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Sample records for nanoparticulate ptru direct

  1. The Mechanism of Direct Formic Acid Fuel Cell Using Pd, Pt and Pt-Ru

    NASA Astrophysics Data System (ADS)

    Kamiya, Nobuyuki; Liu, Yan; Mitsushima, Shigenori; Ota, Ken-Ichiro; Tsutsumi, Yasuyuki; Ogawa, Naoya; Kon, Norihiro; Eguchi, Mika

    The electro-oxidation of formic acid, 2-propanol and methanol on Pd black, Pd/C, Pt-Ru/C and Pt/C has been investigated to clear the reaction mechanism. It was suggested that the formic acid is dehydrogenated on Pd surface and the hydrogen is occluded in the Pd lattice. Thus obtained hydrogen acts like pure hydrogen supplied from the outside and the cell performance of the direct formic acid fuel cell showed as high as that of a hydrogen-oxygen fuel cell. 2-propanol did not show such dehydrogenation reaction on Pd catalyst. Platinum and Pt-Ru accelerated the oxidation of C-OH of 2-propanol and methanol. Slow scan voltammogram (SSV) and chronoamperometry measurements showed that the activity of formic acid oxidation increased in the following order: Pd black > Pd 30wt.%/C > Pt50wt.%/C > 27wt.%Pt-13wt.%Ru/C. A large oxidation current for formic acid was found at a low overpotential on the palladium electrocatalysts. These results indicate that formic acid is mainly oxidized through a dehydrogenation reaction. For the oxidation of 2-propanol and methanol, palladium was not effective, and 27wt.%Pt-13wt.%Ru/C showed the best oxidation activity.

  2. PtRuO 2/Ti anodes with a varying Pt:Ru ratio for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Shao, Zhi-Gang; Zhu, Fuyun; Lin, Wen-Feng; Christensen, Paul A.; Zhang, Huamin

    PtRuO 2/Ti anodes with a varying Pt:Ru ratio were prepared by thermal deposition of a PtRuO 2 catalyst layer onto a Ti mesh for the direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX, and XRD. The catalyst coating layers became porous with increase of the Ru content, and showed oxide and alloy characteristics. The relative activities of the PtRuO 2/Ti electrodes were assessed and compared using half-cell tests and single DMFC experiments. The results showed that these electrodes were very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 38% for a DMFC operating at 20-60 °C.

  3. Synthesis of PtRu nanoparticles from the hydrosilylation reaction and application as catalyst for direct methanol fuel cell.

    PubMed

    Huang, Junchao; Liu, Zhaolin; He, Chaobin; Gan, Leong Ming

    2005-09-01

    Nanosized Pt, PtRu, and Ru particles were prepared by a novel process, the hydrosilylation reaction. The hydrosilylation reaction is an effective method of preparation not only for Pt particles but also for other metal colloids, such as Ru. Vulcan XC-72 was selected as catalyst support for Pt, PtRu, and Ru colloids, and TEM investigations showed nanoscale particles and narrow size distribution for both supported and unsupported metals. All Pt and Pt-rich catalysts showed the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure, whereas the Ru and Ru-rich alloys were more typical of a hexagonal close-packed (hcp) structure. As evidenced by XPS, most Pt and Ru atoms in the nanoparticles were zerovalent, except a trace of oxidation-state metals. The electrooxidation of liquid methanol on these catalysts was investigated at room temperature by cyclic voltammetry and chronoamperometry. The results concluded that some alloy catalysts showed higher catalytic activities and better CO tolerance than the Pt-only catalyst; Pt56Ru44/C have displayed the best electrocatalytic performance among all carbon-supported catalysts. PMID:16853117

  4. Highly transparent and conductive Al-doped ZnO nanoparticulate thin films using direct write processing

    NASA Astrophysics Data System (ADS)

    Vunnam, S.; Ankireddy, K.; Kellar, J.; Cross, W.

    2014-05-01

    Solution processable Al-doped ZnO (AZO) thin films are attractive candidates for low cost transparent electrodes. We demonstrate here an optimized nanoparticulate ink for the fabrication of AZO thin films using scalable, low-cost direct write processing (ultrasonic spray deposition) in air at atmospheric pressure. The thin films were made via thermal processing of as-deposited films. AZO films deposited using the proposed nanoparticulate ink with further reducing in vacuum and rf plasma of forming gas exhibited optical transparency greater than 95% across the visible spectrum, and electrical resistivity of 0.5 Ω cm and it drops down to 7.0 × 10-2 Ω cm after illuminating with UV light, which is comparable to commercially available tin doped indium oxide colloidal coatings. Various structural analyses were performed to investigate the influence of ink chemistry, deposition parameters, and annealing temperatures on the structural, optical, and electrical characteristics of the spray deposited AZO thin films. Optical micrographs confirmed the presence of surface defects and cracks using the AZO NPs ink without any additives. After adding N-(2-Aminoethyl)-3-aminopropylmethyldimethoxy silane to the ink, AZO films exhibited an optical transparency which was virtually identical to that of the plain glass substrate.

  5. Highly transparent and conductive Al-doped ZnO nanoparticulate thin films using direct write processing.

    PubMed

    Vunnam, S; Ankireddy, K; Kellar, J; Cross, W

    2014-05-16

    Solution processable Al-doped ZnO (AZO) thin films are attractive candidates for low cost transparent electrodes. We demonstrate here an optimized nanoparticulate ink for the fabrication of AZO thin films using scalable, low-cost direct write processing (ultrasonic spray deposition) in air at atmospheric pressure. The thin films were made via thermal processing of as-deposited films. AZO films deposited using the proposed nanoparticulate ink with further reducing in vacuum and rf plasma of forming gas exhibited optical transparency greater than 95% across the visible spectrum, and electrical resistivity of 0.5 Ω cm and it drops down to 7.0 × 10(-2) Ω cm after illuminating with UV light, which is comparable to commercially available tin doped indium oxide colloidal coatings. Various structural analyses were performed to investigate the influence of ink chemistry, deposition parameters, and annealing temperatures on the structural, optical, and electrical characteristics of the spray deposited AZO thin films. Optical micrographs confirmed the presence of surface defects and cracks using the AZO NPs ink without any additives. After adding N-(2-Aminoethyl)-3-aminopropylmethyldimethoxy silane to the ink, AZO films exhibited an optical transparency which was virtually identical to that of the plain glass substrate. PMID:24763438

  6. Optimized CeO2 content of the carbon nanofiber support of PtRu catalyst for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Kunitomo, Hikari; Ishitobi, Hirokazu; Nakagawa, Nobuyoshi

    2015-11-01

    A series of CeO2 embedded carbon nanofibers, CECNFs, with different CeO2 contents was prepared by an electrospinning technique. About 15 wt% PtRu nanoparticles were deposited on the fibers, and the effect of the CeO2 content on the methanol oxidation activity of the catalyst, PtRu/CECNF, was investigated. Cyclic voltammetry (CV), chronoamperometry (CA) and CO stripping electrochemical measurements and physical characterization along with X-ray diffraction (XRD) analysis, energy dispersive X-ray (EDX) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were carried out on the prepared catalysts. The mass activity of the PtRu was significantly increased by the CeO2 addition up to Ce/C = 0.4, and the maximized activity was 2 times higher than that without CeO2. The increased activity was attributed to the strong interaction between the metal and oxide in the embedded nanofiber structure. A DMFC with the PtRu/CECNF exhibited more than 2.5 times high power density with one half the PtRu loading compared to that of the commercial catalyst, PtRu/Ccom.

  7. High-activity mesoporous Pt/Ru catalysts for methanol oxidation.

    PubMed

    Franceschini, Esteban A; Bruno, Mariano M; Williams, Federico J; Viva, Federico A; Corti, Horacio R

    2013-11-13

    High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores. PMID:24083938

  8. Template preparation of Pt-Ru and Pt nanowire array electrodes on a Ti/Si substrate for methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Zhao, Guang-Yu; Xu, Cai-Ling; Guo, Dao-Jun; Li, Hua; Li, Hu-Lin

    Pt and Pt-Ru nanowire array electrodes were obtained by dc (direct current) electrodeposition of Pt and Ru into the pores of an anodic aluminum oxide (AAO) template on a Ti/Si substrate. Transmission electron microscope (TEM) examination showed all the nanowires had a uniform diameter of about 30 nm. The brush shaped Pt and Pt-Ru nanowire array electrodes could be seen clearly by scanning electron microscope. Pt and Pt-Ru nanowire array electrodes gave the X-ray diffraction pattern of a face-centered cubic (fcc) crystal structure. The electro-oxidation of methanol on these electrodes was investigated at room temperature using cyclic voltammetry. The results demonstrated that the alloy nanowire array electrode was catalytically more active than a pure platinum nanowire array electrode and the Pt-Ru nanowire array electrode may have good potential for applications in portable fuel cell power sources.

  9. Irrelevance of Carbon Monoxide Poisoning in the Methanol Oxidation Reaction on a PtRu Electrocatalyst.

    PubMed

    Chen, De-Jun; Tong, YuYe J

    2015-08-01

    Based on detailed in situ attenuated total-reflection-surface-enhanced IR reflection absorption spectroscopy (ATR-SEIRAS) studies of the methanol oxidation reaction (MOR) on Ru/Pt thin film and commercial Johnson-Matthey PtRu/C, a revised MOR enhancement mechanism is proposed in which CO on Pt sites is irrelevant but instead Pt-Ru boundary sites catalyze the oxygen insertion reaction that leads to the formation of formate and enhances the direct reaction pathway. PMID:26148459

  10. Alcohol electrooxidation at Pt and Pt-Ru sputtered electrodes under elevated temperature and pressurized conditions

    NASA Astrophysics Data System (ADS)

    Umeda, Minoru; Sugii, Hiromasa; Uchida, Isamu

    2008-05-01

    The electrooxidation properties of methanol and 2-propanol, which are both promising candidates for direct alcohol fuel cells (DAFCs), have been studied under elevated temperature and pressurized conditions. Sputter-deposited Pt and Pt-Ru electrodes were well-characterized and utilized for the electrochemical measurement of the alcohol oxidation at 25-100 °C. The Pt electrode prepared at 600 °C had a flat surface, and the Pt-Ru formed an alloy. The electrochemical measurements were carried out in a gas-tight cell under elevated temperature, which accompanies the pressurized condition. This is a representative example of the DAFC rising temperature operation. As a result, at 25 °C, the onset potential of the 2-propanol oxidation is about 400 mV more negative than that of the methanol oxidation, and current density of the 2-propanol oxidation exceeds that of the methanol oxidation. Conversely, at 100 °C, the methanol oxidation current density overcomes that of 2-propanol, and the onset potentials of the two are almost the same. The highest current density for the methanol oxidation is obtained at the Pt:Ru = 50:50 electrode, whereas at the Pt:Ru = 35:65 for the 2-propanol oxidation. A Tafel plot analysis was employed to investigate the reaction mechanism. For the methanol oxidation, the number of electrons transferred during the rate-determining process is estimated to be 1 at 25 °C and 2 at 100 °C. This suggests that the methanol reaction mechanism differs at 25 and 100 °C. In contrast, the rate-determining process of the 2-propanol oxidation at 25 and 100 °C was expected to be 1-electron transfer which accompanies the proton-elimination reaction to produce acetone. Consequently, it is deduced that methanol and 2-propanol have an advantage under the rising temperature and room temperature operation, respectively.

  11. Bimetallic Wiregauze Supported Pt-Ru Nanocatalysts for Hydrogen Mitigation.

    PubMed

    Sanap, Kiran K; Varma, S; Waghmode, S B; Sharma, P; Manoj, N; Vatsa, R K; Bharadwaj, S R

    2015-05-01

    Passive autocatalytic recombiner (PAR) is one of the most suitable devices for mitigation of hydrogen, generated in nuclear power plant under accidental conditions. For this purpose we report development of stainless steel wire gauze supported Pt-Ru nanoparticles as catalysts. Simultaneous electroless deposition has been employed for the synthesis of the catalysts. Pt-Ru based bimetallic catalysts were characterized for their rate of coating kinetics, noble metal loading, phase purity by XRD and surface morphology by SEM, TEM and elemental analysis by SIMS. Developed catalysts were found to be active for efficient recombination of hydrogen and oxygen in air as well as in presence of various prospective poisons like CO2, CH4, CO and relative humidity. Pt-Ru based bimetallic catalyst with 0.9% loading was found to be active for CO poisoning up to 400 ppm of CO. PMID:26504972

  12. Comparative cytotoxicity assessments of some manufactured and anthropogenic nanoparticulate materials

    NASA Astrophysics Data System (ADS)

    Soto, Karla Fabiola

    toxicity evaluation, cytokine production, mitochondrial function (MTT assay), reactive oxygen species generation (ROS), were assessed after 48 and 336 hours under control and exposed conditions. A simple, direct-contact assay was developed to evaluate the toxicity of anthropogenic particulate matter (PM), without removing it from high volume filter collections and exposing collected PM by direct contact with the human epithelial (A549) cells in culture. The cell viability data revealed that the manufactured nanomaterials exhibit cytotoxic response for the murine alveolar and human macrophage cell line, but in particular to the human epithelial cell line. Assay results for the direct-contact of filter-collected carbonaceous nanoparticulate, showed toxicity for all PM, but with various natural gas combustion PM being the most toxic. Light optical microscopy examination of affected human epithelial cells confirmed quantitative results. These nanoparticulate soots also produced the most reactive oxygen species (ROS) on the A549 cell culture as well as along with the Fe2O3, MWCNT-N, and black carbon (BC). Comparison of polycyclic aromatic hydrocarbon (PAH) content and concentration for the carbonaceous PM showed no PAH correlation with relative cell viability after 48 h. In addition, there was no correlation of cytotoxic response with specific surface area in the manufactured nanoparticulate materials. In conclusion, the manufactured as well as the anthropogenic nanomaterials were observed to generate large amounts of ROS and cytokines. This study suggests that the mechanism of toxicity is likely due to the generation of reactive oxygen species (ROS). Also, the comparative assessments presented, should be viewed as a precaution when considering the inhalation of the corresponding nanoparticulate materials in concentrations approaching those identified to be dangerous for recognized pathogens such as silica, black carbon, and asbestos. Humans should avoid breathing these

  13. Physical and electrochemical characterizations of microwave-assisted polyol preparation of carbon-supported PtRu nanoparticles.

    PubMed

    Liu, Zhaolin; Lee, Jim Yang; Chen, Weixiang; Han, Ming; Gan, Leong Ming

    2004-01-01

    PtRu nanoparticles supported on Vulcan XC-72 carbon and carbon nanotubes were prepared by a microwave-assisted polyol process. The catalysts were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The PtRu nanoparticles, which were uniformly dispersed on carbon, were 2-6 nm in diameter. All PtRu/C catalysts prepared as such displayed the characteristic diffraction peaks of a Pt face-centered cubic structure, excepting that the 2theta values were shifted to slightly higher values. XPS analysis revealed that the catalysts contained mostly Pt(0) and Ru(0), with traces of Pt(II), Pt(IV), and Ru(IV). The electro-oxidation of methanol was studied by cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. It was found that both PtRu/C catalysts had high and more durable electrocatalytic activities for methanol oxidation than a comparative Pt/C catalyst. Preliminary data from a direct methanol fuel cell single stack test cell using the Vulcan-carbon-supported PtRu alloy as the anode catalyst showed high power density. PMID:15745018

  14. Enhancement of ethanol oxidation at Pt and PtRu nanoparticles dispersed over hybrid zirconia-rhodium supports

    NASA Astrophysics Data System (ADS)

    Rutkowska, Iwona A.; Koster, Margaretta D.; Blanchard, Gary J.; Kulesza, Pawel J.

    2014-12-01

    A catalytic material for electrooxidation of ethanol that utilizes PtRu nanoparticles dispersed over thin films of rhodium-free and rhodium-containing zirconia (ZrO2) supports is described here. The enhancement of electrocatalytic activity (particularly in the potential range as low as 0.25-0.5 V vs. RHE), that has been achieved by dispersing PtRu nanoparticles (loading, 100 μg cm-2) over the hybrid Rh-ZrO2 support composed of nanostructured zirconia and metallic rhodium particles, is clearly evident from comparison of the respective voltammetric and chronoamperometric current densities recorded at room temperature (22 °C) in 0.5 mol dm-3 H2SO4 containing 0.5 mol dm-3 ethanol. Porous ZrO2 nanostructures, that provide a large population of hydroxyl groups in acidic medium in the vicinity of PtRu sites, are expected to facilitate the ruthenium-induced removal of passivating CO adsorbates from platinum, as is apparent from the diagnostic experiments with a small organic molecule such as methanol. Although Rh itself does not show directly any activity toward ethanol oxidation, the metal is expected to facilitate C-C bond splitting in C2H5OH. It has also been found during parallel voltammetric and chronoamperometric measurements that the hybrid Rh-ZrO2 support increases activity of the platinum component itself toward ethanol oxidation in the low potential range.

  15. Nanoparticulate systems for polynucleotide delivery

    PubMed Central

    Basarkar, Ashwin; Singh, Jagdish

    2007-01-01

    Nanotechnology has tremendously influenced gene therapy research in recent years. Nanometer-size systems have been extensively investigated for delivering genes at both local and systemic levels. These systems offer several advantages in terms of tissue penetrability, cellular uptake, systemic circulation, and cell targeting as compared to larger systems. They can protect the polynucleotide from a variety of degradative and destabilizing factors and enhance delivery efficiency to the cells. A variety of polymeric and non-polymeric nanoparticles have been investigated in an effort to maximize the delivery efficiency while minimizing the toxic effects. This article provides a review on the most commonly used nanoparticulate systems for gene delivery. We have discussed frequently used polymers, such as, polyethyleneimine, poly (lactide-co-glycolide), chitosan, as well as non-polymeric materials such as cationic lipids and metallic nanoparticles. The advantages and limitations of each system have been elaborated. PMID:18019834

  16. The formation mechanism of bimetallic PtRu alloy nanoparticles in solvothermal synthesis

    NASA Astrophysics Data System (ADS)

    Mi, Jian-Li; Nørby, Peter; Bremholm, Martin; Becker, Jacob; Iversen, Bo B.

    2015-10-01

    An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but it is shown that monometallic Pt nanocrystals nucleate first and rapidly grow to an average size of 5 nm. Subsequently, the PtRu bimetallic alloy is formed in the second nucleation stage through a surface nucleation mechanism related to the reduction of Ru. The calculated average crystallite size of the resulting PtRu nanocrystals is smaller than that of the primary Pt nanocrystals due to the large disorder in the PtRu alloyed structure.An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but

  17. The formation mechanism of bimetallic PtRu alloy nanoparticles in solvothermal synthesis.

    PubMed

    Mi, Jian-Li; Nørby, Peter; Bremholm, Martin; Becker, Jacob; Iversen, Bo B

    2015-10-21

    An understanding of the nucleation and growth mechanism of bimetallic nanoparticles in solvothermal synthesis is important for further development of nanoparticles with tailored nanostructures and properties. Here the formation of PtRu alloy nanoparticles in a solvothermal synthesis using metal acetylacetonate salts as precursors and ethanol as both the solvent and reducing agent has been studied by in situ synchrotron radiation powder X-ray diffraction (SR-PXRD). Unlike the classical mechanism for the synthesis of monodisperse sols, the nucleation and growth processes of bimetallic PtRu nanoparticles occur simultaneously under solvothermal conditions. In the literature co-reduction of Pt and Ru is often assumed to be required to form PtRu bimetallic nanocrystals, but it is shown that monometallic Pt nanocrystals nucleate first and rapidly grow to an average size of 5 nm. Subsequently, the PtRu bimetallic alloy is formed in the second nucleation stage through a surface nucleation mechanism related to the reduction of Ru. The calculated average crystallite size of the resulting PtRu nanocrystals is smaller than that of the primary Pt nanocrystals due to the large disorder in the PtRu alloyed structure. PMID:26382321

  18. Combustion-derived nanoparticulate induces the adverse vascular effects of diesel exhaust inhalation

    PubMed Central

    Mills, Nicholas L.; Miller, Mark R.; Lucking, Andrew J.; Beveridge, Jon; Flint, Laura; Boere, A. John F.; Fokkens, Paul H.; Boon, Nicholas A.; Sandstrom, Thomas; Blomberg, Anders; Duffin, Rodger; Donaldson, Ken; Hadoke, Patrick W.F.; Cassee, Flemming R.; Newby, David E.

    2011-01-01

    Aim Exposure to road traffic and air pollution may be a trigger of acute myocardial infarction, but the individual pollutants responsible for this effect have not been established. We assess the role of combustion-derived-nanoparticles in mediating the adverse cardiovascular effects of air pollution. Methods and results To determine the in vivo effects of inhalation of diesel exhaust components, 16 healthy volunteers were exposed to (i) dilute diesel exhaust, (ii) pure carbon nanoparticulate, (iii) filtered diesel exhaust, or (iv) filtered air, in a randomized double blind cross-over study. Following each exposure, forearm blood flow was measured during intra-brachial bradykinin, acetylcholine, sodium nitroprusside, and verapamil infusions. Compared with filtered air, inhalation of diesel exhaust increased systolic blood pressure (145 ± 4 vs. 133 ± 3 mmHg, P< 0.05) and attenuated vasodilatation to bradykinin (P= 0.005), acetylcholine (P= 0.008), and sodium nitroprusside (P< 0.001). Exposure to pure carbon nanoparticulate or filtered exhaust had no effect on endothelium-dependent or -independent vasodilatation. To determine the direct vascular effects of nanoparticulate, isolated rat aortic rings (n= 6–9 per group) were assessed in vitro by wire myography and exposed to diesel exhaust particulate, pure carbon nanoparticulate and vehicle. Compared with vehicle, diesel exhaust particulate (but not pure carbon nanoparticulate) attenuated both acetylcholine (P< 0.001) and sodium-nitroprusside (P= 0.019)-induced vasorelaxation. These effects were partially attributable to both soluble and insoluble components of the particulate. Conclusion Combustion-derived nanoparticulate appears to predominately mediate the adverse vascular effects of diesel exhaust inhalation. This provides a rationale for testing environmental health interventions targeted at reducing traffic-derived particulate emissions. PMID:21753226

  19. Nanoparticulate drug delivery platforms for advancing bone infection therapies

    PubMed Central

    Uskoković, Vuk; Desai, Tejal A

    2015-01-01

    Introduction The ongoing surge of resistance of bacterial pathogens to antibiotic therapies and the consistently aging median member of the human race signal an impending increase in the incidence of chronic bone infection. Nanotechnological platforms for local and sustained delivery of therapeutics hold the greatest potential for providing minimally invasive and maximally regenerative therapies for this rare but persistent condition. Areas covered Shortcomings of the clinically available treatment options, including poly(methyl methacrylate) beads and calcium sulfate cements, are discussed and their transcending using calcium-phosphate/polymeric nanoparticulate composites is foreseen. Bone is a composite wherein the weakness of each component alone is compensated for by the strength of its complement and an ideal bone substitute should be fundamentally the same. Expert opinion Discrepancy between in vitro and in vivo bioactivity assessments is highlighted, alongside the inherent imperfectness of the former. Challenges entailing the cross-disciplinary nature of engineering a new generation of drug delivery vehicles are delineated and it is concluded that the future for the nanoparticulate therapeutic carriers belongs to multifunctional, synergistic and theranostic composites capable of simultaneously targeting, monitoring and treating internal organismic disturbances in a smart, feedback fashion and in direct response to the demands of the local environment. PMID:25109804

  20. PAMAM-stabilized Pt-Ru nanoparticles for methanol electro-oxidation

    NASA Astrophysics Data System (ADS)

    Gu, Yunlong; Wu, Gang; Hu, Xiao Feng; Chen, Donna A.; Hansen, Tara; Loye, Hans-Conrad zur; Ploehn, Harry J.

    This work utilizes poly(amidoamine) dendrimers (PAMAM) as a protective ligand in solution to produce carbon-supported, Pt-Ru bimetallic nanoparticles for use as methanol electro-oxidation catalysts. UV-vis spectra show that after initial Pt 2+ complexation with PAMAM G4OH dendrimer in water, appropriate adjustment of solution pH permits subsequent Ru 3+ complexation without displacing Pt 2+, demonstrating the formation of an aqueous, bimetallic solution complex. Catalysts (nominally 20 wt% metals, confirmed by AA spectroscopy) are produced by impregnating high surface area carbon black with G4OH-(Pt 2+) x(Ru 3+) y complex solution, drying, and activation in H 2 gas at elevated temperature. XPS results show that activation in H 2 at 400 °C removes virtually all of the PAMAM and reduces all of the Pt and most of the Ru to zero valence. TEM and XRD results show that the use of G4OH in the recipe is crucial for controlling metal particle size, and that the particles are crystalline with lattice parameters indicative of bimetallic Pt-Ru alloys. XRD data also suggest that G4OH promotes greater Pt-Ru alloying when Pt:Ru = 1:1. Catalytic activity for methanol oxidation increases with Ru content and is greatest for the catalyst with 1:1 Pt:Ru ratio. Per unit mass of Pt, the methanol oxidation activity of 20 wt% G4OH-PtRu/C catalyst is about 60% greater than that of E-Tek's commercially available 20 wt% PtRu catalyst.

  1. Extracellular stability of nanoparticulate drug carriers

    PubMed Central

    Liu, Karen C.; Yeo, Yoon

    2014-01-01

    Nanoparticulate (NP) drug carrier systems are attractive vehicles for selective drug delivery to solid tumors. Ideally, NPs should evade clearance by the reticuloendothelial system while maintaining the ability to interact with tumor cells and facilitate cellular uptake. Great effort has been made to fulfill these design criteria, yielding various types of functionalized NPs. Another important consideration in NP design is the physical and functional stability during circulation, which, if ignored, can significantly undermine the promise of intelligently designed NP drug carriers. This commentary reviews several NP examples with stability issues and their consequences, ending in a discussion of experimental methods for reliable prediction of NP stability. PMID:24214175

  2. Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation

    NASA Astrophysics Data System (ADS)

    Chen, Yu; Zhou, Yiming; Tang, Yawen; Lu, Tianhong

    A series of carbon-supported bimetallic Pt-Ru catalysts with high alloying degree and different Pt/Ru atomic ratio have been prepared by a chemical reduction method in the H 2O/ethanol/tetrahydrofuran (THF) mixture solvent. The structural and electronic properties of catalysts are characterized using X-ray reflection (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM). The electrooxidation of formic acid on these Pt-Ru nanoparticles are investigated by using cyclic voltammetry, chronoamperometry and CO-stripping measurements. The results of electrochemical measurements illustrate that the alloying degree and Pt/Ru atomic ratio of Pt-Ru catalyst play an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for formic acid electrooxidation due to the bifunctional mechanism and the electronic effect. Since formic acid is an intermediate in the methanol electrooxidation on Pt electrode in acidic electrolyte, the observation provides an additional fundamental understanding of the structure-activity relationship of Pt-Ru catalyst for methanol electrooxidation.

  3. In Vitro Dissolution Testing Strategies for Nanoparticulate Drug Delivery Systems: Recent Developments and Challenges

    PubMed Central

    Shen, Jie; Burgess, Diane J.

    2013-01-01

    Nanoparticulate systems have emerged as prevalent drug delivery systems over the past few decades. These delivery systems (such as liposomes, emulsions, nanocrystals, and polymeric nanocarriers) have been extensively used to improve bioavailability, prolong pharmacological effects, achieve targeted drug delivery, as well as reduce side effects. Considering that any unanticipated change in product performance of such systems may result in toxicity and/or change in vivo efficacy, it is essential to develop suitable in vitro dissolution/release testing methods to ensure product quality and performance, and to assist in product development. The present review provides an overview of the current in vitro dissolution/release testing methods such as dialysis, sample and separate, as well as continuous flow methods. Challenges and future directions in the development of standardized and biorelevant in vitro dissolution/release testing methods for novel nanoparticulate systems are discussed. PMID:24069580

  4. Supporting PtRu catalysts on various types of carbon nanomaterials for fuel cell applications

    NASA Astrophysics Data System (ADS)

    Suda, Yoshiyuki; Ozaki, Masahiro; Tanoue, Hideto; Takikawa, Hirofumi; Ue, Hitoshi; Shimizu, Kazuki; Muramoto, Hirokazu

    2013-04-01

    PtRu catalysts were supported on five types of carbon nanomaterials of various shapes, sizes, and graphitic properties and the catalyst supports evaluated. The carbon nanomaterial used included three types of nanoparticles: Arc Black (AcB), Vulcan XC-72 (Vulcan) and graphene oxide (GO), and two types of nanofibers: carbon nanocoil (CNC) and carbon nanotube (CNT). Pt and Ru were supported by the reduction method using sodium borohydride. The metal catalyst loading was confirmed by thermo-gravimetric analysis (TGA), electron microscopy, and X-ray diffraction (XRD). Transmission electron microscopy (TEM) and XRD revealed that the diameter of PtRu catalyst nanoparticles loaded on reduced GO (rGO) and AcB were ~2 nm and was the smallest among all the samples. Shifts in Pt (111) XRD peaks of CNC and CNT were larger than those of AcB, Vulcan, and rGO. These results suggest that the diameters of catalyst nanoparticles became smaller by loading on the carbon nanoparticles with a large surface area including rGO, AcB, and Vulcan. Loading onto the carbon nanofibers enhanced the degree of PtRu alloying.

  5. First-principles study of the role of solvent in the dissociation of water over a Pt-Ru alloy

    NASA Astrophysics Data System (ADS)

    Desai, Sanket K.; Neurock, Matthew

    2003-08-01

    Self-consistent gradient-corrected periodic density functional theoretical calculations are used to examine the effects of an aqueous environment on the dissociation of water over a Pt-Ru alloy. This reaction is thought to be one of the rate-limiting steps in oxidative removal of CO from the anode surface of both the direct methanol and reformate fuel cells. The reaction leads to the formation of surface hydroxyl (OH) intermediates that can subsequently oxidize adsorbed CO into CO2. We examine the energetics and mechanism for the dissociation of water over Pt66Ru33(111) in the presence of 23 water molecules (per 615 Å3 unit cell volume) that act as a solution phase and in the absence of solution (vapor phase). The reaction is endothermic by +53 kJ/mol and has an activation barrier of +105 kJ/mol when carried out in the vapor phase, but was found to be much less endothermic (+26 kJ/mol) and has a significantly lower activation barrier (+27 kJ/mol) when carried out in solution. In the vapor phase, the reaction occurs homolytically whereby the dissociation is activated by insertion of a Ru atom into the O-H bond of water. The products formed are adsorbed hydroxyl and hydrogen intermediates. In contrast, in solution, the dissociation occurs via a heterolytic path whereby the solvent molecules are directly involved in activating the O-H bond. The reaction leads to the formation of a hydroxyl intermediate that is bound to the alloy surface and a proton that is released into the solution phase. Ab initio molecular dynamics simulations were performed at 300 K to establish the sequence of elementary steps that can occur. The simulations show that water dissociates over Ru and that the hydroxyl intermediate that first forms over Ru rapidly diffuses along the metal surface, migrating over Pt as well as Ru sites. We believe that this evidence shows that diffusion occurs as the result of the proton transfer between the coadsorbed water and hydroxyl intermediates in an aqueous

  6. Intratumoral Drug Delivery with Nanoparticulate Carriers

    PubMed Central

    Holback, Hillary

    2011-01-01

    Stiff extracellular matrix, elevated interstitial fluid pressure, and the affinity for the tumor cells in the peripheral region of a solid tumor mass have long been recognized as significant barriers to diffusion of small-molecular-weight drugs and antibodies. However, their impacts on nanoparticle-based drug delivery have begun to receive due attention only recently. This article reviews biological features of many solid tumors that influence transport of drugs and nanoparticles and properties of nanoparticles relevant to their intratumoral transport, studied in various tumor models. We also discuss several experimental approaches employed to date for enhancement of intratumoral nanoparticle penetration. The impact of nanoparticle distribution on the effectiveness of chemotherapy remains to be investigated and should be considered in the design of new nanoparticulate drug carriers. PMID:21213021

  7. Transverse susceptibility method in nanoparticulate magnetic media.

    PubMed

    Cimpoesu, Dorin; Spinu, Leonard; Stancu, Alexandru

    2008-06-01

    Transverse susceptibility (TS) method is a reliable method for the determination of anisotropy in nanoparticulate media. To correctly evaluate the value of anisotropy in various modern nanostructured materials, a number of theoretical problems related to the method have to be well understood to avoid significant systematic errors. This paper presents the state of the art in the TS method which includes the expression for single domain particles with any type of anisotropy, the theoretical and micromagnetic, using Landau-Lifshitz-Gilbert (LLG) equation and stochastic LLG equation studies of the effects of ac field amplitude, inter-particle interactions, and magnetic relaxation. The problem of both real and imaginary parts of the TS signal is also discussed. PMID:18681012

  8. Nanoparticulate-catalyzed oxygen transfer processes

    DOEpatents

    Hunt, Andrew T.; Breitkopf, Richard C.

    2009-12-01

    Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

  9. Bioavailability of nanoparticulate hematite to Arabidopsis thaliana.

    PubMed

    Marusenko, Yevgeniy; Shipp, Jessie; Hamilton, George A; Morgan, Jennifer L L; Keebaugh, Michael; Hill, Hansina; Dutta, Arnab; Zhuo, Xiaoding; Upadhyay, Nabin; Hutchings, James; Herckes, Pierre; Anbar, Ariel D; Shock, Everett; Hartnett, Hilairy E

    2013-03-01

    The environmental effects and bioavailability of nanoparticulate iron (Fe) to plants are currently unknown. Here, plant bioavailability of synthesized hematite Fe nanoparticles was evaluated using Arabidopsis thaliana (A. thaliana) as a model. Over 56-days of growing wild-type A. thaliana, the nanoparticle-Fe and no-Fe treatments had lower plant biomass, lower chlorophyll concentrations, and lower internal Fe concentrations than the Fe-treatment. Results for the no-Fe and nanoparticle-Fe treatments were consistently similar throughout the experiment. These results suggest that nanoparticles (mean diameter 40.9 nm, range 22.3-67.0 nm) were not taken up and therefore not bioavailable to A. thaliana. Over 14-days growing wild-type and transgenic (Type I/II proton pump overexpression) A. thaliana, the Type I plant grew more than the wild-type in the nanoparticle-Fe treatment, suggesting Type I plants cope better with Fe limitation; however, the nanoparticle-Fe and no-Fe treatments had similar growth for all plant types. PMID:23262070

  10. Amphiphilic block copolymer-stabilized PtRu nanoparticles highly dispersed on multi-walled carbon nanotube for methanol oxidation.

    PubMed

    Guo, Dao-Jun; Cai, Peng; You, Jin-Mao

    2012-02-15

    We report a one-pot synthesis of amphiphilic block copolymer-stabilized PtRu nanoparticle modified multi-walled carbon nanotubes (MWCNTs) using RuCl(3)·xH(2)O and H(2)PtCl(6)·6H(2)O as ruthenium and platinum sources, and block copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) as stabilizer agent. PtRu alloyed nanoparticles with an average diameter of 4.6nm are well decorated homogeneously on the exterior surfaces of the MWCNTs. The electrochemical catalytic activity for methanol oxidation of PtRu/MWCNTs and commercial PtRu/C (E-TEK) is comparatively investigated using cyclic voltammetry and chronoamperometry. It is revealed that the PtRu nanoparticle modified MWCNT samples display an enhanced electrochemical catalytic activity than commercial PtRu/C electrode. These results show that PtRu nanoparticles may find applications to fuel cells. PMID:22104276

  11. Synthesis of boron and nitrogen doped graphene supporting PtRu nanoparticles as catalysts for methanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Lu, Jiming; Zhou, Yingke; Tian, Xiaohui; Xu, Xiao; Zhu, Hongxi; Zhang, Shaowei; Yuan, Tao

    2014-10-01

    In this study, we demonstrate a single-step heat treatment approach to synthesize boron and nitrogen doped graphene supporting PtRu electrocatalysts for methanol electro-oxidation reaction. The reduction of graphene oxide, boron or nitrogen doping of graphene and loading of PtRu nanoparticles happened simultaneously during the reaction process. The morphologies and microstructures of the as-prepared catalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The electrocatalytic methanol oxidation activity and durability of the obtained catalysts were evaluated by the cyclic voltammetry and chronoamperometric techniques. The results reveal that the boron and nitrogen doped graphene supporting PtRu electrocatalysts can be successfully prepared by the single step heat treatment technique, and the introduction of boron or nitrogen containing function groups into the reduced graphene sheets could modulate the particle size and dispersion of the supporting PtRu nanoparticles and improve the electrocatalytic performance of methanol oxidation reaction. The optimal annealing temperature is 800 °C, the preferable heat treatment time is 60 min for the nitrogen-doped catalysts and 90 min for the boron-doped catalysts, and the catalysts prepared under such conditions present superior catalytic activities for methanol oxidation than those prepared under other heat treatment conditions.

  12. Rapid synthesis of a PtRu nano-sponge with different surface compositions and performance evaluation for methanol electrooxidation

    NASA Astrophysics Data System (ADS)

    Xiao, Meiling; Feng, Ligang; Zhu, Jianbing; Liu, Changpeng; Xing, Wei

    2015-05-01

    A rapid strategy to synthesize a highly active PtRu alloy nano-sponge catalyst system for methanol electro-oxidation is presented. The greatly increased Pt utilization, anti-CO poisoning ability and electronic effect resulting from the porous nano-sponge structure could account for the performance improvement.

  13. Rapid synthesis of a PtRu nano-sponge with different surface compositions and performance evaluation for methanol electrooxidation.

    PubMed

    Xiao, Meiling; Feng, Ligang; Zhu, Jianbing; Liu, Changpeng; Xing, Wei

    2015-06-01

    A rapid strategy to synthesize a highly active PtRu alloy nano-sponge catalyst system for methanol electro-oxidation is presented. The greatly increased Pt utilization, anti-CO poisoning ability and electronic effect resulting from the porous nano-sponge structure could account for the performance improvement. PMID:25966842

  14. Rapid detection of cancer related DNA nanoparticulate biomarkers and nanoparticles in whole blood

    NASA Astrophysics Data System (ADS)

    Heller, Michael J.; Krishnan, Raj; Sonnenberg, Avery

    2010-08-01

    The ability to rapidly detect cell free circulating (cfc) DNA, cfc-RNA, exosomes and other nanoparticulate disease biomarkers as well as drug delivery nanoparticles directly in blood is a major challenge for nanomedicine. We now show that microarray and new high voltage dielectrophoretic (DEP) devices can be used to rapidly isolate and detect cfc-DNA nanoparticulates and nanoparticles directly from whole blood and other high conductance samples (plasma, serum, urine, etc.). At DEP frequencies of 5kHz-10kHz both fluorescent-stained high molecular weight (hmw) DNA, cfc-DNA and fluorescent nanoparticles separate from the blood and become highly concentrated at specific DEP highfield regions over the microelectrodes, while blood cells move to the DEP low field-regions. The blood cells can then be removed by a simple fluidic wash while the DNA and nanoparticles remain highly concentrated. The hmw-DNA could be detected at a level of <260ng/ml and the nanoparticles at <9.5 x 109 particles/ml, detection levels that are well within the range for viable clinical diagnostics and drug nanoparticle monitoring. Disease specific cfc-DNA materials could also be detected directly in blood from patients with Chronic Lymphocytic Leukemia (CLL) and confirmed by PCR genotyping analysis.

