-assembly rate of highly mobile nanoparticles. Furthermore, these results indicate that nanoparticle mobility can dictate the self-assembly mechanism and final nanostructure morphology in a manner similar to interparticle interactions.

  9. The mechanisms for nanoparticle surface diffusion and chain self-assembly determined from real-time nanoscale kinetics in liquid

    DOE PAGESBeta

    Woehl, Taylor J.; Prozorov, Tanya

    2015-08-20

    The mechanisms for nanoparticle self-assembly are often inferred from the morphology of the final nanostructures in terms of attractive and repulsive interparticle interactions. Understanding how nanoparticle building blocks are pieced together during self-assembly is a key missing component needed to unlock new strategies and mechanistic understanding of this process. Here we use real-time nanoscale kinetics derived from liquid cell transmission electron microscopy investigation of nanoparticle self-assembly to show that nanoparticle mobility dictates the pathway for self-assembly and final nanostructure morphology. We describe a new method for modulating nanoparticle diffusion in a liquid cell, which we employ to systematically investigate themore » effect of mobility on self-assembly of nanoparticles. We interpret the observed diffusion in terms of electrostatically induced surface diffusion resulting from nanoparticle hopping on the liquid cell window surface. Slow-moving nanoparticles self-assemble predominantly into linear 1D chains by sequential attachment of nanoparticles to existing chains, while highly mobile nanoparticles self-assemble into chains and branched structures by chain–chain attachments. Self-assembly kinetics are consistent with a diffusion-driven mechanism; we attribute the change in self-assembly pathway to the increased self-assembly rate of highly mobile nanoparticles. Furthermore, these results indicate that nanoparticle mobility can dictate the self-assembly mechanism and final nanostructure morphology in a manner similar to interparticle interactions.« less

  10. Durable, superoleophobic polymer–nanoparticle composite surfaces with re-entrant geometry via solvent-induced phase transformation

    PubMed Central

    Brown, Philip S.; Bhushan, Bharat

    2016-01-01

    Superoleophobic plastic surfaces are useful in a wide variety of applications including anti-fouling, self-cleaning, anti-smudge, and low-drag. Existing examples of superoleophobic surfaces typically rely on poorly adhered coatings or delicate surface structures, resulting in poor mechanical durability. Here, we report a facile method for creating re-entrant geometries desirable for superoleophobicity via entrapment of nanoparticles in polycarbonate surfaces. Nanoparticle incorporation occurs during solvent-induced swelling and subsequent crystallization of the polymer surface. The resulting surface was found to comprise of re-entrant structures, a result of the nanoparticle agglomerates acting as nucleation points for polymer crystallization. Examples of such surfaces were further functionalized with fluorosilane to result in a durable, super-repellent surface. This method of impregnating nanoparticles into polymer surfaces could prove useful in improving the anti-bacterial, mechanical, and liquid-repellent properties of plastic devices. PMID:26876479

  11. Durable, superoleophobic polymer-nanoparticle composite surfaces with re-entrant geometry via solvent-induced phase transformation.

    PubMed

    Brown, Philip S; Bhushan, Bharat

    2016-01-01

    Superoleophobic plastic surfaces are useful in a wide variety of applications including anti-fouling, self-cleaning, anti-smudge, and low-drag. Existing examples of superoleophobic surfaces typically rely on poorly adhered coatings or delicate surface structures, resulting in poor mechanical durability. Here, we report a facile method for creating re-entrant geometries desirable for superoleophobicity via entrapment of nanoparticles in polycarbonate surfaces. Nanoparticle incorporation occurs during solvent-induced swelling and subsequent crystallization of the polymer surface. The resulting surface was found to comprise of re-entrant structures, a result of the nanoparticle agglomerates acting as nucleation points for polymer crystallization. Examples of such surfaces were further functionalized with fluorosilane to result in a durable, super-repellent surface. This method of impregnating nanoparticles into polymer surfaces could prove useful in improving the anti-bacterial, mechanical, and liquid-repellent properties of plastic devices. PMID:26876479

  12. Durable, superoleophobic polymer-nanoparticle composite surfaces with re-entrant geometry via solvent-induced phase transformation

    NASA Astrophysics Data System (ADS)

    Brown, Philip S.; Bhushan, Bharat

    2016-02-01

    Superoleophobic plastic surfaces are useful in a wide variety of applications including anti-fouling, self-cleaning, anti-smudge, and low-drag. Existing examples of superoleophobic surfaces typically rely on poorly adhered coatings or delicate surface structures, resulting in poor mechanical durability. Here, we report a facile method for creating re-entrant geometries desirable for superoleophobicity via entrapment of nanoparticles in polycarbonate surfaces. Nanoparticle incorporation occurs during solvent-induced swelling and subsequent crystallization of the polymer surface. The resulting surface was found to comprise of re-entrant structures, a result of the nanoparticle agglomerates acting as nucleation points for polymer crystallization. Examples of such surfaces were further functionalized with fluorosilane to result in a durable, super-repellent surface. This method of impregnating nanoparticles into polymer surfaces could prove useful in improving the anti-bacterial, mechanical, and liquid-repellent properties of plastic devices.

  13. Understanding electric field-enhanced transport for the measurement of nanoparticles and their assembly on surfaces

    NASA Astrophysics Data System (ADS)

    Tsai, De-Hao

    The goal of this dissertation is to understand the synthesis, characterization, and integration of nanoparticles and nanoparticle-based devices by electric field-enhanced transport of nanoparticles. Chapter I describes the factors used for determining particle trajectories and found that electric fields provide the directional electrostatic force to overcome other non-directional influences on particle trajectories. This idea is widely applied in the nanoparticle classification, characterization, and assembly onto substrate surfaces as investigated in the following chapters. Chapter 2 presents a new assembly method to position metal nanoparticles delivered from the gas phase onto surfaces using the electrostatic force generated by biased p-n junction patterned substrates. Aligned deposition patterns of metal nanoparticles were observed, and the patterning selectivity quantified. A simple model accounting for the generated electric field, and the electrostatic, van der Waals, and image forces was used to explain the observed results. Chapter 2.2 describes a data set for particle size resolved deposition, from which a Brownian dynamics model for the process can be evaluated. Brownian motion and fluid convection of nanoparticles, as well as the interactions between the charged nanoparticles and the patterned substrate, including electrostatic force, image force and van der Waals force, are accounted for in the simulation. Using both experiment and simulation the effects of the particle size, electric field intensity, and the convective flow on coverage selectivity have been investigated. Coverage selectivity is most sensitive to electric field, which is controlled by the applied reverse bias voltage across the p-n junction. A non-dimensional analysis of the competition between the electrostatic and diffusion force is found to provide a means to collapse a wide range of process operating conditions and an effective indicator or process performance. Directed assembly of

  14. Early diagnosis of oral cancer based on the surface plasmon resonance of gold nanoparticles.

    PubMed

    Kah, James Chen Yong; Kho, Kiang Wei; Lee, Caroline Guat Leng; James, Colin; Sheppard, Richard; Shen, Ze Xiang; Soo, Khee Chee; Olivo, Malini Carolene

    2007-01-01

    The high mortality rate in cancer such as oral squamous cell carcinoma is commonly attributed to the difficulties in detecting the disease at an early treatable stage. In this study, we exploited the ability of gold nanoparticles to undergo coupled surface plasmon resonance and set up strong electric fields when closely-spaced to improve the molecular contrast signal in reflectance-based imaging and also to enhance the Raman signal of bioanalytes in cancer. Colloidal gold nanoparticles were synthesized and conjugated to anti-epidermal growth factor receptor (EGFR) for imaging. A self-assembled surface enhanced Raman scattering (SERS)-active gold nanoparticle monolayer film was also developed as a biosensing surface using a simple drop-dry approach. We have shown that gold nanoparticles could elicit an optical contrast to discriminate between cancerous and normal cells and their conjugation with antibodies allowed them to map the expression of relevant biomarkers for molecular imaging under confocal reflectance microscopy. We have also shown that the SERS spectra of saliva from the closely-packed gold nanoparticles films was differentiable between those acquired from normal individuals and oral cancer patients, thus showing promise of a simple SERS-based saliva assay for early diagnosis of oral cancer. PMID:18203445

  15. LaF3 nanoparticles surface modified with tryptophan and their optical properties

    NASA Astrophysics Data System (ADS)

    Safronikhin, Anatoly; Ehrlich, Heinrich; Lisichkin, Georgy

    2014-10-01

    LaF3 nanoparticles were synthesized by the double-jet precipitation technique in presence of tryptophan (Trp). The product was investigated by TEM, IR, absorption, and luminescence spectroscopies. Interaction of Trp with the nanoparticles results in formation of complexes between Trp and La3+ ions on the nanoparticle surface. Surface density of Trp was found as 0.7 molecule nm-2. It is shown that the modifier effects on LaF3 nanoparticle growth and stability of the surface modified LaF3 colloids. Luminescent properties of LaF3 nanoparticles modified with Trp (Trp@LaF3) are investigated. It is determined that Trp@LaF3 and Trp have the same profiles of excitation and photoluminescence spectra. Effects of pH, ionic strength, and Trp concentration on luminescence intensity are studied. At the same Trp amounts in the systems, Trp@LaF3 luminescence intensity is about 6 times less than Trp luminescence intensity. Such products can be used as luminescent labels.

  16. Palladium nanoparticles on hierarchical carbon surfaces: A new architecture for robust nano-catalysts

    NASA Astrophysics Data System (ADS)

    Vijwani, Hema; Mukhopadhyay, Sharmila M.

    2012-12-01

    Surface activity of heterogeneous catalysts can be enhanced if their sizes are reduced to nanometers. However, loose nanomaterials pose potential health and environmental risks. This issue has been addressed by attachment of palladium nanoparticles on multi-scale hierarchical carbon supports that have exceptionally high surface area per volume. The supports consist of porous carbon foam whose surface has been either chemically functionalized, or morphologically altered by grafting of carbon-nanotubes. It is seen that whereas chemical functionalization does provide some increase in nano-catalyst loading, morphological modification is significantly more powerful. It has the potential to create orders of magnitude increase in catalytic activity within the same overall volume. The synthesis techniques have been investigated in sufficient detail to provide significant control over the density and size of nanoparticles. Abundant distribution of nanoparticles is observed even within the deeper pores of the microcellular foam. The nanoparticles are seen to be metallic Pd having face centered cubic structure. Additionally, the nano-particles and nanotubes are durable, and remain attached to the base support after long periods of rapid rotation in water. These robust hybrid structures show promise in future applications such as sensors, water purification systems, fuel cell electrodes and hydrogen storage sponges.

  17. Directed Self-assembly of Nanoparticles at the Polymer Surface by Highly Compressible Supercritical Carbon Dioxide

    SciTech Connect

    M Asada; P Gin; M Endoh; S Satija; T Taniguchi; T Koga

    2011-12-31

    We report a versatile route for self-assembly of polymer-soluble nanoparticles at the polymer surface using highly compressible supercritical carbon dioxide (scCO{sub 2}). Polystyrene and poly(methyl methacrylate)-based nanocomposite thin films with functionalized polyhedral oligomeric silsesquioxane and phenyl C{sub 61} butyric acid methyl ester nanoparticles were prepared on Si substrates and exposed to scCO{sub 2} at different pressures under the isothermal condition of 36 C. The resultant structures could be then preserved by the vitrification process of the glassy polymers via quick pressure quench to atmospheric pressure and subsequently characterized by using various surface sensitive experimental techniques in air. We found that the surface segregation of these nanoparticles is induced in the close vicinity of P = 8.2 MPa where the excess absorption of the fluid into the polymers maximizes. However, when the film thickness becomes less than about 4R{sub g} thick (where R{sub g} is the radius of polymer gyration), the uniform dispersion of the nanoparticles is favorable instead even at the same CO{sub 2} conditions. We clarify that the phase transition is correlated with the emergence of a concentration gradient of the fluid at the polymer/CO{sub 2} interface and is a general phenomenon for different polymer-nanoparticle interactions.

  18. Cytotoxicity of surface-functionalized silicon and germanium nanoparticles: the dominant role of surface charges

    NASA Astrophysics Data System (ADS)

    Bhattacharjee, Sourav; Rietjens, Ivonne M. C. M.; Singh, Mani P.; Atkins, Tonya M.; Purkait, Tapas K.; Xu, Zejing; Regli, Sarah; Shukaliak, Amber; Clark, Rhett J.; Mitchell, Brian S.; Alink, Gerrit M.; Marcelis, Antonius T. M.; Fink, Mark J.; Veinot, Jonathan G. C.; Kauzlarich, Susan M.; Zuilhof, Han

    2013-05-01

    Although it is frequently hypothesized that surface (like surface charge) and physical characteristics (like particle size) play important roles in cellular interactions of nanoparticles (NPs), a systematic study probing this issue is missing. Hence, a comparative cytotoxicity study, quantifying nine different cellular endpoints, was performed with a broad series of monodisperse, well characterized silicon (Si) and germanium (Ge) NPs with various surface functionalizations. Human colonic adenocarcinoma Caco-2 and rat alveolar macrophage NR8383 cells were used to clarify the toxicity of this series of NPs. The surface coatings on the NPs appeared to dominate the cytotoxicity: the cationic NPs exhibited cytotoxicity, whereas the carboxylic acid-terminated and hydrophilic PEG- or dextran-terminated NPs did not. Within the cationic Si NPs, smaller Si NPs were more toxic than bigger ones. Manganese-doped (1% Mn) Si NPs did not show any added toxicity, which favors their further development for bioimaging. Iron-doped (1% Fe) Si NPs showed some added toxicity, which may be due to the leaching of Fe3+ ions from the core. A silica coating seemed to impart toxicity, in line with the reported toxicity of silica. Intracellular mitochondria seem to be the target for the toxic NPs since a dose-, surface charge- and size-dependent imbalance of the mitochondrial membrane potential was observed. Such an imbalance led to a series of other cellular events for cationic NPs, like decreased mitochondrial membrane potential (ΔΨm) and ATP production, induction of ROS generation, increased cytoplasmic Ca2+ content, production of TNF-α and enhanced caspase-3 activity. Taken together, the results explain the toxicity of Si NPs/Ge NPs largely by their surface characteristics, provide insight into the mode of action underlying the observed cytotoxicity, and give directions on synthesizing biocompatible Si and Ge NPs, as this is crucial for bioimaging and other applications in for example

  19. Evolution of the Surface Science of Catalysis from Single Crystals to Metal Nanoparticles under Pressure

    SciTech Connect

    Somorjai, Gabor A.; Park, Jeong Y.