  15. Structure evolution of nanoparticulate Fe2O3

    NASA Astrophysics Data System (ADS)

    Erlebach, Andreas; Kurland, Heinz-Dieter; Grabow, Janet; Müller, Frank A.; Sierka, Marek

    2015-02-01

    The atomic structure and properties of nanoparticulate Fe2O3 are characterized starting from its smallest Fe2O3 building unit through (Fe2O3)n clusters to nanometer-sized Fe2O3 particles. This is achieved by combining global structure optimizations at the density functional theory level, molecular dynamics simulations by employing tailored, ab initio parameterized interatomic potential functions and experiments. With the exception of nearly tetrahedral, adamantane-like (Fe2O3)2 small (Fe2O3)n clusters assume compact, virtually amorphous structures with little or no symmetry. For n = 2-5 (Fe2O3)n clusters consist mainly of two- and three-membered Fe-O rings. Starting from n = 5 they increasingly assume tetrahedral shape with the adamantane-like (Fe2O3)2 unit as the main building block. However, the small energy differences between different isomers of the same cluster-size make precise structural assignment for larger (Fe2O3)n clusters difficult. The tetrahedral morphology persists for Fe2O3 nanoparticles with up to 3 nm in diameter. Simulated crystallization of larger nanoparticles with diameters of about 5 nm demonstrates pronounced melting point depression and leads to formation of ε-Fe2O3 single crystals with hexagonal morphology. This finding is in excellent agreement with the results obtained for Fe2O3 nanopowders generated by laser vaporization and provides the first direct indication that ε-Fe2O3 may be thermodynamically the most stable phase in this size regime.The atomic structure and properties of nanoparticulate Fe2O3 are characterized starting from its smallest Fe2O3 building unit through (Fe2O3)n clusters to nanometer-sized Fe2O3 particles. This is achieved by combining global structure optimizations at the density functional theory level, molecular dynamics simulations by employing tailored, ab initio parameterized interatomic potential functions and experiments. With the exception of nearly tetrahedral, adamantane-like (Fe2O3)2 small (Fe2O3)n

  16. Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

    PubMed

    Johnson, Grant E; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

    2015-08-01

    Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was

  17. Soft Landing of Bare PtRu Nanoparticles for Electrochemical Reduction of Oxygen

    SciTech Connect

    Johnson, Grant E.; Colby, Robert J.; Engelhard, Mark H.; Moon, DaeWon; Laskin, Julia

    2015-08-07

    Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu alloy nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 x 104 ions µm-2 and that their average height is centered at 4 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (STEM-HAADF) further confirm that the soft-landed PtRu alloy nanoparticles are uniform in size and have a Ru core decorated with small regions of Pt on the surface. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in relative atomic concentrations of ~9% and ~33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt4f and Ru3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the alloy nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He+ and O+ ions. The activity of electrodes containing 7 x 104 ions µm-2 of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the alloy nanoparticles supported on glassy

  18. Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen

    NASA Astrophysics Data System (ADS)

    Johnson, Grant E.; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

    2015-07-01

    Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 104 ions μm-2 and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ~9% and ~33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He+ and O+ ions. The activity of electrodes containing 7 × 104 ions μm-2 of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was evaluated by

  19. Ferroportin mediates the intestinal absorption of iron from a nanoparticulate ferritin core mimetic in mice.

    PubMed

    Aslam, Mohamad F; Frazer, David M; Faria, Nuno; Bruggraber, Sylvaine F A; Wilkins, Sarah J; Mirciov, Cornel; Powell, Jonathan J; Anderson, Greg J; Pereira, Dora I A

    2014-08-01

    The ferritin core is composed of fine nanoparticulate Fe(3+) oxohydroxide, and we have developed a synthetic mimetic, nanoparticulate Fe(3+) polyoxohydroxide (nanoFe(3+)). The aim of this study was to determine how dietary iron derived in this fashion is absorbed in the duodenum. Following a 4 wk run-in on an Fe-deficient diet, mice with intestinal-specific disruption of the Fpn-1 gene (Fpn-KO), or littermate wild-type (WT) controls, were supplemented with Fe(2+) sulfate (FeSO4), nanoFe(3+), or no added Fe for a further 4 wk. A control group was Fe sufficient throughout. Direct intestinal absorption of nanoFe(3+) was investigated using isolated duodenal loops. Our data show that FeSO4 and nanoFe(3+) are equally bioavailable in WT mice, and at wk 8 the mean ± SEM hemoglobin increase was 18 ± 7 g/L in the FeSO4 group and 30 ± 5 g/L in the nanoFe(3+) group. Oral iron failed to be utilized by Fpn-KO mice and was retained in enterocytes, irrespective of the iron source. In summary, although nanoFe(3+) is taken up directly by the duodenum its homeostasis is under the normal regulatory control of dietary iron absorption, namely via ferroportin-dependent efflux from enterocytes, and thus offers potential as a novel oral iron supplement. PMID:24776745

  20. Structure of carbon-supported Pt-Ru nanoparticles and their electrocatalytic behavior for hydrogen oxidation reaction

    NASA Astrophysics Data System (ADS)

    Velázquez, Amado; Centellas, Francesc; Garrido, José Antonio; Arias, Conchita; Rodríguez, Rosa María; Brillas, Enric; Cabot, Pere-Lluís

    The electrochemical activity towards hydrogen oxidation reaction (HOR) of a high performance carbon-supported Pt-Ru electrocatalyst (HP 20 wt.% 1:1 Pt-Ru alloy on Vulcan XC-72 carbon black) has been studied using the thin-film rotating disk electrode (RDE) technique. The physical properties of the Pt-Ru nanoparticles in the electrocatalyst were previously determined by transmission electron microscopy (TEM), high resolution TEM, fast Fourier transform (FFT), electron diffraction and X-ray diffraction (XRD). The corresponding compositional and size-shape analyses indicated that nanoparticles generally presented a 3D cubo-octahedral morphology with about 26 at.% Ru in the lattice positions of the face-centred cubic structure of Pt. The kinetics for HOR was studied in a hydrogen-saturated 0.5 M H 2SO 4 solution using thin-film electrodes prepared by depositing an ink of the electrocatalyst with different Nafion contents in a one-step process on a glassy carbon electrode. A maximum electrochemically active surface area (ECSA) of 119 m 2 g Pt -1 was found for an optimum Nafion composition of the film of about 35 wt.%. The kinetic current density in the absence of mass transfer effects was 21 mA cm -2. A Tafel slope of 26 mV dec -1, independent of the rotation rate and Nafion content, was always obtained, evidencing that HOR behaves reversibly. The exchange current density referred to the ECSA of the Pt-Ru nanoparticles was 0.17 mA cm -2, a similar value to that previously found for analogous inks containing pure Pt nanoparticles.

  1. Aggregation-Induced-Emissive Molecule Incorporated into Polymeric Nanoparticulate as FRET Donor for Observing Doxorubicin Delivery.

    PubMed

    Han, Xiongqi; Liu, De-E; Wang, Tieyan; Lu, Hongguang; Ma, Jianbiao; Chen, Qixian; Gao, Hui

    2015-10-28

    Tetraphenylethene (TPE) derivatives characterized with distinct aggregation-induced-emission, attempted to aggregate with doxorubicin (Dox) to formulate the interior compartment of polymeric nanoparticulate, served as fluorescence resonance energy transfer (FRET) donor to promote emission of acceptor Dox. Accordingly, this FRET formulation allowed identification of Dox in complexed form by detecting FRET. Important insight into the Dox releasing can be subsequently explored by extracting complexed Dox (FRET) from the overall Dox via direct single-photon excitation of Dox. Of note, functional catiomers were used to complex with FRET partners for a template formulation, which was verified to induce pH-responsive release in the targeted subcellular compartment. Hence, this well-defined multifunctional system entitles in situ observation of the drug releasing profile and insight on drug delivery journey from the tip of injection vein to the subcellular organelle of the targeted cells. PMID:26448180

  2. CO electrooxidation study on Pt and Pt-Ru in H3PO4 using MEA with PBI-H3PO4 membrane

    NASA Astrophysics Data System (ADS)

    Modestov, A. D.; Tarasevich, M. R.; Leykin, A. Y.

    2011-03-01

    CO electrooxidation on Pt and Pt-Ru in H3PO4 was studied in the temperature range 120-180 °C using CO-N2-H2O gas mixtures of controlled composition. On Pt and Pt-Ru the voltammetry curves exhibited Tafel behavior in a wide potential range with a slope of 80-100 mV per decade. Replacement of Pt with Pt-Ru on the anode resulted mainly in a shift of CO electrooxidation voltammetry curves by approx. -0.3 V. Reaction order in respect to water vapor pressure was found close to unity with both electrocatalysts. Reaction order in respect to CO partial pressure was found negative, close to zero. Values of apparent activation energy of CO electrooxidation on these electrocatalysts were nearly equal, Ea app = 110 ± 15 kJ mol-1. The results were interpreted within the framework of Langmuir-Hinshelwood mechanism. An equation, which describes the observed features of CO electrooxidation on Pt and Pt-Ru, was suggested. Comparing results of the present study with results of earlier studies of CO tolerance of Pt and Pt-Ru electrocatalysts, it was concluded that CO electrooxidation can hardly play a significant role in CO tolerance of PEM FC with PBI-PA membranes.

  3. An experimental and computational investigation of structural dependence of catalytic properties of Pt-Ru nanoparticles

    NASA Astrophysics Data System (ADS)

    Prasai, Binay

    An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models are built by molecular dynamics simulations and further refined against the experimental PDF data by reverse Monte Carlo simulations and analyzed in terms of structural characteristics. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the observed enhancement of the catalytic activity of PtxRu100 -x alloy NPs at x ~ 50. Central Michigan University, Department of Energy.

  4. Factors affecting the spontaneous adsorption of Bi(III) onto Pt and PtRu nanoparticles

    NASA Astrophysics Data System (ADS)

    Sawy, Ehab N. El; Khan, M. Akhtar; Pickup, Peter G.

    2016-02-01

    The influence of Bi(III) concentration and pH on the spontaneous adsorption of Bi species onto Pt nanoparticles has been systematically investigated in order to identify the adsorbing species, determine whether the nature of the adsorbing species changes, and investigate whether the activities of the resulting Bi decorated particles for formic acid oxidation can be influenced. The adsorption of Bi follows a Temkin-type isotherm, with a pH dependence indicating that the adsorbing species is [Bi6O4(OH)4]6+. Activities of Bi decorated Pt nanoparticles for formic acid oxidation are strongly influenced by the Bi coverage, with a maximum enhancement of a factor of ca. 60 at a coverage of 70%, but not by the Bi(III) concentration or pH used to adsorb the Bi species, other than through their influence on Bi coverage. These results support the conclusion that the adsorbing species is [Bi6O4(OH)4]6+ under all conditions investigated. Adsorbed Bi also activates PtRu nanoparticles for formic acid oxidation, although the effect is not as strong as for Pt. The maximum enhancement observed was only a factor of ca. 7. This has been attributed to attenuation of the effects of Bi adatoms that are adsorbed at Ru sites.

  5. Nanoporous PtRu Alloys with Unique Catalytic Activity toward Hydrolytic Dehydrogenation of Ammonia Borane.

    PubMed

    Zhou, Qiuxia; Xu, Caixia

    2016-03-01

    Nanoporous (NP) PtRu alloys with three different bimetallic components were straightforwardly fabricated by dealloying PtRuAl ternary alloys in hydrochloric acid. Selective etching of aluminum from source alloys generates bicontinuous network nanostructures with uniform size and structure. The as-made NP-PtRu alloys exhibit superior catalytic activity toward the hydrolytic dehydrogenation of ammonia borane (AB) than pure NP-Pt and NP-Ru owing to alloying platinum with ruthenium. The NP-Pt70 Ru30 alloy exhibits much higher specific activity toward hydrolytic dehydrogenation of AB than NP-Pt30 Ru70 and NP-Pt50 Ru50 . The hydrolysis activation energy of NP-Pt70 Ru30 was estimated to be about 38.9 kJ mol(-1) , which was lower than most of the reported activation energy values in the literature. In addition, recycling tests show that the NP-Pt70 Ru30 is still highly active in the hydrolysis of AB even after five runs, which indicates that NP-PtRu alloy accompanied by the network nanoarchitecture is beneficial to improve structural stability toward the dehydrogenation of AB. PMID:26573746

  6. Improved reaction kinetics and selectivity by the TiO2-embedded carbon nanofiber support for electro-oxidation of ethanol on PtRu nanoparticles

    NASA Astrophysics Data System (ADS)

    Nakagawa, Nobuyoshi; Ito, Yudai; Tsujiguchi, Takuya; Ishitobi, Hirokazu

    2014-02-01

    The electro-oxidation of ethanol by the catalyst of PtRu nanoparticles supported on a TiO2-embedded carbon nanofiber (PtRu/TECNF), which has recently been proposed by the authors as a highly active catalyst for methanol oxidation, is investigated by cyclic voltammetry using a glassy carbon electrode and by operating a direct ethanol fuel cell (DEFC) with the catalyst. The mass activity obtained from the cyclic voltammogram for the ethanol oxidation is compared to that for the methanol oxidation reported in our recent paper. The mass activity for the ethanol oxidation is comparable or slightly higher than that for the methanol oxidation, and the relationship between the TECNF composition, i.e., the Ti/C mass ratio, and the activity are also similar to that for the methanol oxidation. A DEFC fabricated with the PtRu/TECNF shows a higher power output compared to that with the commercial PtRu/C catalyst. An analysis of the reaction products by a simple two-step reaction model reveals that the PtRu/TECNF increases the rate constant for the reaction steps from ethanol to acetaldehyde and subsequently to CO2, but decreases that from acetaldehyde to acetic acid. This means that the PtRu/TECNF improves not only the kinetics, but also the selectivity to acetaldehyde.

  7. Investigation of acute nanoparticulate aluminum toxicity in zebrafish.

    PubMed

    Griffitt, Robert J; Feswick, April; Weil, Roxana; Hyndman, Kelly; Carpinone, Paul; Powers, Kevin; Denslow, Nancy D; Barber, David S

    2011-10-01

    In freshwater fish, aluminum is a well-recognized gill toxicant, although responses are influenced by pH. Aluminum nanomaterials are being used in diverse applications that are likely to lead to environmental release and exposure. However, it is unclear if the effects of nanoparticulate aluminum are similar to those of other forms of aluminum or require special consideration. To examine the acute toxicological effects of exposure to aluminum nanoparticle (Al-NP)s, adult female zebrafish were exposed to either Al-NPs or aluminum chloride for up to 48 hours in moderately hard fresh water. Al-NPs introduced into test water rapidly aggregated and up to 80% sedimented from the water column during exposures. No mortality was caused by concentrations of Al-NP up to 12.5 mg/L. After exposure, tissue concentrations of aluminum, effects on gill morphology, Na+, K+ -ATPase (NKA) activity, and global gene expression patterns were examined. Exposure to both aluminum chloride and nanoparticulate aluminum resulted in a concentration dependent decrease in sodium potassium ATPase activity, although Al-NP exposure did not alter gill morphology as measured by filament widths. Decreased ATPase activity coincided with decreases in filamental NKA staining and mucous cell counts. Analysis of gill transcriptional responses demonstrated that exposure to 5 mg/L Al-NP only resulted in significant changes in expression of two genes, whereas aluminum chloride exposure significantly affected the expression of 105 genes. Taken together, these results indicate that nanoparticulate aluminum has little acute toxicity for zebrafish in moderately hard freshwater. PMID:21910207

  8. A review of research on nanoparticulate flow undergoing coagulation

    NASA Astrophysics Data System (ADS)

    Lin, Jianzhong; Huo, Linlin

    2015-06-01

    Nanoparticulate flows occur in a wide range of natural phenomena and engineering applications and, hence, have attracted much attention. The purpose of the present paper is to provide a review of the research conducted over the last decade. The research covered relates to the Brownian coagulation of monodisperse and polydisperse particles, the Taylor-series expansion method of moment, and nanoparticle distributions due to coagulation in pipe and channel flow, jet flow, and the mixing layer and in the process of flame synthesis and deposition.

  9. Nanoparticulate formulations of mithramycin analogs for enhanced cytotoxicity.

    PubMed

    Scott, Daniel; Rohr, Jürgen; Bae, Younsoo

    2011-01-01

    Mithramycin (MTM), a natural product of soil bacteria from the Streptomyces genus, displays potent anticancer activity but has been limited clinically by severe side effects and toxicities. Engineering of the MTM biosynthetic pathway has produced the 3-side-chain-modified analogs MTM SK (SK) and MTM SDK (SDK), which have exhibited increased anticancer activity and improved therapeutic index. However, these analogs still suffer from low bioavailability, short plasma retention time, and low tumor accumulation. In an effort to aid with these shortcomings, two nanoparticulate formulations, poly(ethylene glycol)-poly(aspartate hydrazide) self-assembled and cross-linked micelles, were investigated with regard to the ability to load and pH dependently release the drugs. Micelles were successfully formed with both nanoparticulate formulations of each drug analog, with an average size of 8.36 ± 3.21 and 12.19 ± 2.77 nm for the SK and SDK micelles and 29.56 ± 4.67 nm and 30.48 ± 7.00 nm for the SK and SDK cross-linked micelles respectively. All of the drug-loaded formulations showed a pH-dependent release of the drugs, which was accelerated as pH decreased from 7.4 to 5.0. The micelles retained biological activity of SK and SDK entrapped in the micelles, suppressing human A549 lung cancer cells effectively. PMID:22114504

  10. Sol-Gel Process for Making Pt-Ru Fuel-Cell Catalysts

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram; Valdez, Thomas; Kumta, Prashant; Kim, Y.

    2005-01-01

    A sol-gel process has been developed as a superior alternative to a prior process for making platinum-ruthenium alloy catalysts for electro-oxidation of methanol in fuel cells. The starting materials in the prior process are chloride salts of platinum and ruthenium. The process involves multiple steps, is time-consuming, and yields a Pt-Ru product that has relatively low specific surface area and contains some chloride residue. Low specific surface area translates to incomplete utilization of the catalytic activity that might otherwise be available, while chloride residue further reduces catalytic activity ("poisons" the catalyst). In contrast, the sol-gel process involves fewer steps and less time, does not leave chloride residue, and yields a product of greater specific area and, hence, greater catalytic activity. In this sol-gel process (see figure), the starting materials are platinum(II) acetylacetonate [Pt(C5H7O2)2, also denoted Pt-acac] and ruthenium(III) acetylacetonate [Ru(C5H7O2)3, also denoted Ru-acac]. First, Pt-acac and Ru-acac are dissolved in acetone at the desired concentrations (typically, 0.00338 moles of each salt per 100 mL of acetone) at a temperature of 50 C. A solution of 25 percent tetramethylammonium hydroxide [(CH3)4NOH, also denoted TMAH] in methanol is added to the Pt-acac/Ruacac/ acetone solution to act as a high-molecular-weight hydrolyzing agent. The addition of the TMAH counteracts the undesired tendency of Pt-acac and Ru-acac to precipitate as separate phases during the subsequent evaporation of the solvent, thereby helping to yield a desired homogeneous amorphous gel. The solution is stirred for 10 minutes, then the solvent is evaporated until the solution becomes viscous, eventually transforming into a gel. The viscous gel is dried in air at a temperature of 170 C for about 10 hours. The dried gel is crushed to make a powder that is the immediate precursor of the final catalytic product. The precursor powder is converted to the

  11. Concepts and practices used to develop functional PLGA-based nanoparticulate systems

    PubMed Central

    Sah, Hongkee; Thoma, Laura A; Desu, Hari R; Sah, Edel; Wood, George C

    2013-01-01

    The functionality of bare polylactide-co-glycolide (PLGA) nanoparticles is limited to drug depot or drug solubilization in their hard cores. They have inherent weaknesses as a drug-delivery system. For instance, when administered intravenously, the nanoparticles undergo rapid clearance from systemic circulation before reaching the site of action. Furthermore, plain PLGA nanoparticles cannot distinguish between different cell types. Recent research shows that surface functionalization of nanoparticles and development of new nanoparticulate dosage forms help overcome these delivery challenges and improve in vivo performance. Immense research efforts have propelled the development of diverse functional PLGA-based nanoparticulate delivery systems. Representative examples include PEGylated micelles/nanoparticles (PEG, polyethylene glycol), polyplexes, polymersomes, core-shell–type lipid-PLGA hybrids, cell-PLGA hybrids, receptor-specific ligand-PLGA conjugates, and theranostics. Each PLGA-based nanoparticulate dosage form has specific features that distinguish it from other nanoparticulate systems. This review focuses on fundamental concepts and practices that are used in the development of various functional nanoparticulate dosage forms. We describe how the attributes of these functional nanoparticulate forms might contribute to achievement of desired therapeutic effects that are not attainable using conventional therapies. Functional PLGA-based nanoparticulate systems are expected to deliver chemotherapeutic, diagnostic, and imaging agents in a highly selective and effective manner. PMID:23459088

  12. Nanoparticulate mineral matter from basalt dust wastes.

    PubMed

    Dalmora, Adilson C; Ramos, Claudete G; Querol, Xavier; Kautzmann, Rubens M; Oliveira, Marcos L S; Taffarel, Silvio R; Moreno, Teresa; Silva, Luis F O

    2016-02-01

    Ultra-fine and nano-particles derived from basalt dust wastes (BDW) during "stonemeal" soil fertilizer application have been the subject of some concern recently around the world for their possible adverse effects on human health and environmental pollution. Samples of BDW utilized were obtained from companies in the mining district of Nova Prata in southern Brazil for chemical characterization and nano-mineralogy investigation, using an integrated application of advanced characterization techniques such as X-ray diffraction (XRD), High Resolution-Transmission Electron microscopy (HR-TEM)/(Energy Dispersive Spectroscopy) EDS/(selected-area diffraction pattern) SAED, Field Emission-Scanning Electron Microscopy (FE-SEM)/EDS and granulometric distribution analysis. The investigation has revealed that BDW materials are dominated by SiO2, Al2O3 and Fe2O3, with a complex micromineralogy including alkali feldspar, augite, barite, labradorite, hematite, heulandrite, gypsum, kaolinite, quartz, and smectite. In addition we have identified a number of trace metals such as Cd, Cu, Cr, Zn that are preferentially concentrated into the finer, inhalable, dust fraction and could so present a health hazard in the urban areas around the basalt mining zone. The implication of this observation is that use of these nanometric-sized particulates as soil fertilizer may present different health challenges to those of conventional fertilizers, inviting future work regarding the relative toxicities of these materials. Our investigation on the particle size distribution, nano-particle mineralogy and chemical composition in typical BDW samples highlights the need to develop cleaning procedures to minimise exposure to these natural fertilizing basalt dust wastes and is thus of direct relevance to both the industrial sector of basalt mining and to agriculture in the region. PMID:26551199

  13. Effect of reduction temperature on the preparation and characterization of Pt-Ru nanoparticles on multiwalled carbon nanotubes.

    PubMed

    Chetty, Raghuram; Xia, Wei; Kundu, Shankhamala; Bron, Michael; Reinecke, Thomas; Schuhmann, Wolfgang; Muhler, Martin

    2009-04-01

    Carbon nanotubes (CNT) supported platinum-ruthenium (Pt-Ru) catalysts were prepared by impregnation-reduction using an ethanolic solution of H2PtCl6 and RuCl3. The effect of reduction temperatures on particle size, surface area and their relationship to the electrocatalytic activity for methanol oxidation were investigated. Thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, X-ray diffraction (XRD) as well as X-ray photoelectron spectroscopy (XPS) were used for the catalyst characterization. XRD analysis showed that the PtRu/ CNT catalysts possibly consist of separate Pt and Ru phases. XPS analysis showed that the catalysts contain hydrous ruthenium oxide in addition to Pt and Ru metal and oxide species. The electrocatalytic activities of the catalysts were investigated in half-cell experiments using cyclic voltammetry, CO stripping voltammetry, chronoamperometry, and impedance spectroscopy. The results showed that the catalyst reduced at a temperature of 350 degrees C had the largest electrochemical surface area, lowest charge transfer resistance and the highest electrocatalytic activity for methanol oxidation. The superior catalytic activity is discussed based on the presence of appropriate amount of hydrated Ru oxide. PMID:19708258

  14. A TEM analysis of nanoparticulates in a Polar ice core

    SciTech Connect

    Esquivel, E.V.; Murr, L.E

    2004-03-15

    This paper explores the prospect for analyzing nanoparticulates in age-dated ice cores representing times in antiquity to establish a historical reference for atmospheric particulate regimes. Analytical transmission electron microscope (TEM) techniques were utilized to observe representative ice-melt water drops dried down on carbon/formvar or similar coated grids. A 10,000-year-old Greenland ice core was melted, and representative water drops were transferred to coated grids in a clean room environment. Essentially, all particulates observed were aggregates and either crystalline or complex mixtures of nanocrystals. Especially notable was the observation of carbon nanotubes and related fullerene-like nanocrystal forms. These observations are similar with some aspects of contemporary airborne particulates including carbon nanotubes and complex nanocrystal aggregates.

  15. Nanoparticulate carrier system: a novel treatment approach for hyperlipidemia.

    PubMed

    Sharma, Kritika; Kumar, Kulyash; Mishra, Neeraj

    2016-01-01

    Hyperlipidemia is a prevailing risk factor that leads to development and progression of atherosclerosis and consequently cardiovascular diseases. Several antihyperlipidemic drugs are having various disadvantages such as low water solubility and poor bioavailabilty due to presystemic gastrointestinal clearance. Thus, there is a considerable need for the development of efficient delivery methods and carriers. This review focuses on the importance and role of various nanoparticulate systems as carrier for antihyperlipidemic drugs in the treatment of hyperlipidemia. Some nanoparticle technology-based products are approved by FDA for effective treatment of hyperlipidemia, namely Tricor® by Abbott Laboratories (Chicago, IL, USA) and Triglide® by Skye Pharma (London, UK). Efforts to address each of these issues are going on, and should remain the focus on the future studies and look forward to many more clinical products in the future. PMID:24904976

  16. Multifunctional, stimuli-sensitive nanoparticulate systems for drug delivery

    PubMed Central

    Torchilin, Vladimir P.

    2015-01-01

    The use of nanoparticulate pharmaceutical drug delivery systems (NDDSs) to enhance the in vivo effectiveness of drugs is now well established. The development of multifunctional and stimulus-sensitive NDDSs is an active area of current research. Such NDDSs can have long circulation times, target the site of the disease and enhance the intracellular delivery of a drug. This type of NDDS can also respond to local stimuli that are characteristic of the pathological site by, for example, releasing an entrapped drug or shedding a protective coating, thus facilitating the interaction between drug-loaded nanocarriers and target cells or tissues. In addition, imaging contrast moieties can be attached to these carriers to track their real-time biodistribution and accumulation in target cells or tissues. Here, I highlight recent developments with multifunctional and stimuli-sensitive NDDSs and their therapeutic potential for diseases including cancer, cardiovascular diseases and infectious diseases. PMID:25287120

  17. Photo-enhanced activity of Pt and Pt-Ru catalysts towards the electro-oxidation of methanol

    NASA Astrophysics Data System (ADS)

    Arulmani, Dheevesh V.; Eastcott, Jennie I.; Mavilla, Stephanie G.; Easton, E. Bradley

    2014-02-01

    Electrocatalyst materials, consisting of Pt or Pt-Ru supported on carbon with and without TiO2, are evaluated for their activity towards the methanol oxidation reaction (MOR) in 1.0 M H2SO4 at 25 °C in the presence and absence of visible light irradiation. Electrochemical studies showed that enhanced MOR activity is achieved upon irradiation with visible light for each catalyst, in both the presence and absence of TiO2. Irradiation leads to no improvement in activity towards the formic acid oxidation reaction (FAOR) indicating that irradiation aids in the removal of adsorbed intermediate species, such as CO, during MOR. While the presence of a TiO2 support does lead to an increase in activity upon irradiation, about 50% of the improvements arise solely from the irradiation of the metal-containing electrocatalysts themselves.

  18. Microstructures and nanostructures for environmental carbon nanotubes and nanoparticulate soots.

    PubMed

    Murr, L E

    2008-12-01

    This paper examines the microstructures and nanostructures for natural (mined) chrysotile asbestos nanotubes (Mg3 Si2O5 (OH)4) in comparison with commercial multiwall carbon nanotubes (MWCNTs), utilizing scanning and transmission electron microscopy (SEM and TEM). Black carbon (BC) and a variety of specific soot particulate (aggregate) microstructures and nanostructures are also examined comparatively by SEM and TEM. A range of MWCNTs collected in the environment (both indoor and outdoor) are also examined and shown to be similar to some commercial MWCNTs but to exhibit a diversity of microstructures and nanostructures, including aggregation with other multiconcentric fullerenic nanoparticles. MWCNTs formed in the environment nucleate from special hemispherical graphene "caps" and there is evidence for preferential or energetically favorable chiralities, tube growth, and closing. The multiconcentric graphene tubes ( approximately 5 to 50 nm diameter) differentiate themselves from multiconcentric fullerenic nanoparticles and especially turbostratic BC and carbonaceous soot nanospherules ( approximately 8 to 80 nm diameter) because the latter are composed of curved graphene fragments intermixed or intercalated with polycyclic aromatic hydrocarbon (PAH) isomers of varying molecular weights and mass concentrations; depending upon combustion conditions and sources. The functionalizing of these nanostructures and photoxidation and related photothermal phenomena, as these may influence the cytotoxicities of these nanoparticulate aggregates, will also be discussed in the context of nanostructures and nanostructure phenomena, and implications for respiratory health. PMID:19151426

  19. Microstructures and Nanostructures for Environmental Carbon Nanotubes and Nanoparticulate Soots

    PubMed Central

    Murr, L. E.

    2008-01-01

    This paper examines the microstructures and nanostructures for natural (mined) chrysotile asbestos nanotubes (Mg3 Si2O5 (OH)4) in comparison with commercial multiwall carbon nanotubes (MWCNTs), utilizing scanning and transmission electron microscopy (SEM and TEM). Black carbon (BC) and a variety of specific soot particulate (aggregate) microstructures and nanostructures are also examined comparatively by SEM and TEM. A range of MWCNTs collected in the environment (both indoor and outdoor) are also examined and shown to be similar to some commercial MWCNTs but to exhibit a diversity of microstructures and nanostructures, including aggregation with other multiconcentric fullerenic nanoparticles. MWCNTs formed in the environment nucleate from special hemispherical graphene “caps” and there is evidence for preferential or energetically favorable chiralities, tube growth, and closing. The multiconcentric graphene tubes (∼5 to 50 nm diameter) differentiate themselves from multiconcentric fullerenic nanoparticles and especially turbostratic BC and carbonaceous soot nanospherules (∼8 to 80 nm diameter) because the latter are composed of curved graphene fragments intermixed or intercalated with polycyclic aromatic hydrocarbon (PAH) isomers of varying molecular weights and mass concentrations; depending upon combustion conditions and sources. The functionalizing of these nanostructures and photoxidation and related photothermal phenomena, as these may influence the cytotoxicities of these nanoparticulate aggregates, will also be discussed in the context of nanostructures and nanostructure phenomena, and implications for respiratory health. PMID:19151426

  20. Tunable Nanoparticulate Scaffolds from Self assembly in Surfactant Mesophase

    NASA Astrophysics Data System (ADS)

    Sharma, K. P.; Guruswamy, K.; Mondain-Monval, O.; Aswal, V. K.

    2010-03-01

    We examine the organization of silica nanoparticles in non-ionic surfactant, C12E9/water, H1 phase. We show, using SAXS, TEM , Freeze Fracture and Microscopy, that particles with sizes smaller than the mesophase characteristic size, a, template the mesophase; particles with size ˜ a, partition into a dispersed phase and into strand-like aggregates. Particles of size > a phase separate to form particulate strands organized into a scaffold. The particulate network forms by expulsion of particles from growing H1 phase domains; particles are concentrated in the isotropic phase and jam at domain boundaries. Changing the cooling rate into the H1 phase changes the nucleation of domains -- hence providing a route to tune the network mesh size. When the surfactant is heated to the micellar phase, the particles redisperse readily. SANS confirms that C12E9 forms a bilayer on the silica particles, preventing their irreversible aggregation. PEI coated particles (with size >a) also phase separate to form networks. The network of such coated particles can be crosslinked to obtain a free standing nanoparticulate scaffold.

  1. Ultrahigh methanol electro-oxidation activity of PtRu nanoparticles prepared on TiO2-embedded carbon nanofiber support

    NASA Astrophysics Data System (ADS)

    Ito, Yudai; Takeuchi, Taizo; Tsujiguchi, Takuya; Abdelkareem, Mohammad Ali; Nakagawa, Nobuyoshi

    2013-11-01

    A TiO2-embedded carbon nanofiber (TECNF) was proposed as a promising support of the PtRu nanocatalyst for the methanol oxidation reaction. The nanofiber support was prepared by the electrospinning of polyacrylonitrile (PAN) with TiO2 nanoparticles followed by carbonization and steam activation of the nanofiber, and lastly, the PtRu nanoparticles deposition. Cyclic voltammetry (CV) revealed a significantly high MOR activity for the PtRu/TECNF compared to that of the PtRu nanoparticles deposited on different supports, i.e., carbon black (C), TiO2 nanoparticles (TiO2), a mixture of these nanoparticles (C + TiO2) and carbon nanofiber (CNF). The MOR activity was high in the order of PtRu/TECNF > PtRu/CNF > PtRu/(C + TiO2) > PtRu/C >> PtRu/TiO2. The activity of PtRu/TECNF increased with an increase in the weight ratio of Ti/C for TECNF up to 1.0 and then decreased. The MOR mass activity of PtRu/TECNF at the optimum Ti/C ratio was 4 times higher than that of PtRu/C. The ultrahigh catalytic activity of PtRu/TECNF is attributed to the metal-support interaction, which efficiently occurs at the PtRu/TECNF structure. The ultrahigh catalytic activity was also confirmed by the two-times higher DMFC power output using PtRu/TECNF, in spite of quarter the PtRu loading on the electrode, compared to that using the commercial PtRu/C.

  2. Structurally inhomogeneous nanoparticulate catalysts in cobalt-catalyzed carbon nanotube growth

    SciTech Connect

    Kohigashi, Y.; Yoshida, H.; Takeda, S.; Homma, Y.

    2014-08-18

    The structure of nanoparticulate catalysts involved in cobalt-catalyzed chemical vapor deposition growth of carbon nanotubes (CNTs) was investigated by in situ environmental transmission electron microscopy (ETEM). In contrast to previous studies, the analyses of ETEM images showed that the nanoparticulate catalysts were structurally inhomogeneous during CNT growth in the source gas of acetylene at a rate of pressure increase of about 3 Pa/h and at 550 °C. The lattice fringes observed in the nanoparticulate catalysts can be accounted for by not a single crystalline structure but by several possible pairs of structures including pure Co and cobalt carbides. The inhomogeneous structures were unstable with time. The possible origin of the inhomogeneous structures is discussed.

  3. Pharmaceutical development and regulatory considerations for nanoparticles and nanoparticulate drug delivery systems.

    PubMed

    Narang, Ajit S; Chang, Rong-Kun; Hussain, Munir A

    2013-11-01

    Pharmaceutical nanomaterials (NMs) encompass a wide variety of materials including drug nanoparticles (NPs), which can be amorphous or crystalline; or nanoparticulate drug delivery systems, such as micelles, microemulsions, liposomes, drug-polymer conjugates, and antibody-drug conjugates. These NMs are either transient or persistent-depending on whether the integrity of their structure and size is maintained until reaching the site of drug action. Examples of several approved drug products are included as pharmaceutical nanoparticulate systems along with a commentary on the current development issues and paradigms for various categories of NPs. This commentary discusses the preparation of nanoparticulate systems for commercial development, and the biopharmaceutical and pharmacokinetic advantages of these systems. A criterion of criticality is defined that incorporates the structure, in addition to size requirement of pharmaceutical NPs to identify systems that may require special development and regulatory considerations. PMID:24037829

  4. Cellular partitioning of nanoparticulate versus dissolved metals in marine phytoplankton.

    PubMed

    Bielmyer-Fraser, Gretchen K; Jarvis, Tayler A; Lenihan, Hunter S; Miller, Robert J

    2014-11-18

    Discharges of metal oxide nanoparticles into aquatic environments are increasing with their use in society, thereby increasing exposure risk for aquatic organisms. Separating the impacts of nanoparticle from dissolved metal pollution is critical for assessing the environmental risks of the rapidly growing nanomaterial industry, especially in terms of ecosystem effects. Metal oxides negatively affect several species of marine phytoplankton, which are responsible for most marine primary production. Whether such toxicity is generally due to nanoparticles or exposure to dissolved metals liberated from particles is uncertain. The type and severity of toxicity depends in part on whether phytoplankton cells take up and accumulate primarily nanoparticles or dissolved metal ions. We compared the responses of the marine diatom, Thalassiosira weissflogii, exposed to ZnO, AgO, and CuO nanoparticles with the responses of T. weissflogii cells exposed to the dissolved metals ZnCl2, AgNO3, and CuCl2 for 7 d. Cellular metal accumulation, metal distribution, and algal population growth were measured to elucidate differences in exposure to the different forms of metal. Concentration-dependent metal accumulation and reduced population growth were observed in T. weissflogii exposed to nanometal oxides, as well as dissolved metals. Significant effects on population growth were observed at the lowest concentrations tested for all metals, with similar toxicity for both dissolved and nanoparticulate metals. Cellular metal distribution, however, markedly differed between T. weissflogii exposed to nanometal oxides versus those exposed to dissolved metals. Metal concentrations were highest in the algal cell wall when cells were exposed to metal oxide nanoparticles, whereas algae exposed to dissolved metals had higher proportions of metal in the organelle and endoplasmic reticulum fractions. These results have implications for marine plankton communities as well as higher trophic levels, since

  5. The interplay of catechol ligands with nanoparticulate iron oxides.

    PubMed

    Yuen, Alexander K L; Hutton, Georgina A; Masters, Anthony F; Maschmeyer, Thomas

    2012-03-01

    The unique properties exhibited by nanoscale materials, coupled with the multitude of chemical surface derivatisation possibilities, enable the rational design of multifunctional nanoscopic devices. Such functional devices offer exciting new opportunities in medical research and much effort is currently invested in the area of "nanomedicine", including: multimodal imaging diagnostic tools, platforms for drug delivery and vectorisation, polyvalent, multicomponent vaccines, and composite devices for "theranostics". Here we will review the surface derivatisation of nanoparticulate oxides of iron and iron@iron-oxide core-shells. They are attractive candidates for MRI-active therapeutic platforms, being potentially less toxic than lanthanide-based materials, and amenable to functionalisation with ligands. However successful grafting of groups onto the surface of iron-based nanoparticles, thus adding functionality whilst preserving their inherent properties, is one of the most difficult challenges for creating truly useful nanodevices from them. Functionalised catechol-derived ligands have enjoyed success as agents for the masking of superparamagnetic iron-oxide particles, often so as to render them biocompatible with medium to long-term colloidal stability in the complex chemical environments of biological milieux. In this perspective, the opportunities and limitations of functionalising the surfaces of iron-oxide nanoparticles, using coatings containing a catechol-derived anchor, are analysed and discussed, including recent advances using dopamine-terminated stabilising ligands. If light-driven ligand to metal charge transfer (LMCT) processes, and pH-dependent ligand desorption, leading to nanoparticle degradation under physiologically relevant conditions can be suppressed, colloidal stability of samples can be maintained and toxicity ascribed to degradation products avoided. Modulation of the redox behaviour of iron catecholate systems through the introduction of an

  6. Combustion-generated nanoparticulates in the El Paso, TX, USA / Juarez, Mexico Metroplex: their comparative characterization and potential for adverse health effects.

    PubMed

    Murr, L E; Soto, K F; Garza, K M; Guerrero, P A; Martinez, F; Esquivel, E V; Ramirez, D A; Shi, Y; Bang, J J; Venzor, J

    2006-03-01

    In this paper we report on the collection of fine (PM1) and ultrafine (PM0.1), or nanoparticulate, carbonaceous materials using thermophoretic precipitation onto silicon monoxide/formvar-coated 3 mm grids which were examined in the transmission electron microscope (TEM). We characterize and compare diesel particulate matter (DPM), tire particulate matter (TPM), wood burning particulate matter, and other soot (or black carbons (BC)) along with carbon nanotube and related fullerene nanoparticle aggregates in the outdoor air, as well as carbon nanotube aggregates in the indoor air; and with reference to specific gas combustion sources. These TEM investigations include detailed microstructural and microdiffraction observations and comparisons as they relate to the aggregate morphologies as well as their component (primary) nanoparticles. We have also conducted both clinical surveys regarding asthma incidence and the use of gas cooking stoves as well as random surveys by zip code throughout the city of El Paso. In addition, we report on short term (2 day) and longer term (2 week) in vitro assays for black carbon and a commercial multiwall carbon nanotube aggregate sample using a murine macrophage cell line, which demonstrate significant cytotoxicity; comparable to a chrysotile asbestos nanoparticulate reference. The multi-wall carbon nanotube aggregate material is identical to those collected in the indoor and outdoor air, and may serve as a surrogate. Taken together with the plethora of toxic responses reported for DPM, these findings prompt concerns for airborne carbonaceous nanoparticulates in general. The implications of these preliminary findings and their potential health effects, as well as directions for related studies addressing these complex issues, will also be examined. PMID:16823077

  7. Combustion-Generated Nanoparticulates in the El Paso, TX, USA / Juarez, Mexico Metroplex: Their Comparative Characterization and Potential for Adverse Health Effects

    PubMed Central

    Murr, L. E.; Soto, K. F.; Garza, K. M.; Guerrero, P. A.; Martinez, F.; Esquivel, E. V.; Ramirez, D. A.; Shi, Y.; Bang, J. J.; Venzor, J.

    2006-01-01

    In this paper we report on the collection of fine (PM1) and ultrafine (PM0.1), or nanoparticulate, carbonaceous materials using thermophoretic precipitation onto silicon monoxide/formvar-coated 3 mm grids which were examined in the transmission electron microscope (TEM). We characterize and compare diesel particulate matter (DPM), tire particulate matter (TPM), wood burning particulate matter, and other soot (or black carbons (BC)) along with carbon nanotube and related fullerene nanoparticle aggregates in the outdoor air, as well as carbon nanotube aggregates in the indoor air; and with reference to specific gas combustion sources. These TEM investigations include detailed microstructural and microdiffraction observations and comparisons as they relate to the aggregate morphologies as well as their component (primary) nanoparticles. We have also conducted both clinical surveys regarding asthma incidence and the use of gas cooking stoves as well as random surveys by zip code throughout the city of El Paso. In addition, we report on short term (2 day) and longer term (2 week) in vitro assays for black carbon and a commercial multiwall carbon nanotube aggregate sample using a murine macrophage cell line, which demonstrate significant cytotoxicity; comparable to a chrysotile asbestos nanoparticulate reference. The multi-wall carbon nanotube aggregate material is identical to those collected in the indoor and outdoor air, and may serve as a surrogate. Taken together with the plethora of toxic responses reported for DPM, these findings prompt concerns for airborne carbonaceous nanoparticulates in general. The implications of these preliminary findings and their potential health effects, as well as directions for related studies addressing these complex issues, will also be examined. PMID:16823077

  8. Nanoparticulate Delivery of Agents for Induced Elastogenesis in 3-Dimensional Collagenous Matrices

    PubMed Central

    Venkataraman, Lavanya; Sivaraman, Balakrishnan; Vaidya, Pratik; Ramamurthi, Anand

    2014-01-01

    The degradation of elastic matrix in the infrarenal aortic wall is a critical parameter underlying the formation and progression of abdominal aortic aneurysms (AAAs). It is mediated by the chronic overexpression of matrix metalloproteases (MMPs) -2 and -9, leading to a progressive loss of elasticity and weakening of the aortic wall. Delivery of therapeutic agents to inhibit MMPs, while concurrently coaxing cell-based regenerative repair of the elastic matrix represents a potential strategy for slowing or arresting AAA growth. Our prior studies have demonstrated elastogenic induction of healthy and aneurysmal aortic smooth muscle cells (SMCs) and inhibition of MMPs, following exogenous delivery of elastogenic factors such as TGF-β1, as well as MMP-inhibitors such as doxycycline (DOX) in two-dimensional (2-D) culture. Based on these findings, and others that demonstrated elastogenic benefits of nanoparticulate delivery of these agents in 2-D culture, we have developed poly(lactide-co-glycolide) nanoparticles for localized, controlled and sustained delivery of DOX and TGF-β1 to human aortic SMCs (HASMCs) within a three-dimensional (3-D) gels of type-I collagen gel, which closely evoke the arterial tissue microenvironment. DOX and TGF-β1 released from these NPs influenced elastogenic outcomes positively within the collagen constructs over 21 days of culture, which were comparable to that induced by exogenous supplementation of DOX and TGF-β1 within the culture medium. However, this was accomplished at doses ∼20-fold lower than the exogenous dosages of the agents, illustrating that their localized, controlled, and sustained delivery from NPs embedded within a 3-D scaffold is an efficient strategy for directed elastogenesis. PMID:24737693

  9. Dual-functional bio-derived nanoparticulates for apoptotic antitumor therapy.

    PubMed

    Ding, Yang; Wang, Yazhe; Opoku-Damoah, Yaw; Wang, Cheng; Shen, Lingjia; Yin, Lifang; Zhou, Jianping

    2015-12-01

    The application of bio-derived nanoparticulates has gained a remarkable degree of interest as a promising sustained-release, site-targeted and completely biodegradable delivery system for chemotherapeutics. We hereby introduce a dual-functionalized biomimetic nanovector, cell-penetrating peptide (CPP)-anchored recombinant high density lipoproteins (cp-rHDL), which affords high payload and improved targeting of gambogic acid (GA), a therapeutic agent for apoptotic antitumor therapy. GA-loaded cp-rHDL nanoparticles (cp-rHDL/GA) consisted of hydrophobic core modulating GA, apolipoprotein A-I (apo A-I) for attractive integrating and tumor-homing, and lipophilic anchored R6H4 (RRRRRRHHHH, a pH-responsive CPP) offering a pH-controlled penetrating potential. Upon stepwise incubation with apo A-I and R6H4, cp-rHDL/GA presented several merits, including desirable physicochemical properties, superior biostability, and favorable buffering capacity resulting in proton sponge effect. Synergistic intracellular mechanism for scavenger receptor class B type I (SR-BI)-mediated direct transmembrane delivery, and pH-responsive R6H4 associated endocytotic pathway with rapid endo-lysosomal escape was also observed. This tailored cp-rHDL/GA displayed remarkable cytotoxicity and apoptotic effect via triggering p53 pathway, and provided approximately 5-fold increase in IC50 compared to free GA. Moreover, this rational biomimetic therapeutic strategy attained superior tumor accumulation and significant inhibition of tumor growth in HepG2 xenograft tumor animal models without measurable adverse effect. Results of this study demonstrated that bio-derived cp-rHDL/GA presents pH-responsive penetrating potential and efficient cellular internalization. This dual-functionalization model will open an avenue for exploration of multi-functional bio-derived drug delivery, thereby rendering potential broad applications in apoptotic anticancer therapy. PMID:26344366

  10. Nanoparticules d'or: De l'imagerie par resonance magnetique a la radiosensibilisation

    NASA Astrophysics Data System (ADS)

    Hebert, Etienne M.

    Cette thèse approfondit l'étude de nanoparticules d'or de 5 nm de diamètre recouvertes de diamideéthanethioldiethylènetriaminepentacétate de gadolinium (DTDTPA:Gd), un agent de contraste pour l'imagerie par résonance magnétique (IRM). En guise de ciblage passif, la taille des nanoparticules a été contrôlée afin d'utiliser le réseau de néovaisseaux poreux et perméable des tumeurs. De plus les tumeurs ont un drainage lymphatique déficient qui permet aux nanoparticules de demeurer plus longtemps dans le milieu interstitiel de la tumeur. Les expériences ont été effectuées sur des souris Balb/c femelles portant des tumeurs MC7-L1. La concentration de nanoparticules a pu être mesurée à l'IRM in vivo. La concentration maximale se retrouvait à la fin de l'infusion de 10 min. La concentration s'élevait à 0.3 mM dans la tumeur et de 0.12 mM dans le muscle environnant. Les nanoparticules étaient éliminées avec une demi-vie de 22 min pour les tumeurs et de 20 min pour le muscle environnant. Les nanoparticules ont été fonctionnalisées avec le peptide Tat afin de leur conférer des propriétés de ciblage actif La rétention de ces nanoparticules a ainsi été augmentée de 1600 %, passant d'une demi-vie d'élimination de 22 min à 350 min. La survie des souris a été mesurée à l'aide de courbes Kaplan-Meier et d'un modèle mathématique évalue l'efficacité de traitements. Le modèle nous permet, à l'aide de la vitesse de croissance des tumeurs et de l'efficacité des traitements, de calculer la courbe de survie des spécimens. Un effet antagoniste a été observé au lieu de l'effet synergétique attendu entre une infusion de Au@DTDTPA:Gd et l'irradiation aux rayons X. L'absence d'effet synergétique a été attribuée à l'épaisseur du recouvrement de DTDTPA:Gd qui fait écran aux électrons produits par l'or. De plus, le moyen d'ancrage du recouvrement utilise des thiols qui peuvent s'avérer être des capteurs de radicaux. De plus

  11. X-ray phase computed tomography for nanoparticulated imaging probes and therapeutics: preliminary feasibility study

    NASA Astrophysics Data System (ADS)

    Tang, Xiangyang; Yang, Yi; Tang, Shaojie

    2011-03-01

    With the scientific progress in cancer biology, pharmacology and biomedical engineering, the nano-biotechnology based imaging probes and therapeutical agents (namely probes/agents) - a form of theranostics - are among the strategic solutions bearing the hope for the cure of cancer. The key feature distinguishing the nanoparticulated probes/agents from their conventional counterparts is their targeting capability. A large surface-to-volume ratio in nanoparticulated probes/agents enables the accommodation of multiple targeting, imaging and therapeutic components to cope with the intra- and inter-tumor heterogeneity. Most nanoparticulated probes/agents are synthesized with low atomic number materials and thus their x-ray attenuation are very similar to biological tissues. However, their microscopic structures are very different, which may result in significant differences in their refractive properties. Recently, the investigation in the x-ray grating-based differential phase contrast (DPC) CT has demonstrated its advantages in differentiating low-atomic materials over the conventional attenuation-based CT. We believe that a synergy of x-ray grating-based DPC CT and nanoparticulated imaging probes and therapeutic agents may play a significant role in extensive preclinical and clinical applications, or even become a modality for molecular imaging. Hence, we propose to image the refractive property of nanoparticulated imaging probes and therapeutical agents using x-ray grating-based DPC CT. In this work, we conduct a preliminary feasibility study with a focus to characterize the contrast-to-noise ratio (CNR) and contrast-detail behavior of the x-ray grating-based DPC CT. The obtained data may be instructive to the architecture design and performance optimization of the x-ray grating-based DPC CT for imaging biomarker-targeted imaging probes and therapeutic agents, and even informative to the translation of preclinical research in theranostics into clinical applications.

  12. Application of x-ray nano-particulate markers for the visualization of intermediate layers and interfaces using scanning electron microscopy

    NASA Astrophysics Data System (ADS)

    Bessudnova, Nadezda O.; Bilenko, David I.; Zakharevich, Andrey M.

    2012-03-01

    In this study the methodology of biological sample preparation for dental research using SEM/EDX has been elaborated. (1)The original cutting equipment supplied with 3D user-controlled sample fixation and an adjustable cooling system has been designed and evaluated. (2) A new approach to the root dentine drying procedure has been developed to preserve structure peculiarities of root dentine. (3) A novel adhesive system with embedded X-Ray nanoparticulate markers has been designed. (4)The technique allowing for visualization of bonding resins, interfaces and intermediate layers between tooth hard tissues and restorative materials of endodontically treated teeth using the X-ray nano-particulate markers has been developed and approved. These methods and approaches were used to compare the objective depth of penetration of adhesive systems of different generations in root dentine. It has been shown that the depth of penetration in dentine is less for adhesive systems of generation VI in comparison with bonding resins of generation V, which is in agreement with theoretical evidence. The depth of penetration depends on the correlation between the direction of dentinal tubules, bonding resin delivery and gravity.

  13. Application of x-ray nano-particulate markers for the visualization of intermediate layers and interfaces using scanning electron microscopy

    NASA Astrophysics Data System (ADS)

    Bessudnova, Nadezda O.; Bilenko, David I.; Zakharevich, Andrey M.

    2011-10-01

    In this study the methodology of biological sample preparation for dental research using SEM/EDX has been elaborated. (1)The original cutting equipment supplied with 3D user-controlled sample fixation and an adjustable cooling system has been designed and evaluated. (2) A new approach to the root dentine drying procedure has been developed to preserve structure peculiarities of root dentine. (3) A novel adhesive system with embedded X-Ray nanoparticulate markers has been designed. (4)The technique allowing for visualization of bonding resins, interfaces and intermediate layers between tooth hard tissues and restorative materials of endodontically treated teeth using the X-ray nano-particulate markers has been developed and approved. These methods and approaches were used to compare the objective depth of penetration of adhesive systems of different generations in root dentine. It has been shown that the depth of penetration in dentine is less for adhesive systems of generation VI in comparison with bonding resins of generation V, which is in agreement with theoretical evidence. The depth of penetration depends on the correlation between the direction of dentinal tubules, bonding resin delivery and gravity.

  14. Novel Effects of Nanoparticulate Delivery of Zinc on Growth, Productivity, and Zinc Biofortification in Maize (Zea mays L.).

    PubMed

    Subbaiah, Layam Venkata; Prasad, Tollamadugu Naga Venkata Krishna Vara; Krishna, Thimmavajjula Giridhara; Sudhakar, Palagiri; Reddy, Balam Ravindra; Pradeep, Thalappil

    2016-05-18

    In the present investigation, nanoscale zinc oxide particulates (ZnO-nanoparticulates) were prepared using a modified oxalate decomposition method. Prepared ZnO-nanoparticulates (mean size = 25 nm) were characterized using techniques such as transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and zeta potential analyzer. Different concentrations (50, 100, 200, 400, 600, 800, 1000, 1500, and 2000 ppm) of ZnO-nanoparticulates were examined to reveal their effects on maize crop on overall growth and translocation of zinc along with bulk ZnSO4 and control. Highest germination percentage (80%) and seedling vigor index (1923.20) were observed at 1500 ppm of ZnO-nanoparticulates. The yield was 42% more compared to control and 15% higher compared to 2000 ppm of ZnSO4. Higher accumulation of zinc (35.96 ppm) in grains was recorded with application of 100 ppm followed by 400 ppm (31.05 ppm) of ZnO-nanoparticulates. These results indicate that ZnO-nanoparticulates have significant effects on growth, yield, and zinc content of maize grains, which is an important feature in terms of human health. PMID:27089102

  15. Analytical Electron Microscopy for Characterization of Fluid or Semi-Solid Multiphase Systems Containing Nanoparticulate Material

    PubMed Central

    Klang, Victoria; Valenta, Claudia; Matsko, Nadejda B.

    2013-01-01

    The analysis of nanomaterials in pharmaceutical or cosmetic preparations is an important aspect both in formulation development and quality control of marketed products. Despite the increased popularity of nanoparticulate compounds especially in dermal preparations such as emulsions, methods and protocols of analysis for the characterization of such systems are scarce. This work combines an original sample preparation procedure along with different methods of analytical electron microscopy for the comprehensive analysis of fluid or semi-solid dermal preparations containing nanoparticulate material. Energy-filtered transmission electron microscopy, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy and high resolution imaging were performed on model emulsions and a marketed product to reveal different structural aspects of both the emulsion bulk phase and incorporated nanosized material. An innovative analytical approach for the determination of the physical stability of the emulsion under investigation is presented. Advantages and limitations of the employed analytical imaging techniques are highlighted. PMID:24300401

  16. Seeded growth of robust SERS-active 2D Au@Ag nanoparticulate films

    SciTech Connect

    Baker, Gary A; Dai, Sheng; Hagaman, Edward {Ed} W; Mahurin, Shannon Mark; Zhu, Haoguo; Bao, Lili

    2008-01-01

    We demonstrate herein a novel and versatile solution-based methodology for fabricating self-organized two-dimensional (2D) Au nanoparticle arrays on glass using in situ nucleation at an aminosilane monolayer followed by seeded, electroless growth; subsequent deposition of Ag produced Au{at}Ag core-shell nanoparticulate films which proved highly promising as surface-enhanced Raman scattering (SERS) platforms.

  17. Study of an ultrasound-based process analytical tool for homogenization of nanoparticulate pharmaceutical vehicles.

    PubMed

    Cavegn, Martin; Douglas, Ryan; Akkermans, Guy; Kuentz, Martin

    2011-08-01

    There are currently no adequate process analyzers for nanoparticulate viscosity enhancers. This article aims to evaluate ultrasonic resonator technology as a monitoring tool for homogenization of nanoparticulate gels. Aqueous dispersions of colloidal microcrystalline cellulose (MCC) and a mixture of clay particles with xanthan gum were compared with colloidal silicon dioxide in oil. The processing was conducted using a laboratory-scale homogenizing vessel. The study investigated first the homogenization kinetics of the different systems to focus then on process factors in the case of colloidal MCC. Moreover, rheological properties were analyzed offline to assess the structure of the resulting gels. Results showed the suitability of ultrasound velocimetry to monitor the homogenization process. The obtained data were fitted using a novel heuristic model. It was possible to identify characteristic homogenization times for each formulation. The subsequent study of the process factors demonstrated that ultrasonic process analysis was equally sensitive as offline rheological measurements in detecting subtle manufacturing changes. It can be concluded that the ultrasonic method was able to successfully assess homogenization of nanoparticulate viscosity enhancers. This novel technique can become a vital tool for development and production of pharmaceutical suspensions in the future. PMID:21412782

  18. Preparation and characterization of silica nanoparticulate polyacrylonitrile composite and porous nanofibers

    NASA Astrophysics Data System (ADS)

    Ji, Liwen; Saquing, Carl; Khan, Saad A.; Zhang, Xiangwu

    2008-02-01

    In this study, polyacrylonitrile (PAN) composite nanofibers containing different amounts of silica nanoparticulates have been obtained via electrospinning. The surface morphology, thermal properties and crystal structure of PAN/silica nanofibers are characterized using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, wide-angle x-ray diffraction (WAXD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The results indicate that the addition of silica nanoparticulates affects the structure and properties of the nanofibers. In addition to PAN/silica composite nanofibers, porous PAN nanofibers have been prepared by selective removal of the silica component from PAN/silica composite nanofibers using hydrofluoric (HF) acid. ATR-FTIR and thermal gravimetric analysis (TGA) experiments validate the removal of silica nanoparticulates by HF acid, whereas SEM and TEM results reveal that the porous nanofibers obtained from composite fibers with higher silica contents exhibited more nonuniform surface morphology. The Brunauer-Emmett-Teller (BET) surface area of porous PAN nanofibers made from PAN/silica (5 wt%) composite precursors is higher than that of pure nonporous PAN nanofibers.

  19. Evaluation of various adjuvant nanoparticulate formulations for meningococcal capsular polysaccharide-based vaccine.

    PubMed

    Gala, Rikhav P; D'Souza, Martin; Zughaier, Susu M

    2016-06-14

    Neisseria meningitidis is a leading cause of bacterial meningitis and sepsis and its capsular polysaccharides (CPS) are a major virulence factor in meningococcal infections and form the basis for serogroup designation and preventive vaccines. We have formulated a novel meningococcal nanoparticulate vaccine formulation that does not require chemical conjugation, but encapsulates meningococcal CPS polymers in a biodegradable material that slowly release antigens, thereby has antigen depot effect to enhance antigenicity. The novel vaccine formulation is inexpensive and can be stored as a dry powder with extended shelf life that does not require the cold-chain which facilitates storage and distribution. In order to enhance the antigenicity of meningococcal nanoparticulate vaccine, we screened various adjuvants formulated in nanoparticles, for their ability to potentiate antigen presentation by dendritic cells. Here, we report that MF59 and Alum are superior to TLR-based adjuvants in enhancing dendritic cell maturation and antigen presentation markers MHC I, MHC II, CD40, CD80 and CD86 in dendritic cells pulsed with meningococcal CPS nanoparticulate vaccine. PMID:27177946

  20. New Catalysts for Direct Methanol Oxidation Fuel Cells

    SciTech Connect

    Adzic, Radoslav

    1998-08-01

    A new class of efficient electrocatalytic materials based on platinum - metal oxide systems has been synthetized and characterized by several techniques. Best activity was found with NiWO{sub 4}-, CoWO{sub 4}-, and RuO{sub 2}- sr¡pported platinum catalysts. A very similar activity at room temperature was observed with the electrodes prepared with the catalyst obtained from International Fuel Cells Inc. for the same Pt loading. Surprisingly, the two tungstates per se show a small activity for methanol oxidation without any Pt loading. Synthesis of NiWO{sub 4} and CoWO{sub 4} were carried out by solid-state reactions. FTIR spectroscopy shows that the tungstates contain a certain amount of physically adsorbed water even after heating samples at 200{degrees}C. A direct relationship between the activity for methanol oxidation and the amount of adsorbed water on those oxides has been found. The Ru(0001) single crystal shows a very small activity for CO adsorption and oxidation, in contrast to the behavior of polycrystalline Ru. In situ extended x-ray absorption fine structure spectroscopy (EXAFS) and x-ray absorption near edge spectroscopy (XANES) showed that the OH adsorption on Ru in the Pt-Ru alloy appears to be the limiting step in methanol oxidation. This does not occur for Pt-RuO{SUB 2} electrocatalyst, which explains its advantages over the Pt-Ru alloys. The IFCC electrocatalyst has the properties of the Pt-Ru alloy.

  1. Enhanced oral bioavailability of fenofibrate using polymeric nanoparticulated systems: physicochemical characterization and in vivo investigation

    PubMed Central

    Yousaf, Abid Mehmood; Kim, Dong Wuk; Oh, Yu-Kyoung; Yong, Chul Soon; Kim, Jong Oh; Choi, Han-Gon

    2015-01-01

    Background The intention of this research was to prepare and compare various solubility-enhancing nanoparticulated systems in order to select a nanoparticulated formulation with the most improved oral bioavailability of poorly water-soluble fenofibrate. Methods The most appropriate excipients for different nanoparticulated preparations were selected by determining the drug solubility in 1% (w/v) aqueous solutions of each carrier. The polyvinylpyrrolidone (PVP) nanospheres, hydroxypropyl-β-cyclodextrin (HP-β-CD) nanocorpuscles, and gelatin nanocapsules were formulated as fenofibrate/PVP/sodium lauryl sulfate (SLS), fenofibrate/HP-β-CD, and fenofibrate/gelatin at the optimized weight ratios of 2.5:4.5:1, 1:4, and 1:8, respectively. The three solid-state products were achieved using the solvent-evaporation method through the spray-drying technique. The physicochemical characterization of these nanoparticles was accomplished by powder X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and Fourier-transform infrared spectroscopy. Their physicochemical properties, aqueous solubility, dissolution rate, and pharmacokinetics in rats were investigated in comparison with the drug powder. Results Among the tested carriers, PVP, HP-β-CD, gelatin, and SLS showed better solubility and were selected as the most appropriate constituents for various nanoparticulated systems. All of the formulations significantly improved the aqueous solubility, dissolution rate, and oral bioavailability of fenofibrate compared to the drug powder. The drug was present in the amorphous form in HP-β-CD nanocorpuscles; however, in other formulations, it existed in the crystalline state with a reduced intensity. The aqueous solubility and dissolution rates of the nanoparticles (after 30 minutes) were not significantly different from one another. Among the nanoparticulated systems tested in this study, the initial dissolution rates (up to 10 minutes) were higher with

  2. On the mechanism of nanoparticulate CeO2 toxicity to freshwater algae.

    PubMed

    Angel, Brad M; Vallotton, Pascal; Apte, Simon C

    2015-11-01

    The factors affecting the chronic (72-h) toxicity of three nanoparticulate (10-34nm) and one micron-sized form of CeO2 to the green alga, Pseudokirchneriella subcapitata were investigated. To characterise transformations in solution, hydrodynamic diameters (HDD) were measured by dynamic light scatter, zeta potential values by electrophoretic mobility, and dissolution by equilibrium dialysis. The protective effects of humic and fulvic dissolved organic carbon (DOC) on toxicity were also assessed. To investigate the mechanisms of algal toxicity, the CytoViva hyperspectral imaging system was used to visualise algal-CeO2 interactions in the presence and absence of DOC, and the role of reactive oxygen species (ROS) was investigated by 'switching off' ROS production using UV-filtered lighting conditions. The nanoparticulate CeO2 immediately aggregated in solution to HDDs measured in the range 113-193nm, whereas the HDD and zeta potential values were significantly lower in the presence of DOC. Negligible CeO2 dissolution over the time course of the bioassay ruled out potential toxicity from dissolved cerium. The nanoparticulate CeO2 concentration that caused 50% inhibition of algal growth rate (IC50) was in the range 7.6-28mg/L compared with 59mg/L for micron-sized ceria, indicating that smaller particles were more toxic. The presence of DOC mitigated toxicity, with IC50s increasing to greater than 100mg/L. Significant ROS were generated in the nanoparticulate CeO2 bioassays under normal light conditions. However, 'switching off' ROS under UV-filtered light conditions resulted in a similar IC50, indicating that ROS generation was not the toxic mechanism. The CytoViva imaging showed negligible sorption of nanoparticulate CeO2 to algal cells in the presence of DOC, and strong sorption in its absence, suggesting that this was the toxic mechanism. The results suggest that DOC in natural waters will coat CeO2 particles and mitigate toxicity to algal cells. PMID:26461912

  3. Dynamics of nanoparticules detected at 1 AU by S/WAVES onboard STEREO spacecraft

    NASA Astrophysics Data System (ADS)

    Belheouane, Soraya; Issautier, Karine; Meyer-Vernet, Nicole; Le Chat, Gaétan; Czechowski, Andrzej; Zaslavsky, Arnaud; Zouganelis, Yannis; Mann, Ingrid

    In order to interpret in detail the S/WAVES data on the interplanetary nanodust discovered by STEREO at 1 AU [Meyer-Vernet et al., 2009], we study the dynamics of nanoparticles in the inner interplanetary medium as well as the distribution of their velocities and directions of arrival, with a model based on [Czechowski and Mann, 2012]. We deduce the charges released by their impacts on the STEREO spacecraft at 1 AU and their dependence on the position of the spacecraft on their orbits. The model studies nanoparticles of size equal or smaller than about 70 nm, assumed to be created via collisional fragmentation of dust grains of larger size moving on keplerian orbits, and sublimation of dust, meteoroids and comets. The nanoparticles are released near the Sun with initial velocities close to keplerian, and mainly subjected to the Lorentz force calculated with a simple solar wind model. A part of the nanoparticles is accelerated to high speeds of the order of 300 km/s, thereby providing impact charges between 10(-14) and 10(-11) Cb [Belheouane, 2014] which enable them to be detected by S/WAVES, whereas another part is trapped within about 0.2 AU from the Sun. We discuss how the fluxes and direction of arrival at 1 AU are expected to change in function of the solar cycle. These results enable us to interpret in detail the STEREO/WAVES observations [Zaslavsky et al., 2012]; [Pantellini et al., 2013]; [Le Chat et al., 2013]. Belheouane, S. (2014). Nanoparticules dans le vent solaire, observations spatiales et theorie. PhD thesis, Pierre and Marie Curie University UPMC. Czechowski, A. and Mann, I. (2012). Nanodust Dynamics in Interplanetary Space, chapter Nanodust Dynamics in Interplanetary Space. Springer Berlin Heidelberg. Le Chat, G., Zaslavsky, A., Meyer-Vernet, N., Issautier, K., Belheouane, S., Pantellini, F., Maksimovic, M., Zouganelis, I., Bale, S., and Kasper, J. (2013). Interplanetary Nanodust Detection by the Solar Terrestrial Relations Observatory/WAVES Low

  4. Electric relaxation processes in chemodynamics of aqueous metal complexes: from simple ligands to soft nanoparticulate complexants.

    PubMed

    van Leeuwen, Herman P; Buffle, Jacques; Town, Raewyn M

    2012-01-10

    The chemodynamics of metal complexes with nanoparticulate complexants can differ significantly from that for simple ligands. The spatial confinement of charged sites and binding sites to the nanoparticulate body impacts on the time scales of various steps in the overall complex formation process. The greater the charge carried by the nanoparticle, the longer it takes to set up the counterion distribution equilibrium with the medium. A z+ metal ion (z > 1) in a 1:1 background electrolyte will accumulate in the counterionic atmosphere around negatively charged simple ions, as well as within/around the body of a soft nanoparticle with negative structural charge. The rate of accumulation is often governed by diffusion and proceeds until Boltzmann partition equilibrium between the charged entity and the ions in the medium is attained. The electrostatic accumulation proceeds simultaneously with outer-sphere and inner-sphere complex formation. The rate of the eventual inner-sphere complex formation is generally controlled by the rate constant of dehydration of the metal ion, k(w). For common transition metal ions with moderate to fast dehydration rates, e.g., Cu(2+), Pb(2+), and Cd(2+), it is shown that the ionic equilibration with the medium may be the slower step and thus rate-limiting in their overall complexation with nanoparticles. PMID:22126743

  5. Novel Nanoparticulate Gel Formulations of Steroids for the Treatment of Macular Edema

    PubMed Central

    2010-01-01

    Purpose: This article describes the development and characterization of PLGA nanoparticles of dexamethasone (DEX), hydrocortisone acetate (HA), and prednisolone acetate (PA) suspended in thermosensitive gels indicated for the treatment of macular edema (ME). Methods: Nanoparticles were prepared by oil-in-water (O/W) emulsion and dialysis methods using PLGA 50:50 and PLGA 65:35. These particles were characterized for entrapment efficiency, size distribution, surface morphology, crystallinity, and in vitro release. Further, ex vivo permeation studies of DEX in suspension and nanoparticulate formulations were carried out across the rabbit sclera. Results: Entrapment efficiencies of DEX, HA, and PA were found to be lower with the dialysis method. O/W emulsion/solvent evaporation technique resulted in higher entrapment efficiencies, that is, 77.3%, 91.3%, 92.3% for DEX, HA, and PA, respectively. Release from nanoparticles suspended in thermosensitive gels followed zero-order kinetics with no apparent burst effect. Ex vivo permeability studies further confirmed sustained release of DEX from nanoparticles suspended in thermosensitive gels. Conclusions: These novel nanoparticulate systems containing particles suspended in thermosensitive gels may provide sustained retina/choroid delivery of steroids following episcleral administration. PMID:20148659

  6. Progress in nanoparticulate systems for peptide, proteins and nucleic acid drug delivery.

    PubMed

    Slomkowski, Stanislaw; Gosecki, Mateusz

    2011-11-01

    Progress in many therapies, in particular in the therapies based on peptides, proteins and nucleic acids used as bioactive compounds, strongly depends on development of appropriate carriers which would be suitable for controlled delivery of the intact abovementioned compounds to required tissues, cells and intracellular compartments. This review presents last ten years' achievements and problems in development and application of synthetic polymer nanoparticulate carriers for oral, pulmonary and nasal delivery routes of oligopeptides and proteins. Whereas some traditional synthetic polymer carriers are only briefly recalled the main attention is concentrated on nanoparticles produced from functional copolymers mostly with hydroxyl, carboxyl and amino groups, suitable for immobilization of targeting moieties and for assuring prolonged circulation of nanoparticles in blood. Formulations of various nanoparticulate systems are described, including solid particles, polymer micelles, nanovesicles and nanogels, especially systems allowing drug release induced by external stimuli. Discussed are properties of these species, in particular stability in buffers and models of body fluids, loading with drugs and with drug models, drug release processes and results of biological studies. There are also discussed systems for gene delivery with special attention devoted to polymers suitable for compacting nucleic acids into nanoparticles as well as the relations between chemical structure of polymer carriers and ability of the latter for crossing cell membranes and for endosomal escape. PMID:21902630

  7. The Science Behind Nanosun-Screens: Learning about Nanoparticulate Ingredients Used to Block the Sun's Ultraviolet Rays

    ERIC Educational Resources Information Center

    Wise, Alyssa; Schank, Patricia; Stanford, Tina; Horsma, Geri

    2009-01-01

    In this article, the authors provide a brief overview of the emerging field of nanoscience and why it is an important area of education. They next explain the science behind the new nanoparticulate sunscreens, describe the different elements of the unit, and reflect on some of the opportunities and challenges of teaching nanoscience at the high…

  8. Nano-particulate Aluminium Nitride/Al: An Efficient and Versatile Heterogeneous Catalyst for the Synthesis of Biginelli Scaffolds

    NASA Astrophysics Data System (ADS)

    Tekale, S. U.; Tekale, A. B.; Kanhe, N. S.; Bhoraskar, S. V.; Pawar, R. P.

    2011-12-01

    Nano-particulate aluminium nitride/Al (7:1) is reported as a new heterogeneous solid acid catalyst for the synthesis of 3, 4-dihydroxypyrimidi-2-(1H)-ones and their sulphur analogues using the Biginelli reaction. This method involves short reaction time, easy separation, high yields and purity of products.

  9. Generation of Oxidants From the Reaction of Nanoparticulate Zero-Valent Iron and Oxygen for the use in Contaminant Remediation

    NASA Astrophysics Data System (ADS)

    Keenan, C. R.; Lee, C.; Sedlak, D. L.

    2007-12-01

    The reaction of zero-valent iron (ZVI) with oxygen can lead to the formation of oxidants, which may be used to transform recalcitrant contaminants including non-polar organics and certain metals. Nanoparticulate iron might provide a practical mechanism of remediating oxygen-containing groundwater and contaminated soil. To gain insight into the reaction mechanism and to quantify the yield of oxidants, experiments were performed with model organic compounds in the presence of nanoparticulate zero-valent iron and oxygen. At pH values below 5, ZVI nanoparticles were oxidized within 30 minutes with a stoichiometry of approximately two Fe0 oxidized per O2 consumed. Using the oxidation of methanol and ethanol to formaldehyde and acetaldehyde, respectively, we found that less than 2% of the consumed oxygen was converted to reactive oxidants under acidic conditions. The yield of aldehydes increased with pH up to pH 7, with maximum oxidant yields of around 5% relative to the mass of ZVI added. The increase of aldehyde yield with pH was attributable to changes in the processes responsible for oxidant production. At pH values below 5, the corrosion of ZVI by oxygen produces hydrogen peroxide, which subsequently reacts with ferrous iron [Fe(II)] via the Fenton reaction. At higher pH values, the aldehydes are produced when Fe(II), the initial product of ZVI oxidation, reacts with oxygen. The decrease in oxidant yield at pH values above 7 may be attributable to precipitation of Fe(II). The oxidation of benzoic acid and 2-propanol to para-hydroxybenzoic acid and acetone, respectively, followed a very different trend compared to the primary alcohols. In both cases, the highest product yields (approximately 2% with respect to ZVI added) were observed at pH 3. Yields decreased with increasing pH, with no oxidized product detected at neutral pH. These results suggest that two different oxidants may be produced by the system: hydroxyl radical (OH-·) at acidic pH and a more selective

  10. Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts.

    PubMed

    Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

    2015-05-01

    An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the

  11. Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

    NASA Astrophysics Data System (ADS)

    Barry, Louse; Copley, Mark; Holmes, Justin D.; Otway, David J.; Kazakova, Olga; Morris, Michael A.

    2007-12-01

    Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO 2:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.

  12. Development and characterization of nanoparticulate formulation of a water soluble prodrug of dexamethasone by HIP complexation

    PubMed Central

    Gaudana, Ripal; Parenky, Ashwin; Vaishya, Ravi; Samanta, Swapan K.; Mitra, Ashim K.

    2015-01-01

    The objective of this study was to develop and characterize a nanoparticulate-based sustained release formulation of a water soluble dipeptide prodrug of dexamethasone, valine–valine-dexamethasone (VVD). Being hydrophilic in nature, it readily leaches out in the external aqueous medium and hence partitions poorly into the polymeric matrix resulting in minimal entrapment in nanoparticles. Hence, hydrophobic ion pairing (HIP) complexation of the prodrug was employed with dextran sulphate as a complexing polymer. A novel, solid in oil in water emulsion method was employed to encapsulate the prodrug in HIP complex form in poly(lactic-co-glycolic acid) matrix. Nanoparticles were characterized with respect to size, zeta potential, crystallinity of entrapped drug and surface morphology. A significant enhancement in the entrapment of the prodrug in nanoparticles was achieved. Finally, a simple yet novel method was developed which can also be applicable to encapsulate other charged hydrophilic molecules, such as peptides and proteins. PMID:20939702

  13. Nanoparticulated docetaxel exerts enhanced anticancer efficacy and overcomes existing limitations of traditional drugs

    PubMed Central

    Choi, Jinhyang; Ko, Eunjung; Chung, Hye-Kyung; Lee, Jae Hee; Ju, Eun Jin; Lim, Hyun Kyung; Park, Intae; Kim, Kab-Sig; Lee, Joo-Hwan; Son, Woo-Chan; Lee, Jung Shin; Jung, Joohee; Jeong, Seong-Yun; Song, Si Yeol; Choi, Eun Kyung

    2015-01-01

    Nanoparticulation of insoluble drugs improves dissolution rate, resulting in increased bioavailability that leads to increased stability, better efficacy, and reduced toxicity of drugs. Docetaxel (DTX), under the trade name Taxotere™, is one of the representative anticancer chemotherapeutic agents of this era. However, this highly lipophilic and insoluble drug has many adverse effects. Our novel and widely applicable nanoparticulation using fat and supercritical fluid (NUFS™) technology enabled successful nanoscale particulation of DTX (Nufs-DTX). Nufs-DTX showed enhanced dissolution rate and increased aqueous stability in water. After confirming the preserved mechanism of action of DTX, which targets microtubules, we showed that Nufs-DTX exhibited similar effects in proliferation and clonogenic assays using A549 cells. Interestingly, we observed that Nufs-DTX had a greater in vivo tumor growth delay effect on an A549 xenograft model than Taxotere™, which was in agreement with the improved drug accumulation in tumors according to the biodistribution result, and was caused by the enhanced permeability and retention (EPR) effect. Although both Nufs-DTX and Taxotere™ showed negative results for our administration dose in the hematologic toxicity test, Nufs-DTX showed much less toxicity than Taxotere™ in edema, paralysis, and paw-withdrawal latency on a hot plate analysis that are regarded as indicators of fluid retention, peripheral neuropathy, and thermal threshold, respectively, for toxicological tests. In summary, compared with Taxotere™, Nufs-DTX, which was generated by our new platform technology using lipid, supercritical fluid, and carbon dioxide (CO2), maintained its biochemical properties as a cytotoxic agent and had better tumor targeting ability, better in vivo therapeutic effect, and less toxicity, thereby overcoming the current hurdles of traditional drugs. PMID:26457052

  14. Electrohydrodynamic atomization: A two-decade effort to produce and process micro-/nanoparticulate materials

    PubMed Central

    Xie, Jingwei; Jiang, Jiang; Davoodi, Pooya; Srinivasan, M. P.; Wang, Chi-Hwa

    2014-01-01

    Electrohydrodynamic atomization (EHDA), also called electrospray technique, has been studied for more than one century. However, since 1990s it has begun to be used to produce and process micro-/nanostructured materials. Owing to the simplicity and flexibility in EHDA experimental setup, it has been successfully employed to generate particulate materials with controllable compositions, structures, sizes, morphologies, and shapes. EHDA has also been used to deposit micro- and nanoparticulate materials on surfaces in a well-controlled manner. All these attributes make EHDA a fascinating tool for preparing and assembling a wide range of micro- and nanostructured materials which have been exploited for use in pharmaceutics, food, and healthcare to name a few. Our goal is to review this field, which allows scientists and engineers to learn about the EHDA technique and how it might be used to create, process, and assemble micro-/nanoparticulate materials with unique and intriguing properties. We begin with a brief introduction to the mechanism and setup of EHDA technique. We then discuss issues critical to successful application of EHDA technique, including control of composition, size, shape, morphology, structure of particulate materials and their assembly. We also illustrate a few of the many potential applications of particulate materials, especially in the area of drug delivery and regenerative medicine. Next, we review the simulation and modeling of Taylor cone-jet formation for a single and co-axial nozzle. The mathematical modeling of particle transport and deposition is presented to provide a deeper understanding of the effective parameters in the preparation, collection and pattering processes. We conclude this article with a discussion on perspectives and future possibilities in this field. PMID:25684778

  15. Net methylation of mercury in estuarine sediment microcosms amended with dissolved, nanoparticulate, and microparticulate mercuric sulfides.