    2008-03-06

    Vacuum studies of metal single crystal surfaces using electron and molecular beam scattering revealed that the surface atoms relocate when the surface is clean (reconstruction) and when it is covered by adsorbates (adsorbate induced restructuring). It was also discovered that atomic steps and other low coordination surface sites are active for breaking chemical bonds (H-H, O=O, C-H, C=O and C-C) with high reaction probability. Investigations at high reactant pressures using sum frequency generation (SFG)--vibrational spectroscopy and high pressure scanning tunneling microscopy (HPSTM) revealed bond breaking at low reaction probability sites on the adsorbate-covered metal surface, and the need for adsorbate mobility for continued turnover. Since most catalysts (heterogeneous, enzyme and homogeneous) are nanoparticles, colloid synthesis methods were developed to produce monodispersed metal nanoparticles in the 1-10 nm range and controlled shapes to use them as new model catalyst systems in two-dimensional thin film form or deposited in mesoporous three-dimensional oxides. Studies of reaction selectivity in multipath reactions (hydrogenation of benzene, cyclohexene and crotonaldehyde) showed that reaction selectivity depends on both nanoparticle size and shape. The oxide-metal nanoparticle interface was found to be an important catalytic site because of the hot electron flow induced by exothermic reactions like carbon monoxide oxidation.

  20. Near-field Light Scattering Techniques for Measuring Nanoparticle-Surface Interaction Energies and Forces

    PubMed Central

    O'Dell, Dakota; Adam, Ian S.; DiPaolo, Brian; Sabharwal, Manit; Shi, Ce; Hart, Robert; Earhart, Christopher; Erickson, David

    2015-01-01

    Nanoparticles are quickly becoming commonplace in many commercial and industrial products, ranging from cosmetics to pharmaceuticals to medical diagnostics. Predicting the stability of the engineered nanoparticles within these products a priori remains an important and difficult challenge. Here we describe our techniques for measuring the mechanical interactions between nanoparticles and surfaces using near-field light scattering. Particle-surface interfacial forces are measured by optically “pushing” a particle against a reference surface and observing its motion using scattered near-field light. Unlike atomic force microscopy, this technique is not limited by thermal noise, but instead takes advantage of it. The integrated waveguide and microfluidic architecture allow for high-throughput measurements of about 1000 particles per hour. We characterize the reproducibility of and experimental uncertainty in the measurements made using the NanoTweezer surface instrument. We report surface interaction studies on gold nanoparticles with 50 nm diameters, smaller than previously reported in the literature using similar techniques. PMID:26855473

  1. Surface effects and phase stability in metal oxides nanoparticles under visible irradiation

    NASA Astrophysics Data System (ADS)

    Ricci, Pier Carlo; Carbonaro, C. M.; Corpino, R.; Chiriu, D.; Stagi, L.

    2014-10-01

    The light induced phase transformation between stable phases of metal oxides nanoparticles is analyzed. The surrounding atmosphere as well as the defect density at the surface play a fundamental role. It has been found that in oxygen poor chamber atmosphere the phase transformation is favored, while the phase transition cannot be achieved if the defects at the surface are properly passivated. The phase transition is activated by intragap irradiation, able to activate the F- center at the surface connected to oxygen vacancies, and promoting the activation of the surface and the nucleation of neighboring crystallites. The phase transition was studied in Titanium oxide (TiO2) and in Iron oxide (Fe2O3): Maghemite is subjected to a phase transformation to α-Fe2O3 (hematite), Anatase nanoparticles converts to Rutile. The general mechanism of the phase transition and, more in general, the possibility to optically control the surface activity of metal oxides is discussed.

  2. Uniform deposition of ultrathin polymer films on the surfaces of Al2O3 nanoparticles by a plasma treatment

    NASA Astrophysics Data System (ADS)

    Shi, Donglu; Wang, S. X.; van Ooij, Wim J.; Wang, L. M.; Zhao, Jiangang; Yu, Zhou

    2001-02-01

    Surface modification of nanoparticles will present great challenges due to their extremely small dimensions, high surface areas, and high surface energies. In this research, we demonstrate the uniform deposition of ultrathin polymer films of 2 nm on the surfaces of alumina nanoparticles. The deposited film can also be tailored to multilayers. Time-of-flight secondary ion mass spectroscopy was used to confirm the pyrrole thin film on the nanoparticle surfaces. Using such a nanocoating, it is possible to alter the intrinsic properties of materials that cannot be achieved by conventional methods and materials.

  3. Surface modified PLGA nanoparticles for brain targeting of Bacoside-A.

    PubMed

    Jose, S; Sowmya, S; Cinu, T A; Aleykutty, N A; Thomas, S; Souto, E B

    2014-10-15

    The present paper focuses on the development and in vitro/in vivo characterization of nanoparticles composed of poly-(D,L)-Lactide-co-Glycolide (PLGA) loading Bacoside-A, as a new approach for the brain delivery of the neuroprotective drug for the treatment of neurodegenerative disorders (e.g. Alzheimer Disease). Bacoside-A-loaded PLGA nanoparticles were prepared via o/w emulsion solvent evaporation technique. Surface of the nanoparticles were modified by coating with polysorbate 80 to facilitate the crossing of the blood brain barrier (BBB), and the processing parameters (i.e. sonication time, the concentration of polymer (PLGA) and surfactant (polysorbate 80), and drug-polymer ratio) were optimized with the aim to achieve a high production yield. Brain targeting potential of the nanoparticles was evaluated by in vivo studies using Wistar albino rats. The nanoparticles produced by optimal formulation were within the nanosized range (70-200 nm) with relatively low polydispersity index (0.391 ± 1.2). The encapsulation efficiency of Bacoside-A in PLGA nanoparticles was 57.11 ± 7.11%, with a drug loading capacity of 20.5 ± 1.98%. SEM images showed the spherical shape of the PLGA nanoparticles, whereas their low crystallinity was demonstrated by X-ray studies, which also confirmed no chemical interactions between the drug and polymer molecules. The in vitro release of Bacoside-A from the PLGA nanoparticles followed a sustained release pattern with a maximum release of up to 83.04 ± 2.55% in 48 h. When compared to pure drug solution (2.56 ± 1.23 μg/g tissue), in vivo study demonstrated higher brain concentration of Bacoside-A (23.94 ± 1.74 μg/g tissue) suggesting a significant role of surface coated nanoparticles on brain targeting. The results indicate the potential of surface modified PLGA nanoparticles for the delivery of Bacoside-A to the brain. PMID:25010261

  4. Measurement of the proton-air cross section with Telescope Array's Middle Drum detector and surface array in hybrid mode

    NASA Astrophysics Data System (ADS)

    Abbasi, R. U.; Abe, M.; Abu-Zayyad, T.; Allen, M.; Azuma, R.; Barcikowski, E.; Belz, J. W.; Bergman, D. R.; Blake, S. A.; Cady, R.; Chae, M. J.; Cheon, B. G.; Chiba, J.; Chikawa, M.; Cho, W. R.; Fujii, T.; Fukushima, M.; Goto, T.; Hanlon, W.; Hayashi, Y.; Hayashida, N.; Hibino, K.; Honda, K.; Ikeda, D.; Inoue, N.; Ishii, T.; Ishimori, R.; Ito, H.; Ivanov, D.; Jui, C. C. H.; Kadota, K.; Kakimoto, F.; Kalashev, O.; Kasahara, K.; Kawai, H.; Kawakami, S.; Kawana, S.; Kawata, K.; Kido, E.; Kim, H. B.; Kim, J. H.; Kim, J. H.; Kitamura, S.; Kitamura, Y.; Kuzmin, V.; Kwon, Y. J.; Lan, J.; Lim, S. I.; Lundquist, J. P.; Machida, K.; Martens, K.; Matsuda, T.; Matsuyama, T.; Matthews, J. N.; Minamino, M.; Mukai, Y.; Myers, I.; Nagasawa, K.; Nagataki, S.; Nakamura, T.; Nonaka, T.; Nozato, A.; Ogio, S.; Ogura, J.; Ohnishi, M.; Ohoka, H.; Oki, K.; Okuda, T.; Ono, M.; Oshima, A.; Ozawa, S.; Park, I. H.; Pshirkov, M. S.; Rodriguez, D. C.; Rubtsov, G.; Ryu, D.; Sagawa, H.; Sakurai, N.; Scott, L. M.; Shah, P. D.; Shibata, F.; Shibata, T.; Shimodaira, H.; Shin, B. K.; Shin, H. S.; Smith, J. D.; Sokolsky, P.; Springer, R. W.; Stokes, B. T.; Stratton, S. R.; Stroman, T. A.; Suzawa, T.; Takamura, M.; Takeda, M.; Takeishi, R.; Taketa, A.; Takita, M.; Tameda, Y.; Tanaka, H.; Tanaka, K.; Tanaka, M.; Thomas, S. B.; Thomson, G. B.; Tinyakov, P.; Tkachev, I.; Tokuno, H.; Tomida, T.; Troitsky, S.; Tsunesada, Y.; Tsutsumi, K.; Uchihori, Y.; Udo, S.; Urban, F.; Vasiloff, G.; Wong, T.; Yamane, R.; Yamaoka, H.; Yamazaki, K.; Yang, J.; Yashiro, K.; Yoneda, Y.; Yoshida, S.; Yoshii, H.; Zollinger, R.; Zundel, Z.; Telescope Array Collaboration

    2015-08-01

    In this work we are reporting on the measurement of the proton-air inelastic cross section σp-air inel using the Telescope Array detector. Based on the measurement of the σp-air inel, the proton-proton cross section σp -p value is also determined at √{s }=9 5-8+5 TeV . Detecting cosmic ray events at ultrahigh energies with the Telescope Array enables us to study this fundamental parameter that we are otherwise unable to access with particle accelerators. The data used in this report are the hybrid events observed by the Middle Drum fluorescence detector together with the surface array detector collected over five years. The value of the σp-air inel is found to be equal to 567.0 ±70.5 [Stat]-25+29[Sys] mb . The total proton-proton cross section is subsequently inferred from Glauber formalism and the Block, Halzen and Stanev QCD inspired fit and is found to be equal to 17 0-44+48[Stat]-17+19[Sys] mb .

  5. Nanoparticle Properties and Synthesis Effects on Surface-Enhanced Raman Scattering Enhancement Factor: An Introduction

    PubMed Central

    2015-01-01

    Raman spectroscopy has enabled researchers to map the specific chemical makeup of surfaces, solutions, and even cells. However, the inherent insensitivity of the technique makes it difficult to use and statistically complicated. When Raman active molecules are near gold or silver nanoparticles, the Raman intensity is significantly amplified. This phenomenon is referred to as surface-enhanced Raman spectroscopy (SERS). The extent of SERS enhancement is due to a variety of factors such as nanoparticle size, shape, material, and configuration. The choice of Raman reporters and protective coatings will also influence SERS enhancement. This review provides an introduction to how these factors influence signal enhancement and how to optimize them during synthesis of SERS nanoparticles. PMID:25884017

  6. Impact of As-Synthesized Ligands and Low-Oxygen Conditions on Silver Nanoparticle Surface Functionalization.

    PubMed

    Johnston, Kathryn A; Smith, Ashley M; Marbella, Lauren E; Millstone, Jill E

    2016-04-26

    Here, we compare the ligand exchange behaviors of silver nanoparticles synthesized in the presence of two different surface capping agents: poly(vinylpyrrolidone) (MW = 10 or 40 kDa) or trisodium citrate, and under either ambient or low-oxygen conditions. In all cases, we find that the polymer capping agent exhibits features of a weakly bound ligand, producing better ligand exchange efficiencies with an incoming thiolated ligand compared to citrate. The polymer capping agent also generates nanoparticles that are more susceptible to reactions with oxygen during both synthesis and ligand exchange. The influence of the original ligand on the outcome of ligand exchange reactions with an incoming thiolated ligand highlights important aspects of silver nanoparticle surface chemistry, crucial for applications ranging from photocatalysis to antimicrobials. PMID:27077550

  7. Magnetic circular dichroism of non-local surface lattice resonances in magnetic nanoparticle arrays.

    PubMed

    Kataja, Mikko; Pourjamal, Sara; van Dijken, Sebastiaan

    2016-02-22

    Subwavelength metallic particles support plasmon resonances that allow extreme confinement of light down to the nanoscale. Irradiation with left- and right hand circularly polarized light results in the excitation of circular plasmon modes with opposite helicity. The Lorenz force lifts the degeneracy of the two modes in magnetic nanoparticles. Consequently, the confinement and frequency of localized surface plasmon resonances can be tuned by an external magnetic field. In this paper, we experimentally demonstrate this effect for nickel nanoparticles using magnetic circular dichroism (MCD). Besides, we show that non-local surface lattice resonances in periodic arrays of the same nanoparticles significantly enhance the MCD signal. A numerical model based on the modified long wavelength approximation is used to reproduce the main features in the experimental spectra and provide design rules for large MCD effects in sensing applications. PMID:26907013

  8. Acute and subchronic toxicity analysis of surface modified paclitaxel attached hydroxyapatite and titanium dioxide nanoparticles

    PubMed Central

    Venkatasubbu, Gopinath Devanand; Ramasamy, S; Gaddam, Pramod Reddy; Kumar, J

    2015-01-01

    Nanoparticles are widely used for targeted drug delivery applications. Surface modification with appropriate polymer and ligands is carried out to target the drug to the affected area. Toxicity analysis is carried out to evaluate the safety of the surface modified nanoparticles. In this study, paclitaxel attached, folic acid functionalized, polyethylene glycol modified hydroxyapatite and titanium dioxide nanoparticles were used for targeted drug delivery system. The toxicological behavior of the system was studied in vivo in rats and mice. Acute and subchronic studies were carried out. Biochemical, hematological, and histopathological analysis was also done. There were no significant alterations in the biochemical parameters at a low dosage. There was a small change in alkaline phosphatase (ALP) level at a high dosage. The results indicate a safe toxicological profile. PMID:26491315