    PubMed

    Zhang, Tong; Kucharzyk, Katarzyna H; Kim, Bojeong; Deshusses, Marc A; Hsu-Kim, Heileen

    2014-08-19

    The production of methylmercury (MeHg) by anaerobic microorganisms depends in part on the speciation and bioavailability of inorganic mercury to these organisms. Our previous work with pure cultures of methylating bacteria has demonstrated that the methylation potential of mercury decreased during the aging of mercuric sulfides (from dissolved to nanoparticulate and microcrystalline HgS). The objective of this study was to understand the relationship between mercury sulfide speciation and methylation potential in experiments that more closely simulate the complexity of sediment settings. The study involved sediment slurry microcosms that represented a spectrum of salinities in an estuary and were each amended with different forms of mercuric sulfides: dissolved Hg and sulfide, nanoparticulate HgS (3-4 nm in diameter), and microparticulate HgS (>500 nm). The results indicated that net MeHg production was influenced by both the activity of sulfate-reducing microorganisms (roughly represented by the rate of sulfate loss) and the bioavailability of mercury. In the presence of abundant sulfate and carbon sources (supporting relatively high microbial activity), net MeHg production in the slurries amended with dissolved Hg was greater than in slurries amended with nano-HgS, similar to previous experiments with pure bacterial cultures. In microcosms with minimal microbial activity (indicated by low rates of sulfate loss), the addition of either dissolved Hg or nano-HgS resulted in similar amounts of net MeHg production. For all slurries receiving micro-HgS, MeHg production did not exceed abiotic controls. In slurries amended with dissolved and nano-HgS, mercury was mainly partitioned to bulk-scale mineral particles and colloids, indicating that Hg bioavailability was not simply related to dissolved Hg concentration or speciation. Overall, the results suggest that models for mercury methylation potential in the environment will need to balance the relative contributions of

  16. Electronic structures of Pt-Co and Pt-Ru alloys for CO-tolerant anode catalysts in polymer electrolyte fuel cells studied by EC-XPS.

    PubMed

    Wakisaka, Mitsuru; Mitsui, Satoshi; Hirose, Yoshikazu; Kawashima, Katsura; Uchida, Hiroyuki; Watanabe, Masahiro

    2006-11-23

    CO tolerance at pure Pt, Pt-Co, and Pt-Ru alloys was investigated by X-ray photoelectron spectroscopy combined with an electrochemical cell (EC-XPS) in order to discover a hint for designing higher performance anode catalysts. After the electrochemical stabilization and/or CO adsorption, these electrodes were immediately transferred to the XPS chamber without exposure to air to avoid contamination of the surfaces. It was revealed that alloying with Co or Ru modified the electronic structures of Pt atoms, resulting in a positive core level (CL) shift of Pt 4f(7/2) which could weaken the Pt-CO interaction. For the Pt-Co alloy electrode, the Pt 4f(7/2) CL shift remained after the electrochemical stabilization despite Co dissolution and formation of a Pt skin layer. Changes in surface core level shifts (DeltaSCLSs) induced by CO adsorption were evaluated and related to the CO adsorption energy. The values of DeltaSCLS at these alloys were smaller than that of pure Pt, indicating that Ru and Co are effective elements to weaken the bond strength of Pt-CO. PMID:17107203

  17. Influence of polymolybdate adsorbates on electrooxidation of ethanol at PtRu nanoparticles: Combined electrochemical, mass spectrometric and X-ray photoelectron spectroscopic studies

    NASA Astrophysics Data System (ADS)

    Gralec, Barbara; Lewera, Adam; Kulesza, Pawel J.

    2016-05-01

    The role Keggin-type phosphomolybdate (PMo12O403-) ions (adsorbed on carbon-supported PtRu, PtRu/C) on electrooxidation of ethanol is addressed here. The combined results obtained using Differential Electrochemical Mass Spectrometry, X-ray Photoelectron Spectroscopy and Cyclic Voltammetry are consistent with the view that presence of the Keggin-type polyoxometallate, phosphomolybdate, ions (adsorbates) leads to enlargement of the current densities associated with electrooxidation of ethanol at potentials greater than 700 mV vs. RHE. This increase of the anodic currents is correlated with the higher acetaldehyde yield which is likely to reflect changes in the reaction kinetics (e.g. more dynamic dehydrogenation of ethanol leading to acetaldehyde) or in the reaction mechanism defined by the preferential surface modification resulting not only in faster kinetics but also in higher selectivity with respect to acetaldehyde production. It is apparent from the spectroscopic data that modification of PtRu/C nanoparticles with phosphomolybdate ions leads to suppression of the formation of Ru surface oxides.

  18. Active radar guides missile to its target: receptor-based targeted treatment of hepatocellular carcinoma by nanoparticulate systems.

    PubMed

    Yan, Jing-Jun; Liao, Jia-Zhi; Lin, Ju-Sheng; He, Xing-Xing

    2015-01-01

    Patients with hepatocellular carcinoma (HCC) usually present at advanced stages and do not benefit from surgical resection, so drug therapy should deserve a prominent place in unresectable HCC treatment. But chemotherapy agents, such as doxorubicin, cisplatin, and paclitaxel, frequently encounter important problems such as low specificity and non-selective biodistribution. Recently, the development of nanotechnology led to significant breakthroughs to overcome these problems. Decorating the surfaces of nanoparticulate-based drug carriers with homing devices has demonstrated its potential in concentrating chemotherapy agents specifically to HCC cells. In this paper, we reviewed the current status of active targeting strategies for nanoparticulate systems based on various receptors such as asialoglycoprotein receptor, transferrin receptor, epidermal growth factor receptor, folate receptor, integrin, and CD44, which are abundantly expressed on the surfaces of hepatocytes or liver cancer cells. Furthermore, we pointed out their merits and defects and provided theoretical references for further research. PMID:25424700

  19. Zn Sorption Mechanisms onto Sheathed Leptothrix Discophora and the Impact of the Nanoparticulate Biogenic Mn Oxide Coating

    SciTech Connect

    Boonfueng, T.; Axe, L; Yee, N; Hahn, D; Ndiba, P

    2009-01-01

    Zinc sorption on sheathed Leptothrix discophora bacterium, the isolated extracellular polymeric substances (EPS) sheath, and Mn oxide-coated bacteria was investigated with macroscopic and spectroscopic techniques. Complexation with L. discophora was dominated by the outer membrane phosphoryl groups of the phospholipid bilayer while sorption to isolated EPS was dominated by carboxyl groups. Precipitation of nanoparticulate Mn oxide coatings on the cell surface increased site capacity by over twenty times with significant increase in metal sorption. XAS analysis of Zn sorption in the coated system showed Mn oxide phase contributions of 18 to 43% through mononuclear inner-sphere complexes. The coordination environments in coprecipitation samples were identical to those of sorption samples, indicating that, even in coprecipitation, Zn is not incorporated into the Mn oxide structure. Rather, through enzymatic oxidation by L. discophora, Mn(II) is oxidized and precipitated onto the biofilm providing a large surface for metal sequestration. The nanoparticulate Mn oxide coating exhibited significant microporosity (75%) suggesting contributions from intraparticle diffusion. Transient studies conducted over 7 months revealed a 170% increase in Zn loading. However, the intraparticle diffusivity of 10{sup -19} cm{sup 2} s{sup -1} is two orders of magnitude smaller than that for abiotic Mn oxide which we attribute to morphological changes such as reduced pore sizes in the nanoparticulate oxide. Our results demonstrate that the cell-bound Mn oxide particles can sorb significant amounts of Zn over long periods of time representing an important surface for sequestration of metal contaminants.

  20. Zn sorption mechanisms onto sheathed Leptothrix discophora and the impact of the nanoparticulate biogenic Mn oxide coating.

    PubMed

    Boonfueng, Thipnakarin; Axe, Lisa; Yee, Nathan; Hahn, Dittmar; Ndiba, Peter K

    2009-05-15

    Zinc sorption on sheathed Leptothrix discophora bacterium, the isolated extracellular polymeric substances (EPS) sheath, and Mn oxide-coated bacteria was investigated with macroscopic and spectroscopic techniques. Complexation with L. discophora was dominated by the outer membrane phosphoryl groups of the phospholipid bilayer while sorption to isolated EPS was dominated by carboxyl groups. Precipitation of nanoparticulate Mn oxide coatings on the cell surface increased site capacity by over twenty times with significant increase in metal sorption. XAS analysis of Zn sorption in the coated system showed Mn oxide phase contributions of 18 to 43% through mononuclear inner-sphere complexes. The coordination environments in coprecipitation samples were identical to those of sorption samples, indicating that, even in coprecipitation, Zn is not incorporated into the Mn oxide structure. Rather, through enzymatic oxidation by L. discophora, Mn(II) is oxidized and precipitated onto the biofilm providing a large surface for metal sequestration. The nanoparticulate Mn oxide coating exhibited significant microporosity (75%) suggesting contributions from intraparticle diffusion. Transient studies conducted over 7 months revealed a 170% increase in Zn loading. However, the intraparticle diffusivity of 10(-19) cm(2) s(-1) is two orders of magnitude smaller than that for abiotic Mn oxide which we attribute to morphological changes such as reduced pore sizes in the nanoparticulate oxide. Our results demonstrate that the cell-bound Mn oxide particles can sorb significant amounts of Zn over long periods of time representing an important surface for sequestration of metal contaminants. PMID:19268965

  1. Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram; Whitacre, Jay

    2008-01-01

    Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization.

  2. Advances in direct oxidation methanol fuel cells

    NASA Technical Reports Server (NTRS)

    Surampudi, S.; Narayanan, S. R.; Vamos, E.; Frank, H.; Halpert, G.; Laconti, Anthony B.; Kosek, J.; Prakash, G. K. Surya; Olah, G. A.

    1993-01-01

    Fuel cells that can operate directly on fuels such as methanol are attractive for low to medium power applications in view of their low weight and volume relative to other power sources. A liquid feed direct methanol fuel cell has been developed based on a proton exchange membrane electrolyte and Pt/Ru and Pt catalyzed fuel and air/O2 electrodes, respectively. The cell has been shown to deliver significant power outputs at temperatures of 60 to 90 C. The cell voltage is near 0.5 V at 300 mA/cm(exp 2) current density and an operating temperature of 90 C. A deterrent to performance appears to be methanol crossover through the membrane to the oxygen electrode. Further improvements in performance appear possible by minimizing the methanol crossover rate.

  3. Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts

    NASA Astrophysics Data System (ADS)

    Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

    2015-04-01

    An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the

  4. Electrophoretic deposition of TiO2/Er3+ nanoparticulate sols.

    PubMed

    Borlaf, Mario; Colomer, María Teresa; Cabello, Fátima; Serna, Rosalia; Moreno, Rodrigo

    2013-02-14

    TiO(2) and TiO(2)/Er(3+) nanoparticulate sols were obtained by the colloidal sol-gel route. Thanks to the combination of three optical techniques (laser diffraction, LD, dynamic light scattering, DLS, and multiple light scattering, MLS), the peptization time was quantified, demonstrating that erbium(III) ions retard the process. The isoelectric point of TiO(2) shifts up to higher pH's when Er(3+) ions are present, which suggests that they are adsorbed onto the surface of the TiO(2) nanoparticles. Moreover, the viscosity of the sols increases when the erbium(III) amount increases. The xerogels obtained from each sol were characterized by XRD and HRTEM, obtaining in all cases anatase as the major phase, although traces of brookite were also present. In the EPD experiments, the addition of ethanol was necessary to reduce the water hydrolysis and facilitate the drying process. As a result, transparent thin films were obtained at short times and low current densities and opal films for larger current densities and deposition times; in addition, the thickness, measured by ellipsometry, increased gradually, but the refractive index did not change significantly (1.9-2). The topography profile of the films and the particle size were obtained by atomic force microscopy (AFM), giving similar values to those measured by DLS, indicating that the addition of ethanol helps to maintain stabilization without further agglomeration or sedimentation. PMID:22799268

  5. Nonagonistic Dectin-1 ligand transforms CpG into a multitask nanoparticulate TLR9 agonist

    PubMed Central

    Kobiyama, Kouji; Aoshi, Taiki; Narita, Hirotaka; Kuroda, Etsushi; Hayashi, Masayuki; Tetsutani, Kohhei; Koyama, Shohei; Mochizuki, Shinichi; Sakurai, Kazuo; Katakai, Yuko; Yasutomi, Yasuhiro; Saijo, Shinobu; Iwakura, Yoichiro; Akira, Shizuo; Coban, Cevayir; Ishii, Ken J.

    2014-01-01

    CpG DNA, a ligand for Toll-like receptor 9 (TLR9), has been one of the most promising immunotherapeutic agents. Although there are several types of potent humanized CpG oligodeoxynucleotide (ODN), developing “all-in-one” CpG ODNs activating both B cells and plasmacytoid dendritic cells forming a stable nanoparticle without aggregation has not been successful. In this study, we generated a novel nanoparticulate K CpG ODN (K3) wrapped by the nonagonistic Dectin-1 ligand schizophyllan (SPG), K3-SPG. In sharp contrast to K3 alone, K3-SPG stimulates human peripheral blood mononuclear cells to produce a large amount of both type I and type II IFN, targeting the same endosome where IFN-inducing D CpG ODN resides without losing its K-type activity. K3-SPG thus became a potent adjuvant for induction of both humoral and cellular immune responses, particularly CTL induction, to coadministered protein antigens without conjugation. Such potent adjuvant activity of K3-SPG is attributed to its nature of being a nanoparticle rather than targeting Dectin-1 by SPG, accumulating and activating antigen-bearing macrophages and dendritic cells in the draining lymph node. K3-SPG acting as an influenza vaccine adjuvant was demonstrated in vivo in both murine and nonhuman primate models. Taken together, K3-SPG may be useful for immunotherapeutic applications that require type I and type II IFN as well as CTL induction. PMID:24516163

  6. Nonagonistic Dectin-1 ligand transforms CpG into a multitask nanoparticulate TLR9 agonist.

    PubMed

    Kobiyama, Kouji; Aoshi, Taiki; Narita, Hirotaka; Kuroda, Etsushi; Hayashi, Masayuki; Tetsutani, Kohhei; Koyama, Shohei; Mochizuki, Shinichi; Sakurai, Kazuo; Katakai, Yuko; Yasutomi, Yasuhiro; Saijo, Shinobu; Iwakura, Yoichiro; Akira, Shizuo; Coban, Cevayir; Ishii, Ken J

    2014-02-25

    CpG DNA, a ligand for Toll-like receptor 9 (TLR9), has been one of the most promising immunotherapeutic agents. Although there are several types of potent humanized CpG oligodeoxynucleotide (ODN), developing "all-in-one" CpG ODNs activating both B cells and plasmacytoid dendritic cells forming a stable nanoparticle without aggregation has not been successful. In this study, we generated a novel nanoparticulate K CpG ODN (K3) wrapped by the nonagonistic Dectin-1 ligand schizophyllan (SPG), K3-SPG. In sharp contrast to K3 alone, K3-SPG stimulates human peripheral blood mononuclear cells to produce a large amount of both type I and type II IFN, targeting the same endosome where IFN-inducing D CpG ODN resides without losing its K-type activity. K3-SPG thus became a potent adjuvant for induction of both humoral and cellular immune responses, particularly CTL induction, to coadministered protein antigens without conjugation. Such potent adjuvant activity of K3-SPG is attributed to its nature of being a nanoparticle rather than targeting Dectin-1 by SPG, accumulating and activating antigen-bearing macrophages and dendritic cells in the draining lymph node. K3-SPG acting as an influenza vaccine adjuvant was demonstrated in vivo in both murine and nonhuman primate models. Taken together, K3-SPG may be useful for immunotherapeutic applications that require type I and type II IFN as well as CTL induction. PMID:24516163

  7. Nervous system effects of dissolved and nanoparticulate cadmium in rats in subacute exposure.

    PubMed

    Horváth, Edina; Oszlánczi, Gábor; Máté, Zsuzsanna; Szabó, Andrea; Kozma, Gábor; Sápi, András; Kónya, Zoltán; Paulik, Edit; Nagymajtényi, László; Papp, András

    2011-07-01

    Cadmium, a toxic heavy metal with various applications in technology, can affect people both by environmental (foodborne) and occupational (inhalation) exposure and can cause nervous system damage. To model this, rats were subacutely treated either with CdCl(2) solution per os (3.0 mg kg(-1) b.w.) or nanoparticulate CdO(2) (particle size ca 65 nm) by intratracheal instillation (0.04 mg kg(-1) b.w.) alone or in sequential combination. Nervous system effects were observed at different levels of function (open field behavior, cortical electrical activity, nerve action potential) and some general toxicological indicators were also measured. Three weeks of oral plus one week of intratracheal exposure caused significant reduction of body weight gain and open field motility. Lengthening of latency of sensory evoked potentials, observed in all treated rats, was also the most significant in the group receiving oral plus intratracheal treatment. Conduction velocity of the tail nerve was likewise decreased in all treated groups. Several of the effects pointed to a potentiating interaction between the two forms of Cd. Modeling environmental and occupational Cd exposure by oral and intratracheal application in rats was feasible, with results suggesting serious negative health effects in humans suffering such a combined exposure. PMID:21351111

  8. Mechanical degradation of TiO2 nanotubes with and without nanoparticulate silver coating.

    PubMed

    Shivaram, Anish; Bose, Susmita; Bandyopadhyay, Amit

    2016-06-01

    The primary objective of this research was to evaluate the extent of mechanical degradation on TiO2 nanotubes on Ti with and without nano-particulate silver coating using two different lengths of TiO2 nanotubes-300nm and ~1µm, which were fabricated on commercially pure Titanium (cp-Ti) rods using anodization method using two different electrolytic mediums-(1) deionized (DI) water with 1% HF, and (2) ethylene glycol with 1% HF, 0.5wt% NH4F and 10% DI water. Nanotubes fabricated rods were implanted into equine cadaver bone to evaluate mechanical damage at the surface. Silver was electrochemically deposited on these nanotubes and using a release study, silver ion concentrations were measured before and after implantation, followed by surface characterization using a Field Emission Scanning Electron Microscope (FESEM). In vitro cell-material interaction study was performed using human fetal osteoblast cells (hFOB) to understand the effect of silver coating using an MTT assay for proliferation and to determine any cytotoxic effect on the cells and to study its biocompatibility. No significant damage due to implantation was observed for nanotubes up to ~1µm length under current experimental conditions. Cell-materials interaction showed no cytotoxic effects on the cells due to silver coating and anodization of samples. PMID:27017285

  9. Effect of nanoparticulate bioactive glass particles on bioactivity and cytocompatibility of poly(3-hydroxybutyrate) composites

    PubMed Central

    Misra, Superb K.; Ansari, Tahera; Mohn, Dirk; Valappil, Sabeel P.; Brunner, Tobias J.; Stark, Wendelin J.; Roy, Ipsita; Knowles, Jonathan C.; Sibbons, Paul D.; Jones, Eugenia Valsami; Boccaccini, Aldo R.; Salih, Vehid

    2010-01-01

    This work investigated the effect of adding nanoparticulate (29 nm) bioactive glass particles on the bioactivity, degradation and in vitro cytocompatibility of poly(3-hydroxybutyrate) (P(3HB)) composites/nano-sized bioactive glass (n-BG). Two different concentrations (10 and 20 wt %) of nanoscale bioactive glass particles of 45S5 Bioglass composition were used to prepare composite films. Several techniques (Raman spectroscopy, scanning electron microscopy, atomic force microscopy, energy dispersive X-ray) were used to monitor their surface and bioreactivity over a 45-day period of immersion in simulated body fluid (SBF). All results suggested the P(3HB)/n-BG composites to be highly bioactive, confirmed by the formation of hydroxyapatite on material surfaces upon immersion in SBF. The weight loss and water uptake were found to increase on increasing bioactive glass content. Cytocompatibility study (cell proliferation, cell attachment, alkaline phosphatase activity and osteocalcin production) using human MG-63 osteoblast-like cells in osteogenic and non-osteogenic medium showed that the composite substrates are suitable for cell attachment, proliferation and differentiation. PMID:19640877

  10. Transport of polymeric nanoparticulate drug delivery systems in the proximity of silica and sand.

    PubMed

    Chen, I-Cheng; Zhang, Ming; Teipel, Blake; de Araujo, Isa Silveira; Yegin, Yagmur; Akbulut, Mustafa

    2015-03-17

    The contamination of the environment with traditional therapeutics due to metabolic excretion, improper disposal, and industrial waste has been well-recognized. However, knowledge of the environmental distribution and fate of emerging classes of nanomedicine is scarce. This work investigates the effect of surface chemistry of polymeric nanoparticulate drug delivery systems (PNDDS) on their adsorption dynamics and transport in the vicinity of environmentally relevant surfaces for a concentration comparable with hospital and pharmaceutical manufacturing effluents. To this end, five different types of paclitaxel-based nanomedicine having different polymer stabilizers were employed. Their transport behavior was characterized via quartz crystal microbalance, sand column, spectrofluorometry, and dynamic light scattering techniques. PNDDS having positive zeta-potential displayed strong adsorption onto silica surfaces and no mobility in porous media of quartz sand, even in the presence of humic acid. The mobility of negatively charged PNDDS strongly depended on the amount and type of salt present in the aqueous media: Without any salt, such PNDDS demonstrated no adsorption on silica surfaces and high levels of mobility in sand columns. The presence of CaCl2 and CaSO4, even at low ionic strengths (i.e. 10 mM), induced PNDDS adsorption on silica surfaces and strongly limited the mobility of such PNDSS in sand columns. PMID:25695909

  11. Why extreme dilutions reach non-zero asymptotes: a nanoparticulate hypothesis based on froth flotation.

    PubMed

    Chikramane, Prashant S; Kalita, Dhrubajyoti; Suresh, Akkihebbal K; Kane, Shantaram G; Bellare, Jayesh R

    2012-11-13

    Extreme dilutions, especially homeopathic remedies of 30c, 200c, and higher potencies, are prepared by a process of serial dilution of 1:100 per step. As a result, dilution factors of 10(60), 10(400), or even greater are achieved. Therefore, both the presence of any active ingredient and the therapeutic efficacy of these medicines have been contentious because the existence of even traces of the starting raw materials in them is inconceivable. However, physicochemical studies of these solutions have unequivocally established the presence of the starting raw materials in nanoparticulate form even in these extreme (super-Avogadro, >10(23)) dilutions. In this article, we propose and validate a hypothesis to explain how nanoparticles are retained even at such enormous dilution levels. We show that once the bulk concentration is below a threshold level of a few nanograms/milliliter (ng/mL), at the end of each dilution step, all of the nanoparticles levitate to the surface and are accommodated as a monolayer at the top. This dominant population at the air-liquid interface is preserved and carried to the subsequent step, thereby forming an asymptotic concentration. Thus, all dilutions are only apparent and not real in terms of the concentrations of the starting raw materials. PMID:23083226

  12. Nanoparticulate carbon black in cigarette smoke induces DNA cleavage and Th17-mediated emphysema

    PubMed Central

    You, Ran; Lu, Wen; Shan, Ming; Berlin, Jacob M; Samuel, Errol LG; Marcano, Daniela C; Sun, Zhengzong; Sikkema, William KA; Yuan, Xiaoyi; Song, Lizhen; Hendrix, Amanda Y; Tour, James M; Corry, David B; Kheradmand, Farrah

    2015-01-01

    Chronic inhalation of cigarette smoke is the major cause of sterile inflammation and pulmonary emphysema. The effect of carbon black (CB), a universal constituent of smoke derived from the incomplete combustion of organic material, in smokers and non-smokers is less known. In this study, we show that insoluble nanoparticulate carbon black (nCB) accumulates in human myeloid dendritic cells (mDCs) from emphysematous lung and in CD11c+ lung antigen presenting cells (APC) of mice exposed to smoke. Likewise, nCB intranasal administration induced emphysema in mouse lungs. Delivered by smoking or intranasally, nCB persisted indefinitely in mouse lung, activated lung APCs, and promoted T helper 17 cell differentiation through double-stranded DNA break (DSB) and ASC-mediated inflammasome assembly in phagocytes. Increasing the polarity or size of CB mitigated many adverse effects. Thus, nCB causes sterile inflammation, DSB, and emphysema and explains adverse health outcomes seen in smokers while implicating the dangers of nCB exposure in non-smokers. DOI: http://dx.doi.org/10.7554/eLife.09623.001 PMID:26437452

  13. Influence of Particle Size Distribution on Micromechanical Properties of thin Nanoparticulate Coatings

    NASA Astrophysics Data System (ADS)

    Barth, Nina; Schilde, Carsten; Kwade, Arno

    In this study the production of thin nanoparticulate coatings on solid stainless-steel substrates using dip-coating was investigated. Defined particle sizes and particle size distributions of Al2O3-nanoparticles were adjusted by stirred media milling using various operating parameters. Using nanoindentation the influence of particle size and width of the particle size distribution on the mechanical properties was investigated. In particular the establishment of nanoindentation routines for particulate thin films in contrast to hard coatings is discussed. Nanoindentation appears to be an efficient method for analysing mechanical properties of said thin coatings. It will be shown, that the influence of the substrate can be neglected for small indent depth while the coating's surface roughness influences the employed routine of the nanoindentation. The effect of the median particle size and the width of the particle size distribution on the coating structure and the micromechanical coating properties will be discussed. As a result, the maximum indentation force decreases with decreasing particle size but rises again once the nanoparticles reach very small sizes. A change in the width of the particle size distribution influences the micromechanical properties and coating structure as well.

  14. Ice sheets as a significant source of highly reactive nanoparticulate iron to the oceans.

    PubMed

    Hawkings, Jon R; Wadham, Jemma L; Tranter, Martyn; Raiswell, Rob; Benning, Liane G; Statham, Peter J; Tedstone, Andrew; Nienow, Peter; Lee, Katherine; Telling, Jon

    2014-01-01

    The Greenland and Antarctic Ice Sheets cover ~ 10% of global land surface, but are rarely considered as active components of the global iron cycle. The ocean waters around both ice sheets harbour highly productive coastal ecosystems, many of which are iron limited. Measurements of iron concentrations in subglacial runoff from a large Greenland Ice Sheet catchment reveal the potential for globally significant export of labile iron fractions to the near-coastal euphotic zone. We estimate that the flux of bioavailable iron associated with glacial runoff is 0.40-2.54 Tg per year in Greenland and 0.06-0.17 Tg per year in Antarctica. Iron fluxes are dominated by a highly reactive and potentially bioavailable nanoparticulate suspended sediment fraction, similar to that identified in Antarctic icebergs. Estimates of labile iron fluxes in meltwater are comparable with aeolian dust fluxes to the oceans surrounding Greenland and Antarctica, and are similarly expected to increase in a warming climate with enhanced melting. PMID:24845560

  15. Cytotoxic Responses and Potential Respiratory Health Effects of Carbon and Carbonaceous Nanoparticulates in the Paso del Norte Airshed Environment

    PubMed Central

    Soto, K. F.; Murr, L. E.; Garza, K. M.

    2008-01-01

    We have utilized a range of manufactured or commercial nanoparticulate materials, including surrogate carbon nano-PM along with combustion-generated carbonaceous (soot) nano-PM characteristic of environmental nano-PM (both indoor and outdoor) to investigate and compare their cytotoxic response in vitro with an immortalized human epithelial (lung model) cell line (A549). These have included nano-Ag, Al2O3, TiO2, Fe2O3, ZrO2, Si3N4, chrysotile asbestos, BC, 2 types of MWCNT-aggregate PM (MWCNT-R and MWCNT-N), and high-volume glass fiber collected soots: candle, wood, diesel (truck), tire, and 3-types of natural gas kitchen burner-generated soots: yellow (fuel-rich) flame, low-flow blue flame, and normal flow blue flame soot PM. These carbonaceous nano-PM species can be found in either the indoor and outdoor environments or microenvironments. Two-day and two-week in-vitro cultures of A549 showed cell death (or decreased cell viability) for all nanoparticulate materials, but especially significant for all but the TiO2 and candle, wood, and diesel PM. The natural gas kitchen burner combustion PM cell death response was characteristic of BC and MWCNT PM. There was no correlation with total PAH content of the soot PM. Cytokine release (IL-6, IL-8) was detected for the Ag, Fe2 O3, asbestos, BC and the MWCNT PM. Reactive oxygen species (ROS) production was also detected for Ag, Fe2 O3, ZrO2, asbestos, BC, and the MWCNT aggregate PM, as well as the natural gas kitchen burner combustion PM. TEM, FESEM, and optical microscopy examination of these nanomaterials illustrate the wide range in PM morphologies and crystallinities as well as cell morphologies. Taken together, these results illustrate proinflammatory and related respiratory health issues in relation to environmental nanoparticulates. PMID:18441401

  16. Room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders prepared by combustion reaction method

    NASA Astrophysics Data System (ADS)

    Franco, A.; Pessoni, H. V. S.; Soares, M. P.

    2014-04-01

    Nanoparticulate powders of Eu-doped ZnO with 1.0, 1.5, 2.0 and 3.0 at% Eu were synthesized by combustion reaction method using zinc nitrate, europium nitrate and urea as fuel without subsequent heat treatments. X-ray diffraction patterns (XRD) of all samples showed broad peaks consistent with the ZnO wurtzite structure. The absence of extra reflections in the diffraction patterns ensures the phase purity, except for x=0.03 that exhibits small reflection corresponding to Eu2O3 phase. The average crystallite size determined from the most prominent (1 0 1) peak of the diffraction using Scherrer's equation was in good agreement with those determined by transmission electron microscopy (TEM); being ~26 nm. The magnetic properties measurements were performed using a vibrating sample magnetometer (VSM) in magnetic fields up to 2.0 kOe at room temperature. The hysteresis loops, typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure can exist in the Eu-doped ZnO wurtzite structure at room temperature. The room temperature ferromagnetism behavior increases with the Eu3+ doping concentration. All samples exhibited the same Curie temperature (TC) around ~726 K, except for x=0.01; TC~643 K. High resolution transmission electron microscopy (HRTEM) images revealed defects/strain in the lattice and grain boundaries of Eu-doped ZnO nanoparticulate powders. The origin of room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders was discussed in terms of these defects, which increase with the Eu3+ doping concentration.

  17. Cytotoxic responses and potential respiratory health effects of carbon and carbonaceous nanoparticulates in the Paso del Norte airshed environment.

    PubMed

    Soto, K F; Murr, L E; Garza, K M

    2008-03-01

    We have utilized a range of manufactured or commercial nanoparticulate materials, including surrogate carbon nano-PM along with combustion-generated carbonaceous (soot) nano-PM characteristic of environmental nano- PM (both indoor and outdoor) to investigate and compare their cytotoxic response in vitro with an immortalized human epithelial (lung model) cell line (A549). These have included nano-Ag, Al2O3, TiO2, Fe2O3, ZrO2, Si3N4, chrysotile asbestos, BC, 2 types of MWCNT-aggregate PM (MWCNT-R and MWCNT-N), and high-volume glass fiber collected soots: candle, wood, diesel (truck), tire, and 3-types of natural gas kitchen burner-generated soots: yellow (fuel-rich) flame, low-flow blue flame, and normal flow blue flame soot PM. These carbonaceous nano-PM species can be found in either the indoor and outdoor environments or microenvironments. Two-day and two-week in-vitro cultures of A549 showed cell death (or decreased cell viability) for all nanoparticulate materials, but especially significant for all but the TiO2 and candle, wood, and diesel PM. The natural gas kitchen burner combustion PM cell death response was characteristic of BC and MWCNT PM. There was no correlation with total PAH content of the soot PM. Cytokine release (IL-6, IL-8) was detected for the Ag, Fe2 O3, asbestos, BC and the MWCNT PM. Reactive oxygen species (ROS) production was also detected for Ag, Fe2 O3, ZrO2, asbestos, BC, and the MWCNT aggregate PM, as well as the natural gas kitchen burner combustion PM. TEM, FESEM, and optical microscopy examination of these nanomaterials illustrate the wide range in PM morphologies and crystallinities as well as cell morphologies. Taken together, these results illustrate proinflammatory and related respiratory health issues in relation to environmental nanoparticulates. PMID:18441401

  18. Nanospray technology for an in situ gelling nanoparticulate powder as a wound dressing.

    PubMed

    De Cicco, Felicetta; Porta, Amalia; Sansone, Francesca; Aquino, Rita P; Del Gaudio, Pasquale

    2014-10-01

    In the current study the feasibility of the novel nano spray drying technique for the production of stable nanoparticulate dry powder, able to gel when administered locally on a wound, is explored. Gentamicin sulphate (GS) was loaded into alginate/pectin nanoparticles as highly soluble (hygroscopic) model drug with wide range antibacterial agent for wound dressing. The influence of process variables, mainly spray mesh size and feed concentration, on particle size and morphology, powder wound fluid uptake ability and gelling rate, as well as hydrogel water vapour transmission at wound site were studied. Particles morphology was spherical with few exceptions as slightly corrugated particles when the larger nozzle was used. Production of spherical nanoparticles (d50 ∼ 350 nm) in good yield (82-92%) required 4 μm spray mesh whereas 7 μm mesh produced larger wrinkled particles. Nano spray-dried particles showed high encapsulation efficiency (∼ 80%), good flowability, high fluid uptake, fast gel formation (15 min) and proper adhesiveness to fill the wound site and to remove easily the formulation after use. Moreover, moisture transmission of the in situ formed hydrogel was between 95 and 90 g/m(2)/h, an optimum range to avoid wound dehydration or occlusion phenomena. Release of the encapsulated GS, monitored as permeation rate using Franz cells in simulated wound fluid (SWF) was related to particle size and gelling rate. Sustained permeation profiles were obtained achieving total permeation of the drug between 3 and 6 days. However, all nano spray-dried formulations presented a burst effect, suitable to prevent infection spreading at the beginning of the therapy. Antimicrobial tests against Staphylococcus aureus and Pseudomonas aeruginosa showed stronger and prolonged antimicrobial effect of the nanoparticles compared to pure GS both shortly after administration and over time (till 12 days). PMID:24979533

  19. Nanoparticulate STING agonists are potent lymph node–targeted vaccine adjuvants

    PubMed Central

    Hanson, Melissa C.; Crespo, Monica P.; Abraham, Wuhbet; Moynihan, Kelly D.; Szeto, Gregory L.; Chen, Stephanie H.; Melo, Mariane B.; Mueller, Stefanie; Irvine, Darrell J.

    2015-01-01

    Cyclic dinucleotides (CDNs) are agonists of stimulator of IFN genes (STING) and have potential as vaccine adjuvants. However, cyclic di-GMP (cdGMP) injected s.c. shows minimal uptake into lymphatics/draining lymph nodes (dLNs) and instead is rapidly distributed to the bloodstream, leading to systemic inflammation. Here, we encapsulated cdGMP within PEGylated lipid nanoparticles (NP-cdGMP) to redirect this adjuvant to dLNs. Compared with unformulated CDNs, encapsulation blocked systemic dissemination and markedly enhanced dLN accumulation in murine models. Delivery of NP-cdGMP increased CD8+ T cell responses primed by peptide vaccines and enhanced therapeutic antitumor immunity. A combination of a poorly immunogenic liposomal HIV gp41 peptide antigen and NP-cdGMP robustly induced type I IFN in dLNs, induced a greater expansion of vaccine-specific CD4+ T cells, and greatly increased germinal center B cell differentiation in dLNs compared with a combination of liposomal HIV gp41 and soluble CDN. Further, NP-cdGMP promoted durable antibody titers that were substantially higher than those promoted by the well-studied TLR agonist monophosphoryl lipid A and comparable to a much larger dose of unformulated cdGMP, without the systemic toxicity of the latter. These results demonstrate that nanoparticulate delivery safely targets CDNs to the dLNs and enhances the efficacy of this adjuvant. Moreover, this approach can be broadly applied to other small-molecule immunomodulators of interest for vaccines and immunotherapy. PMID:25938786

  20. Characterization and ecological risk assessment of nanoparticulate CeO2 as a diesel fuel catalyst.

    PubMed

    Batley, Graeme E; Halliburton, Brendan; Kirby, Jason K; Doolette, Casey L; Navarro, Divina; McLaughlin, Mike J; Veitch, Colin

    2013-08-01

    Nanoparticulate cerium dioxide (nano-CeO2 ), when combusted as an additive to diesel fuel, was transformed from 6 nm to 14 nm sizes into particles near 43 nm, with no obvious change in the unit cell dimensions or crystalline form. Cerium sulfate, if formed during combustion, was below detection limits. Ceria nanoparticles were agglomerated within the soot matrix, with a mean aerodynamic diameter near 100 nm. The dissolution of cerium from the dried ceria catalyst in synthetic soft water was extremely small (<0.0006% or <0.2 µg Ce/L), with particles being highly agglomerated (<450 nm). Agglomeration was reduced in the presence of humic acid. In the combusted samples, soot was dominant, and the solubility of cerium in soft water showed an almost 100-fold increase in the <1 nm fraction compared to that before combustion. It appeared that the nano-CeO2 remained agglomerated within the soot matrix and would not be present as dispersed nanoparticles in aquatic or soil environments. Despite the increased dissolution, the solubility was not sufficient for the combusted ceria to represent a risk in aquatic ecosystems. The predicted environmental concentrations were still orders of magnitude below the predicted no effects concentration of near 1 mg/L. In the soil environment, any cerium released from soot materials would interact with natural colloids, decreasing cerium concentrations in soil solutions and further minimizing the potential risk to soil organisms. PMID:23595783

  1. A nanoparticulate liquid binding phase based DGT device for aquatic arsenic measurement.

    PubMed

    Liu, Shengwen; Qin, Nannan; Song, Jieyao; Zhang, Ya; Cai, Weiping; Zhang, Haimin; Wang, Guozhong; Zhao, Huijun

    2016-11-01

    A nanomaterials-based DGT device constructed with commercial dialysis membrane as diffusive layer and nanoparticulate Fe3O4 aqueous suspension as binding phase is developed and validated for in situ aquatic arsenic measurement. The Fe3O4NPs binding phase is capable of quantitatively accumulated both As(III) and As(V) species. As(III) and As(V) species coexist in the vast majority of environmental water samples. The large difference in diffusion coefficients of As(III) (DAs(III)=3.05×10(-7)cm(2)s(-1)) and As(V) (DAs(V)=1.63×10(-7)cm(2)s(-1)) makes the accurate DGT determination of total arsenic concentration of samples containing both species difficult. An effective diffusion coefficient (DAs¯=DAs(III)[1/(1+x)]+DAs(V)[x/(1+x)],where,x=As(V)/As(III)) approach is therefore proposed and validated for accurate DGT determination of total arsenic when As(III) and As(V) coexist. The experimental results demonstrate that for samples having As(V)/As(III) ratios between 0.1 and 0.9, the DGT determined total arsenic concentrations using DAs¯are within ±93-99% of that determined by ICP-MS. The general principle demonstrated in this work opens up a new avenue of utilizing functional nanomaterials as DGT binding phase, paving a way for developing new generation nanomaterials-based DGT devices that can be readily produced in massive numbers at low costs, facilitating the widespread use of DGT for large-scale environmental assessment and other applications. PMID:27591608

  2. K-edge ratio method for identification of multiple nanoparticulate contrast agents by spectral CT imaging

    PubMed Central

    Ghadiri, H; Ay, M R; Shiran, M B; Soltanian-Zadeh, H

    2013-01-01

    Objective: Recently introduced energy-sensitive X-ray CT makes it feasible to discriminate different nanoparticulate contrast materials. The purpose of this work is to present a K-edge ratio method for differentiating multiple simultaneous contrast agents using spectral CT. Methods: The ratio of two images relevant to energy bins straddling the K-edge of the materials is calculated using an analytic CT simulator. In the resulting parametric map, the selected contrast agent regions can be identified using a thresholding algorithm. The K-edge ratio algorithm is applied to spectral images of simulated phantoms to identify and differentiate up to four simultaneous and targeted CT contrast agents. Results: We show that different combinations of simultaneous CT contrast agents can be identified by the proposed K-edge ratio method when energy-sensitive CT is used. In the K-edge parametric maps, the pixel values for biological tissues and contrast agents reach a maximum of 0.95, whereas for the selected contrast agents, the pixel values are larger than 1.10. The number of contrast agents that can be discriminated is limited owing to photon starvation. For reliable material discrimination, minimum photon counts corresponding to 140 kVp, 100 mAs and 5-mm slice thickness must be used. Conclusion: The proposed K-edge ratio method is a straightforward and fast method for identification and discrimination of multiple simultaneous CT contrast agents. Advances in knowledge: A new spectral CT-based algorithm is proposed which provides a new concept of molecular CT imaging by non-iteratively identifying multiple contrast agents when they are simultaneously targeting different organs. PMID:23934964

  3. A phase I study of intraperitoneal nanoparticulate paclitaxel (Nanotax®) in patients with peritoneal malignancies

    PubMed Central

    Johnson, Gary A.; Maulhardt, Holly A.; Moore, Kathleen M.; McMeekin, D. S.; Schulz, Thomas K.; Reed, Gregory A.; Roby, Katherine F.; Mackay, Christine B.; Smith, Holly J.; Weir, Scott J.; Wick, Jo A.; Markman, Maurie; diZerega, Gere S.; Baltezor, Michael J.; Espinosa, Jahna; Decedue, Charles J.

    2015-01-01

    Purpose This multicenter, open-label, dose-escalating, phase I study evaluated the safety, tolerability, pharmacokinetics and preliminary tumor response of a nanoparticulate formulation of paclitaxel (Nanotax®) administered intraperitoneally for multiple treatment cycles in patients with solid tumors predominantly confined to the peritoneal cavity for whom no other curative systemic therapy treatment options were available. Methods Twenty-one patients with peritoneal malignancies received Nanotax® in a modified dose-escalation approach utilizing an accelerated titration method. All patients enrolled had previously received chemotherapeutics and undergone surgical procedures, including 33 % with optimal debulking. Six doses (50–275 mg/m2) of Cremophor-free Nanotax® were administered intraperitoneally for one to six cycles (every 28 days). Results Intraperitoneal (IP) administration of Nanotax® did not lead to increases in toxicity over that typically associated with intravenous (IV) paclitaxel. No patient reported ≥Grade 2 neutropenia and/or ≥Grade 3 neurologic toxicities. Grade 3 thrombocytopenia unlikely related to study medication occurred in one patient. The peritoneal concentration–time profile of paclitaxel rose during the 2 days after dosing to peritoneal fluid concentrations 450–2900 times greater than peak plasma drug concentrations and remained elevated through the entire dose cycle. Best response assessments were made in 16/21 patients: Four patients were assessed as stable or had no response and twelve patients had increasing disease. Five of 21 patients with advanced cancers survived longer than 400 days after initiation of Nanotax® IP treatment. Conclusions Compared to IV paclitaxel administration, Cremophor-free IP administration of Nanotax® provides higher and prolonged peritoneal paclitaxel levels with minimal systemic exposure and reduced toxicity. PMID:25898813

  4. Development and characterization of polymeric nanoparticulate delivery system for hydrophillic drug: Gemcitabine

    NASA Astrophysics Data System (ADS)

    Khurana, Jatin

    Gemcitabine is a nucleoside analogue, used in various carcinomas such as non small cell lung cancer, pancreatic cancer, ovarian cancer and breast cancer. The major setbacks to the conventional therapy with gemcitabine include its short half-life and highly hydrophilic nature. The objectives of this investigation were to develop and evaluate the physiochemical properties, drug loading and entrapment efficiency, in vitro release, cytotoxicity, and cellular uptake of polymeric nano-particulate formulations containing gemcitabine hydrochloride. The study also entailed development and validation of a high performance liquid chromatography (HPLC) method for the analysis of gemcitabine hydrochloride. A reverse phase HPLC method using a C18 Luna column was developed and validated. Alginate and Poly lactide co glycolide/Poly-epsilon-caprolactone (PLGA:PCL 80:20) nanoparticles were prepared by multiple emulsion-solvent evaporation methodology. An aqueous solution of low viscosity alginate containing gemcitabine was emulsified into 10% solution of dioctyl-sulfosuccinate in dichloro methane (DCM) by sonication. The primary emulsion was then emulsified in 0.5% (w/v) aqueous solution of polyvinyl alcohol (PVA). Calcium chloride solution (60% w/v) was used to cause cross linking of the polymer. For PLGA:PCL system, the polymer mix was dissolved in dichloromethane (DCM) and an aqueous gemcitabine (with and without sodium chloride) was emulsified under ultrasonic conditions (12-watts; 1-min). This primary emulsion was further emulsified in 2% (w/v) PVA under ultrasonic conditions (24-watts; 3-min) to prepare a multiple-emulsion (w/o/w). In both cases DCM, the organic solvent was evaporated (20- hours, magnetic-stirrer) prior to ultracentrifugation (10000-rpm for PLGA:PCL; 25000-rpm for alginate). The pellet obtained was washed thrice with de-ionized water to remove PVA and any free drug and re-centrifuged. The particles were re-suspended in de-ionized water and then lyophilized to

  5. Segmented Pt/Ru, Pt/Ni, and Pt/RuNi nanorods as model bifunctional catalysts for methanol oxidation.

    PubMed

    Liu, Fang; Lee, Jim Yang; Zhou, Wei Jiang

    2006-01-01

    Five-segment (Pt-Ru-Pt-Ru-Pt, Pt-Ni-Pt-Ni-Pt, and Pt-RuNi-Pt-RuNi-Pt) nanorods with the same overall rod length and the same total Pt segment length were prepared by sequential electrodeposition of the metals into the pores of commercially available anodic aluminum oxide (AAO) membranes. Field-emission scanning electron microscopy (FESEM) showed that the nanorods were about 210 nm in diameter and about 1.5 microm in length. The alternating Pt and oxophilic metal(s) segments could be easily differentiated in backscattered-electron images. X-ray diffraction (XRD) analysis of the nanorods indicated that Pt and Ni were polycrystalline with fcc structures, Ru was hcp, and the co-deposited RuNi adopted the nickel fcc structure with some negative shifts in the Bragg angles. The chemical states of Pt, Ru, and Ni on the nanorod surface were assayed by X-ray photoelectron spectroscopy (XPS), and the presence of Pt(0), Pt(II), Pt(IV), Ru(0), Ru(VI), Ni(0), and Ni(II) was observed. The nanorods were catalytically active for the room-temperature electrooxidation of methanol in acidic solutions. The relative rates of reaction showed the Pt-RuNi pair sites as having the lowest overpotential to dissociate water, the highest catalytic activity in methanol oxidation, and the strongest CO-tolerance in the potential window employed. The use of segmented nanorods with identifiable Pt-oxophilic metal(s) interfaces removes many of the ambiguities in the interpretation of experimental data from conventional alloy catalysts, thereby enabling a direct comparison of the activities of various types of pair sites in methanol oxidation. PMID:17193567

  6. Effect of adsorbed extracellular polymeric substances (EPS) on colloidal mobility of nanoparticulate iron oxides

    NASA Astrophysics Data System (ADS)

    Pradip Narvekar, Sneha; Totsche, Kai Uwe

    2013-04-01

    Solubility and transport of nutrients and pollutants is affected by the presence of colloidal nanoparticles (CNP) which may act as mobile geosorbents. In soils and aquifers, pure and organically modified Fe- and Mn-oxy-hydroxides are of particular importance due to their ubiquitous presence and also due to their progressive use for environmental cleanup. Stability and aggregation behavior control the mobility of CNP and depend on pH, ionic strength, and the presence of monovalent or divalent anions. In natural environments, however, iron oxides are usually covered by organic matter. Such coverage will completely change the colloidal surface properties and impose additional control on the colloidal mobility. Important sources for natural organic coatings are extracellular polymeric substances (EPS), i.e., complex mixtures of biopolymers consisting of polysaccharides and proteins and variable amounts of lipids and nucleic acids. The objective of our study was to quantify the effect of EPS coatings on the colloidal stability, mobility and reactivity of hematite by column experiments. Columns (10 cm × 5 cm) were filled with glass beads (0.25 mm ø) as porous medium and operated in sterile closed flow conditions. Nanoparticulate hematite was coated to different degrees by extracellular polymeric substances (EPS) extracted from, liquid cultures of Bacillus subtillis. The pH was kept constant at 7. The hematite particles exhibited increasing colloidal stability with increasing amounts of EPS. Critical colloidal concentration (CCC) of the particles increased from 95 mM NaCl for uncoated particles to 250 mM NaCl for coated particles. EPS coated hematite did not react with the porous medium and stayed mobile while the uncoated hematite was immobile due to adsorption to the glass beads. Also colloidally unstable hematite particles did not show any mobility. Thus the organic coatings enhanced the colloidal stability, which consecutively increased the mobility of the particles

  7. Particulate Emissions from the Combustion of Diesel Fuel with a Fuel-Borne Nanoparticulate Cerium Catalyst

    NASA Astrophysics Data System (ADS)

    Conny, J. M.; Willis, R. D.; Weinstein, J. P.; Krantz, T.; King, C.

    2013-12-01

    To address the adverse impacts on health and climate from the use of diesel-fueled vehicles, a number of technological solutions have been developed for reducing diesel soot emissions and to improve fuel economy. One such solution is the use fuel-borne metal oxide catalysts. Of current interest are commercially-available fuel additives consisting of nanoparticulate cerium oxide (CeO2). In response to the possible use of CeO2-containing fuels in on-road vehicles in the U.S., the Environmental Protection Agency is conducting research to address the potential toxicity and environmental effects of particulate CeO2 emitted with diesel soot. In this study, emissions from a diesel-fueled electric generator were size-segregated on polished silicon wafers in a nanoparticle cascade impactor. The diesel fuel contained 10 ppm Ce by weight in the form of crystalline CeO2 nanoparticles 4 nm to 7.5 nm in size. Primary CeO2 nanoparticles were observed in the diesel emissions as well as CeO2 aggregates encompassing a broad range of sizes up to at least 200 nm. We report the characterization of individual particles from the size-resolved samples with focused ion-beam scanning electron microscopy and energy-dispersive x-ray spectroscopy. Results show a dependency between the impactor size range and CeO2 agglomeration state: in the larger size fractions of the impactor (e.g., 560 nm to 1000 nm) CeO2 nanoparticles were predominantly attached to soot particles. In the smaller size fractions of the impactor (e.g., 100 nm to 320 nm), CeO2 aggregates tended to be larger and unattached to soot. The result is important because the deposition of CeO2 nanoparticles attached to soot particles in the lung or on environmental surfaces such as plant tissue will likely present different consequences than the deposition of unagglomerated CeO2 particles. Disclaimer The U.S. Environmental Protection Agency through its Office of Research and Development funded and collaborated in the research described

  8. Nanoparticulate assemblies of amphiphiles and diagnostically active materials for multimodality imaging.

    PubMed

    Mulder, Willem J M; Strijkers, Gustav J; van Tilborg, Geralda A F; Cormode, David P; Fayad, Zahi A; Nicolay, Klaas

    2009-07-21

    Modern medicine has greatly benefited from recent dramatic improvements in imaging techniques. The observation of physiological events through interactions manipulated at the molecular level offers unique insight into the function (and dysfunction) of the living organism. The tremendous advances in the development of nanoparticulate molecular imaging agents over the past decade have made it possible to noninvasively image the specificity, pharmacokinetic profiles, biodistribution, and therapeutic efficacy of many novel compounds. Several types of nanoparticles have demonstrated utility for biomedical purposes, including inorganic nanocrystals, such as iron oxide, gold, and quantum dots. Moreover, natural nanoparticles, such as viruses, lipoproteins, or apoferritin, as well as hybrid nanostructures composed of inorganic and natural nanoparticles, have been applied broadly. However, among the most investigated nanoparticle platforms for biomedical purposes are lipidic aggregates, such as liposomal nanoparticles, micelles, and microemulsions. Their relative ease of preparation and functionalization, as well as the ready synthetic ability to combine multiple amphiphilic moieties, are the most important reasons for their popularity. Lipid-based nanoparticle platforms allow the inclusion of a variety of imaging agents, ranging from fluorescent molecules to chelated metals and nanocrystals. In recent years, we have created a variety of multifunctional lipid-based nanoparticles for molecular imaging; many are capable of being used with more than one imaging technique (that is, with multimodal imaging ability). These nanoparticles differ in size, morphology, and specificity for biological markers. In this Account, we discuss the development and characterization of five different particles: liposomes, micelles, nanocrystal micelles, lipid-coated silica, and nanocrystal high-density lipoprotein (HDL). We also demonstrate their application for multimodal molecular imaging

  9. Complement activation as a bioequivalence issue relevant to the development of generic liposomes and other nanoparticulate drugs.

    PubMed

    Szebeni, Janos; Storm, Gert

    2015-12-18

    Liposomes are known to activate the complement (C) system, which can lead in vivo to a hypersensitivity syndrome called C activation-related pseudoallergy (CARPA). CARPA has been getting increasing attention as a safety risk of i.v. therapy with liposomes, whose testing is now recommended in bioequivalence evaluations of generic liposomal drug candidates. This review highlights the adverse consequences of C activation, the unique symptoms of CARPA triggered by essentially all i.v. administered liposomal drugs, and the various features of vesicles influencing this adverse immune effect. For the case of Doxil, we also address the mechanism of C activation and the opsonization vs. long circulation (stealth) paradox. In reviewing the methods of assessing C activation and CARPA, we delineate the most sensitive porcine model and an algorithm for stepwise evaluation of the CARPA risk of i.v. liposomes, which are proposed for standardization for preclinical toxicology evaluation of liposomal and other nanoparticulate drug candidates. PMID:26182876

  10. Coal and tire burning mixtures containing ultrafine and nanoparticulate materials induce oxidative stress and inflammatory activation in macrophages.

    PubMed

    Gasparotto, Juciano; Somensi, Nauana; Caregnato, Fernanda F; Rabelo, Thallita K; DaBoit, Kátia; Oliveira, Marcos L S; Moreira, José C F; Gelain, Daniel P

    2013-10-01

    Ultra-fine and nano-particulate materials resulting from mixtures of coal and non-coal fuels combustion for power generation release to the air components with toxic potential. We evaluated toxicological and inflammatory effects at cellular level that could be induced by ultrafine/nanoparticles-containing ashes from burning mixtures of coal and tires from an American power plant. Coal fly ashes (CFA) samples from the combustion of high-S coal and tire-derived fuel, the latter about 2-3% of the total fuel feed, in a 100-MW cyclone utility boiler, were suspended in the cell culture medium of RAW 264.7 macrophages. Cell viability, assessed by MTT reduction, SRB incorporation and contrast-phase microscopy analysis demonstrated that CFA did not induce acute toxicity. However, CFA at 1mg/mL induced an increase of approximately 338% in intracellular TNF-α, while release of this proinflammatory cytokine was increased by 1.6-fold. The expression of the inflammatory mediator CD40 receptor was enhanced by 2-fold, the receptor for advanced glycation endproducts (RAGE) had a 5.7-fold increase and the stress response protein HSP70 was increased nearly 12-fold by CFA at 1mg/mL. Although CFA did not induce cell death, parameters of oxidative stress and reactive species production were found to be altered at several degrees, such as nitrite accumulation (22% increase), DCFH oxidation (3.5-fold increase), catalase (5-fold increase) and superoxide dismutase (35% inhibition) activities, lipoperoxidation (4.2 fold-increase) and sulfhydryl oxidation (40% decrease in free SH groups). The present results suggest that CFA containing ultra-fine and nano-particulate materials from coal and tire combustion may induce sub-chronic cell damage, as they alter inflammatory and oxidative stress parameters at the molecular and cellular levels, but do not induce acute cell death. PMID:23856402

  11. Thin Film Catalyst Layers for Direct Methanol Fuel Cells

    NASA Technical Reports Server (NTRS)

    Witham, C. K.; Chun, W.; Ruiz, R.; Valdez, T. I.; Narayanan, S. R.

    2000-01-01

    One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

  12. Preparation of nanoparticulate Fe 2O 3—polymaleic monoester alternating Langmuir—Blodgett films with functional organic hydrophobic part

    NASA Astrophysics Data System (ADS)

    Peng, Xiao-Gang; Gao, Man-Lai; Zhao, Ying-Ying; Kang, Shi-Hai; Zhang, Yun-Hang; Zhang, Yan; Wang, De-Jun; Xiao, Liang-Zhi; Li, Tie-Jin; Chen, Hai-Yan

    1993-07-01

    An organic functional group was introduced into the inorganic nanoparticle—organic alternating LB films by the use of the polymaleic monoester with a functional lateral chain ? to replace a fatty acid. Using the polymer (PMANN), the distance between adjacent nanoparticles in the LB films is apparently decreased and the distribution of the nanoparticles in the monolayer is more homegeneous than that in the nanoparticulate Fe 2O 3—stearate monolayer. All these phenomena are ascribed to the carboxylate groups of a polymer molecule bound to two or more nanoparticles. The photovoltage response of n-type (p-type) silicon coated with a monolayer of nanoparticulate Fe 2O 3—PMANN LB films increases (decreases) for two orders.

  13. Synthesis, morphology and antifungal activity of nano-particulated amphotericin-B, ketoconazole and thymoquinone against Candida albicans yeasts and Candida biofilm.

    PubMed

    Randhawa, Mohammad A; Gondal, Mohammed A; Al-Zahrani, Al-Hosain J; Rashid, Siddique G; Ali, Ashraf

    2015-01-01

    In the current study, nano-particulated drugs-Amphotericin-B, Ketoconazole and Thymoquinone (an active ingredient of Nigella sativa)-were prepared using the ball milling technique, and their particle sizes were examined by transmission electron microscopy (TEM) and using a particle size analyzer. The grain sizes of the prepared compounds were found in between 5 to 20 nm, and exhibited quasi-spherical morphology. The antifungal activity of each nano-particulated drug was investigated in vitro against Candida albicans yeasts and Candida biofilm, and compared with their micro-structured conventional forms. Nano-sized drugs were found to be two to four times more effective in disinfecting both the Candida yeasts and Candida biofilm. The study is a first of its kind as nano-forms of drugs have not been studied against Candida and Candida biofilm before. Further investigations are required for the determination of the clinical significance of the nano-formulation of antifungal substances. PMID:25560257

  14. Chemically tuned anode with tailored aqueous hydrocarbon binder for direct methanol fuel cells.

    PubMed

    Lee, Chang Hyun; Lee, So Young; Lee, Young Moo; McGrath, James E

    2009-07-21

    An anode for direct methanol fuel cells was chemically tuned by tailoring an aqueous hydrocarbon catalyst (SPI-BT) binder instead of using a conventional perfluorinated sulfonic acid ionomer (PFSI). SPI-BT designed in triethylamine salt form showed lower proton conductivity than PFSI, but it was stable in the catalyst ink forming the aqueous colloids. The aqueous colloidal particle size of SPI-BT was much smaller than that of PFSI. The small SPI-BT colloidal particles contributed to forming small catalyst agglomerates and simultaneously reducing their pore volume. Consequently, the high filling level of binders in the pores, where Pt-Ru catalysts are mainly located on the wall and physically interconnected, resulted in increased electrochemical active surface area of the anode, leading to high catalyst utilization. In addition, the chemical affinity between the SPI-BT binder and the membrane material derived from their similar chemical structure induced a stable interface on the membrane-electrode assembly (MEA) and showed low electric resistance. Upon adding SPI-BT, the synergistic effect of high catalyst utilization, improved mass transfer behavior to Pt-Ru catalyst, and low interfacial resistance of MEA became greater than the influence of reduced proton conductivity in the electrochemical performance of single cells. The electrochemical performance of MEAs with SPI-BT anode was enhanced to almost the same degree or somewhat higher than that with PFSI at 90 degrees C. PMID:19485372

  15. Anti-biofouling polymer-decorated lutetium-based nanoparticulate contrast agents for in vivo high-resolution trimodal imaging.

    PubMed

    Liu, Zhen; Dong, Kai; Liu, Jianhua; Han, Xueli; Ren, Jinsong; Qu, Xiaogang

    2014-06-25

    Nanomaterials have gained considerable attention and interest in the development of novel and high-resolution contrast agents for medical diagnosis and prognosis in clinic. A classical urea-based homogeneous precipitation route that combines the merits of in situ thermal decomposition and surface modification is introduced to construct polyethylene glycol molecule (PEG)-decorated hybrid lutetium oxide nanoparticles (PEG-UCNPs). By utilizing the admirable optical and magnetic properties of the yielded PEG-UCNPs, in vivo up-conversion luminescence and T1 -enhanced magnetic resonance imaging of small animals are conducted, revealing obvious signals after subcutaneous and intravenous injection, respectively. Due to the strong X-ray absorption and high atomic number of lanthanide elements, X-ray computed-tomography imaging based on PEG-UCNPs is then designed and carried out, achieving excellent imaging outcome in animal experiments. This is the first example of the usage of hybrid lutetium oxide nanoparticles as effective nanoprobes. Furthermore, biodistribution, clearance route, as well as long-term toxicity are investigated in detail after intravenous injection in a murine model, indicating the overall safety of PEG-UCNPs. Compared with previous lanthanide fluorides, our nanoprobes exhibit more advantages, such as facile construction process and nearly total excretion from the animal body within a month. Taken together, these results promise the use of PEG-UCNPs as a safe and efficient nanoparticulate contrast agent for potential application in multimodal imaging. PMID:24610806

  16. Revisiting the Fundamentals in the Design and Control of Nanoparticulate Colloids in the Frame of Soft Chemistry.

    PubMed

    Uskoković, Vuk

    2013-10-01

    This review presents thoughts on some of the fundamental features of conceptual models applied in the design of fine particles in the frames of colloid and soft chemistry. A special emphasis is placed on the limitations of these models, an acknowledgment of which is vital in improving their intricacy and effectiveness in predicting the outcomes of the corresponding experimental settings. Thermodynamics of self-assembly phenomena illustrated on the examples of protein assembly and micellization is analyzed in relation to the previously elaborated thesis that each self-assembly in reality presents a co-assembly, since it implies a mutual reorganization of the assembling system and its immediate environment. Parameters used in the design of fine particles by precipitation are discussed while referring to solubility product, various measures of supersaturation levels, induction time, nucleation and crystal growth rates, interfacial energies, and the Ostwald-Lussac law of phases. Again, the main drawbacks and inadequacies of using the aforementioned parameters in tailoring the materials properties in a soft and colloidal chemical setting were particularly emphasized. The basic and practical limitations of zeta-potential analyses, routinely used to stabilize colloidal dispersions and initiate specific interactions between soft chemical entities, were also outlined. The final section of the paper reiterates the unavoidable presence of practical qualitative models in the design and control of nanoparticulate colloids, which is supported by the overwhelming complexity of quantitative relationships that govern the processes of their formation and assembly. PMID:24490052

  17. Physicochemical characterization and toxicological evaluation of plant-based anionic polymers and their nanoparticulated system for ocular delivery.

    PubMed

    Pathak, Deepa; Kumar, Prashant; Kuppusamy, Gowthamarajan; Gupta, Ankur; Kamble, Bhagyashree; Wadhwani, Ashish

    2014-12-01

    The water-soluble fractions of mucilages and gum from the seeds of fenugreek, isphagula and mango bark exudate were isolated, purified and characterized using X-ray diffraction (XRD) spectrometry, Fourier transform infrared spectroscopy (FT-IR), maldi/GC-MS, elemental analysis, 1D ((1)H and (13)C) and 2D (HMQC, COSY) nuclear magnetic resonance spectroscopy (NMR). The fenugreek mucilage was identified to be a galactomannan chain consisting of 4 units of galactose attached to the backbone of 6 mannose units in 1:1.5 ratio. The isphagula mucilage was identified to be an arabinoxylan polysaccharide chain consisting of 4 units of arabinofuranose attached to the backbone of 9 xylopyrannose units in 1:3 ratio. The mango gum showed the presence of amylose, α-arabinofuranosyl and β-galactopyranosyl, respectively. The characterized mucilages and gum were individually formulated into nanoparticulate system using their complementarily charged polymer chitosan. The particles were observed to be spherical in shape in the range of 61.5-90 nm having zetapotential between 31 and 34 mV and PDI of 0.097-0.241. The prepared nanoparticles were observed to be nonirritant and nontoxic in vitro and in vivo upto 2000 μg/ml. Therefore, these mucilages and gum can be the alternatives of anionic polymers for the ocular drug delivery system. PMID:23952497

  18. Thermal hysteresis kinetic effects of spin crossover nanoparticulated systems studied by FORC diagram method on an Ising-like model

    NASA Astrophysics Data System (ADS)

    Atitoaie, Alexandru; Stoleriu, Laurentiu; Tanasa, Radu; Stancu, Alexandru; Enachescu, Cristian

    2016-04-01

    The scientific community is manifesting a high research interest on spin crossover compounds and their recently synthesized nanoparticles, due to their various appealing properties, such as the bistability between a diamagnetic low spin state and a paramagnetic high spin state (HS), inter-switchable by temperature or pressure changes, light irradiation or magnetic field. The utility of these compounds showing hysteresis covers a broad area of applications, from the development of more efficient designs of temperature and pressure sensors to automotive and aeronautic industries and even a new type of molecular actuators. We are proposing in this work a study regarding the kinetic effects and the distribution of reversible and irreversible components on the thermal hysteresis of spin crossover nanoparticulated systems. We are considering here tridimensional systems with different sizes and also systems of nanoparticles with a Gaussian size distribution. The correlations between the kinetics of the thermal hysteresis, the distributions of sizes and intermolecular interactions and the transition temperature distributions were established by using the FORC (First Order Reversal Curves) method using a Monte Carlo technique within an Ising-like system.

  19. Spin-wave stiffness parameter in ferrimagnetic systems: Nanoparticulate powders of (Mg,Zn ) Fe2O4 mixed ferrites

    NASA Astrophysics Data System (ADS)

    Franco, A.; Pessoni, H. V. S.; Machado, F. L. A.

    2015-11-01

    We have evaluated the spin-wave stiffness parameter in nanoparticulate powders of Mg1 -xZnxFe2O4 ( 0.0 ≤x ≤0.6 ) mixed ferrites from magnetization data obtained at two different ranges of temperature: 5 -300 K and 300 -750 K . At the lower temperature range the T-dependence of the saturation magnetization, Ms, data could be fitted to the Bloch's law with T3 /2 . The spin-wave stiffness parameters D were determined from the coefficient of T3 /2 ; being ˜132 and ˜86 meVÅ for x = 0.0 and 0.6, respectively, with the corresponding exchange constant JAB of ˜1.10 and ˜0.72 meV , respectively. The values of D determined from the experimental Curie temperature Tc were ˜212 and ˜163 meVÅ2 for x = 0.0 and 0.6, respectively, with the corresponding exchange constant JAB of ˜1.77 and ˜1.30 meV . The difference in both JAB and D values obtained from the coefficient of T3 /2 and from Tc may be attributed to the fact that the magnetic measurements were performed at a different range of temperatures. The results are discussed in terms of the cation distribution among A- and B-sites of occupation on these spinel ferrites.

  20. A nanosystem for water-insoluble drugs prepared by a new technology, nanoparticulation using a solid lipid and supercritical fluid.

    PubMed

    Park, Joo Won; Yun, Jeong Min; Lee, Eun Seong; Youn, Yu Seok; Kim, Kab Sig; Oh, Young Taik; Oh, Kyung Teak

    2013-11-01

    While the number and diversity of lead compounds has increased with the development of science technologies, ca. 90 % of new chemical entities under development have shown low aqueous solubility, classified as class II or IV of the biopharmaceutics classification system (BCS). The low aqueous solubility hinders their clinical translations due to low bioavailability and dissolution-limited absorption of orally-administered drugs. Several technologies have been employed to improve the solubility of poorly water-soluble drugs. In this paper, a new method of nanoparticulation using fat and a supercritical fluid (NUFS) for the formulation of hydrophobic drugs was applied to solve the low solubility problem. A typical BCS class II drug, itraconazole, was selected and formulated with hydroxypropyl methylcellulose, emulsification, and anticoagulating agents for NUFS. The non-spherical itraconazole nanoparticles prepared by NUFS were ~300-500 nm in size with a ~15-fold improved dissolution rate compared to non-nanoparticles of itraconazole (i.e., raw itraconazole). In addition, a high drug content of ~46 % by weight and a drug loading efficiency greater than 85 % were achieved. Therefore, the new technology for nano-platforms could be a promising solution for solubilization of poorly water-soluble drugs, resulting in improved bioavailability. PMID:23780798

  1. Revisiting the Fundamentals in the Design and Control of Nanoparticulate Colloids in the Frame of Soft Chemistry1

    PubMed Central

    Uskoković, Vuk

    2013-01-01

    This review presents thoughts on some of the fundamental features of conceptual models applied in the design of fine particles in the frames of colloid and soft chemistry. A special emphasis is placed on the limitations of these models, an acknowledgment of which is vital in improving their intricacy and effectiveness in predicting the outcomes of the corresponding experimental settings. Thermodynamics of self-assembly phenomena illustrated on the examples of protein assembly and micellization is analyzed in relation to the previously elaborated thesis that each self-assembly in reality presents a co-assembly, since it implies a mutual reorganization of the assembling system and its immediate environment. Parameters used in the design of fine particles by precipitation are discussed while referring to solubility product, various measures of supersaturation levels, induction time, nucleation and crystal growth rates, interfacial energies, and the Ostwald–Lussac law of phases. Again, the main drawbacks and inadequacies of using the aforementioned parameters in tailoring the materials properties in a soft and colloidal chemical setting were particularly emphasized. The basic and practical limitations of zeta-potential analyses, routinely used to stabilize colloidal dispersions and initiate specific interactions between soft chemical entities, were also outlined. The final section of the paper reiterates the unavoidable presence of practical qualitative models in the design and control of nanoparticulate colloids, which is supported by the overwhelming complexity of quantitative relationships that govern the processes of their formation and assembly. PMID:24490052

  2. Nanoparticulate Mineralized Collagen Scaffolds and BMP-9 Induce a Long-Term Bone Cartilage Construct in Human Mesenchymal Stem Cells.

    PubMed

    Ren, Xiaoyan; Weisgerber, Daniel W; Bischoff, David; Lewis, Michael S; Reid, Russell R; He, Tong-Chuan; Yamaguchi, Dean T; Miller, Timothy A; Harley, Brendan A C; Lee, Justine C

    2016-07-01

    Engineering the osteochondral junction requires fabrication of a microenvironment that supports both osteogenesis and chondrogenesis. Multiphasic scaffold strategies utilizing a combination of soluble factors and extracellular matrix components are ideally suited for such applications. In this work, the contribution of an osteogenic nanoparticulate mineralized glycosaminoglycan scaffold (MC-GAG) and a dually chondrogenic and osteogenic growth factor, BMP-9, in the differentiation of primary human mesenchymal stem cells (hMSCs) is evaluated. Although 2D cultures demonstrate alkaline phosphatase activity and mineralization of hMSCs induced by BMP-9, MC-GAG scaffolds do not demonstrate significant differences in the collagen I expression, osteopontin expression, or mineralization. Instead, BMP-9 increases expression of collagen II, Sox9, aggrecan (ACAN), and cartilage oligomeric protein. However, the hypertrophic chondrocyte marker, collagen X, is not elevated with BMP-9 treatment. In addition, histologic analyses demonstrate that while BMP-9 does not increase mineralization, BMP-9 treatment results in an increase of sulfated glycosaminoglycans. Thus, the combination of BMP-9 and MC-GAG stimulates chondrocytic and osteogenic differentiation of hMSCs. PMID:27275929

  3. Large-scale Manufacturing of Nanoparticulate-based Lubrication Additives for Improved Energy Efficiency and Reduced Emissions

    SciTech Connect

    Erdemir, Ali

    2013-09-26

    This project was funded under the Department of Energy (DOE) Lab Call on Nanomanufacturing for Energy Efficiency and was directed toward the development of novel boron-based nanocolloidal lubrication additives for improving the friction and wear performance of machine components in a wide range of industrial and transportation applications. Argonne's research team concentrated on the scientific and technical aspects of the project, using a range of state-of-the art analytical and tribological test facilities. Argonne has extensive past experience and expertise in working with boron-based solid and liquid lubrication additives, and has intellectual property ownership of several. There were two industrial collaborators in this project: Ashland Oil (represented by its Valvoline subsidiary) and Primet Precision Materials, Inc. (a leading nanomaterials company). There was also a sub-contract with the University of Arkansas. The major objectives of the project were to develop novel boron-based nanocolloidal lubrication additives and to optimize and verify their performance under boundary-lubricated sliding conditions. The project also tackled problems related to colloidal dispersion, larger-scale manufacturing and blending of nano-additives with base carrier oils. Other important issues dealt with in the project were determination of the optimum size and concentration of the particles and compatibility with various base fluids and/or additives. Boron-based particulate additives considered in this project included boric acid (H{sub 3}BO{sub 3}), hexagonal boron nitride (h-BN), boron oxide, and borax. As part of this project, we also explored a hybrid MoS{sub 2} + boric acid formulation approach for more effective lubrication and reported the results. The major motivation behind this work was to reduce energy losses related to friction and wear in a wide spectrum of mechanical systems and thereby reduce our dependence on imported oil. Growing concern over greenhouse gas

  4. A combined in-situ and post-mortem investigation on local permanent degradation in a direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Bresciani, F.; Rabissi, C.; Zago, M.; Gazdzicki, P.; Schulze, M.; Guétaz, L.; Escribano, S.; Bonde, J. L.; Marchesi, R.; Casalegno, A.

    2016-02-01

    Performance degradation is one of the key issues hindering direct methanol fuel cell commercialization, caused by different mechanisms interplaying locally and resulting in both temporary and permanent contributions. This work proposes a systematic experimental investigation, coupling in-situ diagnostics (electrochemical and mass transport investigation) with ex-situ analyses of pristine, activated and aged components (X-ray photoelectron spectroscopy and transmission electron microscopy), with an in-plane and through-plane local resolution. Such a combined approach allows to identify on one hand the degradation mechanisms, the affected components and the presence of heterogeneities; on the other hand, it allows to quantify the effect of the major mechanisms on performance decay. Thanks to a novel procedure, temporary (21 μV h-1) and permanent degradation (59 μV h-1) are separated, distinguishing the latter in different contributions: the effects of active area loss at both at anode (9 μV h-1) and cathode (31 μV h-1), mass transport issue (15 μV h-1) and membrane decay (4 μV h-1). The post-mortem analysis highlights the effect of degradation mechanisms consistent with the in-situ analysis and reveals the presence of considerable in plane and through plane heterogeneities in: particle size growth in catalyst layers, Pt/Ru and polymer content in catalyst and diffusion layers, Pt/Ru precipitates in the membrane.

  5. Nano-crystalline thin and nano-particulate thick TiO{sub 2} layer: Cost effective sequential deposition and study on dye sensitized solar cell characteristics

    SciTech Connect

    Das, P.; Sengupta, D.; Kasinadhuni, U.; Mondal, B.; Mukherjee, K.

    2015-06-15

    Highlights: • Thin TiO{sub 2} layer is deposited on conducting substrate using sol–gel based dip coating. • TiO{sub 2} nano-particles are synthesized using hydrothermal route. • Thick TiO{sub 2} particulate layer is deposited on prepared thin layer. • Dye sensitized solar cells are made using thin and thick layer based photo-anode. • Introduction of thin layer in particulate photo-anode improves the cell efficiency. - Abstract: A compact thin TiO{sub 2} passivation layer is introduced between the mesoporous TiO{sub 2} nano-particulate layer and the conducting glass substrate to prepare photo-anode for dye-sensitized solar cell (DSSC). In order to understand the effect of passivation layer, other two DSSCs are also developed separately using TiO{sub 2} nano-particulate and compact thin film based photo-anodes. Nano-particles are prepared using hydrothermal synthesis route and the compact passivation layer is prepared by simply dip coating the precursor sol prepared through wet chemical route. The TiO{sub 2} compact layer and the nano-particles are characterised in terms of their micro-structural features and phase formation behavior. It is found that introduction of a compact TiO{sub 2} layer in between the mesoporous TiO{sub 2} nano-particulate layer and the conducting substrate improves the solar to electric conversion efficiency of the fabricated cell. The dense thin passivation layer is supposed to enhance the photo-excited electron transfer and prevent the recombination of photo-excited electrons.

  6. The Production and Export of Bioavailable Iron from Ice Sheets - the Importance of Colloidal and Nanoparticulate Phases

    NASA Astrophysics Data System (ADS)

    Hawkings, J.; Wadham, J. L.; Tranter, M.; Raiswell, R.; Benning, L. G.; Statham, P. J.; Tedstone, A.; Nienow, P. W.; Telling, J.; Bagshaw, E.