  9. Glutathione-coated luminescent gold nanoparticles: a surface ligand for minimizing serum protein adsorption.

    PubMed

    Vinluan, Rodrigo D; Liu, Jinbin; Zhou, Chen; Yu, Mengxiao; Yang, Shengyang; Kumar, Amit; Sun, Shasha; Dean, Andrew; Sun, Xiankai; Zheng, Jie

    2014-08-13

    Ultrasmall glutathione-coated luminescent gold nanoparticles (GS-AuNPs) are known for their high resistance to serum protein adsorption. Our studies show that these NPs can serve as surface ligands to significantly enhance the physiological stability and lower the serum protein adsorption of superparamagnetic iron oxide nanoparticles (SPIONs), in addition to rendering the NPs the luminescence property. After the incorporation of GS-AuNPs onto the surface of SPIONs to form the hybrid nanoparticles (HBNPs), these SPIONs' protein adsorption was about 10-fold lower than those of the pure glutathione-coated SPIONs suggesting that GS-AuNPs are capable of providing a stealth effect against serum proteins. PMID:25029478

  10. Glutathione-Coated Luminescent Gold Nanoparticles: A Surface Ligand for Minimizing Serum Protein Adsorption

    PubMed Central

    2015-01-01

    Ultrasmall glutathione-coated luminescent gold nanoparticles (GS-AuNPs) are known for their high resistance to serum protein adsorption. Our studies show that these NPs can serve as surface ligands to significantly enhance the physiological stability and lower the serum protein adsorption of superparamagnetic iron oxide nanoparticles (SPIONs), in addition to rendering the NPs the luminescence property. After the incorporation of GS-AuNPs onto the surface of SPIONs to form the hybrid nanoparticles (HBNPs), these SPIONs’ protein adsorption was about 10-fold lower than those of the pure glutathione-coated SPIONs suggesting that GS-AuNPs are capable of providing a stealth effect against serum proteins. PMID:25029478

  11. Prediction of Surface and pH-Specific Binding of Peptides to Metal and Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Heinz, Hendrik; Lin, Tzu-Jen; Emami, Fateme Sadat; Ramezani-Dakhel, Hadi; Naik, Rajesh; Knecht, Marc; Perry, Carole C.; Huang, Yu

    2015-03-01

    The mechanism of specific peptide adsorption onto metallic and oxidic nanostructures has been elucidated in atomic resolution using novel force fields and surface models in comparison to measurements. As an example, variations in peptide adsorption on Pd and Pt nanoparticles depending on shape, size, and location of peptides on specific bounding facets are explained. Accurate computational predictions of reaction rates in C-C coupling reactions using particle models derived from HE-XRD and PDF data illustrate the utility of computational methods for the rational design of new catalysts. On oxidic nanoparticles such as silica and apatites, it is revealed how changes in pH lead to similarity scores of attracted peptides lower than 20%, supported by appropriate model surfaces and data from adsorption isotherms. The results demonstrate how new computational methods can support the design of nanoparticle carriers for drug release and the understanding of calcification mechanisms in the human body.

  12. Surface modification of a proton exchange membrane and hydrogen storage in a metal hydride for fuel cells

    NASA Astrophysics Data System (ADS)

    Andrews, Lisa

    Interest in fuel cell technology is rising as a result of the need for more affordable and available fuel sources. Proton exchange membrane fuel cells involve the catalysis of a fuel to release protons and electrons. It requires the use of a polymer electrolyte membrane to transfer protons through the cell, while the electrons pass through an external circuit, producing electricity. The surface modification of the polymer, NafionRTM, commonly researched as a proton exchange membrane, may improve efficiency of a fuel cell. Surface modification can change the chemistry of the surface of a polymer while maintaining bulk properties. Plasma modification techniques such as microwave discharge of an argon and oxygen gas mixture as well as vacuum-ultraviolet (VUV) photolysis may cause favorable chemical and physical changes on the surface of Nafion for improved fuel cell function. A possible increase in hydrophilicity as a result of microwave discharge experiments may increase proton conductivity. Grafting of acrylic acid from the surface of modified Nafion may decrease the permeation of methanol in a direct methanol fuel cell, a process which can decrease efficiency. Modification of the surface of Nafion samples were carried out using: 1) An indirect Ar/O2 gas mixture plasma investigating the reaction of oxygen radicals with the surface, 2) A direct Ar/O2 gas mixture plasma investigating the reaction of oxygen radicals and VUV radiation with the surface and, 3) VUV photolysis investigating exclusively the interaction of VUV radiation with the surface and any possible oxidation upon exposure to air. Acrylic acid was grafted from the VUV photolysed Nafion samples. All treated surfaces were analyzed using X-ray photoelectron spectroscopy (XPS). Fourier transform infrared spectroscopy (FTIR) was used to analyze the grafted Nafion samples. Scanning electron microscopy (SEM) and contact angle measurements were used to analyze experiments 2 and 3. Using hydrogen as fuel is a

  13. Wetting of nanofluids with nanoparticles of opposite surface potentials on pristine CVD graphene

    NASA Astrophysics Data System (ADS)

    Lee, Woorim; Kihm, Kenneth David; Park, Jae Sung; Lee, Woomin; Kim, Honggoo; Lee, Changhyuk; Cheon, Sosan; Lim, Gyumin

    2016-07-01

    Comparative wettability studies of graphene are conducted for two different nanofluids with opposite surface potentials of +53 mV (45-nm alumina nanoparticles) and -45 mV (28-nm silica nanoparticles), respectively. Aged graphene surface, which has adsorbed abundant hydrocarbon contaminants, shows weak hydrophobicity of about 90° wetting angles for both nanofluids for the tested volume concentration range from 0 to 10 %. For pristine graphene surfaces, however, the contact angle of alumina nanofluids continually increases from 50° to 70° for the same volume concentration increase, but the contact angle of silica nanofluids shows first increase of up to about 1 % concentration and then remains nearly unchanged with further increasing concentration. Since the nanoparticle-graphene interaction at the solid-liquid (SL) interface is expected to be the most crucial in determining the nanofluid wetting angles, the corresponding surface energy γ_{{SL}} is examined from elaboration of F_{{DLVO}}, the Derjaguin-Landau-Verwey-Overbeek force. The magnitudes of both the repulsive F_{{DLVO}} on the alumina nanoparticles and the attractive F_{{DLVO}} on the silica nanoparticles show rapid decreases up to 1 % volume concentration and exhibit slower decreases thereafter. The reduced repulsive F_{{DLVO}} of the alumina nanoparticle drives the increasing aggregation of nanoparticles on the SL interface with increasing concentration, thus increasing the SL interfacial energy γ_{{SL}}. On the contrary, the reduced attractive F_{{DLVO}} on the silica nanoparticle retards their aggregation on the SL interface with increasing concentration and slows the increase in γ_{{SL}}, eventually settling on the saturated level of γ_{{SL}} from a certain concentration onwards. These distinctive behaviors of γ_{{SL}} are consistent with the measured contact angles that gradually increase with increasing concentration for the positive surface potential (alumina), but initially increase and then

  14. Surface Protonation at the Rutile (110) Interface: Explicit Incorporation of Solvation Structure within the Refined MUSIC Model Framework

    SciTech Connect

    Machesky, Michael L.; Predota, M.; Wesolowski, David J

    2008-11-01

    The detailed solvation structure at the (110) surface of rutile ({alpha}-TiO{sub 2}) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 {angstrom} of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 C that agrees quantitatively with the experimentally determined value (5.4 {+-} 0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pH{sub znpc} values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pH{sub znpc} value of the rutile (110) surface at 25 C into quantitative agreement with the experimental value (4.8 {+-} 0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic

  15. Surface protonation at the rutile (110) interface: explicit incorporation of solvation structure within the refined MUSIC model framework.

    PubMed

    Machesky, Michael L; Predota, Milan; Wesolowski, David J; Vlcek, Lukas; Cummings, Peter T; Rosenqvist, Jörgen; Ridley, Moira K; Kubicki, James D; Bandura, Andrei V; Kumar, Nitin; Sofo, Jorge O

    2008-11-01

    The detailed solvation structure at the (110) surface of rutile (alpha-TiO2) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 A of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 degrees C that agrees quantitatively with the experimentally determined value (5.4+/-0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pHznpc values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 degrees C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pHznpcvalue of the rutile (110) surface at 25 degrees C into quantitative agreement with the experimental value (4.8+/-0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength

  16. In vitro and in vivo anticancer activity of surface modified paclitaxel attached hydroxyapatite and titanium dioxide nanoparticles.

    PubMed

    Venkatasubbu, G Devanand; Ramasamy, S; Reddy, G Pramod; Kumar, J

    2013-08-01

    Targeted drug delivery using nanocrystalline materials delivers the drug at the diseased site. This increases the efficacy of the drug in killing the cancer cells. Surface modifications were done to target the drug to a particular receptor on the cell surface. This paper reports synthesis of hydroxyapatite and titanium dioxide nanoparticles and modification of their surface with polyethylene glycol (PEG) followed by folic acid (FA). Paclitaxel, an anticancer drug, is attached to functionalized hydroxyapatite and titanium dioxide nanoparticles. The pure and functionalised nanoparticles are characterised with XRD, TEM and UV spectroscopy. Anticancer analysis was carried out in DEN induced hepatocarcinoma animals. Biochemical, hematological and histopathological analysis show that the surface modified paclitaxel attached nanoparticles have an higher anticancer activity than the pure paclitaxel and surface modified nanoparticles without paclitaxel. This is due to the targeting of the drug to the folate receptor in the cancer cells. PMID:23615724

  17. Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

    NASA Astrophysics Data System (ADS)

    Salvadori, M. C.; Teixeira, F. S.; Sgubin, L. G.; Cattani, M.; Brown, I. G.

    2014-08-01

    There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in the insulating matrix. These nanocomposites have been characterized by measuring the resistivity of the composite layer as a function of the implantation dose. The experimental results are compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement is found between the experimental results and the predictions of the theory. We conclude in that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

  18. Nanoparticle self-structuring in a nanofluid film spreading on a solid surface.

    PubMed

    Nikolov, Alex; Kondiparty, Kirti; Wasan, Darsh

    2010-06-01

    Liquids containing nanoparticles (nanofluids) exhibit different spreading or thinning behaviors on solids than liquids without nanoparticles. Previous experiments and theoretical investigations have demonstrated that the spreading of nanofluids on solid surfaces is enhanced compared to the spreading of base fluids without nanoparticles. However, the mechanisms for the observed enhancement in the spreading of nanofluids on solid substrates are not well understood. The complex nature of the interactions between the particles in the nanofluid and with the solid substrate alters the spreading dynamics [Wasan, D. T.; Nikolov, A. D. Nature 2003, 423, 156]. Here, we report, for the first time, the results of an experimental observation of nanoparticles self-structuring in a nanofluid film formed between an oil drop and a solid surface. Using a silica-nanoparticle aqueous suspension (with a nominal diameter of 19 nm and 10 vol %) and reflected light interferometry, we show the nanoparticle layering (i.e., stratification) phenomenon during film thinning on a smooth hydrophilic glass surface. Our experiments revealed that the film thickness stability on a solid substrate depends on the film size (i.e., the drop size). A film formed from a small drop (with a high capillary pressure) is thicker and contains more particle layers than a film formed from a large drop (with a lower capillary pressure). The data for the film-meniscus contact angle verses film thickness (corresponding to the different number of particle layers) were obtained and used to calculate the film structural energy isotherm. These results may provide a better understanding of the complex phenomena involved in the enhanced spreading of nanofluids on solid surfaces. PMID:20438106

  19. Synthesis of surface protein-imprinted nanoparticles endowed with reversible physical cross-links.

    PubMed

    Yang, Chongchong; Yan, Xianming; Guo, Hao; Fu, Guoqi

    2016-01-15

    Researches on protein molecularly imprinted polymers have been challenged by the difficulties in facilitating biomacromolecular transfer, in particular upon the template removal step, and enhancing their recognition performance. Addressing these issues, herein we report synthesis of core–shell structured surface protein-imprinted nanoparticles with reversible physical cross-links formed in the imprinted nanoshells. The imprinted layers over nanoparticle supports are fabricated via aqueous precipitation polymerization (PP) of di(ethylene glycol) methyl ether methacrylate (MEO2MA), a thermo-responsive monomer bearing no strong H-bond donor, and other functional and cross-linking monomers. During polymerization, physical cross-links together with chemical cross-links are in site produced within the imprinted shells based on hydrophobic association among the PMEO2MA, favoring formation of high-quality imprints. While cooled appropriately below the polymerization temperature, these physical cross-links can be dissociated rapidly, thus facilitating removal of the embedded template. For proof of this concept, lysozyme-imprinted nanoparticles were synthesized at 37 °C over the nanoparticles functionalized with carboxylic and vinyl groups. The template removal from the imprinted nanoparticles was readily achieved by washing with a dilute acidic detergent solution at 4 °C. As-prepared imprinted nanoparticles showed greatly higher imprinting factor and specific rebinding than obtained with the same recipe but by solution polymerization (SP). Moreover, such imprinted nanomaterials exhibited satisfactory rebinding selectivity, kinetics and reusability. PMID:26313422

  20. Surface-Enhanced Raman Spectroscopy of Polyelectrolyte-Wrapped Gold Nanoparticles in Colloidal Suspension

    PubMed Central

    Sivapalan, Sean T.; DeVetter, Brent M.; Yang, Timothy K.; Schulmerich, Matthew V.; Bhargava, Rohit; Murphy, Catherine J.