    2013-12-01

    Glaciers cover approximately 10% of the world's land surface at present, but our knowledge of biogeochemical processes occurring beneath them is still limited, as is our understanding of their impact on downstream ecosystems via the export of nutrients in runoff. Recent work has suggested that glaciers are a primary source of nutrients to near coastal areas(1). For example, macronutrients, such as nitrogen and phosphorus, and micronutrients, such as iron, may support primary production(2,3). Nutrient limitation of primary producers is known to be prevalent in large sectors of the world's oceans and iron is a significant limiting nutrient in Polar waters(4,5). Significantly, large oceanic algal blooms have been observed in polar areas where glacial influence is large(6,7). Our knowledge of iron speciation, concentrations and export dynamics in glacial meltwater is limited due, in part, to problems associated with collecting trace measurements in remote field locations. For example, recent work has indicated large uncertainty in 'dissolved' meltwater iron concentrations (0.2 - 4000 μM(8,9)). There is currently a dearth of information about labile nanoparticulate iron in glacial meltwaters, as well as export dynamics from large ice sheet catchments. Existing research has focused on small catchment examples(8,10), which behave differently to larger catchments(11). Presented here is the first time series of daily variations in meltwater iron concentrations (dissolved, filterable colloidal/nanoparticulate and bioavailable suspended sediment bound) from two large contrasting glacial catchments in Greenland over the 2012 and 2013 summer melt seasons. We also present the first estimates of iron concentrations in Greenlandic icebergs, which have been identified as hot spots of biological activity in the open ocean(12,13). Budgets for ice sheets based on our data demonstrate the importance of glaciers in global nutrient cycles, and reveal a large and previously under

  7. Hazard and risk assessment of a nanoparticulate cerium oxide-based diesel fuel additive - a case study.

    PubMed

    Park, Barry; Donaldson, Kenneth; Duffin, Rodger; Tran, Lang; Kelly, Frank; Mudway, Ian; Morin, Jean-Paul; Guest, Robert; Jenkinson, Peter; Samaras, Zissis; Giannouli, Myrsini; Kouridis, Haris; Martin, Patricia

    2008-04-01

    Envirox is a scientifically and commercially proven diesel fuel combustion catalyst based on nanoparticulate cerium oxide and has been demonstrated to reduce fuel consumption, greenhouse gas emissions (CO(2)), and particulate emissions when added to diesel at levels of 5 mg/L. Studies have confirmed the adverse effects of particulates on respiratory and cardiac health, and while the use of Envirox contributes to a reduction in the particulate content in the air, it is necessary to demonstrate that the addition of Envirox does not alter the intrinsic toxicity of particles emitted in the exhaust. The purpose of this study was to evaluate the safety in use of Envirox by addressing the classical risk paradigm. Hazard assessment has been addressed by examining a range of in vitro cell and cell-free endpoints to assess the toxicity of cerium oxide nanoparticles as well as particulates emitted from engines using Envirox. Exposure assessment has taken data from modeling studies and from airborne monitoring sites in London and Newcastle adjacent to routes where vehicles using Envirox passed. Data have demonstrated that for the exposure levels measured, the estimated internal dose for a referential human in a chronic exposure situation is much lower than the no-observed-effect level (NOEL) in the in vitro toxicity studies. Exposure to nano-size cerium oxide as a result of the addition of Envirox to diesel fuel at the current levels of exposure in ambient air is therefore unlikely to lead to pulmonary oxidative stress and inflammation, which are the precursors for respiratory and cardiac health problems. PMID:18444008

  8. Nanoparticulate TiO2 protection of midgut damage in the silkworm (Bombyx mori) following phoxim exposure.

    PubMed

    Wang, Ling; Su, Mingyu; Zhao, Xiaoyang; Hong, Jie; Yu, Xiaohong; Xu, Bingqing; Sheng, Lei; Liu, Dong; Shen, Weide; Li, Bing; Hong, Fashui

    2015-04-01

    Bombyx mori (B. mori) is often subjected to phoxim poisoning in China due to phoxim exposure, which leads to a decrease in silk production. Nanoparticulate (NP) titanium dioxide (nano-TiO2) has been shown to attenuate damages in B. mori caused by phoxim exposure. However, little is known about the molecular mechanisms of midgut injury due to organophosphorus insecticide exposure and its repair by nano-TiO2 pretreatment. In this study, phoxim exposure for 36 h led to significant decreases in body weight and survival and increased oxidative stress and midgut injury. Pretreatment with nano-TiO2 attenuated the phoxim-induced midgut injury, increased body weight and survival, and decreased oxidative stress in the midgut of B. mori. Digital gene-expression data showed that exposure to phoxim results in significant changes in the expression of 254 genes in the phoxim-exposed midgut and 303 genes in phoxim + nano-TiO2-exposed midgut. Specifically, phoxim exposure led to upregulation of Tpx, α-amylase, trypsin, and glycoside hydrolase genes involved in digestion and absorption. Phoxim exposure also led to the downregulation of Cyp450 and Cyp4C1 genes involved in an antioxidant capacity. In contrast, a combination of both phoxim and nano-TiO2 treatment significantly decreased the change in α-amylase, trypsin, and glycoside hydrolases (GHs), which are involved in digestion and absorption. These results indicated that Tpx, α-amylase, trypsin, GHs, Cyp450, and Cyp4C1 may be potential biomarkers of midgut toxicity caused by phoxim exposure and the attenuation of these toxic impacts by nano-TiO2. PMID:25552327

  9. Brain targeted nanoparticulate drug delivery system of rasagiline via intranasal route.

    PubMed

    Mittal, Deepti; Md, Shadab; Hasan, Quamrul; Fazil, Mohammad; Ali, Asgar; Baboota, Sanjula; Ali, Javed

    2016-01-01

    The aim of the present study was to prepare and evaluate a rasagiline-loaded chitosan glutamate nanoparticles (RAS-CG-NPs) by ionic gelation of CG with tripolyphosphate anions (TPP). RAS-loaded CG-NPs were characterized for particle size, size distribution, encapsulation efficiency and in vitro drug release. The mean particles size, polydispersity index (PDI) and encapsulation efficiency was found to be 151.1 ± 10.31, 0.380 ± 0.01 and 96.43 ± 4.23, respectively. Biodistribution of RAS formulations in the brain and blood of mice following intranasal (i.n.) and intravenous (i.v.) administration was performed using HPLC analytical method. The drug concentrations in brain following the i.n. of CG-NPs were found to be significantly higher at all the time points compared to both drug (i.n.) and drug CG-NPs (i.v.). The Cmax (999.25 ng/ml) and AUC (2086.60 ng h/ml) of formulation CG-NPs (i.n) were found to be significantly higher than CG-NPs (i.v.) and RAS solution (i.n.). The direct transport percentage (DTP%) values of RAS-loaded CG-NPs (i.n.) as compared to drug solution (i.n.) increased from 66.27 ± 1.8 to 69.27 ± 2.1%. The results showed significant enhancement of bioavailability in brain, after administration of the RAS-loaded CG-NPs which could be a substantial achievement of direct nose to brain targeting in Parkinson's disease therapy. PMID:24786489

  10. A Nanoparticulate Ferritin-Core Mimetic Is Well Taken Up by HuTu 80 Duodenal Cells and Its Absorption in Mice Is Regulated by Body Iron12

    PubMed Central

    Latunde-Dada, Gladys O; Pereira, Dora IA; Tempest, Bethan; Ilyas, Hibah; Flynn, Angela C; Aslam, Mohamad F; Simpson, Robert J; Powell, Jonathan J

    2014-01-01

    Background: Iron (Fe) deficiency anemia remains the largest nutritional deficiency disorder worldwide. How the gut acquires iron from nano Fe(III), especially at the apical surface, is incompletely understood. Objective: We developed a novel Fe supplement consisting of nanoparticulate tartrate-modified Fe(III) poly oxo-hydroxide [here termed nano Fe(III)], which mimics the Fe oxide core of ferritin and effectively treats iron deficiency anemia in rats. Methods: We determined transfer to the systemic circulation of nano Fe(III) in iron-deficient and iron-sufficient outbread Swiss mouse strain (CD1) mice with use of 59Fe-labeled material. Iron deficiency was induced before starting the Fe-supplementation period through reduction of Fe concentrations in the rodent diet. A control group of iron-sufficient mice were fed a diet with adequate Fe concentrations throughout the study. Furthermore, we conducted a hemoglobin repletion study in which iron-deficient CD1 mice were fed for 7 d a diet supplemented with ferrous sulfate (FeSO4) or nano Fe(III). Finally, we further probed the mechanism of cellular acquisition of nano Fe(III) by assessing ferritin formation, as a measure of Fe uptake and utilization, in HuTu 80 duodenal cancer cells with targeted inhibition of divalent metal transporter 1 (DMT1) and duodenal cytochrome b (DCYTB) before exposure to the supplemented iron sources. Differences in gene expression were assessed by quantitative polymerase chain reaction. Results: Absorption (means ± SEMs) of nano Fe(III) was significantly increased in iron-deficient mice (58 ± 19%) compared to iron-sufficient mice (18 ± 17%) (P = 0.0001). Supplementation of the diet with nano Fe(III) or FeSO4 significantly increased hemoglobin concentrations in iron-deficient mice (170 ± 20 g/L, P = 0.01 and 180 ± 20 g/L, P = 0.002, respectively). Hepatic hepcidin mRNA expression reflected the nonheme-iron concentrations of the liver and was also comparable for both nano Fe(III)– and

  11. 1-(3'-Amino)propylsilatrane derivatives as covalent surface linkers to nanoparticulate metal oxide films for use in photoelectrochemical cells.

    PubMed

    Brennan, Bradley J; Keirstead, Amy E; Liddell, Paul A; Vail, Sean A; Moore, Thomas A; Moore, Ana L; Gust, Devens

    2009-12-16

    A triethanolamine-protected silane, 1-(3'-amino)propylsilatrane, was incorporated into the structure of porphyrin- and ruthenium-based dyes and used to link them to transparent semiconductor nanoparticulate metal oxide films. Silatrane reacts with the metal oxide to form strong, covalent silyl ether bonds. In this study, silatrane-functionalized dyes and analogous carboxylate-functionalized dyes were used as visible light sensitizers for porous nanoparticulate SnO(2) photoanodes. The performance of the dyes was compared in photoelectrochemical cells incorporating either non-regenerative or regenerative redox components. The non-regenerative cell used NADH (beta-nicotinamide adenine dinucleotide) as a sacrificial electron donor and Hg(2)SO(4)/Hg as a sacrificial cathode, whereas the regenerative cell used the iodide/triiodide redox couple. Experiments showed that the silyl ether bonding gave the electrodes increased stability toward sensitizer desorption compared to carboxylate surface linkages. Porphyrin-silatrane dyes also demonstrated similar or better performance than their carboxylate analogs in photoelectrochemical cells. The improvement correlates with the results from transient absorbance spectroscopy, which show that the longer linker on the silatrane porphyrins slows charge recombination between oxidized porphyrin and the electrode surface. The improved photoelectrochemical cell efficiency and stability of the silatrane-based dyes compared to carboxylates demonstrate that silatranes are promising agents for bonding organic molecules to metal oxide surfaces. PMID:19923652

  12. Effects of Chemical Conjugation of l-Leucine to Chitosan on Dispersibility and Controlled Release of Drug from a Nanoparticulate Dry Powder Inhaler Formulation.

    PubMed

    Muhsin, Mohammad D A; George, Graeme; Beagley, Kenneth; Ferro, Vito; Wang, Hui; Islam, Nazrul

    2016-05-01

    This study investigated l-leucine-conjugated chitosan as a drug delivery vehicle in terms of dispersibility and controlled release from a nanoparticulate dry powder inhaler (DPI) formulation for pulmonary delivery using diltiazem hydrochloride (DH) as the model drug. DH-loaded nanoparticles of chitosan and conjugate were prepared by water-in-oil emulsification followed by glutaraldehyde cross-linking. Nanoparticles were characterized by dynamic light scattering for particle size, X-ray photoelectron spectroscopy for surface composition, and twin stage impinger for drug dispersibility. The controlled release of DH was studied in phosphate-buffered saline (pH 7.3 ± 0.2, 37 °C) using UV spectrophotometry. The fine particle fractions of conjugated chitosan with and without drug were higher than those of nonconjugated chitosan nanoparticles. The conjugate nanoparticles were superior to those of unmodified chitosan in drug loading, entrapment efficiency, and controlled release profile. The higher dispersibility was attributed to the amphiphilic environment of the l-leucine conjugate and hydrophobic cross-links, and the release profile reflects the greater swelling. The conjugated chitosan nanoparticles could be useful, after appropriate testing for biodegradability and toxicity, as an alternative carrier for lung drug delivery with enhanced aerosolization and prolonged drug release from nanoparticulate DPI formulations. PMID:26998555

  13. Vesicular (liposomal and nanoparticulated) delivery of curcumin: a comparative study on carbon tetrachloride–mediated oxidative hepatocellular damage in rat model

    PubMed Central

    Choudhury, Somsubhra Thakur; Das, Nirmalendu; Ghosh, Swarupa; Ghosh, Debasree; Chakraborty, Somsuta; Ali, Nahid

    2016-01-01

    The liver plays a vital role in biotransforming and extricating xenobiotics and is thus prone to their toxicities. Short-term administration of carbon tetrachloride (CCl4) causes hepatic inflammation by enhancing cellular reactive oxygen species (ROS) level, promoting mitochondrial dysfunction, and inducing cellular apoptosis. Curcumin is well accepted for its antioxidative and anti-inflammatory properties and can be considered as an effective therapeutic agent against hepatotoxicity. However, its therapeutic efficacy is compromised due to its insolubility in water. Vesicular delivery of curcumin can address this limitation and thereby enhance its effectiveness. In this study, it was observed that both liposomal and nanoparticulated formulations of curcumin could increase its efficacy significantly against hepatotoxicity by preventing cellular oxidative stress. However, the best protection could be obtained through the polymeric nanoparticle-mediated delivery of curcumin. Mitochondria have a pivotal role in ROS homeostasis and cell survivability. Along with the maintenance of cellular ROS levels, nanoparticulated curcumin also significantly (P<0.0001) increased cellular antioxidant enzymes, averted excessive mitochondrial destruction, and prevented total liver damage in CCl4-treated rats. The therapy not only prevented cells from oxidative damage but also arrested the intrinsic apoptotic pathway. In addition, it also decreased the fatty changes in hepatocytes, centrizonal necrosis, and portal inflammation evident from the histopathological analysis. To conclude, curcumin-loaded polymeric nanoparticles are more effective in comparison to liposomal curcumin in preventing CCl4-induced oxidative stress–mediated hepatocellular damage and thereby can be considered as an effective therapeutic strategy. PMID:27274242

  14. Nebulization of nanoparticulate amorphous or crystalline tacrolimus--single-dose pharmacokinetics study in mice.

    PubMed

    Sinswat, Prapasri; Overhoff, Kirk A; McConville, Jason T; Johnston, Keith P; Williams, Robert O

    2008-08-01

    Developing a pulmonary composition of tacrolimus (TAC) provides direct access to the graft in lung transplant offering the possibility of high drug levels. The objective of this study was to investigate the physicochemical and pharmacokinetic characteristics of the nanostructured aggregates containing amorphous or crystalline nanoparticles of TAC produced by ultra-rapid freezing (URF). TAC and lactose (1:1 ratio; URF-TAC:LAC) and TAC alone (URF-TAC) were investigated for pulmonary delivery and compared to unprocessed TAC. X-ray diffraction (XRD) results indicated that URF-TAC was crystalline, whereas URF-TAC:LAC was amorphous. In vitro results revealed the superior physiochemical characteristics of both URF formulations compared to unprocessed TAC. The surface area of URF processed TAC was higher (25-29 m2/g) than that of the unprocessed TAC (0.53 m2/g) and subsequently enhanced dissolution rates. In addition, URF-TAC:LAC displayed the ability to supersaturate in the dissolution media to about 11 times the crystalline equilibrium solubility. Similar aerodynamic particle sizes of 2-3 microm, and fine particle fraction between 70% and 75% were found in both formulations. The local and systemic pharmacokinetic studies in mice showed similar AUC(0-24), higher Cmax, and lower Tmax for the URF-TAC:LAC compared to the URF-TAC. Nanostructured aggregates containing amorphous or crystalline nanoparticles of TAC were demonstrated to be effectively delivered via nebulization, with similar in vitro and in vivo performances. PMID:18406587

  15. Catalyst inks and method of application for direct methanol fuel cells

    DOEpatents

    Zelenay, Piotr; Davey, John; Ren, Xiaoming; Gottesfeld, Shimshon; Thomas, Sharon C.

    2004-02-24

    Inks are formulated for forming anode and cathode catalyst layers and applied to anode and cathode sides of a membrane for a direct methanol fuel cell. The inks comprise a Pt catalyst for the cathode and a Pt--Ru catalyst for the anode, purified water in an amount 4 to 20 times that of the catalyst by weight, and a perfluorosulfonic acid ionomer in an amount effective to provide an ionomer content in the anode and cathode surfaces of 20% to 80% by volume. The inks are prepared in a two-step process while cooling and agitating the solutions. The final solution is placed in a cooler and continuously agitated while spraying the solution over the anode or cathode surface of the membrane as determined by the catalyst content.

  16. Highly-optimized membrane electrode assembly for direct methanol fuel cell prepared by sedimentation method

    NASA Astrophysics Data System (ADS)

    Liu, Jing Hua; Jeon, Min Ku; Choi, Won Choon; Woo, Seong Ihl

    An electrode for a direct methanol fuel cell (DMFC) is prepared by means of the sedimentation method. A suspension containing Pt black, PTFE and water was filtered through a polycarbonate film and a thin catalyst layer remains on this film. This catalyst layer is then transferred to a gas-diffusion layer by applying a pressure to the assembly and then peeling off the filter film. For the anode catalyst layer, the suspension contained Pt-Ru black and water. The preparation process is optimized and single-cell performance is examined under different operating conditions. Operated at 60 °C, the output power density of the membrane electrode assembly (MEA) fabricated by the sedimentation method is 70% higher than that for an assembly prepared by the conventional brushing technique.

  17. Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

    2014-01-01

    Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode.

  18. Control Banding Nanotool: Evaluation of a qualitative risk assessment method for the control of nanoparticulate exposures

    SciTech Connect

    Zalk, D; Paik, S; Swuste, P

    2009-01-27

    Control Banding strategies offer a simplified control of worker exposures when there is an absence of firm toxicological and exposure information. The nanotechnology industry fits this classification as there are overwhelming uncertainties of work-related health risks posed by nanomaterials. Many experts have suggested Control Banding as a solution for these issues. A recent survey shows a majority of nanomaterial users are not performing a basic risk assessment of their product in use. A Control Banding Nanotool has been developed and implemented to afford a qualitative risk assessment toward the control of nanoparticle exposures. The international use of the Control Banding Nanotool reflects on both its need and its possibilities. By developing this dynamic Control Banding Nanotool within the realm of the scientific information available, this application of Control Banding appears to be a useful approach for assessing the risk of nanomaterial operations. This success can be seen in providing recommendations for appropriate engineering controls, facilitating the allocation of resources to the activities that most need them, and initiating an appropriate discussion of these risks with nonexperts. Experts have requested standardization of toxicological parameters, affording better utility and consistency of research. This database of toxicological research findings should be harnessed and presented in a format feeding directly into the Control Banding Nanotool severity and probability risk matrix. Making the latest research available for experts and practitioners alike will provide the best protection of workers in the nanotechnology industries. This presentation will also show the science behind the simplified Control Banding Nanotool approach, its structure, weighting of risks, utility for exposure mitigation, and the research needs to bolster its effectiveness.

  19. Synthese de nanoparticules plasmoniques par laser femtoseconde en milieu liquide pour des applications biomedicales

    NASA Astrophysics Data System (ADS)

    Besner, Sebastien

    The femtosecond laser synthesis of plasmonic nanoparticles (Au, Ag, Cu, AuAg, AuCu) is described. The approach relies on the fs laser ablation of a target immersed in a liquid, followed by the laser-induced fragmentation and growth of nanoparticles in solution. This two-step methodology significantly enhances the production rate, the reproducibility and the size control of nanoparticles in comparison to the direct laser ablation based technique. For gold, the laser-induced growth of nanometric seeds initially formed by laser ablation in the presence of a stabilizing agent allows the synthesis of functionalized nanoparticles with sizes ranging from 3-76 nm and coefficients of variation (COV) varying between 15-30%. In comparison to the direct laser ablation, the size control is much simpler, as it uniquely depends on the gold to stabilizing agent molecular concentration ratio. The approach has been described for dextran and polyethylene glycol (PEG), but can be extended to all stabilizing agents and open new avenues in the formation of various novel bioconjugates. The fs laser ablation and fragmentation also allow the synthesis of stable and low dispersed Au nanoparticles in pure water. These nanoparticles are unique for sensing applications with high sensitivity based on surface enhanced Raman scattering (SERS), since they greatly reduce the noise associated with surface contaminants and byproducts found in solution. The formation of various nanospheres with predetermined size, shape and composition (AuxAg(1-x), AuxCu(1-x) ) is also reported by the use of a fs irradiation of a mixture of two pure metallic ix colloidal solutions in a very simple chemical environment, e.g. water and a stabilizing agent. From a chemical point of view, oxidation of silver nanoparticles is significantly reduced by the incorporation of a small amount of gold and is completely inhibited for a gold atomic fraction larger than 0.4-0.5. The bifunctional nature related to the partial

  20. Nanoparticulate flurbiprofen reduces amyloid-β42 generation in an in vitro blood–brain barrier model

    PubMed Central

    2013-01-01

    Introduction The amyloid-β42 (Aβ42) peptide plays a crucial role in the pathogenesis of Alzheimer’s disease (AD), the most common neurodegenerative disorder affecting the elderly. Over the past years, several approaches and compounds developed for the treatment of AD have failed in clinical studies, likely in part due to their low penetration of the blood–brain barrier (BBB). Since nanotechnology-based strategies offer new possibilities for the delivery of drugs to the brain, this technique is studied intensively for the treatment of AD and other neurological disorders. Methods The Aβ42 lowering drug flurbiprofen was embedded in polylactide (PLA) nanoparticles by emulsification-diffusion technique and their potential as drug carriers in an in vitro BBB model was examined. First, the cytotoxic potential of the PLA-flurbiprofen nanoparticles on endothelial cells and the cellular binding and uptake by endothelial cells was studied. Furthermore, the biological activity of the nanoparticulate flurbiprofen on γ-secretase modulation as well as its in vitro release was examined. Furthermore, the protein corona of the nanoparticles was studied as well as their ability to transport flurbiprofen across an in vitro BBB model. Results PLA-flurbiprofen nanoparticles were endocytosed by endothelial cells and neither affected the vitality nor barrier function of the endothelial cell monolayer. The exposure of the PLA-flurbiprofen nanoparticles to human plasma occurred in a rapid protein corona formation, resulting in their decoration with bioactive proteins, including apolipoprotein E. Furthermore, luminally administered PLA-flurbiprofen nanoparticles in contrast to free flurbiprofen were able to modulate γ-secretase activity by selectively decreasing Aβ42 levels in the abluminal compartment of the BBB model. Conclusions In this study, we were able to show that flurbiprofen can be transported by PLA nanoparticles across an in vitro BBB model and most importantly, the

  1. Sinusoidal potential cycling operation of a direct ethanol fuel cell to improving carbon dioxide yields

    NASA Astrophysics Data System (ADS)

    Majidi, Pasha; Pickup, Peter G.

    2014-12-01

    A direct ethanol fuel cell has been operated under sinusoidal (AC) potential cycling conditions in order to increase the yield of carbon dioxide and thereby increase cell efficiency relative to operation at a fixed potential. At 80 °C, faradaic yields of CO2 as high as 25% have been achieved with a PtRu anode catalyst, while the maximum CO2 production at constant potential was 13%. The increased yields under cycling conditions have been attributed to periodic oxidative stripping of adsorbed CO. These results will be important in the optimization of operating conditions for direct ethanol fuel cells, where the benefits of potential cycling are projected to increase as catalysts that produce CO2 more efficiently are implemented.

  2. Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV-phosphate

    NASA Astrophysics Data System (ADS)

    Latta, Drew E.; Kemner, Kenneth M.; Mishra, Bhoopesh; Boyanov, Maxim I.

    2016-02-01

    The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV-Ca-PO4 analog to ningyoite (CaUIV(PO4)2·1-2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV-phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2 = 0.17 ± 0.075 h-1 vs. kobs,UIVPO4 = 0.30 ± 0.25 h-1). Addition of up to 400 μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV-phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na-uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15 mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5 × 10-7 M). Oxidation of UIV-phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3 × 10-8 M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV-phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca-UVI-PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between

  3. Major to ultra trace element bulk rock analysis of nanoparticulate pressed powder pellets by LA-ICP-MS

    NASA Astrophysics Data System (ADS)

    Peters, Daniel; Pettke, Thomas

    2016-04-01

    An efficient, clean procedure for bulk rock major to trace element analysis by 193 nm Excimer LA-ICP-MS analysis of nanoparticulate pressed powder pellets (PPPs) employing a binder is presented. Sample powders are milled in water suspension in a planetary ball mill, reducing average grain size by about one order of magnitude compared to common dry milling protocols. Microcrystalline cellulose (MCC) is employed as a binder, improving the mechanical strength of the PPP and the ablation behaviour, because MCC absorbs 193 nm laser light well. Use of MCC binder allows for producing cohesive pellets of materials that cannot be pelletized in their pure forms, such as quartz powder. Rigorous blank quantification was performed on synthetic quartz treated like rock samples, demonstrating that procedural blanks are irrelevant except for a few elements at the 10 ng g‑1 concentration level. The LA-ICP-MS PPP analytical procedure was optimised and evaluated using six different SRM powders (JP-1, UB-N, BCR-2, GSP-2, OKUM, and MUH-1). Calibration based on external standardization using SRM 610, SRM 612, BCR-2G, and GSD-1G glasses allows for evaluation of possible matrix effects during LA-ICP-MS analysis. The data accuracy of the PPP LA-ICP-MS analytical procedure compares well to that achieved for liquid ICP-MS and LA-ICP-MS glass analysis, except for element concentrations below ˜30 ng g‑1, where liquid ICP-MS offers more precise data and in part lower limits of detection. Uncertainties on the external reproducibility of LA-ICP-MS PPP element concentrations are of the order of 0.5 to 2 % (1σ standard deviation) for concentrations exceeding ˜1 μg g‑1. For lower element concentrations these uncertainties increase to 5-10% or higher when analyte-depending limits of detection (LOD) are approached, and LODs do not significantly differ from glass analysis. Sample homogeneity is demonstrated by the high analytical precision, except for very few elements where grain size

  4. Combustion Synthesis of Nanoparticulate LiMgxMn1-xPO4 (x=0, 0.1, 0.2) Carbon Composites

    SciTech Connect

    Doeff, Marca M; Chen, Jiajun; Conry, Thomas E.; Wang, Ruigang; Wilcox, James; Aumentado, Albert

    2009-12-14

    A combustion synthesis technique was used to prepare nanoparticulate LiMgxMn1-xPO4 (x=0, 0.1,0.2)/carbon composites. Powders consisted of carbon-coated particles about 30 nm in diameter, which were partly agglomerated into larger secondary particles. The utilization of the active materials in lithium cells depended most strongly upon the post-treatment and the Mg content, and was not influenced by the amount of carbon. Best results were achieved with a hydrothermally treated LiMg0.2Mn0.8PO4/C composite, which exhibited close to 50percent utilization of the theoretical capacity at a C/2 discharge rate.

  5. Hybrid polymeric hydrogels for ocular drug delivery: nanoparticulate systems from copolymers of acrylic acid-functionalized chitosan and N-isopropylacrylamide or 2-hydroxyethyl methacrylate

    NASA Astrophysics Data System (ADS)

    Barbu, Eugen; Verestiuc, Liliana; Iancu, Mihaela; Jatariu, Anca; Lungu, Adriana; Tsibouklis, John

    2009-06-01

    Nanoparticulate hybrid polymeric hydrogels (10-70 nm) have been obtained via the radical-induced co-polymerization of acrylic acid-functionalized chitosan with either N-isopropylacrylamide or 2-hydroxyethyl methacrylate, and the materials have been investigated for their ability to act as controlled release vehicles in ophthalmic drug delivery. Studies on the effects of network structure upon swelling properties, adhesiveness to substrates that mimic mucosal surfaces and biodegradability, coupled with in vitro drug release investigations employing ophthalmic drugs with differing aqueous solubilities, have identified nanoparticle compositions for each of the candidate drug molecules. The hybrid nanoparticles combine the temperature sensitivity of N-isopropylacrylamide or the good swelling characteristics of 2-hydroxyethyl methacrylate with the susceptibility of chitosan to lysozyme-induced biodegradation.

  6. A direct 2-propanol polymer electrolyte fuel cell

    NASA Astrophysics Data System (ADS)

    Cao, Dianxue; Bergens, Steven H.

    We report the performance of a polymer electrolyte membrane direct 2-propanol fuel cell (DPFC). The cell consisted of a Pt-Ru (atomic ratio of 1:1) black anode, a Pt black cathode, and a Nafion ®-117 membrane electrolyte. The cell was operated at 90 °C with aqueous 2-propanol as fuel and with oxygen as oxidant. The performance of the cell operating on 2-propanol is substantially higher than when it was operating on methanol at current densities lower than ˜200 mA/cm 2. The electrical efficiency of the direct 2-propanol fuel cell is nearly 1.5 times that of the direct methanol fuel cell at power densities below 128 mW/cm 2. Studies on the effects of electrocatalyst loading, of 2-propanol concentration, and of oxygen pressure on cell performance indicate that the cells operating on 2-propanol require lower anode and cathode loadings than cells operating on methanol. Cathode poisoning by 2-propanol is less severe than by methanol. Hydrogen gas evolution observed at the anode at low current densities indicated that catalytic dehydrogenation of 2-propanol occurred over the anode catalyst. A rapid voltage drop occurred at high current densities and after operating the cell for extended periods of time at constant current. The rapid voltage drop is an anode phenomenon.

  7. PtRu/Ti anodes with varying Pt ratio: Ru ratio prepared by electrodeposition for the direct methanol fuel cell.

    PubMed

    Shao, Zhi-Gang; Zhu, Fuyun; Lin, Wen-Feng; Christensen, Paul A; Zhang, Huamin

    2006-06-21

    PtRu/Ti anodes with varying Pt ratio Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20 degrees C and 11 at.% at 60 degrees C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90 degrees C. PMID:16763704

  8. Performance of direct methanol polymer electrolyte fuel cell

    SciTech Connect

    Shin, Dong Ryul; Jung, Doo Hwan; Lee, Chang Hyeong; Chun, Young Gab

    1996-12-31

    Direct methanol fuel cells (DMFC) using polymer electrolyte membrane are promising candidate for application of portable power sources and transportation applications because they do not require any fuel processing equipment and can be operated at low temperature of 60{degrees}C - 130{degrees}C. Elimination of the fuel processor results in simpler design, higher operation reliability, lower weight volume, and lower capital and operating cost. However, methanol as a fuel is relatively electrochemical inert, so that kinetics of the methanol oxidation is too slow. Platinum and Pt-based binary alloy electrodes have been extensively studied for methanol electro-oxidation in acid electrolyte at ambient and elevated temperatures. Particularly, unsupported carbon Pt-Ru catalyst was found to be superior to the anode of DMFC using a proton exchange membrane electrolyte (Nafion). The objective of this study is to develop the high performance DNTC. This paper summarizes the results from half cell and single cell tests, which focus on the electrode manufacturing process, catalyst selection, and operating conditions of single cell such as methanol concentration, temperature and pressure.

  9. One-Pot and Facile Fabrication of Hierarchical Branched Pt-Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells.

    PubMed

    Cao, Yanqin; Yang, Yong; Shan, Yufeng; Huang, Zhengren

    2016-03-01

    Hierarchical branched nanoparticles are one promising nanostructure with three-dimensional open porous structure composed of integrated branches for superior catalysis. We have successfully synthesized Pt-Cu hierarchical branched nanoparticles (HBNDs) with small size of about 30 nm and composed of integrated ultrathin branches by using a modified polyol process with introduction of poly(vinylpyrrolidone) and HCl. This strategy is expected to be a general strategy to prepare various metallic nanostructures for catalysis. Because of the special open porous structure, the as-prepared Pt-Cu HBNDs exhibit greatly enhanced specific activity toward the methanol oxidation reaction as much as 2.5 and 1.7 times compared with that of the commercial Pt-Ru and Pt-Ru/C catalysts, respectively. Therefore, they are potentially applicable as electrocatalysts for direct methanol fuel cells. PMID:26885678

  10. Nanoparticulate Mn3O4/VGCF composite conversion-anode material with extraordinarily high capacity and excellent rate capability for lithium ion batteries.

    PubMed

    Ma, Feng; Yuan, Anbao; Xu, Jiaqiang

    2014-10-22

    In this work, highly conductive vapor grown carbon fiber (VGCF) was applied as an electrically conductive agent for facile synthesis of a nanoparticulate Mn3O4/VGCF composite material. This material exhibits super high specific capacity and excellent rate capability as a conversion-anode for lithium ion batteries. Rate performance test result demonstrates that at the discharge/charge current density of 0.2 A g(-1) a reversible capacity of ca. 950 mAh g(-1) is delivered, and when the current rate is increased to a high current density of 5 A g(-1), a reversible capacity of ca. 390 mAh g(-1) is retained. Cyclic performance examination conducted at the current density of 0.5 A g(-1) reveals that in the initial 20 cycles the reversible capacity decreases gradually from 855 to 747 mAh g(-1). However, since then, it increases gradually with cycle number increasing, and after 200 cycles an extraordinarily high reversible capacity of 1391 mAh g(-1) is achieved. PMID:25247688

  11. Intraparticulate speciation analysis of soft nanoparticulate metal complexes. The impact of electric condensation on the binding of Cd(2+)/Pb(2+)/Cu(2+) by humic acids.

    PubMed

    Town, Raewyn M; van Leeuwen, Herman P

    2016-04-21

    In aqueous dispersions of soft, charged nanoparticles, the physicochemical conditions prevailing within the particle body generally differ substantially from those in the bulk medium. Accordingly it is necessary to define intrinsic descriptors that appropriately reflect the chemical speciation inside the particle's microenvironment. Herein the speciation of divalent metal ions within the body of negatively charged soft nanoparticulate complexants is elaborated for the example case of humic acid association with Cd(ii), Pb(ii) and Cu(ii). The electrostatic effects are described by a two-state model that accounts for counterion condensation in the intraparticulate double layer shell at the particle/medium interface and Donnan partitioning within the bulk of the particle body. Inner-sphere complex formation is defined by an intrinsic binding constant expressed in terms of local reactant concentrations as controlled by the pertinent electrostatic conditions. For the high particle charge density case (Debye length smaller than charged site separation), three distinct intraparticulate metal species are identified, namely free hydrated ions, electrostatically condensed ions, and inner-sphere metal-humic complexes. For all metal ions studied, the electrostatic contribution to the association of the metal ion with the oppositely charged particle is found to account for a substantial fraction of the total metal bound. PMID:27004844

  12. Norfloxacin Loaded pH Triggered Nanoparticulate in-situ Gel for Extraocular Bacterial Infections: Optimization, Ocular Irritancy and Corneal Toxicity

    PubMed Central

    Upadhayay, Preeti; Kumar, Manish; Pathak, Kamla

    2016-01-01

    In order to achieve prolong corneal contact time of norfloxacin (NFX) for treatment of extra ocular diseases, a pH triggered nanoparticulate in-situ gelling system was designed to explore dual advantage of nanoparticles and in-situ gelling system, for its ocular delivery. NFX loaded nanocarriers were developed by ionotropic gelation technique using chitosan as a matrix forming polymer, cross-linked by an anionic crosslinker sodium tripolyphosphate (TPP). Optimization of nanoformulations was done by 32 full factorial design using chitosan and TPP concentration(s) as the independent variables and particle size, % entrapment efficiency and % cumulative drug release as the responses. The experimental design was validated by extra design check point formulation (N10). The optimized formulation (N4) selected on the basis of highest desirability factor (0.895) was developed as in-situ gelling system using carbapol934 and evaluated. The best in-situ gelling formulation (N4G5) was sufficiently mucoadhesive, corneal toxicity, antibacterial activity and free from ocular irritancy. PMID:27610144

  13. Design, characterization, and aerosolization of organic solution advanced spray-dried moxifloxacin and ofloxacin dipalmitoylphosphatidylcholine (DPPC) microparticulate/nanoparticulate powders for pulmonary inhalation aerosol delivery

    PubMed Central

    Duan, Jinghua; Vogt, Frederick G; Li, Xiaojian; Hayes, Don; Mansour, Heidi M

    2013-01-01

    The aim of this study was to design and develop respirable antibiotics moxifloxacin (MOXI) hydrochloride and ofloxacin (OFLX) microparticles and nanoparticles, and multifunctional antibiotics particles with or without lung surfactant 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) for targeted dry powder inhalation delivery as a pulmonary nanomedicine. Particles were rationally designed and produced by advanced spray-drying particle engineering from an organic solution in closed mode (no water) from dilute solution. Scanning electron microscopy indicated that these particles had both optimal particle morphology and surface morphology, and the particle size distributions were suitable for pulmonary delivery. Comprehensive and systematic physicochemical characterization and in vitro aerosol dispersion performance revealed significant differences between these two fluoroquinolone antibiotics following spray drying as drug aerosols and as cospray-dried antibiotic drug: DPPC aerosols. Fourier transform infrared spectroscopy and confocal Raman microspectroscopy were employed to probe composition and interactions in the solid state. Spray-dried MOXI was rendered noncrystalline (amorphous) following organic solution advanced spray drying. This was in contrast to spray-dried OFLX, which retained partial crystallinity, as did OFLX:DPPC powders at certain compositions. Aerosol dispersion performance was conducted using inertial impaction with a dry powder inhaler device approved for human use. The present study demonstrates that the use of DPPC offers improved aerosol delivery of MOXI as cospray-dried microparticulate/nanoparticulate powders, whereas residual partial crystallinity influenced aerosol dispersion of OFLX and most of the compositions of OFLX:DPPC inhalation powders. PMID:24092972

  14. Design, Characterization, and Aerosol Dispersion Performance Modeling of Advanced Spray-Dried Microparticulate/Nanoparticulate Mannitol Powders for Targeted Pulmonary Delivery as Dry Powder Inhalers

    PubMed Central

    Li, Xiaojian; Vogt, Frederick G.; Hayes, Don

    2014-01-01

    Abstract Background: The purpose was to design and characterize inhalable microparticulate/nanoparticulate dry powders of mannitol with essential particle properties for targeted dry powder delivery for cystic fibrosis mucolytic treatment by dilute organic solution spray drying, and, in addition, to tailor and correlate aerosol dispersion performance delivered as dry powder inhalers based on spray-drying conditions and solid-state physicochemical properties. Methods: Organic solution advanced spray drying from dilute solution followed by comprehensive solid-state physicochemical characterization and in vitro dry powder aerosolization were used. Results: The particle size distribution of the spray-dried (SD) powders was narrow, unimodal, and in the range of ∼500 nm to 2.0 μm. The particles possessed spherical particle morphology, relatively smooth surface morphology, low water content and vapor sorption (crystallization occurred at exposure above 65% relative humidity), and retention of crystallinity by polymorphic interconversion. The emitted dose, fine particle fraction (FPF), and respirable fraction (RF) were all relatively high. The mass median aerodynamic diameters were below 4 μm for all SD mannitol aerosols. Conclusion: The in vitro aerosol deposition stage patterns could be tailored based on spray-drying pump rate. Positive linear correlation was observed between both FPF and RF values with spray-drying pump rates. The interplay between various spray-drying conditions, particle physicochemical properties, and aerosol dispersion performance was observed and examined, which enabled tailoring and modeling of high aerosol deposition patterns. PMID:24502451

  15. Norfloxacin Loaded pH Triggered Nanoparticulate in-situ Gel for Extraocular Bacterial Infections: Optimization, Ocular Irritancy and Corneal Toxicity.

    PubMed

    Upadhayay, Preeti; Kumar, Manish; Pathak, Kamla

    2016-01-01

    In order to achieve prolong corneal contact time of norfloxacin (NFX) for treatment of extra ocular diseases, a pH triggered nanoparticulate in-situ gelling system was designed to explore dual advantage of nanoparticles and in-situ gelling system, for its ocular delivery. NFX loaded nanocarriers were developed by ionotropic gelation technique using chitosan as a matrix forming polymer, cross-linked by an anionic crosslinker sodium tripolyphosphate (TPP). Optimization of nanoformulations was done by 3(2) full factorial design using chitosan and TPP concentration(s) as the independent variables and particle size, % entrapment efficiency and % cumulative drug release as the responses. The experimental design was validated by extra design check point formulation (N10). The optimized formulation (N4) selected on the basis of highest desirability factor (0.895) was developed as in-situ gelling system using carbapol934 and evaluated. The best in-situ gelling formulation (N4G5) was sufficiently mucoadhesive, corneal toxicity, antibacterial activity and free from ocular irritancy. PMID:27610144

  16. Polyphosphate-enhanced production of reactive oxidants by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen: Yield and nature of oxidants.

    PubMed

    Kim, Hak-Hyeon; Lee, Hongshin; Kim, Hyung-Eun; Seo, Jiwon; Hong, Seok Won; Lee, Jeong-Yong; Lee, Changha

    2015-12-01

    The production of reactive oxidants from nanoparticulate zero-valent iron (nZVI) and ferrous ion (Fe(II)) in the presence of oxygen was greatly enhanced by the addition of tetrapolyphosphate (TPP) as an iron-chelating agent. Compared to other ligands, TPP exhibited superior activity in improving the oxidant yields. The nZVI/TPP/O2 and the Fe(II)/TPP/O2 systems showed similar oxidant yields with respect to the iron consumed, indicating that nZVI only serves as a source of Fe(II). The degradation efficacies of selected organic compounds were also similar in the two systems. It appeared that both hydroxyl radical (OH) and ferryl ion (Fe(IV)) are produced, and OH dominates at acidic pH. However, at pH > 6, little occurrence of hydroxylated oxidation products suggests that Fe(IV) is a dominant oxidant. The degradation rates of selected organic compounds by the Fe(II)/TPP/O2 system had two optimum points at pH 6 and 9, and these pH-dependent trends are likely attributed to the speciation of Fe(IV) with different reactivities. PMID:26093796

  17. Quasi-Instantaneous Bacterial Inactivation on Cu-Ag Nanoparticulate 3D Catheters in the Dark and Under Light: Mechanism and Dynamics.

    PubMed

    Rtimi, Sami; Sanjines, Rosendo; Pulgarin, Cesar; Kiwi, John

    2016-01-13

    The first evidence for Cu-Ag (50%/50%) nanoparticulate hybrid coatings is presented leading to a complete and almost instantaneous bacterial inactivation in the dark (≤5 min). Dark bacterial inactivation times on Cu-Ag (50%/50%) were observed to coincide with the times required by actinic light irradiation. This provides the evidence that the bimetal Cu-Ag driven inactivation predominates over a CuO/Cu2O and Ag2O oxides inducing a semiconductor driven behavior. Cu- or Ag-coated polyurethane (PU) catheters led to bacterial inactivation needing about ∼30 min. The accelerated bacterial inactivation by Cu-Ag coated on 3D catheters sputtered was investigated in a detailed way. The release of Cu/Ag ions during bacterial inactivation was followed by inductively coupled plasma mass-spectrometry (ICP-MS) and the amount of Cu and Ag-ions released were below the cytotoxicity levels permitted by the sanitary regulations. By stereomicroscopy the amount of live/dead cells were followed during the bacterial inactivation time. By Fourier transform infrared spectroscopy (FTIR), the systematic shift of the -(CH2) band stretching of the outer lipo-polysaccharide bilayer (LPS) was followed to monitor the changes leading to cell lysis. A hydrophobic to hydrophilic transformation of the Cu-Ag PU catheter surface under light was observed within 30 min followed concomitantly to a longer back transformation to the hydrophobic initial state in the dark. Physical insight is provided for the superior performance of Cu-Ag films compared to Cu or Ag films in view of the drastic acceleration of the bacterial inactivation observed on bimetal Cu-Ag films coating PU catheters. A mechanism of bacterial inactivation is suggested that is consistent with the findings reported in this study. PMID:26699928

  18. Osteogenic and Antimicrobial Nanoparticulate Calcium Phosphate and Poly-(D, L-Lactide-co-Glycolide) Powders for the Treatment of Osteomyelitis

    PubMed Central

    Uskoković, Vuk; Hoover, Charles; Vukomanović, Marija; Uskoković, Dragan P.; Desai, Tejal A.

    2013-01-01

    Development of a material for simultaneous sustained and localized delivery of antibiotics and induction of spontaneous regeneration of hard tissues affected by osteomyelitis stands for an important clinical need. In this work, a comparative analysis of the bacterial and osteoblastic cell response to two different nanoparticulate carriers of clindamycin, an antibiotic commonly prescribed in the treatment of bone infection, one composed of calcium phosphate and the other comprising poly-(D,L-lactide-co-glycolide)-coated calcium phosphate, was carried out. Three different non-cytotoxic phases of calcium phosphate, exhibiting dissolution and drug release profiles in the range of one week to two months to one year, respectively, were included in the analysis: monetite, amorphous calcium phosphate and hydroxyapatite. Spherical morphologies and narrow size distribution of both types of nanopowders were confirmed in transmission and scanning electron microscopic analyses. The antibiotic-containing powders exhibited sustained drug release contingent upon the degradation rate of the carrier. Assessment of the antibacterial performance of the antibiotic-encapsulated powders against Staphylococcus aureus, the most common pathogen isolated from infected bone, yielded satisfactory results both in broths and on blood agar plates for all the analyzed powders. In contrast, no cytotoxic behavior was detected upon the incubation of the antibiotic powders with the osteoblastic MC3T3-E1 cell line for up to three weeks. The cells were shown to engage in a close contact with the antibiotic-containing particles, irrespective of their internal or surface phase composition, polymeric or mineral. At the same time, both types of particles upregulated the expression of osteogenic markers osteocalcin, osteopontin, Runx2 and protocollagen type I, suggesting their ability to promote osteogenesis and enhance remineralization of the infected site in addition to eliminating the bacterial source of

  19. Novel silicon and tin alloy nano-particulate materials via spark erosion for high performance and high capacity anodes in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    White, Emma Marie Hamilton

    The advent and popularity of portable electronics, as well as the need to reduce carbon-based fuel dependence for environmental and economic reasons, has led to the search for higher energy density portable power storage methods. Lithium ion batteries offer the highest energy density of any portable energy storage technology, but their potential is limited by the currently used materials. Theoretical capacities of silicon (3580 mAh/g) and tin (990 mAh/g) are significantly higher than existing graphitic anodes (372 mAh/g). However, silicon and tin must be scaled down to the nano-level to mitigate the pulverization from drastic volume changes in the anode structure during lithium ion insertion/extraction. The available synthesis techniques for silicon and tin nano-particles are complicated and scale-up is costly. A unique one-step process for synthesizing Si-Sn alloy and Sn nano-particles via spark plasma erosion has been developed to achieve the ideal nano-particulate size and carbon coating architecture. Spark erosion produces crystalline and amorphous spherical nano-particles, averaging 5-500nm in diameter. Several tin and silicon alloys have been spark eroded and thoroughly characterized using SEM, TEM, EDS, XPS, Auger spectroscopy, NMR spectroscopy and TGA. The resulting nano-particles show improved performance as anodes over commercialized materials. In particular, pure sparked Sn particles show stable reversible capacity at ˜460 mAh/g with >99.5% coulombic efficiency for over 100 cycles. These particles are drop-in ready for existing commercial anode processing techniques and by only adding 10% of the sparked Sn particles the total current cell capacity will increase by ˜13%.

  20. A model for treating avian aspergillosis: serum and lung tissue kinetics for Japanese quail (Coturnix japonica) following single and multiple aerosol exposures of a nanoparticulate itraconazole suspension.

    PubMed

    Rundfeldt, Chris; Wyska, Elżbieta; Steckel, Hartwig; Witkowski, Andrzej; Jeżewska-Witkowska, Grażyna; Wlaź, Piotr

    2013-11-01

    Aspergillosis is frequently reported in parrots, falcons and other birds held in captivity. Inhalation is the main route of infection for Aspergillus fumigatus, resulting in both acute and chronic disease conditions. Itraconazole (ITRA) is an antifungal commonly used in birds, but administration requires repeated oral dosing and the safety margin is narrow. We describe lung tissue and serum pharmacokinetics of a nanoparticulate ITRA suspension administered to Japanese quail by aerosol exposure. Aerosolized ITRA (1 and 10% suspension) administered over 30 min did not induce adverse clinical reactions in quail upon single or 5-day repeated doses. High lung concentrations, well above the inhibitory levels for A. fumigatus, of 4.14 ± 0.19 μg/g and 27.5 ± 4.58 μg/g (mean ± SEM, n = 3), were achieved following single-dose inhalation of 1% and 10% suspension, respectively. Upon multiple dose administration of 10% suspension, mean lung concentrations reached 104.9 ± 10.1 μg/g. Drug clearance from the lungs was slow with terminal half-lives of 19.7 h and 35.8 h following inhalation of 1% and 10% suspension, respectively. Data suggest that lung clearance is solubility driven. Lung concentrations of hydroxy-itraconazole reached 1-2% of the ITRA lung tissue concentration indicating metabolism in lung tissue. Steady, but low, serum concentrations of ITRA could be measured after multiple dose administration, reaching less than 0.1% of the lung tissue concentration. This formulation may represent a novel, easy to administer treatment modality for fungal lung infection, preventing high systemic exposure. It may also be useful as metaphylaxis to prevent the outbreak of aspergillosis in colonized animals. PMID:23815436

  1. On the response of semitransparent nanoparticulated films of LuPO4:Eu in poly-energetic X-ray imaging applications

    NASA Astrophysics Data System (ADS)

    Seferis, I. E.; Zeler, J.; Michail, C.; Valais, I.; Fountos, G.; Kalyvas, N.; Bakas, A.; Kandarakis, I.; Zych, E.

    2016-05-01

    In the present work, we demonstrate the fabrication technique of highly translucent layers of nanoparticulated (~50 nm) LuPO4:Eu phosphor, present their basic luminescent properties and give results of their performance in a planar imaging system coupled to a CMOS photodetector. For comparison, the imaging performance of an opaque Gd2O2S:Eu phosphor screen prepared by sedimentation is also shown. The X-ray detection parameters as well as the luminescence efficiency of the investigated films were discussed. Results show that the in-line transmittance at ~600-700 nm, in the range of the phosphor luminescence, varies with respect to the thickness of the films from 40 to 50 % for a film of 67 μm thick to 4-12 % when the thickness increases to 460 μm. Yet, X-ray detection parameters get enhanced as the thickness of the films increases. Those results affect the luminescence efficiency curves of the films under poly-energetic X-ray radiation of various tube energies. The normalized noise power spectrum values were found similar for LuPO4:Eu films and a phosphor screen made using commercial Gd2O2S:Eu powder. The detective quantum efficiency of our films is clearly lower compared to the Gd2O2S:Eu screen from 2 to 10 cycles mm-1 frequency range while the modulation transfer function is lower from 0 to 5.5 cycles mm-1 frequency range. The acquired data allow to predict that high-temperature sintering of our films under pressure may help to improve their imaging quality, since such a processing should increase the luminescence efficiency without significant growth of the grains and thus without sacrificing their translucent character.

  2. Reactivity Descriptors for Direct Methanol Fuel Cell Anode Catalysts

    SciTech Connect

    Ferrin, Peter; Nilekar, Anand U.; Greeley, Jeffrey P.; Mavrikakis, Manos; Rossmeisl, Jan

    2008-11-01

    We have investigated the anode reaction in direct methanol fuel cells using a database of adsorption free energies for 16 intermediates on 12 close-packed transition metal surfaces calculated with periodic, selfconsistent, density functional theory (DFT–GGA). This database, combined with a simple electrokinetic model of the methanol electrooxidation reaction, yields mechanistic insights that are consistent with previous experimental and theoretical studies on Pt, and extends these insights to a broad spectrum of other transition metals. In addition, by using linear scaling relations between the adsorption free energies of various intermediates in the reaction network, we find that the results determined with the full database of adsorption energies can be estimated by knowing only two key descriptors for each metal surface: the free energies of OH and CO on the surface. Two mechanisms for methanol oxidation to CO₂ are investigated: an indirect mechanism that goes through a CO intermediate and a direct mechanism where methanol is oxidized to CO₂ without the formation of a CO intermediate. For the direct mechanism, we find that, because of CO poisoning, only a small current will result on all non-group 11 transition metals; of these metals, Pt is predicted to be the most active. For methanol decomposition via the indirect mechanism, we find that the onset potential is limited either by the ability to activate methanol, by the ability to activate water, or by surface poisoning by CO* or OH*/O*. Among pure metals, there is no obvious candidate for a good anode catalyst, and in order to design a better catalyst, one has to look for bi-functional surfaces such as the well-studied PtRu alloy.

  3. Tungsten carbides as potential alternative direct methanol fuel cell anode electrocatalysts

    NASA Astrophysics Data System (ADS)

    Zellner, Michael

    The reduction of precious metal loading and the improvement of sluggish kinetics at the anode electrocatalyst are two primary concerns for economical development of direct methanol fuel cells (DMFC). The purpose of this research is to examine the feasibility of using tungsten carbides as alternative fuel cell anode electrocatalysts. The anodic chemistry of the direct methanol fuel cell requires the oxidation of methanol and the decomposition of water to produce protons, electrons, and gas-phase CO2. Currently, the most effective anode electrocatalyst for DMFC is the Pt/Ru bimetallic catalyst, which efficiently oxidizes methanol, as well as decomposes water for the oxidation and removal of adsorbed CO species. Although the Pt/Ru bimetallic system exhibits desirable electrochemical activities, both Pt and Ru are expensive due to limited supplies. In addition, strong chemisorption of CO on Pt and Ru makes the electrocatalyst susceptible to CO poisoning, blocking the active sites for methanol oxidation. This work began by examining the reactions of methanol, water, and CO on carbide-modified tungsten (C/W) single crystal surfaces, with and without submonolayer coverages of Pt. These fundamental surface science results demonstrated the potential for tungsten carbides to be used as anode catalysts in DMFC, exhibiting decomposition of both methanol and water along with significantly lowered CO desorption temperatures. Additionally, submonolayer Pt-modification of the C/W surfaces resulted in a synergistic effect, eliminating the undesired reaction pathway on the C/W surface that produced gas-phase CH4. To bridge the materials gap between model single crystal surfaces and the more realistic thin film electrocatalysts, polycrystalline tungsten carbide thin films were created via physical vapor deposition (PVD) and carburization of polycrystalline tungsten foil. Fundamental surface science techniques were applied to the PVD films to examine the reaction pathways of DMFC

  4. Direct alcohol fuel cells: Increasing platinum performance by modification with sp-group metals

    NASA Astrophysics Data System (ADS)

    Figueiredo, Marta C.; Sorsa, Olli; Doan, Nguyet; Pohjalainen, Elina; Hildebrand, Helga; Schmuki, Patrik; Wilson, Benjamin P.; Kallio, Tanja

    2015-02-01

    By using sp group metals as modifiers, the catalytic properties of Pt can be improved toward alcohols oxidation. In this work we report the performance increase of direct alcohol fuel cells (DAFC) fuelled with ethanol or 2-propanol with platinum based anode electrodes modified with Bi and Sb adatoms. For example, by simply adding Sb to the Pt/C based anode ink during membrane electrode assembly fabrication of a direct ethanol fuel cell (DEFC) its performance is improved three-fold, with more than 100 mV increase in the open circuit potential. For the fuel cell fuelled with 2-propanol high power densities are obtained at very high potentials with these catalyst materials suggesting a great improvement for practical applications. Particularly in the case of Pt/C-Bi, the improvement is such that within 0.6 V (from 0.7 to 0.1 V) the power densities are between 7 and 9 mW/cm2. The results obtained with these catalysts are in the same range as those obtained with other bimetallic catalysts comprising of PtRu and PtSn, which are currently considered to be the best for these type of fuel cells and that are obtained by more complicated (and consequently more expensive) methods.

  5. Performance of PEM Liquid-Feed Direct Methanol-Air Fuel Cells

    NASA Technical Reports Server (NTRS)

    Narayanan, S. R.

    1995-01-01

    A direct methanol-air fuel cell operating at near atmospheric pressure, low-flow rate air, and at temperatures close to 60oC would tremendously enlarge the scope of potential applications. While earlier studies have reported performance with oxygen, the present study focuses on characterizing the performance of a PEM liquid feed direct methanol-air cell consisting of components developed in house. These cells employ Pt-Ru catalyst in the anode, Pt at the cathode and Nafion 117 as the PEM. The effect of pressure, flow rate of air and temperature on cell performance has been studied. With air, the performance level is as high as 0.437 V at 300 mA/cm2 (90oC, 20 psig, and excess air flow) has been attained. Even more significant is the performance level at 60oC, 1 atm and low flow rates of air (3-5 times stoichiometric), which is 0.4 V at 150 mA/cm2. Individual electrode potentials for the methanol and air electrode have been separated and analyzed. Fuel crossover rates and the impact of fuel crossover on the performance of the air electrode have also been measured. The study identifies issues specific to the methanol-air fuel cell and provides a basis for improvement strategies.

  6. Preparation and performance of a Nafion ®/montmorillonite nanocomposite membrane for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Jung, D. H.; Cho, S. Y.; Peck, D. H.; Shin, D. R.; Kim, J. S.

    Direct methanol fuel cells (DMFC) have major technical problems, e.g. slow methanol oxidation kinetics and high methanol crossover, to use as power sources for several applications. To overcome these problems it has been proposed to increase the fuel cell operating temperature to over 100-150 °C and to reduce the methanol permeability. In this work, we made Nafion ®/montmorillonite (MMT) nanocomposite membranes and carried out diverse tests. The nanocomposite membranes were produced by direct melt intercalation of perfluorosulfonylfluoride copolymer resin (Nafion ® resin) into the montmorillonite and modified montmorillonite (m-MMT) which was organized by dodecylamine. The membrane-electrode assembly (MEA) has been made using a hot pressing method and the electrode prepared using PtRu black and Pt black catalysts for anode and cathode, respectively. The morphology of the nanocomposite membranes has been investigated using SEM and TEM. The nanocomposite membranes and MMT and m-MMT were analyzed using by FT-IR and X-ray diffraction (XRD). The thermal and mechanical properties of those membranes were also investigated and the methanol permeability was measured by gas chromatography (GC). The performance of the MEA using the nanocomposite membrane was evaluated by single cell test. The results show that the performance of the MEA using the nanocomposite membrane was higher than that of a commercial Nafion ® membrane at high operating temperature.

  7. Mesenchymal stem cell responses to bone-mimetic electrospun matrices composed of polycaprolactone, collagen I and nanoparticulate hydroxyapatite.

    PubMed

    Phipps, Matthew C; Clem, William C; Catledge, Shane A; Xu, Yuanyuan; Hennessy, Kristin M; Thomas, Vinoy; Jablonsky, Michael J; Chowdhury, Shafiul; Stanishevsky, Andrei V; Vohra, Yogesh K; Bellis, Susan L

    2011-01-01

    The performance of biomaterials designed for bone repair depends, in part, on the ability of the material to support the adhesion and survival of mesenchymal stem cells (MSCs). In this study, a nanofibrous bone-mimicking scaffold was electrospun from a mixture of polycaprolactone (PCL), collagen I, and hydroxyapatite (HA) nanoparticles with a dry weight ratio of 50/30/20 respectively (PCL/col/HA). The cytocompatibility of this tri-component scaffold was compared with three other scaffold formulations: 100% PCL (PCL), 100% collagen I (col), and a bi-component scaffold containing 80% PCL/20% HA (PCL/HA). Scanning electron microscopy, fluorescent live cell imaging, and MTS assays showed that MSCs adhered to the PCL, PCL/HA and PCL/col/HA scaffolds, however more rapid cell spreading and significantly greater cell proliferation was observed for MSCs on the tri-component bone-mimetic scaffolds. In contrast, the col scaffolds did not support cell spreading or survival, possibly due to the low tensile modulus of this material. PCL/col/HA scaffolds adsorbed a substantially greater quantity of the adhesive proteins, fibronectin and vitronectin, than PCL or PCL/HA following in vitro exposure to serum, or placement into rat tibiae, which may have contributed to the favorable cell responses to the tri-component substrates. In addition, cells seeded onto PCL/col/HA scaffolds showed markedly increased levels of phosphorylated FAK, a marker of integrin activation and a signaling molecule known to be important for directing cell survival and osteoblastic differentiation. Collectively these results suggest that electrospun bone-mimetic matrices serve as promising degradable substrates for bone regenerative applications. PMID:21346817

  8. In Vitro Analysis of Nanoparticulate Hydroxyapatite/Chitosan Composites as Potential Drug Delivery Platforms for the Sustained Release of Antibiotics in the Treatment of Osteomyelitis

    PubMed Central

    USKOKOVIĆ, VUK; DESAI, TEJAL A.

    2014-01-01

    Nanoparticulate composites of hydroxyapatite (HAp) and chitosan were synthesized by ultrasound-assisted sequential precipitation and characterized for their microstructure at the atomic scale, surface charge, drug release properties, and combined antibacterial and osteogenic response. Crystallinity of HAp nanoparticles was reduced because of the interference of the surface layers of chitosan with the dissolution/reprecipitation-mediated recrystallization mechanism that conditions the transition from the as-precipitated amorphous calcium phosphate phase to the most thermodynamically stable one—HAp. Embedment of 5–10 nm sized, narrowly dispersed HAp nanoparticles within the polymeric matrix mitigated the burst release of the small molecule model drug, fluorescein, bound to HAp by physisorption, and promoted sustained-release kinetics throughout the 3 weeks of release time. The addition of chitosan to the particulate drug carrier formulation, however, reduced the antibacterial efficacy against S aureus. Excellent cell spreading and proliferation of osteoblastic MC3T3-E1 cells evidenced on microscopic conglomerates of HAp nanoparticles in vitro also markedly diminished on HAp/chitosan composites. Mitochondrial dehydrogenase activity exhibited normal values only for HAp/chitosan particle concentrations of up to 2 mg/cm2 and significantly dropped, by about 50%, at higher particle concentrations (4 and 8 mg/cm2). The gene expression of osteocalcin, a mineralization inductor, and the transcription factor Runx2 was downregulated in cells incubated in the presence of 3 mg/cm2 HAp/chitosan composite particles, whereas the expression of osteopontin, a potent mineralization inhibitor, was upregulated, further demonstrating the partially unfavorable osteoblastic cell response to the given particles. The peak in the expression of osteogenic markers paralleling the osteoblastic differentiation was also delayed most for the cell population incubated with HAp/chitosan particles

  9. Performance of vapor-fed direct dimethyl ether fuel cell utilizing high temperature polybenzimidazole polymer electrolyte membrane

    NASA Astrophysics Data System (ADS)

    Neutzler, Jay; Qian, Guoqing; Huang, Kevin; Benicewicz, Brian

    2012-10-01

    There is increasing interest in dimethyl ether (DME) as a synthetic fuel. It has present-day relevance and introduces an effective path forward as an energy-dense, low-pressure hydrogen carrier/storage fuel for fuel cells with applications in transportation, stationary, and portable power. Direct reaction DME fuel cells have particular relevance to portable power. This study presents the performance of the vapor-fed direct reaction of DME using high temperature Polybenzimidazole (PBI) Polymer Electrolyte Membrane (PEM). Catalyzed PBI membrane utilized a Pt/Ru black anode and a Pt/C supported cathode. Performance was evaluated from temperatures of 180 °C-210 °C and at pressures from 100 kPa to 300 kPa. A strong performance correlation was observed in this study for these temperatures and pressures. A peak power density of 50 mW cm-2 was achieved at 180 °C without back pressure, whereas, an increase to 129 mW cm-2 was achieved at 210 °C at 300 kPa pressure. The performance of high temperature PBI PEMFCs with direct vapor-fed DME are investigated with emphasis on the critical variables of cell operation; temperature, back pressure, and humidity.

  10. L-Ascorbic acid as an alternative fuel for direct oxidation fuel cells

    NASA Astrophysics Data System (ADS)

    Fujiwara, Naoko; Yamazaki, Shin-ichi; Siroma, Zyun; Ioroi, Tsutomu; Yasuda, Kazuaki

    L-Ascorbic acid (AA) was directly supplied to polymer electrolyte fuel cells (PEFCs) as an alternative fuel. Only dehydroascorbic acid (DHAA) was detected as a product released by the electrochemical oxidation of AA via a two-electron transfer process regardless of the anode catalyst used. The ionomer in the anode may inhibit the mass transfer of AA to the reaction sites by electrostatic repulsion. In addition, polymer resins without an ionic group such as poly(vinylidene fluoride) and poly(vinyl butyral) were also useful for reducing the contact resistance between Nafion membrane and carbon black used as an anode, although an ionomer like Nafion is needed for typical PEFCs. A reaction mechanism at the two-phase boundaries between AA and carbon black was proposed for the anode structure of DAAFCs, since lack of the proton conductivity was compensated by AA. There was too little crossover of AA through a Nafion membrane to cause a serious technical problem. The best performance (maximum power density of 16 mW cm -2) was attained with a Vulcan XC72 anode that included 5 wt.% Nafion at room temperature, which was about one-third of that for a DMFC with a PtRu anode.

  11. Selective electrocatalysts toward a prototype of the membraneless direct methanol fuel cell

    PubMed Central

    Feng, Yan; Yang, Jinhua; Liu, Hui; Ye, Feng; Yang, Jun

    2014-01-01

    Mastery over the structure of nanomaterials enables control of their properties to enhance their performance for a given application. Herein we demonstrate the design and fabrication of Pt-based nanomaterials with enhanced catalytic activity and superior selectivity toward the reactions in direct methanol fuel cells (DMFCs) upon the deep understanding of the mechanisms of these electrochemical reactions. In particular, the ternary Au@Ag2S-Pt nanocomposites display superior methanol oxidation reaction (MOR) selectivity due to the electronic coupling effect among different domains of the nanocomposites, while the cage-bell structured Pt-Ru nanoparticles exhibit excellent methanol tolerance for oxygen reduction reaction (ORR) at the cathode because of the differential diffusion of methanol and oxygen in the porous Ru shell of the cage-bell nanoparticles. The good catalytic selectivity of these Pt-based nanomaterials via structural construction enables a DMFC to be built without a proton exchange membrane between the fuel electrode and the oxygen electrode. PMID:24448514

  12. Performance improvement of passive direct methanol fuel cells with surface-patterned Nafion® membranes

    NASA Astrophysics Data System (ADS)

    Pu, Longjuan; Jiang, Jingjing; Yuan, Ting; Chai, Jieshi; Zhang, Haifeng; Zou, Zhiqing; Li, Xue-Mei; Yang, Hui

    2015-02-01

    Nafion® 115 membrane, patterned by thermal imprint lithography on the anode side, is used for passive direct methanol fuel cells (DMFCs). The membrane roughness factor, defined as the ratio between the actual and projected membrane surface area, was investigated for its effects on the performance of the DMFCs. When the anode Pt-Ru (1:1) catalyst loading is 1.0 mg cm-2, the maximum power density of the DMFC with a surface-patterned membrane (roughness factor: 5.4) using 3.0 M methanol as the fuel at 25 ± 1 °C reaches 27.2 ± 0.3 mW cm-2, an increase of ∼57.2% in comparison to DMFC using the pristine membrane (roughness factor: ∼1.0). Further, electrochemical characterization indicates that increased roughness factor of the membrane results in increased electrochemically active surface area and reduced charge transfer resistance in the cell. These performance improvements are ascribed to the increased surface roughness which enlarges the membrane/catalyst interface, possibly facilitating mass transport of the fuel and improving anode catalyst utilization. Thus, patterned membranes have great potential in improving the performance of fuel cells and reducing catalyst loading.

  13. Sol-gel based silica electrodes for inorganic membrane direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Kim, Hyea; Kohl, Paul A.

    Inorganic glass electrodes are of interest for use with inorganic proton exchange membranes for direct methanol fuel cells. Platinum-ruthenium glass electrodes (PtRu/C-SiO 2) have been prepared by incorporating the PtRu/C nanoparticles into a silica-based matrix. The SiO 2 matrix was synthesized through the sol-gel reaction of 3-(trihydroxysilyl)-1-propanesulfonic acid (3TPS) and 3-glycidoxypropyltrimethoxysilane (GPTMS). The distribution of the PtRu/C particles can be controlled by changing the properties of the gel matrix. The effect of gelation time, mole fraction of reactants within the sol, curing temperature, and glass ionomer content were investigated. The adhesion of the catalyst layer on the membrane, catalytic activity for methanol oxidation, and inhibition of methanol permeation through the membrane have been characterized and optimized. The electroless deposition of PtRu onto the PtRu/C nanoparticles was performed to increase the sheet conductivity of the electrode. It was found that the electrolessly deposited metal improved the catalytic activity for methanol oxidation and decreased the methanol cross-over. The methanol fuel cell performance using the inorganic membrane electrode assembly was 236 μA cm -2 at 0.4 V and was stable for more than 10 days.

  14. Aggregate breakdown of nanoparticulate titania

    NASA Astrophysics Data System (ADS)

    Venugopal, Navin

    Six nanosized titanium dioxide powders synthesized from a sulfate process were investigated. The targeted end-use of this powder was for a de-NOx catalyst honeycomb monolith. Alteration of synthesis parameters had resulted principally in differences in soluble ion level and specific surface area of the powders. The goal of this investigation was to understand the role of synthesis parameters in the aggregation behavior of these powders. Investigation via scanning electron microscopy of the powders revealed three different aggregation iterations at specific length scales. Secondary and higher order aggregate strength was investigated via oscillatory stress rheometry as a means of simulating shear conditions encountered during extrusion. G' and G'' were measured as a function of the applied oscillatory stress. Oscillatory rheometry indicated a strong variation as a function of the sulfate level of the particles in the viscoelastic yield strengths. Powder yield stresses ranged from 3.0 Pa to 24.0 Pa of oscillatory stress. Compaction curves to 750 MPa found strong similarities in extrapolated yield point of stage I and II compaction for each of the powders (at approximately 500 MPa) suggesting that the variation in sulfate was greatest above the primary aggregate level. Scanning electron microscopy of samples at different states of shear in oscillatory rheometry confirmed the variation in the linear elastic region and the viscous flow regime. A technique of this investigation was to approach aggregation via a novel perspective: aggregates are distinguished as being loose open structures that are highly disordered and stochastic in nature. The methodology used was to investigate the shear stresses required to rupture the various aggregation stages encountered and investigate the attempt to realign the now free-flowing constituents comprising the aggregate into a denser configuration. Mercury porosimetry was utilized to measure the pore size of the compact resulting from compaction via dry pressing and tape casting secondary scale aggregates. Mercury porosimetry of tapes cast at 0.85 and 9.09 cm/sec exhibited pore sizes ranging from 200-500 nm suggesting packing of intact micron-sized primary aggregates. Porosimetry further showed that this peak was absent in pressed pellets corroborating arguments of ruptured primary aggregates during compaction to 750 MPa.

  15. Investigation of nano Pt and Pt-based alloys electrocatalysts for direct methanol fuel cells and their properties

    NASA Astrophysics Data System (ADS)

    Suo, Chunguang; Zhang, Wenbin; Shi, Xinghua; Ma, Chuxia

    2014-03-01

    The electrocatalysts used in micro direct methanol fuel cell (μDMFC), such as Pt/C and Pt alloy/C, prepared by liquid-phase NaBH4 reduction method have been investigated. XC-72 (Cobalt corp. Company, U.S.A) is chosen as the activated carrier for the electrocatalysts to keep the catalysts powder in the range of several nanometers. The XRD, SEM, EDX analyses indicated that the catalysts had small particle size in several nanometers, in excellent dispersed phase and the molar ratio of the precious metals was found to be optimal. The performances of the DMFCs using cathodic catalyst with Pt percentage of 30wt% and different anodic catalysts (Pt-Ru, Pt-Ru-Mo) were tested. The polarization curves and power density curves of the cells were measured to determine the optimal alloy composition and condition for the electrocatalysts. The results showed that the micro direct methanol fuel cell with 30wt% Pt/C as the cathodic catalyst and n(Pt):n(Ru):n(Mo) = 3:2:2 PtRuMo/C as the anodic catalyst at room temperature using 2.0mol/L methanol solution has the best performances.

  16. Study of catalysis for solid oxide fuel cells and direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Jiang, Xirong

    Fuel cells offer the enticing promise of cleaner electricity with lower environmental impact than traditional energy conversion technologies. Driven by the interest in power sources for portable electronics, and distributed generation and automotive propulsion markets, active development efforts in the technologies of both solid oxide fuel cell (SOFC) and direct methanol fuel cell (DMFC) devices have achieved significant progress. However, current catalysts for fuel cells are either of low catalytic activity or extremely expensive, presenting a key barrier toward the widespread commercialization of fuel cell devices. In this thesis work, atomic layer deposition (ALD), a novel thin film deposition technique, was employed to apply catalytic Pt to SOFC, and investigate both Pt skin catalysts and Pt-Ru catalysts for methanol oxidation, a very important reaction for DMFC, to increase the activity and utilization levels of the catalysts while simultaneously reducing the catalyst loading. For SOFCs, we explored the use of ALD for the fabrication of electrode components, including an ultra-thin Pt film for use as the electrocatalyst, and a Pt mesh structure for a current collector for SOFCs, aiming for precise control over the catalyst loading and catalyst geometry, and enhancement in the current collect efficiency. We choose Pt since it has high chemical stability and excellent catalytic activity for the O2 reduction reaction and the H2 oxidation reaction even at low operating temperatures. Working SOFC fuel cells were fabricated with ALD-deposited Pt thin films as an electrode/catalyst layer. The measured fuel cell performance reveals that comparable peak power densities were achieved for ALD-deposited Pt anodes with only one-fifth of the Pt loading relative to a DC-sputtered counterpart. In addition to the continuous electrocatalyst layer, a micro-patterned Pt structure was developed via the technique of area selective ALD. By coating yttria-stabilized zirconia, a

  17. Functionalized carbon nanotube-poly(arylene sulfone) composite membranes for direct methanol fuel cells with enhanced performance

    NASA Astrophysics Data System (ADS)

    Joo, Sang Hoon; Pak, Chanho; Kim, Eun Ah; Lee, Yoon Hoi; Chang, Hyuk; Seung, Doyoung; Choi, Yeong Suk; Park, Jong-Bong; Kim, Tae Kyoung

    A new type of composite membrane, consisting of functionalized carbon nanotubes (CNTs) and sulfonated poly(arylene sulfone) (sPAS), is prepared for direct methanol fuel cell (DMFC) applications. The CNTs modified with sulfonic acid or PtRu nanopaticles are dispersed within the sPAS matrix by a solution casting method to afford SO 3CNT-sPAS or PtRu/CNT-sPAS composite membranes, respectively. Characterization of the composite membranes reveals that the functionalized CNTs are homogeneously distributed within the sPAS matrix and the composite membranes contain smaller ion clusters than the neat sPAS. The composite membranes exhibit enhanced mechanical properties in terms of tensile strength, strain and toughness, which leads to improvements in ion conductivity and methanol permeability compared with the neat sPAS membrane. In DMFC performance tests, the use of a PtRu/CNT-sPAS membrane yields high power density compared with the neat sPAS membrane, which demonstrates that the improved properties of the composite membranes induce an increase in power density. The strategy for CNT-sPAS composite membranes presented in this work can potentially be extended to other CNT-polymer composite systems.

  18. Directing 101.

    ERIC Educational Resources Information Center

    Pintoff, Ernest

    Providing an introduction to anyone considering directing as a field of study or career, this book takes a broad look at the process of directing and encourages students and professionals alike to look outside of the movie industry for inspiration. Chapters in the book discuss selecting and acquiring material; budgeting and financing; casting and…

  19. Advance directives

    PubMed Central

    O’Sullivan, Rory; Mailo, Kevin; Angeles, Ricardo; Agarwal, Gina

    2015-01-01

    Abstract Objective To establish the prevalence of patients with advance directives in a family practice, and to describe patients’ perspectives on a family doctor’s role in initiating discussions about advance directives. Design A self-administered patient questionnaire. Setting A busy urban family medicine teaching clinic in Hamilton, Ont. Participants A convenience sample of adult patients attending the clinic over the course of a typical business week. Main outcome measures The prevalence of advance directives in the patient population was determined, and the patients’ expectations regarding the role of their family doctors were elucidated. Results The survey population consisted of 800 participants (a response rate of 72.5%) well distributed across age groups; 19.7% had written advance directives and 43.8% had previously discussed the topic of advance directives, but only 4.3% of these discussions had occurred with family doctors. In 5.7% of cases, a family physician had raised the issue; 72.3% of respondents believed patients should initiate the discussion. Patients who considered advance directives extremely important were significantly more likely to want their family doctors to start the conversation (odds ratio 3.98; P < .05). Conclusion Advance directives were not routinely addressed in the family practice. Most patients preferred to initiate the discussion of advance directives. However, patients who considered the subject extremely important wanted their family doctors to initiate the discussion. PMID:25873704

  20. Improved Anode for a Direct Methanol Fuel Cell

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas; Narayanan, Sekharipuram

    2005-01-01

    A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the

  1. Spin-glass state in nanoparticulate (La0.7Sr0.3Mn O3) 1 -x(BaTi O3)x solid solutions: Experimental and density-functional studies

    NASA Astrophysics Data System (ADS)

    Nayek, Chiranjib; Samanta, S.; Manna, Kaustuv; Pokle, A.; Nanda, B. R. K.; Anil kumar, P. S.; Murugavel, P.

    2016-03-01

    We report the transition from robust ferromagnetism to a spin-glass state in nanoparticulate L a0.7S r0.3Mn O3 through solid solution with BaTi O3 . The field- and temperature-dependent magnetization and the frequency-dependent ac magnetic susceptibility measurements strongly indicate the existence of a spin-glass state in the system, which is further confirmed from memory effect measurements. The breaking of long-range ordering into short-range magnetic domains is further investigated using density-functional calculations. We show that Ti ions remain magnetically inactive due to insufficient electron leakage from L a0.7S r0.3Mn O3 to the otherwise unoccupied Ti -d states. This results in the absence of a Mn-Ti-Mn spin exchange interaction and hence the breaking of the long-range ordering. Total-energy calculations suggest that the segregation of nonmagnetic Ti ions leads to the formation of short-range ferromagnetic Mn domains.