    2013-01-01

    The rapidly expanding field of surface-enhanced Raman spectroscopy (SERS) has helped fuel an intense interest in noble metal nanoparticle synthesis. An in-suspension approach for quantifying SERS enhancement and relating that enhancement to a spontaneous Raman equivalent signal is described. Gold nanoparticles of various shapes were wrapped with polyelectrolyte multilayers that trapped Raman reporter molecules at defined distances from the metal core. Electrospray ionization liquid chromatography mass spectrometry (ESI-LC-MS) on digested samples was employed to measure the average number of bound Raman reporter molecules per gold nanoparticle, and inductively coupled plasma mass spectrometry (ICP-MS) was used to measure the average number of gold atoms per nanoparticle. Using these data, SERS signal intensity was compared to a spontaneous Raman calibration curve to compute a spontaneous Raman equivalent factor. Three different geometries of gold nanoparticles (cubes, spheres, and trisoctahedra) were synthesized to investigate edge and corner effects using these quantitative techniques. Finite element method (FEM) electromagnetic simulations examined the relationship between the different geometries and the observed SERS signal intensities. The experimental observations and theoretical results indicate that cubic gold nanoparticles have the highest effective signal. PMID:24224064

  1. The influence of surface functionalization on the enhanced internalization of magnetic nanoparticles in cancer cells

    NASA Astrophysics Data System (ADS)

    Villanueva, Angeles; Cañete, Magdalena; Roca, Alejandro G; Calero, Macarena; Veintemillas-Verdaguer, Sabino; Serna, Carlos J; del Puerto Morales, María; Miranda, Rodolfo

    2009-03-01

    The internalization and biocompatibility of iron oxide nanoparticles surface functionalized with four differently charged carbohydrates have been tested in the human cervical carcinoma cell line (HeLa). Neutral, positive, and negative iron oxide nanoparticles were obtained by coating with dextran, aminodextran, heparin, and dimercaptosuccinic acid, resulting in colloidal suspensions stable at pH 7 with similar aggregate size. No intracellular uptake was detected in cells incubated with neutral charged nanoparticles, while negative particles showed different behaviour depending on the nature of the coating. Thus, dimercaptosuccinic-coated nanoparticles showed low cellular uptake with non-toxic effects, while heparin-coated particles showed cellular uptake only at high nanoparticle concentrations and induced abnormal mitotic spindle configurations. Finally, cationic magnetic nanoparticles show excellent properties for possible in vivo biomedical applications such as cell tracking by magnetic resonance imaging (MRI) and cancer treatment by hyperthermia: (i) they enter into cells with high effectiveness, and are localized in endosomes; (ii) they can be easily detected inside cells by optical microscopy, (iii) they are retained for relatively long periods of time, and (iv) they do not induce any cytotoxicity.

  2. Magnetic iron oxide nanoparticles for biomedical applications.

    PubMed

    Laurent, Sophie; Bridot, Jean-Luc; Elst, Luce Vander; Muller, Robert N

    2010-03-01

    Due to their high magnetization, superparamagnetic iron oxide nanoparticles induce an important decrease in the transverse relaxation of water protons and are, therefore, very efficient negative MRI contrast agents. The knowledge and control of the chemical and physical characteristics of nanoparticles are of great importance. The choice of the synthesis method (microemulsions, sol-gel synthesis, laser pyrolysis, sonochemical synthesis or coprecipitation) determines the magnetic nanoparticle's size and shape, as well as its size distribution and surface chemistry. Nanoparticles can be used for numerous in vivo applications, such as MRI contrast enhancement and hyperthermia drug delivery. New developments focus on targeting through molecular imaging and cell tracking. PMID:21426176

  3. Scaling Laws for Proton Acceleration from the Rear Surface of Laser-Irradiated Thin Foils

    SciTech Connect

    Fuchs, J.; Antici, P.; D'Humieres, E.; Lefebvre, E.; Borghesi, M.; Cecchetti, C. A.; Brambrink, E.; Audebert, P.; Kaluza, M.; Schreiber, J.; Malka, V.; Manclossi, M.; Meyroneinc, S.; Mora, P.; Toncian, T.; Pepin, H.

    2006-04-07

    In the last few years, intense research has been conducted on the topic of laser-accelerated ion sources and their applications. Ultra-bright beams of multi-MeV protons are produced by irradiating thin metallic foils with ultra-intense short laser pulses. These sources open new opportunities for ion beam generation and control, and could stimulate development of compact ion accelerators for many applications, in particular proton therapy of deep-seated tumours. Here we show that scaling laws deduced from fluid models reproduce well the acceleration of proton beams for a large range of laser and target parameters. These scaling laws show that, in our regime, there is an optimum in the laser pulse duration of {approx}200 fs-1 ps, with a needed laser energy level of 30 to 100 J, in order to achieve e.g. 200 MeV energy protons necessary for proton therapy.

  4. Carbon monoxide protonation in condensed phases and bonding to surface superacidic Brønsted centers.

    PubMed

    Stoyanov, Evgenii S; Malykhin, Sergei E

    2016-02-14

    Using infrared (IR) spectroscopy and density functional theory (DFT) calculations, interaction of CO with the strongest known pure Brønsted carborane superacids, H(CHB11Hal11) (Hal = F, Cl), was studied. CO readily interacted at room temperature with H(CHB11F11) acid, forming a mixture of bulk salts of formyl and isoformyl cations, which were in equilibrium An(-)H(+)CO COH(+)An(-). The bonding of CO to the surface Brønsted centers of the weaker acid, H(CHB11Cl11), resulted in breaking of the bridged H-bonds of the acid polymers without proton transfer (PT) to CO. The binding occurred via the C atom (blue shift ΔνCO up to +155-167 cm(-1), without PT) or via O atom (red shift ΔνCO up to -110 cm(-1), without PT) always simultaneously, regardless of whether H(+) is transferred to CO. IR spectra of all species were interpreted by B3LYP/cc-pVQZ calculations of the simple models, which adequately mimic the ability of carborane acids to form LH(+)CO, LH(+)CO, COH(+)L, and COH(+)L compounds (L = bases). The CO bond in all compounds was triple. Acidic strength of the Brønsted centers of commonly used acid catalysts, even so-called superacidic catalysts, is not sufficient for the formation of the compounds studied. PMID:26805010

  5. Nanovalve Activation by Surface-Attached Photoacids

    PubMed Central

    Guardado-Alvarez, T. M.; Russell, M. M.

    2015-01-01

    Proton transfer caused by excitation of a photoacid attached to the surface of a mesoporous silica nanoparticle activates a nanovalve and causes release of trapped molecules. The protonation of an aniline- based stalk releases a noncovalently bound cyclodextrin molecule that blocked a pore. The results show that pH-responsive molecular delivery systems can be externally controlled using light. PMID:24942753

  6. Cell and nanoparticle transport in tumour microvasculature: the role of size, shape and surface functionality of nanoparticles.

    PubMed

    Li, Ying; Lian, Yanping; Zhang, Lucy T; Aldousari, Saad M; Hedia, Hassan S; Asiri, Saeed A; Liu, Wing Kam

    2016-02-01

    Through nanomedicine, game-changing methods are emerging to deliver drug molecules directly to diseased areas. One of the most promising of these is the targeted delivery of drugs and imaging agents via drug carrier-based platforms. Such drug delivery systems can now be synthesized from a wide range of different materials, made in a number of different shapes, and coated with an array of different organic molecules, including ligands. If optimized, these systems can enhance the efficacy and specificity of delivery compared with those of non-targeted systems. Emerging integrated multiscale experiments, models and simulations have opened the door for endless medical applications. Current bottlenecks in design of the drug-carrying particles are the lack of knowledge about the dispersion of these particles in the microvasculature and of their subsequent internalization by diseased cells (Bao et al. 2014 J. R. Soc. Interface 11, 20140301 (doi:10.1098/rsif.2014.0301)). We describe multiscale modelling techniques that study how drug carriers disperse within the microvasculature. The immersed molecular finite-element method is adopted to simulate whole blood including blood plasma, red blood cells and nanoparticles. With a novel dissipative particle dynamics method, the beginning stages of receptor-driven endocytosis of nanoparticles can be understood in detail. Using this multiscale modelling method, we elucidate how the size, shape and surface functionality of nanoparticles will affect their dispersion in the microvasculature and subsequent internalization by targeted cells. PMID:26855759

  7. Impact of surface modification in BSA nanoparticles for uptake in cancer cells.

    PubMed

    Choi, Jin-Seok; Meghani, Nilesh

    2016-09-01

    Recent studies have shown that cellular uptake of nanoparticles are strongly affected by the presence and physicochemical characteristics of protein on the surface of these nanoparticles. Hence, We developed surface-modified bovine serum albumin (BSA) nanoparticles (NPs) and evaluated the effect of surface modification on cellular uptake in two types of cancer cells, MCF-7 and A549. BSA NPs were prepared by desolvation method and their surface was modified with apo-transferrin, hyaluronic acid, and Poly(allylamine hydrochloride) (PAH). Morphology of surface-modified BSA NPs was characterized by field emission scanning electron microscopy and differential scanning calorimetry. In vitro-fluorescence release study was performed in phosphate buffered saline with trypsin (100μL/mL (v/v)) for 24h. Confocal microscopy was performed to evaluate cellular uptake followed by fluorescence analysis to evaluate the quantitative uptake of nanoparticles at 0.5, 1, and 2h. Different types of BSA NPs with a mean size of ∼100nm were successfully prepared. In vitro-fluorescent release showed sustained release pattern in surface-modified BSA NPs compared to unmodified BSA NPs. Surface-modified BSA NPs showed more cellular internalization than unmodified BSA NPs. The uptake of PAH-BSA NPs was about 2 times higher than that of unmodified BSA NPs in both cell types. In conclusion, surface-modified BSA NPs showed enhanced cellular uptake, and PAH-BSA NPs are more effective compared to ligand-specific surface-modified BSA NPs (HA-BSA NPs and Tf-BSA NPs). PMID:27289306

  8. Exposure of the yeast Saccharomyces cerevisiae to functionalized polystyrene latex nanoparticles: influence of surface charge on toxicity.

    PubMed

    Nomura, Toshiyuki; Miyazaki, Jumpei; Miyamoto, Akihisa; Kuriyama, Yuta; Tokumoto, Hayato; Konishi, Yasuhiro

    2013-04-01

    Novel nanoparticles with unique physicochemical characteristics are being developed with increasing frequency, leading to higher probability of nanoparticle release and environmental accumulation. Therefore, it is important to assess the potential environmental and biological adverse effects of nanoparticles. In this study, we investigated the toxicity and behavior of surface-functionalized nanoparticles toward yeast (Saccharomyces cerevisiae). The colony count method and confocal microscopy were used to examine the cytotoxicity of manufactured polystyrene latex (PSL) nanoparticles with various functional groups (amine, carboxyl, sulfate, and nonmodified). S. cerevisiae were exposed to PSL nanoparticles (40 mg/L) dispersed in 5-154 mM NaCl solutions for 1 h. Negatively charged nanoparticles had little or no toxic effect. Interestingly, nanoparticles with positively charged amine groups (p-Amine) were not toxic in 154 mM NaCl, but highly toxic in 5 mM NaCl. Confocal microscopy indicated that in 154 mM NaCl, the p-Amine nanoparticles were internalized by endocytosis, whereas in 5 mM NaCl they covered the dead cell surfaces. This demonstrates that nanoparticle-induced cell death might to be related to their adhesion to cells rather than their internalization. Together, these findings identify important factors in determining nanoparticle toxicity that might affect their impact on the environment and human health. PMID:23448545

  9. Delineating the extracellular water-accessible surface of the proton-coupled folate transporter.

    PubMed

    Duddempudi, Phaneendra Kumar; Goyal, Raman; Date, Swapneeta Sanjay; Jansen, Michaela

    2013-01-01

    The proton-coupled folate transporter (PCFT) was recently identified as the major uptake route for dietary folates in humans. The three-dimensional structure of PCFT and its detailed interplay with function remain to be determined. We screened the water-accessible extracellular surface of HsPCFT using the substituted-cysteine accessibility method, to investigate the boundaries between the water-accessible surface and inaccessible buried protein segments. Single-cysteines, engineered individually at 40 positions in a functional cysteine-less HsPCFT background construct, were probed for plasma-membrane expression in Xenopus oocytes with a bilayer-impermeant primary-amine-reactive biotinylating agent (sulfosuccinimidyl 6-(biotinamido) hexanoate), and additionally for water-accessibility of the respective engineered cysteine with the sulfhydryl-selective biotinylating agent 2-((biotinoyl)amino)ethyl methanethiosulfonate. The ratio between Cys-selective over amine-selective labeling was further used to evaluate three-dimensional models of HsPCFT generated by homology / threading modeling. The closest homologues of HsPCFT with a known experimentally-determined three-dimensional structure are all members of one of the largest membrane protein super-families, the major facilitator superfamily (MFS). The low sequence identity--14% or less--between HsPCFT and these templates necessitates experiment-based evaluation and model refinement of homology/threading models. With the present set of single-cysteine accessibilities, the models based on GlpT and PepTSt are most promising for further refinement. PMID:24205192

  10. Characterization of localized surface plasmon resonance transducers produced from Au25 nanoparticle multilayers

    PubMed Central

    Vaccarello, Paul; Tran, Linh; Meinen, Julia; Kwon, Chuhee; Abate, Yohannes; Shon, Young-Seok

    2012-01-01

    This article reports the preparation of gold plasmonic transducers using a nanoparticle self-assembly/heating method and the characterization of the films using scattering-type scanning near-field optical microscopy (s-SNOM). Nanoparticle-polymer multilayer films were prepared by the layer-by-layer assembly on glass slides by alternating exposures to monodisperse Au25 nanoparticles and ionic polymer linkers. Thermal evaporation of organic matters from the nanoparticle-polymer multilayer films at 600 °C allowed the nanoparticles to coalescence and form nanostructured films. Characterization of the nanostructured films generated from Au25 nanoparticles using atomic force microscopy (AFM) showed that the films have rounded, small, island-like morphologies (d: 30-50 nm) with a pit in the center of many islands. However, further characterizations with s-SNOM revealed that the produced nanoislands contain a single gold cluster in a pit surrounded by donut-shaped dielectric species. Formation of such a structure is thought to be resulted from the embedding of gold clusters under the reorganized polysiloxane binder coatings and glass surfaces during heat treatment of the Au25 nanoparticle multilayer films. The nanostructured films displayed strong surface plasmon resonance bands in UV-vis spectra with a peak absorbance occurring at ~545-550 nm. The optical sensing capability of the films was examined using D-glucose-functionalized gold island films with the interaction of Concanavalin A (ConA). The result showed that the adsorption of ConA on island films causes a large change in the LSPR band intensity. PMID:22822292

  11. Surface modification of PLGA nanoparticles by carbopol to enhance mucoadhesion and cell internalization.

    PubMed

    Surassmo, Suvimol; Saengkrit, Nattika; Ruktanonchai, Uracha Rungsardthong; Suktham, Kunat; Woramongkolchai, Noppawan; Wutikhun, Tuksadon; Puttipipatkhachorn, Satit

    2015-06-01

    Mucoadhesive poly (lactic-co-glycolic acid) (PLGA) nanoparticles having a modified shell-matrix derived from polyvinyl alcohol (PVA) and Carbopol (CP), a biodegradable polymer coating, to improve the adhesion and cell transfection properties were developed. The optimum formulations utilized a CP concentration in the range of 0.05-0.2%w/v, and were formed using modified emulsion-solvent evaporation technique. The resulting CP-PLGA nanoparticles were characterized in terms of their physical and chemical properties. The absorbed CP on the PLGA shell-matrix was found to affect the particle size and surface charge, with 0.05% CP giving rise to smooth spherical particles (0.05CP-PLGA) with the smallest size (285.90 nm), and strong negative surface charge (-25.70 mV). The introduction of CP results in an enhancement of the mucoadhesion between CP-PLGA nanoparticles and mucin particles. In vitro cell internalization studies highlighted the potential of 0.05CP-PLGA nanoparticles for transfection into SiHa cells, with uptake being time dependent. Additionally, cytotoxicity studies of CP-PLGA nanoparticles against SiHa cancer cells indicated that low concentrations of the nanoparticles were non-toxic to cells (cell viability >80%). From the various formulations studied, 0.05CP-PLGA nanoparticles proved to be the optimum model carrier having the required mucoadhesive profile and could be an alternative therapeutic efficacy carrier for targeted mucosal drug delivery systems with biodegradable polymer. PMID:25937384

  12. Surface functionalization of nanoparticles to control cell interactions and drug release.

    PubMed

    Luo, Rongcong; Neu, Björn; Venkatraman, Subbu S

    2012-08-20

    Nanoparticles made from poly(dl-lactide-co-glycolide) (PLGA) are used to deliver a wide range of bioactive molecules, due to their biocompatibility and biodegradability. This study investigates the surface modification of PLGA nanoparticles via the layer-by-layer (LbL) deposition of polyelectrolytes, and the effects of these coatings on the release behavior, cytotoxicity, hemolytic activity, and cellular uptake efficiency. PLGA nanoparticles are modified via LbL adsorption of two polyelectrolyte pairs: 1) poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) and 2) poly(L-lysine hydrobromide) (PLL) and dextran sulfate (DES). It is demonstrated that both PAH/PSS and PLL/DES coatings suppress the burst release usually observed for unmodified PLGA nanoparticles and that the release behavior can be adjusted by changing the layer numbers, layer materials, or by crosslinking the layer constituents. Neither bare nor polyelectrolyte-modified PLGA nanoparticles show any signs of cytotoxicity. However, nanoparticles with a positively charged polyelectrolyte as the outermost layer induce hemolysis, whereas uncoated particles or particles with a negatively charged polyelectrolyte as the outermost layer show no hemolytic activity. Furthermore, particles with either PAH or PLL as the outermost layer also demonstrate a higher uptake efficiency by L929 fibroblast cells, due to a higher cell-particle affinity. This study suggests that LbL coating of PLGA nanoparticles can control the release behavior of bioactive molecules as well as the surface activity, therefore providing a promising strategy to enhance the efficiency of nanoparticulate drug-delivery systems. PMID:22674655

  13. SURFACE CHEMISTRY INFLUENCE CANCER KILLING EFFECT OF TiO2 NANOPARTICLES

    PubMed Central

    Thevenot, Paul; Cho, Jai; Wavhal, Dattatray; Timmons, Richard B.; Tang, Liping

    2008-01-01

    Photocatalyzed TiO2 nanoparticles have been shown to eradicate cancer cells. However the required in situ introduction of UV light limits the use of such a therapy in patients. In the present study, the non-photocatalyic anti-cancer effect of surface functionalized TiO2 was examined. Nanoparticles bearing -OH, -NH2, or –COOH surface groups, were tested for their effect on in vitro survival of several cancer and control cell lines. The cells tested included B16F10 melanoma, Lewis lung carcinoma (LLC), JHU prostate cancer cells, and 3T3 fibroblasts. Cell viability was observed to depend on particle concentrations, cell types, and surface chemistry. Specifically, -NH2 and -OH groups exhibited significantly higher toxicity than -COOH. Microscopic and spectrophotometric studies revealed nanoparticle-mediated cell membrane disruption leading to cell death. The results suggest that functionalized TiO2, and presumably other nanoparticles, may be surface engineered for targeted cancer therapy. PMID:18502186

  14. Nanoparticle-decorated ceramic as substrate in surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Nedyalkov, N.; Nikov, Ru.; Koleva, M.; Atanasov, P. A.; Constantinescu, C.; Delaporte, Ph.; Grojo, D.

    2015-05-01

    Laser-assisted method for fabrication of nanoparticles on the surface of ceramic substrate is presented. The method is based on laser dewetting of thin metal film deposited on the substrate. Using this technique, gold nanoparticles on alumina ceramic surface are fabricated. It is shown that the processing parameters can influence the properties of the fabricated structure, as at certain conditions a homogeneous cover of nanoparticles with narrow size distribution can be achieved. The processed surfaces are tested as substrates in surface enhanced Raman spectroscopy of a standard dye. The efficiency of the substrates is estimated by the ability of detection of the dye at nM concentration and it is compared to that of thin gold film on ceramic substrate. The strongest enhancement is observed for the sample where Au film is not completely decomposed and the structure consists of thin film and nanoparticles aggregates. The proposed method has potential application in fabrication of cheap and reliable substrates for Raman spectroscopy analysis with high sensitivity and also in catalysis.

  15. Microstructure and micromorphology of Cu/Co nanoparticles: Surface texture analysis

    NASA Astrophysics Data System (ADS)

    Ţălu, Ştefan; Bramowicz, Miroslaw; Kulesza, Slawomir; Ghaderi, Atefeh; Dalouji, Vali; Solaymani, Shahram; Khalaj, Zahra

    2016-07-01

    This paper analyses the three-dimensional (3-D) surface texture of Cu/Co thin films deposited by DC-Magnetron sputtering method on the silicon substrates. The prepared Cu/Co nanoparticles were used as research materials. Three groups of samples were deposited on silicon substrates in the argon atmosphere and gradually cooled down to room temperature. The crystalline structures and elemental compositions were analyzed by X-ray diffraction (XRD) spectrum with conventional Bragg-Brentano geometry. X-ray diffraction profile indicates that Co and Cu interpenetrating crystalline structures are formed in these films. The sample surface images were recorded using atomic force microscopy (AFM) and analyzed by means of the fractal geometry. Statistical, fractal and functional surface properties of prepared samples were computed to describe major characteristics of the spatial surface texture of Cu/Co nanoparticles. Presented deposition method is a versatile, costeffective, and simple method to synthesize nano- and microstructures of Cu/Co thin films. This type of 3-D morphology allows to understand the structure/property relationships and to investigate defect-related properties of Cu/Co nanoparticles. Presented results confirm the possibility of preparing high-quality Cu/Co nanoparticles via DC-Magnetron sputtering method on silicon substrates.

  16. Manganese Phosphate Self-assembled Nanoparticle Surface and Its application for Superoxide Anion Detection.

    PubMed

    Shen, Xiaohui; Wang, Qi; Liu, Yuhong; Xue, Wenxiao; Ma, Lie; Feng, Shuaihui; Wan, Mimi; Wang, Fenghe; Mao, Chun

    2016-01-01

    Quantitative analysis of superoxide anion (O2(·-)) has increasing importance considering its potential damages to organism. Herein, a novel Mn-superoxide dismutase (MnSOD) mimics, silica-manganous phosphate (SiO2-Mn3(PO4)2) nanoparticles, were designed and synthesized by surface self-assembly processes that occur on the surface of silica-phytic acid (SiO2-PA) nanoparticles. The composite nanoparticles were characterized by fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), electron diffraction pattern, energy dispersive spectroscopy (EDS) and elemental mapping. Then the electrochemical measurements of O2(·-) based on the incorporation of SiO2-Mn3(PO4)2 onto the surface of electrodes were performed, and some satisfactory results were obtained. This is the first report that manganous phosphate (Mn3(PO4)2) nanoparticles with shape-controlled, but not multilayer sheets, were utilized for O2(·-) detection. The surface self-assembly technology we proposed will offer the ideal material to construct more types biosensor and catalytic system for its nanosized effect. PMID:27357008

  17. Cellular Stress Response to Engineered Nanoparticles: Effect of Size, Surface Coating, and Cellular Uptake

    EPA Science Inventory

    CELLULAR STRESS RESPONSE TO ENGINEERED NANOPARTICLES: EFFECT OF SIZE, SURFACE COATING, AND CELLULAR UPTAKE RY Prasad 1, JK McGee2, MG Killius1 D Ackerman2, CF Blackman2 DM DeMarini2 , SO Simmons2 1 Student Services Contractor, US EPA, RTP, NC 2 US EPA, RTP, NC The num...

  18. Manganese Phosphate Self-assembled Nanoparticle Surface and Its application for Superoxide Anion Detection

    PubMed Central

    Shen, Xiaohui; Wang, Qi; Liu, Yuhong; Xue, Wenxiao; Ma, Lie; Feng, Shuaihui; Wan, Mimi; Wang, Fenghe; Mao, Chun

    2016-01-01

    Quantitative analysis of superoxide anion (O2·−) has increasing importance considering its potential damages to organism. Herein, a novel Mn-superoxide dismutase (MnSOD) mimics, silica-manganous phosphate (SiO2-Mn3(PO4)2) nanoparticles, were designed and synthesized by surface self-assembly processes that occur on the surface of silica-phytic acid (SiO2-PA) nanoparticles. The composite nanoparticles were characterized by fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), scanning electronic microscopy (SEM), electron diffraction pattern, energy dispersive spectroscopy (EDS) and elemental mapping. Then the electrochemical measurements of O2·− based on the incorporation of SiO2-Mn3(PO4)2 onto the surface of electrodes were performed, and some satisfactory results were obtained. This is the first report that manganous phosphate (Mn3(PO4)2) nanoparticles with shape-controlled, but not multilayer sheets, were utilized for O2·− detection. The surface self-assembly technology we proposed will offer the ideal material to construct more types biosensor and catalytic system for its nanosized effect. PMID:27357008

  19. Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding.

    PubMed

    Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M; Ke, Pu Chun; Ding, Feng

    2014-07-21

    Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation - a common strategy for solubilizing and functionalizing fullerene - on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding. PMID:24934397

  20. Pool boiling of nanoparticle-modified surface with interlaced wettability

    PubMed Central

    2012-01-01

    This study investigated the pool boiling heat transfer under heating surfaces with various interlaced wettability. Nano-silica particles were used as the coating element to vary the interlaced wettability of the surface. The experimental results revealed that when the wettability of a surface is uniform, the critical heat flux increases with the more wettable surface; however, when the wettability of a surface is modified interlacedly, regardless of whether the modified region becomes more hydrophilic or hydrophobic, the critical heat flux is consistently higher than that of the isotropic surface. In addition, this study observed that critical heat flux was higher when the contact angle difference between the plain surface and the modified region was smaller. PMID:22607462

  1. Pool boiling of nanoparticle-modified surface with interlaced wettability

    NASA Astrophysics Data System (ADS)

    Hsu, Chin-Chi; Su, Tsung-Wen; Chen, Ping-Hei

    2012-05-01

    This study investigated the pool boiling heat transfer under heating surfaces with various interlaced wettability. Nano-silica particles were used as the coating element to vary the interlaced wettability of the surface. The experimental results revealed that when the wettability of a surface is uniform, the critical heat flux increases with the more wettable surface; however, when the wettability of a surface is modified interlacedly, regardless of whether the modified region becomes more hydrophilic or hydrophobic, the critical heat flux is consistently higher than that of the isotropic surface. In addition, this study observed that critical heat flux was higher when the contact angle difference between the plain surface and the modified region was smaller.

  2. Effect of Surface Treated Silicon Dioxide Nanoparticles on Some Mechanical Properties of Maxillofacial Silicone Elastomer

    PubMed Central

    Zayed, Sara M.; Alshimy, Ahmad M.; Fahmy, Amal E.

    2014-01-01

    Current materials used for maxillofacial prostheses are far from ideal and there is a need for novel improved materials which mimic as close as possible the natural behavior of facial soft tissues. This study aimed to evaluate the effect of adding different concentrations of surface treated silicon dioxide nanoparticles (SiO2) on clinically important mechanical properties of a maxillofacial silicone elastomer. 147 specimens of the silicone elastomer were prepared and divided into seven groups (n = 21). One control group was prepared without nanoparticles and six study groups with different concentrations of nanoparticles, from 0.5% to 3% by weight. Specimens were tested for tear strength (ASTM D624), tensile strength (ASTM D412), percent elongation, and shore A hardness. SEM was used to assess the dispersion of nano-SiO2 within the elastomer matrix. Data were analyzed by one-way ANOVA and Scheffe test (α = 0.05). Results revealed significant improvement in all mechanical properties tested, as the concentration of the nanoparticles increased. This was supported by the results of the SEM. Hence, it can be concluded that the incorporation of surface treated SiO2 nanoparticles at concentration of 3% enhanced the overall mechanical properties of A-2186 silicone elastomer. PMID:25574170

  3. Nanoparticle doping in nematic liquid crystals: distinction between surface and bulk effects by numerical simulations.