  2. Improved Cathode Structure for a Direct Methanol Fuel Cell

    NASA Technical Reports Server (NTRS)

    Valdez, Thomas; Narayanan, Sekharipuram

    2005-01-01

    An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been

  3. Recent advances in direct methanol fuel cells at Los Alamos National Laboratory

    NASA Astrophysics Data System (ADS)

    Ren, Xiaoming; Zelenay, Piotr; Thomas, Sharon; Davey, John; Gottesfeld, Shimshon

    This paper describes recent advances in the science and technology of direct methanol fuel cells (DMFCs) made at Los Alamos National Laboratory (LANL). The effort on DMFCs at LANL includes work devoted to portable power applications, funded by the Defense Advanced Research Project Agency (DARPA), and work devoted to potential transport applications, funded by the US DOE. We describe recent results with a new type of DMFC stack hardware that allows to lower the pitch per cell to 2 mm while allowing low air flow and air pressure drops. Such stack technology lends itself to both portable power and potential transport applications. Power densities of 300 W/l and 1 kW/l seem achievable under conditions applicable to portable power and transport applications, respectively. DMFC power system analysis based on the performance of this stack, under conditions applying to transport applications (joint effort with U.C. Davis), has shown that, in terms of overall system efficiency and system packaging requirements, a power source for a passenger vehicle based on a DMFC could compete favorably with a hydrogen-fueled fuel cell system, as well as with fuel cell systems based on fuel processing on board. As part of more fundamental studies performed, we describe optimization of anode catalyst layers in terms of PtRu catalyst nature, loading and catalyst layer composition and structure. We specifically show that, optimized content of recast ionic conductor added to the catalyst layer is a sensitive function of the nature of the catalyst. Other elements of membrane/electrode assembly (MEA) optimization efforts are also described, highlighting our ability to resolve, to a large degree, a well-documented problem of polymer electrolyte DMFCs, namely "methanol crossover". This was achieved by appropriate cell design, enabling fuel utilization as high as 90% in highly performing DMFCs.

  4. Atomic layer deposition of ruthenium surface-coating on porous platinum catalysts for high-performance direct ethanol solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Jeong, Heon Jae; Kim, Jun Woo; Jang, Dong Young; Shim, Joon Hyung

    2015-09-01

    Pt-Ru bi-metallic catalysts are synthesized by atomic layer deposition (ALD) of Ru surface-coating on sputtered Pt mesh. The catalysts are evaluated in direct ethanol solid oxide fuel cells (DESOFCs) in the temperature range of 300-500 °C. Island-growth of the ALD Ru coating is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) analyses. The performance of the DESOFCs is evaluated based on the current-voltage output and electrochemical impedance spectroscopy. Genuine reduction of the polarization impedance, and enhanced power output with improved surface kinetics are achieved with the optimized ALD Ru surface-coating compared to bare Pt. The chemical composition of the Pt/ALD Ru electrode surface after fuel cell operation is analyzed via XPS. Enhanced cell performance is clearly achieved, attributed to the effective Pt/ALD Ru bi-metallic catalysis, including oxidation of Cdbnd O by Ru, and de-protonation of ethanol and cleavage of C-C bonds by Pt, as supported by surface morphology analysis which confirms formation of a large amount of carbon on bare Pt after the ethanol-fuel-cell test.

  5. Characterisation of zirconium and titanium phosphates and direct methanol fuel cell (DMFC) performance of functionally graded Nafion(R) composite membranes prepared out of them

    NASA Astrophysics Data System (ADS)

    Bauer, F.; Willert-Porada, M.

    Pure layered phosphates of varying crystalline phases and crystallinity and composites of gradient layers of zirconium phosphate in Nafion 117-membranes have been prepared. The proton conductivity and, in case of the composites, also the dynamic mechanical properties of these materials were measured under different conditions of temperature and humidity. Membrane-electrode assemblies with low platinum catalyst loading of 0.4 mg cm -2 Pt at the cathode and 1.9 mg cm -2 Pt-Ru at the anode were examined in a direct methanol fuel cell (DMFC) at medium temperatures (130 °C). The conductivity of the layered zirconium phosphates is superior to the titanium phosphates and increases with decreasing crystallite size. The electrical performance of the composites in a DMFC-environment is slightly decreased as compared to the unmodified membrane but taking the reduced methanol crossover into account, higher efficiencies can be reached with the zirconium phosphate modified membrane. Furthermore, the mechanical properties are significantly improved by the presence of the inorganic compound.

  6. DIRECTIONAL COUPLERS

    DOEpatents

    Nigg, D.J.

    1961-12-01

    A directional coupler of small size is designed. Stripline conductors of non-rectilinear configuration, and separated from each other by a thin dielectric spacer. cross each other at least at two locations at right angles, thus providing practically pure capacitive coupling which substantially eliminates undesirable inductive coupling. The conductors are sandwiched between a pair of ground planes. The coupling factor is dependent only on the thickness and dielectric constant of the dielectric spacer at the point of conductor crossover. (AEC)

  7. DIRECTIONAL ANTENNA

    DOEpatents

    Bittner, B.J.

    1958-05-20

    A high-frequency directional antenna of the 360 d scaring type is described. The antenna has for its desirable features the reduction in both size and complexity of the mechanism for rotating the antenna through its scanning movement. These advantages result from the rotation of only the driven element, the reflector remaining stationary. The particular antenna structure comprises a refiector formed by a plurality of metallic slats arranged in the configuration of an annular cage having the shape of a zone of revolution. The slats are parallel to each other and are disposed at an angle of 45 d to the axis of the cage. A directional radiator is disposed inside the cage at an angle of 45 d to the axis of the cage in the same direction as the reflecting slats which it faces. As the radiator is rotated, the electromagnetic wave is reflected from the slats facing the radiator and thereafter passes through the cage on the opposite side, since these slats are not parallel with the E vector of the wave.

  8. Nanostructured self-assembly materials from neat and aqueous solutions of C18 lipid pro-drug analogues of Capecitabine—a chemotherapy agent. Focus on nanoparticulate cubosomes™ of the oleyl analogue

    SciTech Connect

    Gong, Xiaojuan; Moghaddam, Minoo J.; Sagnella, Sharon M.; Conn, Charlotte E.; Mulet, Xavier; Danon, Stephen J.; Waddington, Lynne J.; Drummond, Calum J.

    2014-09-24

    A series of prodrug analogues based on the established chemotherapy agent, 5-fluorouracil, have been prepared and characterized. C18 alkyl and alkenyl chains with increasing degree of unsaturation were attached to the N4 position of the 5-fluorocytosine (5-FC) base via a carbamate bond. Physicochemical characterization of the prodrug analogues was carried out using a combination of differential scanning calorimetry, cross-polarized optical microscopy, X-ray diffraction and small-angle X-ray scattering. The presence of a monounsaturated oleyl chain was found to promote lyotropic liquid crystalline phase formation in excess water with a fluid lamellar phase observed at room temperature and one or more bicontinuous cubic phases at 37 °C. The bulk phase was successfully dispersed into liposomes or cubosomes at room and physiological temperature respectively. In vitro toxicity of the nanoparticulate 5-FCOle dispersions was evaluated against several normal and cancer cell types over a 48 h period and exhibited an IC50 of -100 μM against all cell types. The in vivo efficacy of 5-FCOle cubosomes was assessed against the highly aggressive mouse 4T1 breast cancer model and compared to Capecitabine (a water-soluble commercially available 5-FU prodrug) delivered at the same dosages. After 21 days of treatment, the 0.5 mmol 5-FCOle treatment group exhibited a significantly smaller average tumour volume than all other treatment groups including Capecitabine at similar dosage. These results exemplify the potential of self-assembled amphiphile prodrugs for delivery of bioactives in vivo.

  9. Direct ELISA.

    PubMed

    Lin, Alice V

    2015-01-01

    First described by Engvall and Perlmann, the enzyme-linked immunosorbent assay (ELISA) is a rapid and sensitive method for detection and quantitation of an antigen using an enzyme-labeled antibody. Besides routine laboratory usage, ELISA has been utilized in medical field and food industry as diagnostic and quality control tools. Traditionally performed in 96-well or 384-well polystyrene plates, the technology has expanded to other platforms with increase in automation. Depending on the antigen epitope and availability of specific antibody, there are variations in ELISA setup. The four basic formats are direct, indirect, sandwich, and competitive ELISAs. Direct ELISA is the simplest format requiring an antigen and an enzyme-conjugated antibody specific to the antigen. This chapter describes the individual steps for detection of a plate-bound antigen using a horseradish peroxidase (HRP)-conjugated antibody and luminol-based enhanced chemiluminescence (ECL) substrate. The methodological approach to optimize the assay by chessboard titration is also provided. PMID:26160564

  10. Direct cervicoplasty.

    PubMed

    Jordan, J Randall

    2012-02-01

    The sagging neck, or "turkey gobbler" deformity, is one of the more common reasons that patients present to facial plastic surgeons. Although many of these patients might be best improved by a full rhytidectomy with periauricular incisions, skin flap undermining, and platysmal tightening, there are some patients who do not wish to undergo a full rhytidectomy. Some of these patients may be reasonably well served by a direct cervicoplasty or submentoplasty. The advantages of this approach include shorter operative time, faster recovery, and lower complication rates. The primary disadvantage is an anterior cervical incision that may be visible under some conditions. This article will review the options for skin incisions as well as technical details that may lead to a successful rejuvenation of the submental region. PMID:22418816

  11. Future direction of direct writing

    NASA Astrophysics Data System (ADS)

    Kim, Nam-Soo; Han, Kenneth N.

    2010-11-01

    Direct write technology using special inks consisting of finely dispersed metal nanoparticles in liquid is receiving an undivided attention in recent years for its wide range of applicability in modern electronic industry. The application of this technology covers radio frequency identification-tag (RFID-tag), flexible-electronics, organic light emitting diodes (OLED) display, e-paper, antenna, bumpers used in flip-chip, underfilling, frit, miniresistance applications and biological uses, artificial dental applications and many more. In this paper, the authors have reviewed various direct write technologies on the market and discussed their advantages and shortfalls. Emphasis has given on microdispensing deposition write (MDDW), maskless mesoscale materials deposition (M3D), and ink-jet technologies. All of these technologies allow printing various patterns without employing a mask or a resist with an enhanced speed with the aid of computer. MDDW and M3D are capable of drawing patterns in three-dimension and MDDW, in particular, is capable of writing nanoinks with high viscosity. However, it is still far away for direct write to be fully implemented in the commercial arena. One of the hurdles to overcome is in manufacturing conductive inks which are chemically and physically stable, capable of drawing patterns with acceptable conductivity, and also capable of drawing patterns with acceptable adhesiveness with the substrates. The authors have briefly discussed problems involved in manufacturing nanometal inks to be used in various writing devices. There are numerous factors to be considered in manufacturing such inks. They are reducing agents, concentrations, oxidation, compact ability allowing good conductivity, and stability in suspension.

  12. Multilayered gold/silica nanoparticulate bilayer devices using layer-by-layer self organisation for flexible bending and pressure sensing applications

    SciTech Connect

    Shah Alam, Md.; Mohammed, Waleed S.; Dutta, Joydeep

    2014-02-17

    A pressure and bending sensor was fabricated using multilayer thin films fabricated on a flexible substrate based on layer-by-layer self-organization of 18 nm gold nanoparticles separated by a dielectric layer of 30 nm silica nanoparticles. 50, 75, and 100 gold-silica bi-layered films were deposited and the device characteristics were studied. A threshold voltage was required for electron conduction which increases from 2.4 V for 50 bi-layers to 3.3 V for 100 bi-layers. Upon bending of the device up to about 52°, the threshold voltage and slope of the I-V curves change linearly. Electrical characterization of the multilayer films was carried out under ambient conditions with different pressures and bending angles in the direct current mode. This study demonstrates that the developed multilayer thin films can be used as pressure as well as bending sensing applications.

  13. Direct cervicoplasty.

    PubMed

    Jordan, J Randall; Yellin, Seth

    2014-08-01

    Rejuvenation of the aging neck is one of the common reasons for the patients presented to facial plastic surgeons. In the author's opinion, most of these patients will be best served by a full rhytidectomy approach with periauricular incisions, skin flap undermining, and platysmaplasty. There is a subset of patients, however, who presented with complaints limited to the so-called Turkey Gobbler deformity, and who do not wish to undergo a full rhytidectomy approach. These patients may be well served by a lesser procedure such as a direct cervicoplasty or submentoplasty. The advantages of this approach include shorter operative time, faster recovery, and lower complication rates. The primary disadvantage of these more limited approaches is that there is an anterior cervical scar that may be visible under some conditions. This article will review the multiple options for skin incisions as well as details of the technique that the authors have found may lead to a successful rejuvenation of the submental region. PMID:25076453

  14. Novel anode structure for the direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Allen, R. G.; Lim, Chan; Yang, L. X.; Scott, K.; Roy, S.

    Pt-Ru catalysts have been made by a thermal decomposition and electrodeposition method onto a titanium mesh for the electrooxidation of methanol. Galvanostatic polarisations were used to assess and compare the relative activities of the electrodes. SEM and XRD are employed to study the morphology and structure of the catalyst layers. The performance of the anodes in fuel cell assemblies is also discussed. We can see that the mesh perform well in half and full cell tests despite significant apparent physical differences, which are yet to be explored.

  15. High performance and durable nanostructured TiN supported Pt50-Ru50 anode catalyst for direct methanol fuel cell (DMFC)

    NASA Astrophysics Data System (ADS)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Jampani, Prashanth H.; Hong, Daeho; Poston, James A.; Manivannan, Ayyakkannu; Kumta, Prashant N.

    2015-10-01

    The design of high performance and durable electro-catalyst has been of particular interest for DMFC anodes. Pt(Ru) has been considered the most active DMFC anode catalyst. In this work, the reaction kinetics of Pt(Ru) electro-catalyst has been improved by synthesizing high active surface area Pt50(Ru50) catalyst supported on highly conductive nanostructured titanium nitride, TiN. The Pt(Ru)/TiN has been synthesized by a complexed sol-gel (CSG) process using non-halide precursors of Pt and Ru. High surface area Pt(Ru)/TiN shows promising electrochemical performance for methanol oxidation, showing ∼52% improved catalytic activity at ∼0.65 V (vs NHE) and stability/durability in comparison with commercial JM-Pt(Ru). Single cell DMFC performance shows 56% improved maximum power density and superior electrochemical stability for CSG-Pt(Ru)/TiN compared to that of commercial JM-Pt(Ru). This is attributed to the uniform dispersion of Pt(Ru) achieved on the nanostructured TiN (support) yielding higher electrochemical active surface area and lower charge transfer resistance than commercial JM-Pt(Ru). Thus, the present study demonstrates the potential of nanostructured TiN as a support for Pt(Ru) based anode electro-catalyst for DMFC applications.

  16. Optical Properties of Silver Nanoparticulate Glasses

    NASA Astrophysics Data System (ADS)

    Evans, Rachel N.; Cannavino, Sarah A.; King, Christy A.; Lamartina, Joseph A.; Magruder, Robert H.; Ferrara, Davon W.

    The ion exchange method of embedding metal nanoparticles (NPs) into float glass is an often used technique of fabricating colored glasses and graded-index waveguides. The depth and size of NP formation in the glass depends on the concentration and temperature of metal ions in the molten bath. In this study we explore the dichroic properties of silver metal ion exchange restricted to only one side of a glass microscope slide using reflection and transmission spectroscopy and its dependence on temperature, concentration of silver ions, and length of time in the molten bath.

  17. Micro- and nanoparticulates for DNA vaccine delivery.

    PubMed

    Farris, Eric; Brown, Deborah M; Ramer-Tait, Amanda E; Pannier, Angela K

    2016-05-01

    DNA vaccination has emerged as a promising alternative to traditional protein-based vaccines for the induction of protective immune responses. DNA vaccines offer several advantages over traditional vaccines, including increased stability, rapid and inexpensive production, and flexibility to produce vaccines for a wide variety of infectious diseases. However, the immunogenicity of DNA vaccines delivered as naked plasmid DNA is often weak due to degradation of the DNA by nucleases and inefficient delivery to immune cells. Therefore, biomaterial-based delivery systems based on micro- and nanoparticles that encapsulate plasmid DNA represent the most promising strategy for DNA vaccine delivery. Microparticulate delivery systems allow for passive targeting to antigen presenting cells through size exclusion and can allow for sustained presentation of DNA to cells through degradation and release of encapsulated vaccines. In contrast, nanoparticle encapsulation leads to increased internalization, overall greater transfection efficiency, and the ability to increase uptake across mucosal surfaces. Moreover, selection of the appropriate biomaterial can lead to increased immune stimulation and activation through triggering innate immune response receptors and target DNA to professional antigen presenting cells. Finally, the selection of materials with the appropriate properties to achieve efficient delivery through administration routes conducive to high patient compliance and capable of generating systemic and local (i.e. mucosal) immunity can lead to more effective humoral and cellular protective immune responses. In this review, we discuss the development of novel biomaterial-based delivery systems to enhance the delivery of DNA vaccines through various routes of administration and their implications for generating immune responses. PMID:27048557

  18. Vapor Synthesis and Thermal Modification of Supportless Platinum–Ruthenium Nanotubes and Application as Methanol Electrooxidation Catalysts

    DOE PAGESBeta

    Atkinson III, Robert W.; Unocic, Raymond R.; Unocic, Kinga A.; Veith, Gabriel M.; Zawodzinski, Jr., Thomas A.; Papandrew, Alexander B.

    2015-04-23

    Metallic, mixed-phase, and alloyed bimetallic Pt-Ru nanotubes were synthesized by a novel route based on the sublimation of metal acetylacetonate precursors and their subsequent vapor deposition within anodic alumina templates. Nanotube architectures were tuned by thermal annealing treatments. As-synthesized nanotubes are composed of nanoparticulate, metallic platinum and hydrous ruthenium oxide whose respective thicknesses depend on the sample chemical composition. The Pt-decorated, hydrous Ru oxide nanotubes may be thermally annealed to promote a series of chemical and physical changes to the nanotube structures including alloy formation, crystallite growth and morphological evolution. Annealed Pt-Ru alloy nanotubes and their as-synthesized analogs demonstrate relativelymore » high specific activities for the oxidation of methanol. As-synthesized, mixed-phase Pt-Ru nanotubes (0.39 mA/cm2) and metallic alloyed Pt64Ru36NTs (0.33 mA/cm2) have considerably higher area-normalized activities than PtRu black (0.22 mA/cm2) at 0.65 V vs. RHE.« less

  19. Vapor Synthesis and Thermal Modification of Supportless Platinum–Ruthenium Nanotubes and Application as Methanol Electrooxidation Catalysts

    SciTech Connect

    Atkinson III, Robert W.; Unocic, Raymond R.; Unocic, Kinga A.; Veith, Gabriel M.; Zawodzinski, Jr., Thomas A.; Papandrew, Alexander B.

    2015-04-23

    Metallic, mixed-phase, and alloyed bimetallic Pt-Ru nanotubes were synthesized by a novel route based on the sublimation of metal acetylacetonate precursors and their subsequent vapor deposition within anodic alumina templates. Nanotube architectures were tuned by thermal annealing treatments. As-synthesized nanotubes are composed of nanoparticulate, metallic platinum and hydrous ruthenium oxide whose respective thicknesses depend on the sample chemical composition. The Pt-decorated, hydrous Ru oxide nanotubes may be thermally annealed to promote a series of chemical and physical changes to the nanotube structures including alloy formation, crystallite growth and morphological evolution. Annealed Pt-Ru alloy nanotubes and their as-synthesized analogs demonstrate relatively high specific activities for the oxidation of methanol. As-synthesized, mixed-phase Pt-Ru nanotubes (0.39 mA/cm2) and metallic alloyed Pt64Ru36NTs (0.33 mA/cm2) have considerably higher area-normalized activities than PtRu black (0.22 mA/cm2) at 0.65 V vs. RHE.

  20. Direct Antiglobulin Test

    MedlinePlus

    ... be limited. Home Visit Global Sites Search Help? Direct Antiglobulin Test Share this page: Was this page helpful? Also known as: DAT; Direct Coombs Test; Direct Anti-human Globulin Test Formal ...

  1. On directed interacting animals and directed percolation

    NASA Astrophysics Data System (ADS)

    Knezevic, Milan; Vannimenus, Jean

    2002-03-01

    We study the phase diagram of fully directed lattice animals with nearest-neighbour interactions on the square lattice. This model comprises several interesting ensembles (directed site and bond trees, bond animals, strongly embeddable animals) as special cases and its collapse transition is equivalent to a directed bond percolation threshold. Precise estimates for the animal size exponents in the different phases and for the critical fugacities of these special ensembles are obtained from a phenomenological renormalization group analysis of the correlation lengths for strips of width up to n = 17. The crossover region in the vicinity of the collapse transition is analysed in detail and the crossover exponent φ is determined directly from the singular part of the free energy. We show using scaling arguments and an exact relation due to Dhar that φ is equal to the Fisher exponent σ governing the size distribution of large directed percolation clusters.

  2. Direct Manipulation Interfaces.

    ERIC Educational Resources Information Center

    Hutchins, Edwin L.; And Others

    This paper presents a cognitive account of both the advantages and disadvantages of direct manipulation interfaces, i.e., the use of icons to manipulate and interact directly with data rather than writing programs or calling on a set of statistical subroutines. Two underlying phenomena that give rise to the sensation of directness are identified.…

  3. Descendants and advance directives.

    PubMed

    Buford, Christopher

    2014-01-01

    Some of the concerns that have been raised in connection to the use of advance directives are of the epistemic variety. Such concerns highlight the possibility that adhering to an advance directive may conflict with what the author of the directive actually wants (or would want) at the time of treatment. However, at least one objection to the employment of advance directives is metaphysical in nature. The objection to be discussed here, first formulated by Rebecca Dresser and labeled by Allen Buchanan as the slavery argument and David DeGrazia the someone else problem, aims to undermine the legitimacy of certain uses of advance directives by concluding that such uses rest upon an incorrect assumption about the identity over time of those ostensibly governed by the directives. There have been numerous attempts to respond to this objection. This paper aims to assess two strategies that have been pursued to cope with the problem. PMID:25743056

  4. Decisions Concerning Directional Dependence

    ERIC Educational Resources Information Center

    von Eye, Alexander; DeShon, Richard P.

    2012-01-01

    In this rejoinder, von Eye and DeShon discuss the decision strategies proposed in their original article ("Directional Dependence in Developmental Research," this issue), as well as the ones proposed by the authors of the commentary (Pornprasertmanit and Little, "Determining Directional Dependency in Causal Associations," this issue). In addition,…

  5. Modelling Directional Solidification

    NASA Technical Reports Server (NTRS)

    Wilcox, William R.; Regel, Liya L.; Zhou, Jian; Yuan, Weijun

    1992-01-01

    The long range goal of this program has been to develop an improved understanding of phenomena of importance to directional solidification, in order to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Current emphasis is on determining the influence of perturbations on directional solidification.

  6. Modelling directional solidification

    NASA Technical Reports Server (NTRS)

    Wilcox, William R.

    1991-01-01

    The long range goal of this program is to develop an improved understanding of phenomena of importance to directional solidification and to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Current emphasis is on determining the influence of perturbations on directional solidification.

  7. Direct Conversion of Energy.

    ERIC Educational Resources Information Center

    Corliss, William R.

    This publication is one of a series of information booklets for the general public published by the United States Atomic Energy Commission. Direct energy conversion involves energy transformation without moving parts. The concepts of direct and dynamic energy conversion plus the laws governing energy conversion are investigated. Among the topics…

  8. Direct Electron Detectors.

    PubMed

    McMullan, G; Faruqi, A R; Henderson, R

    2016-01-01

    Direct electron detectors have played a key role in the recent increase in the power of single-particle electron cryomicroscopy (cryoEM). In this chapter, we summarize the background to these recent developments, give a practical guide to their optimal use, and discuss future directions. PMID:27572721

  9. Direct current transformer

    NASA Technical Reports Server (NTRS)

    Khanna, S. M.; Urban, E. W. (Inventor)

    1979-01-01

    A direct current transformer in which the primary consists of an elongated strip of superconductive material, across the ends of which is direct current potential is described. Parallel and closely spaced to the primary is positioned a transformer secondary consisting of a thin strip of magnetoresistive material.

  10. Direct Instruction News, 2001.

    ERIC Educational Resources Information Center

    Tarver, Sara, Ed.

    2001-01-01

    These three issues of a newsletter offer diverse kinds of information deemed to be of interest to Association for Direct Instruction (ADI) members--stories of successful implementations in different settings, write-ups of ADI awards, tips on "how to" deliver direct instruction (DI) more effectively, topical articles focused on particular types of…

  11. Highly directional acoustic receivers.

    PubMed

    Cray, Benjamin A; Evora, Victor M; Nuttall, Albert H

    2003-03-01

    The theoretical directivity of a single combined acoustic receiver, a device that can measure many quantities of an acoustic field at a collocated point, is presented here. The formulation is developed using a Taylor series expansion of acoustic pressure about the origin of a Cartesian coordinate system. For example, the quantities measured by a second-order combined receiver, denoted a dyadic sensor, are acoustic pressure, the three orthogonal components of acoustic particle velocity, and the nine spatial gradients of the velocity vector. The power series expansion, which can be of any order, is cast into an expression that defines the directivity of a single receiving element. It is shown that a single highly directional dyadic sensor can have a directivity index of up to 9.5 dB. However, there is a price to pay with highly directive sensors; these sensors can be significantly more sensitive to nonacoustic noise sources. PMID:12656387

  12. Multimode Directional Coupler

    NASA Technical Reports Server (NTRS)

    Simons, Rainee N. (Inventor); Wintucky, Edwin G. (Inventor)

    2016-01-01

    A multimode directional coupler is provided. In some embodiments, the multimode directional coupler is configured to receive a primary signal and a secondary signal at a first port of a primary waveguide. The primary signal is configured to propagate through the primary waveguide and be outputted at a second port of the primary waveguide. The multimode directional coupler also includes a secondary waveguide configured to couple the secondary signal from the primary waveguide with no coupling of the primary signal into the secondary waveguide. The secondary signal is configured to propagate through the secondary waveguide and be outputted from a port of the secondary waveguide.

  13. Direct nuclear pumped laser

    DOEpatents

    Miley, George H.; Wells, William E.; DeYoung, Russell J.

    1978-01-01

    There is provided a direct nuclear pumped gas laser in which the lasing mechanism is collisional radiated recombination of ions. The gas laser active medium is a mixture of the gases, with one example being neon and nitrogen.

  14. Tevatron direct photon results.

    SciTech Connect

    Kuhlmann, S.

    1999-09-21

    Tevatron direct photon results since DIS98 are reviewed. Two new CDF measurements are discussed, the Run Ib inclusive photon cross section and the photon + Muon cross section. Comparisons with the latest NLO QCD calculations are presented.

  15. Refrigerant directly cooled capacitors

    DOEpatents

    Hsu, John S.; Seiber, Larry E.; Marlino, Laura D.; Ayers, Curtis W.

    2007-09-11

    The invention is a direct contact refrigerant cooling system using a refrigerant floating loop having a refrigerant and refrigeration devices. The cooling system has at least one hermetic container disposed in the refrigerant floating loop. The hermetic container has at least one electronic component selected from the group consisting of capacitors, power electronic switches and gating signal module. The refrigerant is in direct contact with the electronic component.

  16. Directional gear ratio transmissions

    NASA Technical Reports Server (NTRS)

    Lafever, A. E. (Inventor)

    1984-01-01

    Epicyclic gear transmissions which transmit output at a gear ratio dependent only upon the input's direction are considered. A transmission housing envelops two epicyclic gear assemblies, and has shafts extending from it. One shaft is attached to a sun gear within the first epicyclic gear assembly. Planet gears are held symmetrically about the sun gear by a planet gear carrier and are in mesh with both the sun gear and a ring gear. Two unidirectional clutches restrict rotation of the first planet gear carrier and ring gear to one direction. A connecting shaft drives a second sun gear at the same speed and direction as the first planet gear carrier while a connecting portion drives a second planet gear carrier at the same speed and direction as the first ring gear. The transmission's output is then transmitted by the second ring gear to the second shaft. Input is transmitted at a higher gear ratio and lower speed for all inputs in the first direction than in the opposite direction.

  17. A direct advance on advance directives.

    PubMed

    Shaw, David

    2012-06-01

    Advance directives (ADs), which are also sometimes referred to as 'living wills', are statements made by a person that indicate what treatment she should not be given in the event that she is not competent to consent or refuse at the future moment in question. As such, ADs provide a way for patients to make decisions in advance about what treatments they do not want to receive, without doctors having to find proxy decision-makers or having recourse to the doctrine of necessity. While patients can request particular treatments in an AD, only refusals are binding. This paper will examine whether ADs safeguard the autonomy and best interests of the incompetent patient, and whether legislating for the use of ADs is justified, using the specific context of the legal situation in the United Kingdom to illustrate the debate. The issue of whether the law should permit ADs is itself dependent on the issue of whether ADs are ethically justified; thus we must answer a normative question in order to answer the legislative one. It emerges that ADs suffer from two major problems, one related to autonomy and one to consent. First, ADs' emphasis on precedent autonomy effectively sentences some people who want to live to death. Second, many ADs might not meet the standard criteria for informed refusal of treatment, because they fail on the crucial criterion of sufficient information. Ultimately, it transpires that ADs are typically only appropriate for patients who temporarily lose physical or mental capacity. PMID:21133977

  18. Directed network modules

    NASA Astrophysics Data System (ADS)

    Palla, Gergely; Farkas, Illés J.; Pollner, Péter; Derényi, Imre; Vicsek, Tamás

    2007-06-01

    A search technique locating network modules, i.e. internally densely connected groups of nodes in directed networks is introduced by extending the clique percolation method originally proposed for undirected networks. After giving a suitable definition for directed modules we investigate their percolation transition in the Erdos Rényi graph both analytically and numerically. We also analyse four real-world directed networks, including Google's own web-pages, an email network, a word association graph and the transcriptional regulatory network of the yeast Saccharomyces cerevisiae. The obtained directed modules are validated by additional information available for the nodes. We find that directed modules of real-world graphs inherently overlap and the investigated networks can be classified into two major groups in terms of the overlaps between the modules. Accordingly, in the word-association network and Google's web-pages, overlaps are likely to contain in-hubs, whereas the modules in the email and transcriptional regulatory network tend to overlap via out-hubs.

  19. Directivity of singers

    NASA Astrophysics Data System (ADS)

    Jers, Harald

    2005-09-01

    Studies of acoustical balance between singers within a choir by means of room acoustical measurements have shown that the directional sound propagation of the source is important. For this reason the directivity of female and male singers for different vowels has been measured in this investigation. Measurements of a pilot study and some first measurements in 1998 have been supplemented with new measurements and an enhanced setup. A special measurement setup with reference and recording microphones was used to collect the directivity data. A resolution of 10 deg for azimuth and elevation angle was obtained. The results will be shown in 3D spherical plots with frequency adjustments in semitones from 80 to 8000 Hz. The measurements are compared to an artificial singer's directivity, and the influence of a sheet music binder in front of a singer will be shown. The results give information on the directivity of singers and are relevant for the prediction of self-to-other-ratios that result from placement and formation aspects within a choir.

  20. Direct Photons at RHIC

    SciTech Connect

    Gabor,D.

    2008-07-29

    Direct photons are ideal tools to investigate kinematical and thermodynamical conditions of heavy ion collisions since they are emitted from all stages of the collision and once produced they leave the interaction region without further modification by the medium. The PHENIX experiment at RHIC has measured direct photon production in p+p and Au+Au collisions at 200 GeV over a wide transverse momentum (p{sub T}) range. The p+p measurements allow a fundamental test of QCD, and serve as a baseline when we try to disentangle more complex mechanisms producing high p{sub T} direct photons in Au+Au. As for thermal photons in Au+Au we overcome the difficulties due to the large background from hadronic decays by measuring 'almost real' virtual photons which appear as low invariant mass e{sup +}e{sup -} pairs: a significant excess of direct photons is measured above the above next-to-leading order perturbative quantum chromodynamics calculations. Additional insights on the origin of direct photons can be gained with the study of the azimuthal anisotropy which benefits from the increased statistics and reaction plane resolution achieved in RHIC Year-7 data.

  1. Direct conversion technology

    NASA Technical Reports Server (NTRS)

    Massier, Paul F.; Bankston, C. P.; Williams, R.; Underwood, M.; Jeffries-Nakamura, B.; Fabris, G.

    1989-01-01

    The overall objective of the Direct Conversion Technology task is to develop an experimentally verified technology base for promising direct conversion systems that have potential application for energy conservation in the end-use sectors. This report contains progress of research on the Alkali Metal Thermal-to-Electric Converter (AMTEC), and on the Two-Phase Liquid-Metal Magnetohydrodynamic Electrical Generator (LMMHD) for the period January 1, 1989 through December 31, 1989. Research on these concepts was initiated during October 1987. Reports prepared on previous occasions contain discussions on the following other direct conversion concepts: thermoelectric, pyroelectric, thermionic, thermophotovoltaic, thermoacoustic, thermomagnetic, thermoelastic (nitinol heat engines); and also, more complete discussions of AMTEC and LMMHD systems.

  2. Highly directional thermal emitter

    DOEpatents

    Ribaudo, Troy; Shaner, Eric A; Davids, Paul; Peters, David W

    2015-03-24

    A highly directional thermal emitter device comprises a two-dimensional periodic array of heavily doped semiconductor structures on a surface of a substrate. The array provides a highly directional thermal emission at a peak wavelength between 3 and 15 microns when the array is heated. For example, highly doped silicon (HDSi) with a plasma frequency in the mid-wave infrared was used to fabricate nearly perfect absorbing two-dimensional gratings structures that function as highly directional thermal radiators. The absorption and emission characteristics of the HDSi devices possessed a high degree of angular dependence for infrared absorption in the 10-12 micron range, while maintaining high reflectivity of solar radiation (.about.64%) at large incidence angles.

  3. Direct conversion technology

    SciTech Connect

    Massier, P.F.; Back, L.H.; Ryan, M.A.; Fabris, G.

    1992-01-07

    The overall objective of the Direct Conversion Technology task is to develop an experimentally verified technology base for promising direct conversion systems that have potential application for energy conservation in the end-use sectors. This report contains progress of research on the Alkali Metal Thermal-to-Electric Converter (AMTEC) and on the Two-Phase Liquid-Metal MHD Electrical Generator (LMMHD) for the period January 1, 1991 through December 31, 1991. Research on AMTEC and on LMMHD was initiated during October 1987. Reports prepared on previous occasions (Refs. 1--5) contain descriptive and performance discussions of the following direct conversion concepts: thermoelectric, pyroelectric, thermionic, thermophotovoltaic, thermoacoustic, thermomagnetic, thermoelastic (Nitionol heat engine); and also, more complete descriptive discussions of AMTEC and LMMHD systems.

  4. Direct conversion technology

    NASA Astrophysics Data System (ADS)

    Massier, Paul F.; Bankston, C. P.; Williams, R.; Underwood, M.; Jeffries-Nakamura, B.; Fabris, G.

    1989-12-01

    The overall objective of the Direct Conversion Technology task is to develop an experimentally verified technology base for promising direct conversion systems that have potential application for energy conservation in the end-use sectors. This report contains progress of research on the Alkali Metal Thermal-to-Electric Converter (AMTEC), and on the Two-Phase Liquid-Metal Magnetohydrodynamic Electrical Generator (LMMHD) for the period January 1, 1989 through December 31, 1989. Research on these concepts was initiated during October 1987. Reports prepared on previous occasions contain discussions on the following other direct conversion concepts: thermoelectric, pyroelectric, thermionic, thermophotovoltaic, thermoacoustic, thermomagnetic, thermoelastic (nitinol heat engines); and also, more complete discussions of AMTEC and LMMHD systems.

  5. Microsegregation during directional solidification

    NASA Technical Reports Server (NTRS)

    Coriell, S. R.; Mcfadden, G. B.

    1984-01-01

    During the directional solidification of alloys, solute inhomogeneities transverse to the growth direction arise due to morphological instabilities (leading to cellular or dendritic growth) and/or due to convection in the melt. In the absence of convection, the conditions for the onset of morphological instability are given by the linear stability analysis of Mullins and Sekerka. For ordinary solidification rates, the predictions of linear stability analysis are similar to the constitutional supercooling criterion. However, at very rapid solidification rates, linear stability analysis predicts a vast increase in stabilization in comparison to constitutional supercooling.

  6. Modelling directional solidification

    NASA Technical Reports Server (NTRS)

    Wilcox, William R.; Regel, Liya L.

    1994-01-01

    This grant, NAG8-831, was a continuation of a previous grant, NAG8-541. The long range goal of this program has been to develop an improved understanding of phenomena of importance to directional solidification, in order to enable explanation and prediction of differences in behavior between solidification on Earth and in space. Emphasis in the recently completed grant was on determining the influence of perturbations on directional solidification of InSb and InSb-GaSb alloys. In particular, the objective was to determine the influence of spin-up/spin-down (ACRT), electric current pulses and vibrations on compositional homogeneity and grain size.

  7. Direct Conversion Technology

    SciTech Connect

    Back, L.H.; Fabris, G.; Ryan, M.A.

    1992-07-01

    The overall objective of the Direct Conversion Technology task is to develop an experimentally verified technology base for promising direct conversion systems that have potential application for energy conservation in the end-use sectors. Initially, two systems were selected for exploratory research and advanced development. These are Alkali Metal Thermal-to-Electric Converter (AMTEC) and Two-Phase Liquid Metal MD Generator (LMMHD). This report describes progress that has been made during the first six months of 1992 on research activities associated with these two systems. (GHH)

  8. The direction of acceleration

    NASA Astrophysics Data System (ADS)

    Wilhelm, Thomas; Burde, Jan-Philipp; Lück, Stephan

    2015-11-01

    Acceleration is a physical quantity that is difficult to understand and hence its complexity is often erroneously simplified. Many students think of acceleration as equivalent to velocity, a ˜ v. For others, acceleration is a scalar quantity, which describes the change in speed Δ|v| or Δ|v|/Δt (as opposed to the change in velocity). The main difficulty with the concept of acceleration therefore lies in developing a correct understanding of its direction. The free iOS app AccelVisu supports students in acquiring a correct conception of acceleration by showing acceleration arrows directly at moving objects.

  9. Directed flux motor

    NASA Technical Reports Server (NTRS)

    Wilson, Andrew (Inventor); Punnoose, Andrew (Inventor); Strausser, Katherine (Inventor); Parikh, Neil (Inventor)

    2011-01-01

    A directed flux motor described utilizes the directed magnetic flux of at least one magnet through ferrous material to drive different planetary gear sets to achieve capabilities in six actuated shafts that are grouped three to a side of the motor. The flux motor also utilizes an interwoven magnet configuration which reduces the overall size of the motor. The motor allows for simple changes to modify the torque to speed ratio of the gearing contained within the motor as well as simple configurations for any number of output shafts up to six. The changes allow for improved manufacturability and reliability within the design.

  10. Directional spherical multipole wavelets

    SciTech Connect

    Hayn, Michael; Holschneider, Matthias

    2009-07-15

    We construct a family of admissible analysis reconstruction pairs of wavelet families on the sphere. The construction is an extension of the isotropic Poisson wavelets. Similar to those, the directional wavelets allow a finite expansion in terms of off-center multipoles. Unlike the isotropic case, the directional wavelets are not a tight frame. However, at small scales, they almost behave like a tight frame. We give an explicit formula for the pseudodifferential operator given by the combination analysis-synthesis with respect to these wavelets. The Euclidean limit is shown to exist and an explicit formula is given. This allows us to quantify the asymptotic angular resolution of the wavelets.