    PubMed

    Urbanski, Martin; Mirzaei, Javad; Hegmann, Torsten; Kitzerow, Heinz-S

    2014-05-19

    Doping nematic liquid crystals with small amounts of nanoparticles can significantly alter the electro-optic response of the nematic host. Some of these effects result from nanoparticles influencing the liquid crystal/substrate interface, while other effects are caused by nanoparticles in the bulk. So far, little attention has been paid to the influence of surface interactions on the determination of bulk properties. In the present study, these effects are investigated experimentally and confirmed by numerical simulations. The splay-type Fréedericksz-transition of the nematic liquid crystal 5CB doped with CdSe quantum dots is investigated, as these dispersions are known from earlier studies to affect the initial alignment layers. In comparison, dispersions of chemically and thermally stable silanized gold nanoparticles in the apolar nematic host FELIX-2900-03 are analyzed, which are expected to be bulk-active only. A data fitting routine is presented which allows a distinction between bulk and surface effects of nanoparticle doping. For the quantum dots, an increase of pretilt angle proportional to the doping concentration is found, as well as a slight decrease of the anchoring energy of molecules at the confining substrates. The silanized gold particles show no influence on the boundary conditions up to doping concentrations of 2.5 % (w). For higher concentrations an increase of pretilt angle is reported. PMID:24482304

  4. Star-like gold nanoparticles as highly active substrate for surface enhanced Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Morasso, Carlo; Mehn, Dora; Vanna, Renzo; Bedoni, Marzia; Pascual García, César; Prosperi, Davide; Gramatica, Furio

    2013-02-01

    Surface Enhanced Raman Spectroscopy (SERS) is a popular method in bio-analytical chemistry and a potentially powerful enabling technology for in vitro diagnostics. SERS combines the excellent chemical specificity of Raman spectroscopy with the good sensitivity provided by enhancement of the signal that is observed when a molecule is located on (or very close to) the surface of nanostructured metallic materials. Star-like gold nanoparticles (SGN) are a new class of multibranched nanoparticles that in the last few years have attracted the attention of SERS community for their plasmonic properties. In this work we present a new method to prepare star-like gold nanoparticles with a simple one step protocol at room temperature using hydroquinone as reducing agent. Besides we compare the enhancement of Raman signal of malachite green, a dye commonly employed as label in biological studies, by star-like gold nanoparticles having different size, directly in liquid. This study shows that SGN provide good enhancement of Raman signal and that the effect of their dimension is strongly dependent on the wavelength used. Moreover preliminary results suggest that SGN produced using this method are characterized by good physical-chemical properties and they can be functionalized using the standard thiol chemistry. Overall, these results suggest that star-like gold nanoparticles produced through this method could be used for the further development of highly specific and sensitive SERS-based bio-analytical tests.

  5. Synthesis of TiO2 Nanoparticles on the Au(111) Surface

    SciTech Connect

    Biener, J; Farfan-Arribas, E; Biener, M M; Friend, C M; Madix, R J

    2005-01-11

    The growth of titanium oxide nanoparticles on reconstructed Au(111) surfaces was investigated by scanning tunneling microscopy and X-ray photoelectron spectroscopy. Ti was deposited by physical vapor deposition at 300 K. Regular arrays of titanium nanoparticles form by preferential nucleation of Ti at the elbow sites of the herringbone reconstruction. Titanium oxide clusters were synthesized by subsequent exposure to O{sub 2} at 300 K. Two- and three-dimensional titanium oxide nanocrystallites form during annealing in the temperature range from 600 to 900 K. At the same time, the Au(111) surface assumes a serrated, <110> oriented step-edge morphology, suggesting step-edge pinning by titanium oxide nanoparticles. The oxidation state of these titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO{sub 2} nanocrystals as judged by the observed XPS binding energies. Nano-dispersed TiO{sub 2} on Au(111) is an ideal system to test the various models explaining the enhanced catalytic reactivity of supported Au nanoparticles.

  6. Silica Supported Ceria Nanoparticles: A Hybrid Nanostructure To Increase Stability And Surface Reactivity Of Nano-crystalline Ceria

    SciTech Connect

    Munusamy, Prabhakaran; Sanghavi, Shail P.; Varga, Tamas; Thevuthasan, Suntharampillai

    2014-01-21

    The mixed oxidation state (3+/4+) of ceria nanoparticles of smaller sizes make them attractive materials for their catalytic antioxidant biological properties. However the unmodified smaller ceria nanoparticles are limited in their use due to particles agglomeration and reduced surface chemical reactivity in the solutions used to disperse the nanoparticles. This work describes an effort to stabilize small ceria nanoparticles, retaining their desired activity, on a larger stable silica support. The ceria nanoparticles attached to silica was synthesized by a solution synthesis technique in which the surface functional groups of silica nanoparticles were found to be essential for the formation of smaller ceria nanoparticles. The surface chemical and vibrational spectroscopy analysis revealed cerium–silicate (Ce-O-Si) covalent bond linkage between silica and cerium oxide nanoparticles. The colloidal properties (agglomerate particle size and suspension stability) of ceria attached to silica was significantly improved due to inherent physico-chemical characteristics of silica against random collision and gravitation settling as opposed to unmodified ceria nanoparticles in solution. The bio-catalytic activity of ceria nanoparticles in the 3+ oxidation state was not found to be limited by attachment to the silica support as measured by free radical scavenging activity in different biological media conditions.

  7. Surface NMR measurement of proton relaxation times in medium to coarse-grained sand aquifer.

    PubMed

    Shushakov, O A

    1996-01-01

    A surface NMR investigation of groundwater in the geomagnetic field is under study. To detect the surface NMR a wire loop with a diameter of about 100 m, being an antenna for both an exciting field source and the NMR signal receiver, is laid out on the ground. A sinusoidal current pulse with a rectangular envelope is passed through the loop to excite the NMR signal. The carrier frequency of the oscillating current in this pulse is equal to the Larmor frequency of protons in the Earth's magnetic field. The current amplitude is changed up to 200 amps and the pulse duration is fixed and is equal to 40 ms. The exciting pulse is followed by an induction emf signal caused by the Larmor nuclear precession in geomagnetic field. The relaxation times T1, T2, and T2* were measured by the surface NMR for both groundwater in medium to coarse-grained sand at borehole and for bulk water under the ice surface of frozen lake. To determine T1, a longitudinal interference in experiments with repeated pulses was measured. A sequence with equal period between equal excitation pulses was used. The relaxation times T1, T2, measured for bulk water under the ice of the Ob reservoir were 1.0 s and 0.7 s, respectively. To estimate an influence of dissolved oxygen T1 of the same water at the same temperature was measured by lab NMR with and without pumping of oxygen. The relaxation time T1 measured for water in the medium to coarse-grained sand is 0.65 s. The relaxation time T2 estimated by spin echo sequence is found to be equal to 0.15 s. The relaxation time T2* is found to be about 80 ms. This result contradicts published earlier phenomenological correlation between relaxation time T2* and grain size of water-bearing rock. This could be as a result of unsound approach based on grain size or influence of paramagnetic impurities. PMID:8970122

  8. Surface Enhanced Raman Spectroscopy of Organic Molecules on Magnetite (Fe3O4) Nanoparticles.

    PubMed

    Lee, Namhey; Schuck, P James; Nico, Peter S; Gilbert, Benjamin

    2015-03-19

    Surface-enhanced Raman spectroscopy (SERS) of species bound to environmentally relevant oxide nanoparticles is largely limited to organic molecules structurally related to catechol that facilitate a chemical enhancement of the Raman signal. Here, we report that magnetite (Fe3O4) nanoparticles provide a SERS signal from oxalic acid and cysteine via an electric field enhancement. Magnetite thus likely provides an oxide substrate for SERS study of any adsorbed organic molecule. This substrate combines benefits from both metal-based and chemical SERS by providing an oxide surface for studies of environmentally and catalytically relevant detailed chemical bonding information with fewer restrictions of molecular structure or binding mechanisms. Therefore, the magnetite-based SERS demonstrated here provides a new approach to establishing the surface interactions of environmentally relevant organic ligands and mineral surfaces. PMID:26262854

  9. Characterization of gas-expanded liquid-deposited gold nanoparticle films on substrates of varying surface energy.

    PubMed

    Hurst, Kendall M; Roberts, Christopher B; Ashurst, W Robert

    2011-01-18

    Dodecanethiol-stabilized gold nanoparticles (AuNPs) were deposited via a gas-expanded liquid (GXL) technique utilizing CO(2)-expanded hexane onto substrates of different surface energy. The different surface energies were achieved by coating silicon (100) substrates with various organic self-assembled monolayers (SAMs). Following the deposition of AuNP films, the films were characterized to determine the effect of substrate surface energy on nanoparticle film deposition and growth. Interestingly, the critical surface tension of a given substrate does not directly describe nanoparticle film morphology. However, the results in this study indicate a shift between layer-by-layer and island film growth based on the critical surface tension of the capping ligand. Additionally, the fraction of surface area covered by the AuNP film decreases as the oleophobic nature of the surfaces increases. On the basis of this information, the potential exists to engineer nanoparticle films with desired morphologies and characteristics. PMID:21174390

  10. First Observation of Charge Reduction and Desorption Kinetics of Multiply Protonated Peptides Soft Landed onto Self-Assembled Monolayer Surfaces

    SciTech Connect

    Hadjar, Omar; Futrell, Jean H.; Laskin, Julia

    2007-12-13

    The kinetics of charge reduction and desorption of different species produced by soft-landing of mass-selected ions was studied using in situ secondary ion mass spectrometry (SIMS) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). The improved SIMS capability described in this work utilizes an in-line 8 keV Cs+ ion gun and allows us to interrogate the surface both during the ion deposition and after the deposition is terminated. As a model system doubly protonated ions of Gramicidin S were deposited onto a fluorinated self-assembled monolayer (FSAM) surface. Our results demonstrate for the first time that various peptide-related peaks in FT-ICR SIMS spectra follow very different kinetics. We obtained unique kinetics signatures for doubly protonated, singly protonated and neutral peptides retained on the surface and followed their evolution as a function of time. The experimental results are in excellent agreement with a kinetic model that takes into account charge reduction and thermal desorption of different species from the surface.

  11. Tuning the properties of ZnO, hematite, and Ag nanoparticles by adjusting the surface charge.

    PubMed

    Zhang, Jianhui; Dong, Guanjun; Thurber, Aaron; Hou, Yayi; Gu, Min; Tenne, Dmitri A; Hanna, C B; Punnoose, Alex

    2012-03-01

    A poly (acryl acid) (PAA) post-treatment method is performed to modify the surface charge of ZnO nanospheres, hematite nanocubes, and Ag nanoprisms from highly positive to very negative by adjusting the PAA concentration, to and greatly modify their photoluminescence, cytotoxicity, magnetism, and surface plasmon resonance. This method provides a general way to tune the nanoparticle properties for broad physicochemical and biological applications. PMID:22298490

  12. Facile production of monodisperse nanoparticles on a liquid surface.

    PubMed

    Anantha, P; Cheng, T; Tay, Y Y; Wong, C C; Ramanujan, R V

    2015-10-28

    The emergence of monodispersity during particle growth on a liquid substrate was investigated both by experimental methods and by computer simulation. Monodispersity arises through a novel mechanism (termed "shared coarsening"), associated with the spatial distribution of the particles; smaller particles are simultaneously consumed by several larger particles. Particle monodispersity was predicted by kinetic Monte Carlo simulation for suitable substrate adsorption probability and adatom diffusion length conditions. High particle monodispersity is predicted for low adsorption probability and low/intermediate diffusion length values. Experimentally, the formation of uniformly sized copper nanoparticles by physical vapor deposition on a liquid substrate was demonstrated. These results demonstrate, by experiment and simulation, the facile production of monodisperse particles on liquid substrates. PMID:26399544

  13. Discrete nanoparticles induce loss of Legionella pneumophila biofilms from surfaces.

    PubMed

    Raftery, Tara D; Kerscher, Petra; Hart, Ashley E; Saville, Steven L; Qi, Bin; Kitchens, Christopher L; Mefford, Olin Thompson; McNealy, Tamara L

    2014-08-01

    Nanoparticles (NPs) have been shown to induce dispersal events in microbial biofilms but the mechanism of the dispersal is unknown. Biofilms contaminate many man-made aquatic systems such as cooling towers, spas and dental lines. Within these biofilms, Legionella pneumophila is a primary pathogen, leading to these environments serving as sources for disease outbreaks. Here we show a reduction in biofilm bio-volume upon treatment with citrate-coated 6-nm platinum NPs, polyethylene glycol (PEG)-coated 11-nm gold NPs, and PEG-coated 8-nm iron oxide NPs. Treatment with citrate-coated 8-nm silver NPs, however, did not reduce biomass. The synthesis of NPs that remain dispersed and resist irreversible aggregation in the exposure media appears to be a key factor in the ability of NPs to induce biofilm dispersal. PMID:23586422

  14. Detection of circulating tumor cells using targeted surface-enhanced Raman scattering nanoparticles and magnetic enrichment

    NASA Astrophysics Data System (ADS)

    Shi, Wei; Paproski, Robert J.; Moore, Ronald; Zemp, Roger

    2014-05-01

    While more than 90% of cancer deaths are due to metastases, our ability to detect circulating tumor cells (CTCs) is limited by low numbers of these cells in the blood and factors confounding specificity of detection. We propose a magnetic enrichment and detection technique for detecting CTCs with high specificity. We targeted both magnetic and surface-enhanced Raman scattering (SERS) nanoparticles to cancer cells. Only cells that are dual-labeled with both kinds of nanoparticles demonstrate an increasing SERS signal over time due to magnetic trapping.

  15. Surface-Enhanced Raman Spectroscopy Sensors From Nanobiosilica With Self-Assembled Plasmonic Nanoparticles

    PubMed Central

    Ren, Fanghui; Campbell, Jeremy; Rorrer, Gregory L.; Wang, Alan X.

    2014-01-01

    We present an innovative surface-enhanced Raman spectroscopy (SERS) sensor based on a biological-plasmonic hybrid nanostructure by self-assembling silver (Ag) nanoparticles into diatom frustules. The photonic-crystal-like diatom frustules provide a spatially confined electric field with enhanced intensity that can form hybrid photonic-plasmonic modes through the optical coupling with Ag nanoparticles. The experimental results demonstrate 4–6× and 9–12× improvement of sensitivities to detect the Raman dye for resonance and nonresonance SERS sensing, respectively. Such low-cost and high-sensitivity SERS sensors have significant potentials for label-free biosensing. PMID:25309113

  16. Surface plasmon excitation via Au nanoparticles in n-CdSe /p-Si heterojunction diodes

    NASA Astrophysics Data System (ADS)

    Konda, R. B.; Mundle, R.; Mustafa, H.; Bamiduro, O.; Pradhan, A. K.; Roy, U. N.; Cui, Y.; Burger, A.

    2007-11-01

    We report on the significant enhancement of photocurrent in pn heterojunction diode, consisting of n-CdSe /p-Si substrates, in situ deposited with Au nanoparticles on the surface by the pulsed-laser deposition technique. This is attributed due to the large enhancement in electromagnetic field that occurs in the vicinity of the metal surface, causing surface plasmons. The large enhancement in Raman and photoluminescence intensity was observed due to surface plasmon resonance. Our results suggest that the photodetectors, optoelectronic, such as high-performance thin-film solar cells, optical communication, and sensing devices, including bio- and molecular sensors, can be fabricated with improved functionality.

  17. 3d-shell contribution to the energy loss of protons during grazing scattering from Cu(111) surfaces

    SciTech Connect

    Gravielle, M. S.; Alducin, M.; Juaristi, J. I.; Silkin, V. M.

    2007-10-15

    Motivated by a recent experimental work [S. Lederer and H. Winter, Phys. Rev. A 73, 054901 (2006)] we study the contribution of the 3d shell electrons to the energy loss of 100 keV protons scattered off from the Cu(111) surface. To describe this process we use a multiple collision formalism, where the interaction of the projectile with 3d electrons is described by means of a sequence of single encounters with atoms belonging to the first atomic layer. In order to compare the theoretical energy loss with the experimental data, we add the contribution of valence electrons, which is evaluated in linear response theory using a response function that incorporates information on the surface band structure. For completeness, the energy lost by protons is also calculated within a jellium model that includes 3d and valence electrons with equal footing. Fair agreement between theory and experiment exists when the 3d shell is taken into account in the calculation.

  18. Surface modification of oleylamine-capped Ag–Cu nanoparticles to fabricate low-temperature-sinterable Ag–Cu nanoink

    NASA Astrophysics Data System (ADS)

    Kim, Na Rae; Jong Lee, Yung; Lee, Changsoo; Koo, Jahyun; Lee, Hyuck Mo

    2016-08-01

    By treating oleylamine (OA)-capped Ag–Cu nanoparticles with tetramethylammonium hydroxide (TMAH), we obtained metal nanoparticles that are suspended in polar solvents and sinterable at low temperatures. The simple process with ultra sonication enables synthesis of monodispersed and high purity nanoparticles in an organic base, where the resulting nanoparticles are dispersible in polar solvents such as ethanol and isopropyl alcohol. To investigate the surface characteristics, we conducted Fourier-transform infrared and zeta-potential analyses. After thermal sintering at 200 °C, which is approximately 150 °C lower than the thermal decomposition temperature of OA, an electrically conductive thin film was obtained. Electrical resistivity measurements of the TMAH-treated ink demonstrate that surface modified nanoparticles have a low resistivity of 13.7 × 10‑6 Ω cm. These results confirm the prospects of using low-temperature sinterable nanoparticles as the electrode layer for flexible printed electronics without damaging other stacked polymer layers.

  19. Toxicity of bare and surfaced functionalized iron oxide nanoparticles towards microalgae.

    PubMed

    Toh, Pey Yi; Tai, Wan Yii; Ahmad, Abdul Latif; Lim, Jit Kang; Chan, Derek Juinn Chieh

    2016-06-01

    This study investigates the toxicity of bare iron oxide nanoparticles (IONPs) and surface functionalization iron oxide nanoparticles (SF-IONPs) to the growth of freshwater microalgae Chlorella sp. This study is important due to the increased interest on the application of the magnetic responsive IONPs in various fields, such as biomedical, wastewater treatment, and microalgae harvesting. This study demonstrated that the toxicity of IONPs was mainly contributed by the indirect light shading effect from the suspending nanoparticles which is nanoparticles concentration-dependent, direct light shading effect caused by the attachment of IONPs on cell and the cell aggregation, and the oxidative stress from the internalization of IONPs into the cells. The results showed that the layer of poly(diallyldimethylammonium chloride) (PDDA) tended to mask the IONPs and hence eliminated oxidative stress toward the protein yield but it in turn tended to enhance the toxicity of IONPs by enabling the IONPs to attach on cell surfaces and cause cell aggregation. Therefore, the choice of the polymer that used for surface functionalize the IONPs is the key factor to determine the toxicity of the IONPs. PMID:26389846

  20. Dendrimer-Capped Gold Nanoparticles for Highly Reliable and Robust Surface Enhanced Raman Scattering.

    PubMed

    Kim, Kwanghyun; Lee, Jeongyeop; Jo, Gyeongcheon; Shin, Seungmin; Kim, Jin-Baek; Jang, Ji-Hyun

    2016-08-10

    Dendrimer-stabilized gold nanoparticles (Au-Den) were prepared by a facile solution based method for a highly reliable and robust surface enhanced Raman scattering (SERS) substrate. Au-Den was selectively attached on the surface of reduced graphene oxide (rGO) by noncovalent interactions between the Au capping dendrimer and the graphene surface. Au-Den/rGO exhibits the outstandingly stable and highly magnified Raman signal with an enhancement factor (EF) of 3.9 × 10(7) that enables detection of R6G dyes with concentration as low as 10 nM, retaining 95% of the Raman signal intensity after 1 year. The remarkable stability and enhancement originated not only from a simple combination of the electromagnetic and chemical mechanism of SERS but also from intensified packing density of stable Au-Den on the graphene substrate due to the firm binding between the dendrimer capped metal nanoparticles and the graphene substrate. This method is not limited to the gold nanoparticles and G4 dendrimer used herein, but also can be applied to other dendrimers and metal nanoparticles, which makes the material platform suggested here superior to other SERS substrates. PMID:27403733

  1. Theoretical characterization of the surface composition of ruthenium nanoparticles in equilibrium with syngas

    NASA Astrophysics Data System (ADS)

    Cusinato, Lucy; Martínez-Prieto, Luis M.; Chaudret, Bruno; Del Rosal, Iker; Poteau, Romuald

    2016-05-01

    A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction of CO and H with the surface of the catalyst. In this context, the single- and co-adsorption of CO and H to the surface of a 1 nm ruthenium nanoparticle has been investigated with density functional theory. Using several indexes (d-band center, crystal overlap Hamilton population, density of states), a systematic analysis of the bond properties and of the electronic states has also been done, in order to bring an understanding of structure/property relationships at the nanoscale. The H : CO surface composition of this ruthenium nanoparticle exposed to syngas has been evaluated according to a thermodynamic model fed with DFT energies. Such ab initio thermodynamic calculations give access to the optimal H : CO coverage values under a wide range of experimental conditions, through the construction of free energy phase diagrams. Surprisingly, under the Fischer-Tropsch synthesis experimental conditions, and in agreement with new experiments, only CO species are adsorbed at the surface of the nanoparticle. These findings shed new light on the possible reaction pathways underlying the Fischer-Tropsch synthesis, and specifically the initiation of the reaction. It is finally shown that the joint knowledge of the surface composition and energy descriptors can help to identify possible reaction intermediates.A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction

  2. Surface Activation of Electrocatalysis at Oxide Electrodes. Concerted Electron-Proton Transfer

    SciTech Connect

    Gagliardi, Christopher J.; Jurss, Jonah W.; Thorp, H. Holden; Meyer, Thomas J.

    2011-03-21

    Dramatic rate enhancements are observed for the oxidation of phenols, including tyrosine, at indium-tin oxide electrodes modified by the addition of the electron-transfer relays [MII(bpy)2(4,4'-(HO)2P(O)CH2)2bpy)]2+ (M = Ru, Os) with clear evidence for the importance of proton-coupled electron transfer and concerted electron-proton transfer.

  3. Identification of the functional groups on the surface of nanoparticles formed in photonucleation of aldehydes generated during forest fire events

    NASA Astrophysics Data System (ADS)

    Dultsev, Fedor N.; Mik, Ivan A.; Dubtsov, Sergei N.; Dultseva, Galina G.

    2014-11-01

    We describe the new procedure developed to determine the functional groups on the surface of nanoparticles formed in photonucleation of furfural, one of the aldehydes generated during forest fire events. The procedure is based on the detection of nanoparticle rupture from chemically modified surface of the quartz crystal microbalance oscillating in the thickness shear mode under voltage sweep. The rupture force is determined from the voltage at which the rupture occurs. It depends on particle mass and on the affinity of the surface functional groups of the particle to the groups that are present on the modified QCM surface. It was demonstrated with the amine modification of the surface that the nanoparticles formed in furfural photonucleation contain carbonyl and carboxyl groups. The applicability of the method for the investigation of functional groups on the surface of the nanoparticles of atmospheric aerosol is demonstrated.

  4. Size and surface chemistry of nanoparticles lead to a variant behavior in the unfolding dynamics of human carbonic anhydrase

    NASA Astrophysics Data System (ADS)

    Nasir, Irem; Lundqvist, Martin; Cabaleiro-Lago, Celia

    2015-10-01

    The adsorption induced conformational changes of human carbonic anhydrase I (HCAi) and pseudo wild type human carbonic anhydrase II truncated at the 17th residue at the N-terminus (trHCAii) were studied in presence of nanoparticles of different sizes and polarities. Isothermal titration calorimetry (ITC) studies showed that the binding to apolar surfaces is affected by the nanoparticle size in combination with the inherent protein stability. 8-Anilino-1-naphthalenesulfonic acid (ANS) fluorescence revealed that HCAs adsorb to both hydrophilic and hydrophobic surfaces, however the dynamics of the unfolding at the nanoparticle surfaces drastically vary with the polarity. The size of the nanoparticles has opposite effects depending on the polarity of the nanoparticle surface. The apolar nanoparticles induce seconds timescale structural rearrangements whereas polar nanoparticles induce hours timescale structural rearrangements on the same charged HCA variant. Here, a simple model is proposed where the difference in the timescales of adsorption is correlated with the energy barriers for initial docking and structural rearrangements which are firmly regulated by the surface polarity. Near-UV circular dichorism (CD) further supports that both protein variants undergo structural rearrangements at the nanoparticle surfaces regardless of being ``hard'' or ``soft''. However, the conformational changes induced by the apolar surfaces differ for each HCA isoform and diverge from the previously reported effect of silica nanoparticles.The adsorption induced conformational changes of human carbonic anhydrase I (HCAi) and pseudo wild type human carbonic anhydrase II truncated at the 17th residue at the N-terminus (trHCAii) were studied in presence of nanoparticles of different sizes and polarities. Isothermal titration calorimetry (ITC) studies showed that the binding to apolar surfaces is affected by the nanoparticle size in combination with the inherent protein stability. 8-Anilino

  5. On the protonation of oxo- and hydroxo- groups of the goethite (α-FeOOH) surface: A FTIR spectroscopic investigation of surface O-H stretching vibrations.

    SciTech Connect

    Boily, Jean F; Felmy, Andrew R

    2008-06-01

    The O–H stretching region of goethite particles evaporated at different levels of acidity was investigated by Attenuated Total Reflectance (ATR)-Fourier Transform InfraRed (FTIR) spectroscopy. Two-dimensional IR Correlation Spectroscopy was used to identify correlations between different sets of discrete surface OH stretches and a Multivariate Curve Resolution analysis was used to resolve the predominant spectral components. Two dominant groups of hydroxyls were identified on the basis of their differences in proton affinity. Group I hydroxyls appear as two 3698/3541 and 3660/3490 cm-1 band pairs. Group II hydroxyls are manifested through the 3648 and 3578 cm-1 bands at greater levels of surface proton loading. There is consequently no correlation between O–H stretching frequencies and proton affinity. Groups I and II were assigned to mostly singly- (–OH) and doubly- (μ-OH) coordinated hydroxyls, respectively. Stretches arising from triply-coordinated (μ3-OH) are proposed to be embedded within the dominant O–H band of bulk goethite. The possibility that these sites contribute to Group I and II hydroxyls should, however, not be entirely dismissed without further investigations. A reexamination of Temperature Programmed Desorption (TPD)-FTIR data of one goethite sample evaporated from alkaline conditions [Boily J.-F., Szanyi J., Felmy A. R. (2006) A combined FTIR and TPD study on the bulk and surface dehydroxylation and decarbonation of synthetic goethite. Geochim. Cosmochim. Acta70, 3613–3624] provided further constraints to this band assignment by providing clues to the network of surface hydrogen bonds. Important cooperative effects between hydrogen-bonded surface hydroxyls are suggested to play a crucial role on the variations of the position and intensity of discrete O–H stretching bands as a function of protonation level and temperature.

  6. On the protonation of oxo- and hydroxo-groups of the goethite (α-FeOOH) surface: A FTIR spectroscopic investigation of surface O H stretching vibrations

    NASA Astrophysics Data System (ADS)

    Boily, Jean-François; Felmy, Andrew R.

    2008-07-01

    The O-H stretching region of goethite particles evaporated at different levels of acidity was investigated by Attenuated Total Reflectance (ATR)-Fourier Transform InfraRed (FTIR) spectroscopy. Two-dimensional IR Correlation Spectroscopy was used to identify correlations between different sets of discrete surface OH stretches and a Multivariate Curve Resolution analysis was used to resolve the predominant spectral components. Two dominant groups of hydroxyls were identified on the basis of their differences in proton affinity. Group I hydroxyls appear as two 3698/3541 and 3660/3490 cm -1 band pairs. Group II hydroxyls are manifested through the 3648 and 3578 cm -1 bands at greater levels of surface proton loading. There is consequently no correlation between O-H stretching frequencies and proton affinity. Groups I and II were assigned to mostly singly- (-OH) and doubly- (μ-OH) coordinated hydroxyls, respectively. Stretches arising from triply-coordinated (μ 3-OH) are proposed to be embedded within the dominant O-H band of bulk goethite. The possibility that these sites contribute to Group I and II hydroxyls should, however, not be entirely dismissed without further investigations. A reexamination of Temperature Programmed Desorption (TPD)-FTIR data of one goethite sample evaporated from alkaline conditions [Boily J.-F., Szanyi J., Felmy A. R. (2006) A combined FTIR and TPD study on the bulk and surface dehydroxylation and decarbonation of synthetic goethite. Geochim. Cosmochim. Acta70, 3613-3624] provided further constraints to this band assignment by providing clues to the network of surface hydrogen bonds. Important cooperative effects between hydrogen-bonded surface hydroxyls are suggested to play a crucial role on the variations of the position and intensity of discrete O-H stretching bands as a function of protonation level and temperature.

  7. High spatial resolution mapping of surface plasmon resonance modes in single and aggregated gold nanoparticles assembled on DNA strands

    NASA Astrophysics Data System (ADS)

    Diaz-Egea, Carlos; Sigle, Wilfried; van Aken, Peter A.; Molina, Sergio I.

    2013-07-01

    We present the mapping of the full plasmonic mode spectrum for single and aggregated gold nanoparticles linked through DNA strands to a silicon nitride substrate. A comprehensive analysis of the electron energy loss spectroscopy images maps was performed on nanoparticles standing alone, dimers, and clusters of nanoparticles. The experimental results were confirmed by numerical calculations using the Mie theory and Gans-Mie theory for solving Maxwell's equations. Both bright and dark surface plasmon modes have been unveiled.

  8. Surface modified electrospun poly(vinyl alcohol) membranes for extracting nanoparticles from water

    NASA Astrophysics Data System (ADS)

    Mahanta, Narahari; Valiyaveettil, Suresh

    2011-11-01

    Contamination of water from nanomaterials will be an emerging problem in the future due to incorporation of nanomaterials in many commercial products and improper disposal of waste materials. In this report, electrospun polyvinyl alcohol nanofibers (PVA NFs) with diameters ranging between 300 and 500 nm were used for the extraction of nanosized contaminants from the aqueous environment. To obtain the best extraction efficiency, surface hydroxyl groups of PVA NFs were chemically modified with functional groups, such as thiols and amines. Two model nanoparticles (silver and gold) dissolved in water were used for adsorption studies. Depending on the nature of the surface functionalities, the fibers showed unique ability to adsorb nanoparticles. The extraction studies revealed that the amine and thiol modified PVA NFs showed 90% extraction efficiency for both silver and gold nanoparticles. The thiol and amine functionalized PVA NFs showed maximum adsorption capacities (Qt) towards Au NPs, which were around 79-84 mg g-1. Similarly for Ag NP extraction, amine functionalized PVA NFs showed a value for Qt at 56 mg g-1. Our results highlight that functionalized nanofibers have high extraction efficiency for dissolved nanoparticles in water and can be used for removal of the nanocontaminants from the aqueous environment.Contamination of water from nanomaterials will be an emerging problem in the future due to incorporation of nanomaterials in many commercial products and improper disposal of waste materials. In this report, electrospun polyvinyl alcohol nanofibers (PVA NFs) with diameters ranging between 300 and 500 nm were used for the extraction of nanosized contaminants from the aqueous environment. To obtain the best extraction efficiency, surface hydroxyl groups of PVA NFs were chemically modified with functional groups, such as thiols and amines. Two model nanoparticles (silver and gold) dissolved in water were used for adsorption studies. Depending on the nature of

  9. Effect of metal support interaction on surface segregation in Pd Pt nanoparticles

    NASA Astrophysics Data System (ADS)

    De Sarkar, A.; Menon, Mahesh; Khanra, Badal C.

    2001-10-01

    In this work, we present the results of our Monte Carlo (MC) simulation studies for the segregation behavior of supported, clean and gas-covered Pd-Pt nanoparticles as a function of the metal-support interaction. For preferential Pd-support interaction, the base of the nanoparticle is found to get enriched with Pd atoms; while for preferential interaction of Pt atoms with the support the base gets enriched in Pt. The composition of the rest of the particle changes slightly with the metal-support interaction. The presence of oxygen and hydrogen atoms does not influence the role of the metal-support interaction on the surface composition of Pd-Pt nanoparticles. The simulation results are found to be in total agreement with the known experimental results.

  10. Surface enhanced Raman scattering of amino acids assisted by gold nanoparticles and Gd(3+) ions.

    PubMed

    López-Neira, Juan Pablo; Galicia-Hernández, José Mario; Reyes-Coronado, Alejandro; Pérez, Elías; Castillo-Rivera, Francisco

    2015-05-01

    The surface enhanced raman scattering (SERS) signal from the l-tyrosine (tyr) molecule adsorbed on gold nanoparticles (Au-tyr) is compared with the SERS signal assisted by the presence of gadolinium ions (Gd(3+)) coordinated with the Au-tyr system. An enhancement factor of the SERS signal in the presence of Gd(3+) ions was ∼5 times higher than that produced by l-tyrosine adsorbed on gold nanoparticles. The enhancement of the SERS signal can be attributed to a corresponding increase in the local electric field due to the presence of Gd(3+) ions in the vicinity of a gold dimer configuration. This scenario was confirmed by solving numerically Maxwell equations, showing an increase of 1 order of magnitude in the local electric scattered field when the Gd(3+) ion is located in between a gold dimer compared with naked gold nanoparticles. PMID:25860315

  11. Drug targeting to infectious diseases by nanoparticles surface functionalized with special biomolecules

    PubMed Central

    Sundar, Shyam; Prajapati, Vijay Kumar

    2012-01-01

    The potential to deliver nanoparticles directly into the targeted cells is important in the therapeutic applications for infectious diseases. The possibility of therapeutic agent being attached to the nanoparticles by chemical modification has provided a novel drug delivery option. Interestingly, the discovery of carbon nanotubes and graphene has given an excellent imaging and therapeutic agent for the biomedical applications. In spite of continuous advancement in pharmaceutical drug delivery viz. micelles, vesicles and liquid crystals etc. during the past decades, their prohibitive production has limited their use. Nanomaterials with their properties of biodegradation, equal biodistribution, mass production and long time storage make them attractive alternative for future biomedical applications. Nanoparticles surface functionalized with specific biomolecules based drug delivery has driven new direction for modulating the pharmacokinetics and pharmacodynamics, biorecognition; and increasing the efficacy of targeted drugs. These new strategies are likely to minimize drug degradation and loss, increase drug availability, and opens up new vistas for drug delivery. PMID:22612703

  12. Enhancing optical forces on fluorescent up-converting nanoparticles by surface charge tailoring.

    PubMed

    Rodríguez-Rodríguez, Héctor; Rodríguez Sevilla, Paloma; Martín Rodríguez, Emma; Ortgies, Dirk H; Pedroni, Marco; Speghini, Adolfo; Bettinelli, Marco; Jaque, Daniel; Haro-González, Patricia

    2015-04-01

    3D remote control of multifunctional fluorescent up-converting nanoparticles (UCNPs) using optical forces is being required for a great variety of applications including single-particle spectroscopy, single-particle intracellular sensing, controlled and selective light-activated drug delivery and light control at the nanoscale. Most of these potential applications find a serious limitation in the reduced value of optical forces (tens of fN) acting on these nanoparticles, due to their reduced dimensions (typically around 10 nm). In this work, this limitation is faced and it is demonstrated that the magnitude of optical forces acting on UCNPs can be enhanced by more than one order of magnitude by a controlled modification of the particle/medium interface. In particular, substitution of cationic species at the surface by other species with higher mobility could lead to UCNPs trapping with constants comparable to those of spherical metallic nanoparticles. PMID:25451550

  13. Investigation of Influence of Surface Nanoparticle on Emission Properties of Scandia-Doped Dispenser Cathodes

    NASA Astrophysics Data System (ADS)

    Zhang, Xizhu; Wang, Jinshu; Wang, Yiman; Liu, Wei; Zhou, Meiling; Gao, Zhiyuan

    2013-08-01

    The microstructure of a fully activated scandia doped dispenser (SDD) cathode has been studied by scanning electron microscope (SEM). The observation results display that nanoparticles appear at the growth steps and the surface of tungsten grains of the fully activated SDD cathode. To study the influence of the nanoparticles on the emission, the local electric field strengths around the nanoparticles have been calculated by Maxwell 2D code and Comsol. The calculation results show that the local electric field strengths are enhanced by 1.1 to 3.8 times to average value based on different model conditions. The highest field strength is about 1.54 × 105 V/cm at an average field strength of 40 KV/cm, which is related to a space-charge limited (SCL) current density of 100 A/cm2 in the experimental configuration. This implies the field strength is not high enough to cause field emission.

  14. Broadband tunability of surface plasmon resonance in graphene-coating silica nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhe, Shi; Yang, Yang; Lin, Gan; Zhi-Yuan, Li

    2016-05-01

    Graphene decorated nanomaterials and nanostructures can potentially be used in military and medical science applications. In this article, we study the optical properties of a graphene wrapping silica core–shell spherical nanoparticle under illumination of external light by using the Mie theory. We find that the nanoparticle can exhibit surface plasmon resonance (SPR) that can be broadly tuned from mid infrared to near infrared via simply changing the geometric parameters. A simplified equivalent dielectric permittivity model is developed to better understand the physics of SPR, and the calculation results agree well qualitatively with the rigorous Mie theory. Both calculations suggest that a small radius of graphene wrapping nanoparticle with high Fermi level could move the SPR wavelength of graphene into the near infrared regime. Project supported by the National Natural Science Foundation of China (Grant Nos. 11204365 and 11434017) and the National Basic Research Program of China (Grant No. 2013CB632704).

  15. Gold Nanoparticle Assemblies on Surfaces: Reactivity Tuning through Capping-Layer and Cross-Linker Design.

    PubMed

    Shankar, Sreejith; Orbach, Meital; Kaminker, Revital; Lahav, Michal; van der Boom, Milko E

    2016-01-26

    The immobilization of metal nanoparticles (NPs) with molecular control over their organization is challenging. Herein, we report the formation of molecularly cross-linked AuNP assemblies using a layer-by-layer approach. We observed four types of assemblies: 1) small aggregates of individual AuNPs, 2) large aggregates of individual AuNPs, 3) networks of fused AuNPs, and 4) gold islands. Interestingly, these assemblies with the different cross-linkers and capping layers represent different stages in the complete fusion of AuNPs to afford islands of continuous gold. We demonstrate that the stability toward fusion of the nanoparticles of the on-surface structures can be controlled by the reactivity of the cross-linkers and the hydrophilicity/hydrophobicity of the nanoparticles. PMID:26743768

  16. Surface nonuniformity effects on metal oxides in going from proton adsorption equilibria to the kinetics of acid catalyzed reactions. Final report

    SciTech Connect

    Schwarz, J.A.

    1997-03-01

    Proton transfer processes at the solid oxide/aqueous interface are controlled primarily by the structure and composition of the solid surface; these processes can be accessed from potentiometric titration data. A research effort was proposed which sought to exploit this simple technique for catalyst characterization in terms of proton affinity spectra.

  17. Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations.

    PubMed

    Xia, Shu-Hua; Xie, Bin-Bin; Fang, Qiu; Cui, Ganglong; Thiel, Walter

    2015-04-21

    Excited-state intramolecular proton transfer (ESIPT) between two highly electronegative atoms, for example, oxygen and nitrogen, has been intensely studied experimentally and computationally, whereas there has been much less theoretical work on ESIPT to other atoms such as carbon. We have employed CASSCF, MS-CASPT2, RI-ADC(2), OM2/MRCI, DFT, and TDDFT methods to study the mechanistic photochemistry of 2-phenylphenol, for which such an ESIPT has been observed experimentally. According to static electronic structure calculations, irradiation of 2-phenylphenol populates the bright S1 state, which has a rather flat potential in the Franck-Condon region (with a shallow enol minimum at the CASSCF level) and may undergo an essentially barrierless ESIPT to the more stable S1 keto species. There are two S1/S0 conical intersections that mediate relaxation to the ground state, one in the enol region and one in the keto region, with the latter one substantially lower in energy. After S1 → S0 internal conversion, the transient keto species can return back to the S0 enol structure via reverse ground-state hydrogen transfer in a facile tautomerization. This mechanistic scenario is verified by OM2/MRCI-based fewest-switches surface-hopping simulations that provide detailed dynamic information. In these trajectories, ESIPT is complete within 118 fs; the corresponding S1 excited-state lifetime is computed to be 373 fs in vacuum. Most of the trajectories decay to the ground state via the S1/S0 conical intersection in the keto region (67%), and the remaining ones via the enol region (33%). The combination of static electronic structure computations and nonadiabatic dynamics simulations is expected to be generally useful for understanding the mechanistic photophysics and photochemistry of molecules with intramolecular hydrogen bonds. PMID:25711992

  18. 2.6 MeV Proton Irradiation Effects on the Surface Integrity of Depleted UO2

    SciTech Connect

    Pakarinen, Janne; He, Lingfeng; Gupta, Mahima; Gan, Jian; Nelson, Andrew; El-Azab, Anter; Allen, Todd

    2014-01-01

    The effect of low temperature proton irradiation in depleted uranium dioxide was examined as a function of fluence. With 2.6 MeV protons, the fluence limit for preserving a good surface quality was found to be relatively low, about 1.4 and 7.0 x 1017 protons/cm2 for single and poly crystalline samples, respectively. Upon increasing the fluence above this threshold, severe surface flaking and disintegration of samples was observed. Based on scanning electron microscopy (SEM) and X-ray diffraction (XRD) observations the causes of surface failure were associated to high H atomic percent at the peak damage region due to low solubility of H in UO2. The resulting lattice stress is believed to exceed the fracture stress of the crystal at the observed fluencies. The oxygen point defects from the displacement damage may hinder the H diffusion and further increase the lattice stress, especially at the peak damage region.

  19. Effects of gestational age and surface modification on materno-fetal transfer of nanoparticles in murine pregnancy

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Sun, Cuiji; Fan, Zhenlin; Tian, Xin; Yan, Liang; Du, Libo; Liu, Yang; Chen, Chunying; Liang, Xing-Jie; Anderson, Gregory J.; Keelan, Jeffrey A.; Zhao, Yuliang; Nie, Guangjun

    2012-11-01

    Nanoparticle exposure in pregnancy may result in placental damage and fetotoxicity; however, the factors that determine fetal nanoparticle exposure are unclear. Here we have assessed the effect of gestational age and nanoparticle composition on fetal accumulation of maternally-administered nanomaterials in mice. We determined the placental and fetal uptake of 13 nm gold nanoparticles with different surface modifications (ferritin, PEG and citrate) following intravenous administration at E5.5-15.5. We showed that prior to E11.5, all tested nanoparticles could be visualized and detected in fetal tissues in significant amounts; however, fetal gold levels declined dramatically post-E11.5. In contrast, Au-nanoparticle accumulation in the extraembryonic tissues (EET) increased 6-15 fold with gestational age. Fetal and EET accumulation of ferritin- and PEG-modified nanoparticles was considerably greater than citrate-capped nanoparticles. No signs of toxicity were observed. Fetal exposure to nanoparticles in murine pregnancy is, therefore, influenced by both stage of embryonic/placental maturation and nanoparticle surface composition.

  20. Surface Analysis of Gold Nanoparticles Functionalized with Thiol-Modified Glucose SAMs for Biosensor Applications

    PubMed Central

    Spampinato, Valentina; Parracino, Maria Antonietta; La Spina, Rita; Rossi, Francois; Ceccone, Giacomo

    2016-01-01

    In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Principal Component Analysis (PCA) and X-ray Photoelectron Spectroscopy (XPS) have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP). The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules. Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behavior of the glucose-modified particles in the presence of the maltose binding protein. PMID:26973830